CN117440942A

CN117440942A - Monomer and polymer compositions and methods of making and using the same

Info

Publication number: CN117440942A
Application number: CN202280035251.6A
Authority: CN
Inventors: U·U·乔杜里; J·K·苏; J·M·查韦斯; M·C·科勒; R·B·泰
Original assignee: Align Technology Inc
Current assignee: Align Technology Inc
Priority date: 2021-04-23
Filing date: 2022-04-25
Publication date: 2024-01-23
Also published as: CN117321108A

Abstract

The present disclosure provides photopolymerizable monomers, photocurable resins comprising one or more such monomers, and polymeric materials formed from the photocurable resins. Further provided herein are methods for preparing the compositions and for use in the manufacture of medical devices (e.g., orthodontic appliances).

Description

Monomer and polymer compositions and methods of making and using the same

Cross reference

The present application is a continuation of U.S. provisional patent application Ser. No. 63/179,004 filed on day 2021, month 4 and 23 and U.S. provisional patent application Ser. No. 63/179,007 filed on day 2021, month 4, each of which is incorporated herein by reference in its entirety.

Incorporation by reference

All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference.

Background

The most recent production methods can be achieved by increasing the viscosity of the material and/or using components with lower vapor pressure and/or high boiling point, and provide better thermo-mechanical properties for many applications by increasing the physical interactions between chains, increasing the average weight of the monomer, the spatial freedom of the monomer (e.g., its potential to rotate around certain chemical bonds, etc.). Thus, it may be advantageous to provide curable resins having components with lower vapor pressures to achieve a high temperature printing process.

Disclosure of Invention

Additive manufacturing techniques, such as photolithography-based additive manufacturing (L-AM), include various techniques for manufacturing objects, such as three-dimensional objects, from photopolymerisable materials. It has traditionally proven difficult to form many medical devices by additive manufacturing techniques. One problem is that existing materials for additive manufacturing are not biocompatible and are less suitable for use in the intra-oral environment or other parts of the human body. Another problem is that existing materials used in additive manufacturing are often not sufficiently tacky to form the precise and/or customizable features required for many appliances. Moreover, many current additive manufacturing techniques have relatively low curing or reaction temperatures for safety and cost considerations, which, for many medical appliances (including dental appliances), undermine the ability to produce products that are stable at and/or above human body temperatures. Yet another problem is that existing materials used for additive manufacturing do not provide the physical, chemical and/or thermo-mechanical properties (elongation, temporal stress relaxation, modulus, durability, toughness, etc.) required for appliances, other dental appliances, hearing aids and/or many medical devices. Thus, existing materials for additive manufacturing lack the ability to deliver forces, torques, moments, and/or other movements that are accurate and consistent with a treatment plan, for many of the properties required in medical devices.

The most recent production methods can be achieved by increasing the viscosity of the material and/or using components with lower vapor pressure and/or high boiling point, and provide better thermo-mechanical properties for many applications by increasing the physical interactions between chains, increasing the average weight of the monomer, the spatial freedom of the monomer (e.g., its potential to rotate around certain chemical bonds, etc.).

In view of the problems mentioned herein, the present disclosure aims to provide curable compositions, for example for high Wen Guangke based photopolymerization processes. These curable compositions may be used in a variety of applications, including those used to form medical devices and/or for use in an intraoral environment, such as intraoral devices, such as orthotics, dilators, or spacers. In particular, in view of the challenges of using printable resins at elevated temperatures, the present disclosure provides photocurable resins that include one or more polymerizable monomers having a low vapor pressure, high boiling point, and in each case the polymerizable monomers have the ability to act as a viscosity modifier, a glass transition temperature modifier, and a crosslinking agent for other polymerizable components present in the curable compositions provided herein. Such polymerizable monomers can provide (e.g., upon photocuring) polymeric materials having properties particularly suitable for use in medical devices (e.g., orthodontic appliances), and thus can meet the need for photocurable compositions that allow for the preparation of materials having a wide range of specific mechanical properties.

In various aspects, the present disclosure provides polymerizable monomers according to formula (I):

(I)

wherein:

x is O, S, NR ⁶ Or SiR ⁷ R ⁸ ；

R ¹ Is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ² is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _3-6 Carbonyl, substituted or unsubstituted C _3-6 Carboxyl, substitutedOr unsubstituted ring (C) _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

R ³ 、R ⁴ and R is ⁵ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y- (CH) ₂ ) _n -R ⁹ The method comprises the steps of carrying out a first treatment on the surface of the Or R is ⁴ And R is ⁵ Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

wherein Y is O, S, NH or C (O) O;

n is an integer from 0 to 6;

R ⁶ 、R ⁷ and R is ⁸ Independently H or substituted or unsubstituted C _1-6 An alkyl group; and is also provided with

R ⁹ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some aspects, R ³ H. In some aspects, R ⁴ H. In some aspects, R ¹ Is H or methyl. In some aspects, X is O. In some aspects, R ⁵ H. In some aspects, R ² Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In some aspects, the polymerizable monomer is selected from:

in some aspects, R ⁵ Is substituted or unsubstituted C _1-6 An alkoxy group. In some aspects, the polymerizable monomers are:

in some aspects, X is S or SiR ⁷ R ⁸ And R is ⁵ Is substituted or unsubstituted C _1-6 An alkyl group. In some aspects, the polymerizable monomers are:

in various aspects, provided herein are polymerizable monomers according to formula (II):

(II)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ¹⁰ is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

R ¹¹ and R is ¹² Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X- (CH) ₂ ) _n -R ¹³ The method comprises the steps of carrying out a first treatment on the surface of the Or R is ¹¹ And R is ¹² Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

wherein X is O, S, NH or C (O) O;

n is an integer from 0 to 6; and is also provided with

R ¹³ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some aspects, R ¹¹ H. In some aspects, R ¹² H. In some aspects, R ¹ Is H or methyl. In some aspects, R ¹⁰ Is substituted or unsubstituted C _1-6 An alkoxy group. In some aspects, the polymerizable monomers are:

In various aspects, provided herein are polymerizable monomers according to formula (III):

(III)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ¹⁴ is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted ring (C) _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substitutedOr unsubstituted heteroaryl;

R ¹⁵ and R is ¹⁶ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X- (CH) ₂ ) _n -R ¹⁷ The method comprises the steps of carrying out a first treatment on the surface of the Or R is ¹⁵ And R is ¹⁶ Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

wherein X is O, S, NH or C (O) O;

n is an integer from 0 to 6; and is also provided with

R ¹⁷ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some aspects, R ¹ Is H or methyl. In some aspects, R ¹⁴ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In some aspects, R ¹⁴ Is a substituted or unsubstituted aryl group. In some aspects, R ¹⁵ And R is ¹⁶ Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl group. In some aspects, the polymerizable monomers are:

in various aspects, provided herein are polymerizable monomers according to formula (IV):

(IV)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ¹⁸ is substituted C _2-6 Alkyl, substituted or unsubstituted C _3-6 Alkyl or substituted or unsubstituted C _3-6 A heteroalkyl group; and is also provided with

R ¹⁹ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl or substituted or unsubstituted C _1-6 And (3) carboxyl.

In some aspects, R ¹ Is H or methyl. In some aspects, R ¹⁸ Is substituted C _2-6 Alkyl and R ¹⁹ Is unsubstituted C _1-6 An alkyl group. In some aspects, the polymerizable monomers are:

in various aspects, provided herein are polymerizable monomers according to formula (V):

(V)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ²⁰ and R is ²² Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl group,Substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ¹ -(CH ₂ ) _a -R ²⁸ ；

R ²¹ And R is ²³ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ² -(CH ₂ ) _b -R ²⁹ ；

R ²⁴ And R is ²⁶ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ³ -(CH ₂ ) _c -R ³⁰ ；

R ²⁵ And R is ²⁷ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁴ -(CH ₂ ) _d -R ³¹ ；

X ¹ 、X ² 、X ³ And X ⁴ Each independently is a bond, O or S;

a. b, c and d are each independently integers from 0 to 6; and is also provided with

R ²⁸ 、R ²⁹ 、R ³⁰ And R is ³¹ Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some aspects, the polymerizable monomer is selected from:

in various aspects, provided herein are polymerizable monomers according to formula (VI):

(VI)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ³² and R is ³⁴ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁵ -(CH ₂ ) _e -R ⁴² ；

R ³³ And R is ³⁵ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁶ -(CH ₂ ) _f -R ⁴³ ；

R ³⁶ And R is ³⁸ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substitutedOr unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁷ -CH ₂ ) _g -R ⁴⁴ ；

R ³⁷ And R is ³⁹ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁸ -(CH ₂ ) _h -R ⁴⁵ ；

R ⁴⁰ Is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _3-6 Alkoxy, substituted or unsubstituted C _3-6 Thioalkoxy, substituted or unsubstituted C _3-6 Carbonyl, substituted or unsubstituted C _3-6 Carboxyl or-X ⁹ -(CH ₂ ) _i -R ⁴⁶ ；

R ⁴¹ Is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ¹⁰ -(CH ₂ ) _j -R ⁴⁷ ；

X ⁵ 、X ⁶ 、X ⁷ 、X ⁸ 、X ⁹ And X ¹⁰ Each independently is a bond, O or S;

e. f, g, h, i and j are each independently integers from 0 to 6; and is also provided with

R ⁴² 、R ⁴³ 、R ⁴⁴ 、R ⁴⁵ 、R ⁴⁶ And R is ⁴⁷ Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some aspects, R ¹ Is H or methyl. In some aspects, the polymerizable monomer is selected from:

in various aspects, provided herein are compounds according to formula (I)

Polymerizable monomer of (IX):

(IX)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ⁷⁷ is nitrile, substituted or unsubstituted C _1-6 Alkyl cyanide or substituted or unsubstituted C _1-6 A carbonyl group;

R ⁷⁸ is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

R ⁷⁹ and R is ⁸⁰ Each independently H, C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstitutedSubstituted heteroaryl; and is also provided with

R ⁸¹ Is substituted or unsubstituted C _1-6 An alkoxy group.

In some aspects, the polymerizable monomer according to any one of formulas (I) - (IV) and (IX) has a vapor pressure of up to 12Pa at 60 ℃. In some aspects, such polymerizable monomers have a vapor pressure of 2Pa to 10Pa at 60 ℃. In some aspects, such polymerizable monomers have a vapor pressure of 2Pa to 5Pa at 60 ℃. In some aspects, such polymerizable monomers have a mass loss of less than 0.5% after heating at 90 ℃ for 2 hours. In some aspects, such polymerizable monomers have a mass loss of 0.1% to 0.45% after heating at 90 ℃ for 2 hours. In some aspects, such polymerizable monomers have a mass loss of 0.05% to 0.25% after heating at 90 ℃ for 2 hours. In some aspects, such polymerizable monomers have a melting point of at least 30 ℃. In some aspects, R of the polymerizable monomer according to any one of formulas (I) - (IV) and (IX) ¹ -R ⁴⁷ Or R is ⁷⁷ -R ⁸¹ One or more of them being halogen, OH, NH ₂ 、NH(C _1-6 Alkyl), N (C) _1-6 Alkyl) (C) _1-6 Alkyl) or C _1-3 Alkyl substitution.

In various aspects, the present disclosure provides a photocurable resin comprising: the polymerizable monomer of any one of claims 1-42; and a photoinitiator. In some examples, the polymerizable monomer reduces the viscosity of the photocurable resin by at least 5% as compared to a resin that does not include the polymerizable monomer. In some examples, the polymerizable monomer reduces the viscosity of the photocurable resin by at least 10%, 20%, 30%, 40%, or 50%. In some examples, such resins may further comprise telechelic oligomers, telechelic polymers, or combinations thereof. In some examples, the telechelic oligomer has a number average molecular weight greater than 500Da but less than 3 kDa. In some examples, the telechelic polymer has a number average molecular weight greater than 5kDa but less than 50 kDa. In some examples, the oligomer and telechelic polymer comprise photoreactive moieties at both ends thereof. In some examples, the photoreactive moiety is an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, siliconCarbene, alkynyl, alkenyl, vinyl ether, maleimide, fumarate, maleate, itaconate, or styryl moieties. In some examples, the photoreactive moiety is an acrylate or methacrylate. In some examples, the photocurable resin is capable of 3D printing at temperatures above 25 ℃. In some examples, the temperature is at least 30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃, or 100 ℃. In some examples, the photocurable resin has a viscosity of 30cP to 50,000cP at the printing temperature. In some examples, the printing temperature is 20 ℃ to 150 ℃. In some examples, the photocurable resin comprises less than 20wt% hydrogen bond units. In some examples, the photocurable resin further comprises a crosslinking modifier, a light blocker, a solvent, a glass transition temperature modifier, or a combination thereof. In some examples, the photocurable resin further comprises from 0.5 to 99.5wt%, from 1 to 99wt%, from 10 to 95wt%, from 20 to 90wt%, from 25 to 60wt%, or from 35 to 50wt% of a polymerizable monomer, oligomer, or combination thereof. In some examples, the photocurable resin is capable of undergoing polymerization-induced phase separation during photocuring. In some examples, the photocurable resin, when polymerized, comprises one or more polymer phases. In some examples, at least one of the one or more polymer phases is a glass transition temperature (T _g ) An amorphous phase of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃ or at least 110 ℃. In some examples, the polymerizable monomer in polymerized form is T _g At least one amorphous phase component at least 60 ℃, 80 ℃, 90 ℃, 100 ℃ or at least 110 ℃. In some examples, at least one of the one or more polymer phases is a crystalline phase comprising a polymeric material. In some examples, the crystalline polymeric material has a melting point of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃. In some examples, at least one of the one or more polymer phases is three-dimensional and has at least one dimension less than 1000 μm, less than 500 μm, less than 250 μm, or less than 200 μm in length.

In various aspects, the present disclosure provides a polymeric material formed from the photocurable resin of any one of claims 43-65. In some examples, the polymeric material hasThere are one or more of the following features: (A) a storage modulus greater than or equal to 200 MPa; (B) Residual flexural stress and/or flexural modulus after 24 hours in a humid environment at 37 ℃ is greater than or equal to 1.5 mpa; (C) Elongation at break greater than or equal to 5% before and after 24 hours in a humid environment at 37 ℃; (D) The water absorption is less than 25wt% when measured after 24 hours in a humid environment at 37 ℃; (E) After 24 hours in a humid environment at 37 ℃, the visible light transmission through the polymeric material is at least 30%; and (F) comprises a plurality of polymer phases, wherein T of at least one of the one or more polymer phases _g At least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃. In some examples, the polymeric material has at least two features of (a), (B), (C), (D), (E), and (F). In some examples, the polymeric material has at least three features of (a), (B), (C), (D), (E), and (F). In some examples, wherein the polymeric material has at least four features of (a), (B), (C), (D), (E), and (F). In some examples, the polymeric material has at least five features of (a), (B), (C), (D), (E), and (F). In some examples, the polymeric material has all of the features in (a), (B), (C), (D), (E), and (F). In some examples, the polymeric material is characterized by a water absorption of less than 20wt%, less than 15wt%, less than 10wt%, less than 5wt%, less than 4wt%, less than 3wt%, less than 2wt%, less than 1wt%, less than 0.5wt%, less than 0.25wt%, or less than 0.1wt%, as measured after 24 hours in a humid environment at 37 ℃. In some examples, the polymeric material has a double bond to single bond conversion of greater than 60% as compared to the photocurable resin as measured by FTIR. In some examples, the ultimate tensile strength of the polymeric material is 10MPa to 100MPa, 15MPa to 80MPa, 20MPa to 60MPa, 10MPa to 50MPa, 10MPa to 45MPa, 25MPa to 40MPa, 30MPa to 45MPa, or 30MPa to 40MPa after 24 hours in a humid environment at 37 ℃. In some examples, the polymeric material is characterized by an elongation at break of greater than 10%, an elongation at break of greater than 20%, an elongation at break of greater than 30%, an elongation at break of 5% to 250%, an elongation at break of 20% to 250%, or an elongation at break of greater than 20% after 24 hours in a humid environment at 37 °c The values are 40% to 250%. In some examples, the polymeric material is characterized by a storage modulus of 0.1MPa to 4000MPa, a storage modulus of 300MPa to 3000MPa, or a storage modulus of 750MPa to 3000MPa after 24 hours in a humid environment at 37 ℃. In some examples, the polymeric material has a flexural stress and/or flexural modulus of 400MPa or greater, 300MPa or greater, 200MPa or greater, 180MPa or greater, 160MPa or greater, 120MPa or greater, 100MPa or greater, 80MPa or greater, 70MPa or greater, 60MPa or greater after 24 hours in a humid environment at 37 ℃. In some examples, at least 40%, 50%, 60%, or 70% of the visible light passes through the polymeric material after 24 hours in a humid environment at 37 ℃. In some examples, the polymeric material is biocompatible, bioinert, or a combination thereof. In some examples, the polymeric material is capable of being 3D printed.

Further provided herein are polymeric films comprising the polymeric materials of the present disclosure. In some examples, the film has a thickness of at least 100 μm and no greater than 3mm.

Further provided herein is an apparatus comprising the polymeric material of the present disclosure or the polymeric film of the present disclosure.

Further provided herein is a medical device comprising the polymeric material of the present disclosure or the polymeric film of the present disclosure.

Further provided herein is a medical device comprising a polymer, wherein the polymer comprises a monomer of formula (VII):

(VII)

wherein:

x is N or CR ⁵⁹ ；

R ¹ Is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ⁴⁸ 、R ⁴⁹ and R is ⁵⁰ Each independently is H, nitrile, substituted or unsubstituted C _1-6 Alkyl cyanide, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y groups ¹ -(CH ₂ ) _a -R ⁶⁰ The method comprises the steps of carrying out a first treatment on the surface of the Or R is ⁴⁸ And R is ⁴⁹ Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

R ⁵¹ 、R ⁵² 、R ⁵³ and R is ⁵⁴ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y groups ² -(CH ₂ ) _b -R ⁶¹ ；

R ⁵⁵ 、R ⁵⁶ 、R ⁵⁷ And R is ⁵⁸ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y groups ³ -(CH ₂ ) _c -R ⁶² ；

R ⁵⁹ Is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y groups ⁴ -(CH ₂ ) _d -R ⁶³ ；

Y ¹ 、Y ² 、Y ³ And Y ⁴ Each independently is a bond, O or S;

R ⁶⁰ 、R ⁶¹ 、R ⁶² And R is ⁶³ Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

Further provided herein is a medical device comprising a polymer, wherein the polymer comprises a monomer of formula (VIII):

(VIII)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ⁶⁴ 、R ⁶⁵ 、R ⁶⁶ and R is ⁶⁷ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ¹ -(CH ₂ ) _a -R ⁷⁴ ；

R ⁶⁸ 、R ⁶⁹ 、R ⁷⁰ And R is ⁷¹ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ² -(CH ₂ ) _b -R ⁷⁵ ；

R ⁷² And R is ⁷³ Each independently isH. Substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ³ -(CH ₂ ) _c -R ⁷⁶ ；

X ¹ 、X ² And X ³ Each independently is a bond, O or S;

a. b and c are each independently integers from 0 to 6; and is also provided with

R ⁷⁴ 、R ⁷⁵ And R is ⁷⁶ Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some examples, R of formula (VII) or (VIII) ¹ Or R is ⁴⁸ -R ⁷⁶ One or more of them being halogen, OH, NH ₂ 、NH(C _1-6 Alkyl), N (C) _1-6 Alkyl) (C) _1-6 Alkyl) or C _1-3 Alkyl substitution. In some examples, the medical instrument is a dental instrument. In some examples, the dental appliance is a dental appliance, a dental dilator, or a dental spacer. In some examples, the medical device can be produced by 3D printing.

In various aspects, provided herein are methods of synthesizing a polymerizable monomer according to any one of formulas (I) - (VI) and (IX), the method comprising isolating the polymerizable monomer in a chemical yield of at least 25%. In such cases, the polymerizable monomer can be synthesized in a chemical yield of at least about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or at least about 97%. Further, the polymerizable monomers of the present disclosure can be synthesized and isolated with a chemical purity of at least about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 97%, or at least about 99%.

In various aspects, provided herein is a method ofA method of forming a polymeric material, the method comprising: (i) providing a photocurable resin of the present disclosure; (ii) exposing the photocurable resin to a light source; and (iii) curing the photocurable resin to form a polymeric material. In some aspects, the method further comprises inducing phase separation during photocuring. In some aspects, inducing phase separation includes generating one or more polymer phases in the polymer material during photocuring. In some aspects, at least one of the one or more polymer phases is a glass transition temperature (T _g ) An amorphous phase of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃ or at least 110 ℃. In some aspects, at least 25%, 50% or 75% of the polymer phase produced during photocuring has a glass transition temperature (T) of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 DEG _g ). In some aspects, the glass transition temperature (T _g ) At least one amorphous phase that is at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃ comprises a polymerizable monomer incorporated into its polymer structure. In some aspects, at least one of the one or more polymer phases is a crystalline phase comprising a crystalline polymer material. In some aspects, the crystalline polymeric material has a melting point of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃. In some aspects, at least one of the one or more polymer phases is three-dimensional and has at least one dimension less than 1000 μm, less than 500 μm, less than 250 μm, or less than 200 μm in length. In some aspects, the polymeric material is characterized by one or more of the following: (i) a storage modulus greater than or equal to 200MPa; (ii) Residual flexural stress and/or flexural modulus after 24 hours in a humid environment at 37 ℃ is greater than or equal to 1.5MPa; (iii) Elongation at break greater than or equal to 5% before and after 24 hours in a humid environment at 37 ℃; (iv) The water absorption is less than 25wt% when measured after 24 hours in a humid environment at 37 ℃; and (v) a visible light transmission through the polymeric material of at least 30% after 24 hours in a humid environment at 37 ℃. In some aspects, the method further comprises manufacturing the medical device from a polymeric material. In some aspects, the medical device is a dental appliance. In some aspects, the dental appliance is a dental appliance, a dental expander, or Dental spacers.

Further provided herein is a method of repositioning teeth of a patient, the method comprising: (i) Generating a treatment plan for the patient, the plan including a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial tooth arrangement to a final tooth arrangement; (ii) Producing a dental appliance according to claim 89 or comprising the polymeric material of any one of claims 66-81; and (iii) moving at least one tooth of the patient with the dental appliance in a plan toward the intermediate tooth arrangement or the final tooth arrangement. In some aspects, producing the dental appliance includes 3D printing of the dental appliance. In some aspects, the method may further include tracking progress of the patient's teeth along the treatment path after the dental appliance is applied to the patient, the tracking including comparing the current arrangement of the patient's teeth to the planned arrangement of the patient's teeth. In some aspects, greater than 60% of the patient's teeth are treated according to the treatment plan 2 weeks after treatment. In some aspects, the dental appliance has at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% of the retained repositioning force on the at least one tooth of the patient after 2 days.

Drawings

The novel features of the invention are set forth with particularity in the appended claims. The patent or application file contains at least one color drawing. After paying the necessary fee, the present office will provide a copy of the patent or patent application publication and color drawing. A better understanding of the features and advantages of the present disclosure will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings of which:

fig. 1A illustrates a tooth repositioning appliance according to an embodiment.

Fig. 1B illustrates a tooth repositioning system according to an embodiment.

Fig. 1C illustrates an orthodontic treatment method using a plurality of appliances according to an embodiment.

Fig. 2 illustrates a method for designing an orthodontic appliance according to an embodiment.

Fig. 3 illustrates a method for digitally planning orthodontic treatment according to an embodiment.

Fig. 4 illustrates the generation and administration of a treatment according to an embodiment of the present disclosure.

FIG. 5 shows a graph of tensile stress as a function of tensile strain at 2 different strain rates (1.7 mm/min and 510 mm/min) for 3 different photocurable polymeric materials P1-P3 each comprising different monomers.

Fig. 6 shows a graph of Dynamic Mechanical Analysis (DMA) results obtained for the polymeric materials P1-P3.

Fig. 7 shows a graph of stress relaxation of polymeric materials P1-P3.

Fig. 8 illustrates lateral and vertical dimensions as used herein.

Fig. 9 shows a schematic configuration of a high Wen Zengcai manufacturing apparatus for curing the curable composition of the present disclosure by using a 3D printing process.

Detailed description of the invention

I. Summary of the invention

The present disclosure provides polymerizable monomers, polymerizable compositions (e.g., curable resins) comprising such monomers, and methods of using and producing such polymerizable monomers and compositions. In various embodiments, the presently described monomers and compositions are photopolymerizable. Thus, in each case, the polymerizable or photopolymerizable monomers of the present disclosure may be compounds according to any of formulas (I) - (VI) and (IX), or polymerized forms as shown in formulas (VII) and (VIII), as part of the polymers used in the medical devices described herein. In various cases, photopolymerizable compositions comprising one or more photopolymerizable monomers can be used in a method of producing a polymeric material. Such methods may include exposing such photopolymerizable compositions to electromagnetic radiation of an appropriate wavelength to initiate the polymerization reaction. In various instances, the present disclosure provides curable (e.g., photocurable) resins that are capable of allowing polymerization-induced phase separation to occur during curing. Such phase separation may produce one or more polymer phases. In some examples, at least one of the one or more phases is an amorphous polymer phase. In some examples, at least one of the one or more phases is a crystalline polymer phase. Such phase separation may provide a polymeric material having physical and mechanical properties that is ideal for use in medical devices such as orthodontic appliances. Thus, in various embodiments, provided herein are medical devices, such as orthodontic appliances, that may include one or more polymeric materials including one or more polymerizable monomers of the present disclosure in polymeric form.

All terms, chemical names, expressions and names have the usual meaning known to a person skilled in the art. As used herein, the terms "comprise" and "comprising" are to be construed as non-limiting, i.e., may include other components than the explicitly named components.

The numerical ranges are to be understood as inclusive, i.e. to include the indicated lower and upper limits. Furthermore, the term "about" as used herein generally refers to and includes plus or minus 10% of the indicated value unless specifically indicated otherwise. For example, "about 10%" may mean a range of 9% to 11%, and "about 1" may include a range of 0.9-1.1.

As used herein, the term "polymer" generally refers to a molecule composed of repeating structural units linked by covalent chemical bonds, characterized by a plurality of repeating units (e.g., equal to or greater than 20 repeating units, typically equal to or greater than 100 repeating units and typically equal to or greater than 200 repeating units) and a molecular weight of greater than or equal to 5,000 daltons (Da) or 5kDa, such as greater than or equal to 10kDa, 15kDa, 20kDa, 30kDa, 40kDa, 50kDa, or 100 kDa. The polymer is typically the polymerization product of one or more monomer precursors. The term polymer includes homopolymers, i.e., polymers consisting essentially of a single repeating monomer species. The term polymer also includes copolymers that are formed when two or more different types of monomers are linked in the same polymer. Copolymers may include two or more monomer subunits and include random, block, alternating, segmented, grafted, tapered, and other copolymers. The term "crosslinked polymer" generally refers to a polymer having one or more linkages between at least two polymer chains, which may result from multivalent monomers that form crosslinking sites upon polymerization.

As used herein, the term "oligomer" generally refers to a molecule composed of repeating structural units linked by covalent chemical bonds, characterized by a number of repeating units that is less than the number of repeating units of the polymer (e.g., equal to or less than 10 repeating units) and a molecular weight that is less than the polymer (e.g., less than 5,000da or 2,000 da). In some examples, the oligomer may be the polymerization product of one or more monomer precursors. In one embodiment, the oligomer or monomer itself cannot be considered a polymer.

As used herein, the terms "telechelic polymer" and "telechelic oligomer" generally refer to polymers or oligomers whose molecules are capable of entering further polymerized molecules through reactive groups.

As used herein, the term "reactive diluent" generally refers to a substance that reduces the viscosity of another substance (e.g., a monomer or curable resin). The reactive diluent may be part of another substance, such as a polymer obtained by a polymerization process. In some examples, the reactive diluent is a curable monomer that, when mixed with the curable resin, reduces the viscosity of the resulting formulation and is incorporated into the polymer resulting from the polymerization of the formulation.

The oligomer and polymer mixtures can be characterized and distinguished from other mixtures of oligomers and polymers by measuring molecular weight and molecular weight distribution.

The average molecular weight (M) is the average number n of repeating units multiplied by the molecular weight or molar mass of the repeating units (M _i ). Number average molecular weight (M) _n ) Is an arithmetic mean, representing the total weight of molecules present divided by the total number of molecules.

Photoinitiators described in the present disclosure can include those that can be activated with light and initiate polymerization of the polymerizable components of the formulation. As used herein, "photoinitiator" generally refers to a compound that is capable of generating free radical species and/or promoting a free radical reaction upon exposure to radiation (e.g., UV or visible light).

As used herein, the term "biocompatible" refers to a material that does not cause immune rejection or deleterious effects when it is disposed of in an in vivo biological environment, referred to herein as an adverse immune response. For example, in embodiments, the biomarker indicative of an immune response varies by less than 10% or less than 20% or less than 25% or less than 40% or less than 50% from a baseline value when a human or animal is exposed to or contacted with the biocompatible material. Alternatively, the immune response may be determined histologically, wherein the local immune response is assessed by visual assessment of markers within and near the material, including immune cells or markers involved in the immune response pathway. In one aspect, the biocompatible material or device does not significantly alter the histologically-determined immune response. In some embodiments, the present disclosure provides biocompatible devices configured for long-term use, e.g., over a period of about several weeks to several months, without eliciting an adverse immune response. Biological effects can be initially assessed by measuring cytotoxicity, sensitization, irritation and intradermal reactivity, acute systemic toxicity, pyrogenicity, subacute/sub-chronic toxicity and/or implantation. Biological tests for supplemental assessment include tests for chronic toxicity.

"bioinert" refers to a material that does not elicit the immune response of a human or animal when it is being disposed of in an in vivo biological environment. For example, when a human or animal is exposed to or contacted with a bioinert material, the biomarker indicative of an immune response remains substantially constant (plus or minus 5% of baseline value). In some embodiments, the present disclosure provides a bioinert device.

When a group of substituents is disclosed herein, it is to be understood that all individual members of the group and all subgroups, including any isomers, enantiomers, and diastereomers of the members of the group, are individually disclosed. When markush groups or other groupings are used herein, all individual members of the group, as well as all combinations and possible subcombinations of the group, are intended to be individually included in this disclosure. When a compound described herein is such that a particular isomer, enantiomer or diastereomer of the compound is not specified, for example, in a formula or chemical name, the description is intended to include each isomer and enantiomer of the compound described alone or in any combination. Moreover, unless otherwise specified, all isotopic variations of the compounds disclosed herein are intended to be encompassed by the present disclosure. The specific names of compounds are intended to be exemplary, as it is known to one of ordinary skill in the art that the same compounds may be named differently.

It should be noted that, as used herein and in the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a monomer" includes a plurality of such monomers and equivalents thereof known to those skilled in the art, and so forth. Furthermore, the terms "a" (or "an"), "one or more" and "at least one" can be used interchangeably herein. It should also be noted that the terms "comprising," "including," and "having" are used interchangeably.

As used herein, "comprising" is synonymous with "including," "containing," or "characterized by" (and is inclusive or open-ended) and does not exclude additional, unrecited elements or method steps. As used herein, "consisting of" does not include any element, step or ingredient not specified in the claim elements. As used herein, "consisting essentially of (consisting essentially of)" does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claims.

As used herein, the term "group" may refer to a functional group of a compound. The group of the compounds of the present invention refers to an atom or collection of atoms that are part of the compound. The groups of the present disclosure may be attached to other atoms of the compound by one or more covalent bonds. Groups may also be characterized in terms of their valency. The present disclosure includes groups characterized by monovalent, divalent, trivalent equivalent states.

As used herein, the term "substituted" refers to a compound (e.g., an alkyl chain) in which hydrogen is substituted with another functional group or atom, as described herein.

As used herein, a polyline in a chemical structure may be used to indicate a bond with the rest of a molecule. For example, the number of the cells to be processed,in (a) and (b)For designating the 1-position as the point of attachment of the 1-methylcyclopentanoate to the rest of the molecule. Alternatively, for example +.>In (a) and (b)Can be used to indicate that a given moiety, i.e., the cyclohexyl moiety in this example, is attached to the molecule by a bond that is "blocked" with a wavy line.

Alkyl includes straight chain, branched and cyclic alkyl groups unless otherwise defined for a compound or genus of compounds. Alkyl groups include those having 1 to 30 carbon atoms unless otherwise defined. Thus, alkyl groups may include small alkyl groups having 1 to 3 carbon atoms, medium length alkyl groups having 4 to 10 carbon atoms, and long alkyl groups having more than 10 carbon atoms, particularly those having 10 to 30 carbon atoms. The term "cycloalkyl" particularly refers to an alkyl group having a ring structure, e.g., a ring structure comprising 3-30 carbon atoms, optionally 3-20 carbon atoms, and optionally 3-10 carbon atoms, including alkyl groups having one or more rings. Cycloalkyl includes those having a 3-, 4-, 5-, 6-, 7-, 8-, 9-or 10-membered carbocyclic ring, especially those having a 3-, 4-, 5-, 6-, 7-or 8-membered ring. Carbocycles in cycloalkyl groups may also carry alkyl groups. Cycloalkyl groups may include bicycloalkyl and tricycloalkyl groups. Alkyl groups are optionally substituted as described herein. Wherein substituted alkyl groups may include alkyl groups substituted with aryl groups, which in turn may be optionally substituted. Specific alkyl groups include methyl, ethyl, n-propyl, isopropyl, and cyclopropyl Group, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, branched pentyl, cyclopentyl, n-hexyl, branched hexyl and cyclohexyl, all of which are optionally substituted. Unless otherwise defined herein, substituted alkyl includes perhalogenated or semi-halogenated alkyl groups, such as alkyl groups having one or more hydrogens substituted with one or more fluorine, chlorine, bromine and/or iodine atoms. Thus, substituted alkyl groups may include fully fluorinated or semi-fluorinated alkyl groups, such as alkyl groups in which one or more hydrogens are replaced with one or more fluorine atoms. Alkoxy is an alkyl group modified by attachment to oxygen, may be represented by the formula R-O, and may also be referred to as an alkyl ether group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, and heptoxy. Alkoxy includes substituted alkoxy groups in which the alkenyl portion of the group is substituted, as provided herein in connection with the description of alkyl. As used herein, meO-refers to CH ₃ O-. Furthermore, as used herein, thioalkoxy is an alkyl group modified by attachment to a sulfur atom (rather than oxygen) and may be represented by the formula R-S.

Alkenyl includes straight chain, branched, and cyclic alkenyl. Alkenyl groups include those having 1, 2, or more double bonds, and those in which two or more double bonds are conjugated double bonds. Alkenyl groups include those having 2 to 20 carbon atoms unless otherwise defined herein. Alkenyl groups include small alkenyl groups having 2 to 3 carbon atoms. Alkenyl groups include medium length alkenyl groups having 4 to 10 carbon atoms. Alkenyl groups include alkenyl groups having more than 10 carbon atoms, particularly those having 10 to 20 carbon atoms. Cycloalkenyl groups include those wherein the double bond is in the ring or in an alkenyl group attached to the ring. The term cycloalkenyl refers in particular to alkenyl groups having a ring structure, including those having a 3-, 4-, 5-, 6-, 7-, 8-, 9-or 10-membered carbocyclic ring and in particular having a 3-, 4-, 5-, 6-, 7-or 8-membered ring. Carbocycles in cycloalkenyl groups may also carry alkyl groups. Cycloalkenyl groups may include bicycloalkenyl and tricycloalkenyl. Alkenyl groups are optionally substituted. Unless otherwise defined herein, wherein substituted alkenyl groups include those substituted with alkyl or aryl groups, these groups may in turn be optionally substituted. Specific alkenyl groups include vinyl, prop-1-enyl, prop-2-enyl, cycloprop-1-enyl, but-2-enyl, cyclobut-1-enyl, cyclobut-2-enyl, pent-1-enyl, pent-2-enyl, branched pentenyl, cyclopent-1-enyl, hex-1-enyl, branched hexenyl, cyclohexenyl, all of which are optionally substituted. Substituted alkenyl groups may include fully halogenated or semi-halogenated alkenyl groups, such as alkenyl groups having one or more hydrogens substituted with one or more fluorine, chlorine, bromine, and/or iodine atoms. Substituted alkenyl groups include fully fluorinated or semi-fluorinated alkenyl groups, such as alkenyl groups having one or more hydrogen atoms substituted with one or more fluorine atoms.

Aryl includes groups having one or more 5-, 6-, 7-, or 8-membered aromatic rings (including heterocyclic aromatic rings). The term heteroaryl refers in particular to an aryl group having at least one 5-, 6-, 7-or 8-membered heterocyclic aromatic ring. An aryl group may comprise one or more fused aromatic rings, including one or more fused heteroaromatic rings, and/or a combination of one or more aromatic rings and one or more non-aromatic rings that may be fused or linked by covalent bonds. The heterocyclic aromatic ring may include one or more N, O or S atoms in the ring. The heterocyclic aromatic ring may include those having one, two or three N atoms, those having one or two O atoms and those having one or two S atoms or combinations of one or two or three N, O or S atoms. Aryl is optionally substituted. Wherein substituted aryl groups include those substituted with alkyl or aryl groups, which groups may in turn be optionally substituted. Specific aryl groups include phenyl, biphenyl, pyrrolidinyl, imidazolidinyl, tetrahydrofuranyl, tetrahydrothienyl, furanyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl,Group, thiazolyl, pyrazolyl, pyridinyl, benzo +. >Azolyl, benzothiadiazolyl and naphthyl, all of which are optionally substituted. Taking outSubstituted aryl groups may include fully halogenated or semi-halogenated aryl groups, such as aryl groups having one or more hydrogens substituted with one or more fluorine, chlorine, bromine and/or iodine atoms. Substituted aryl groups include fully fluorinated or semi-fluorinated aryl groups, such as aryl groups in which one or more hydrogens are replaced with one or more fluorine atoms. Aryl groups include, but are not limited to, aromatic-or heterocyclic-aromatic-containing groups corresponding to any of the following: benzene, naphthalene, naphthoquinone, diphenylmethane, fluorene, anthracene, anthraquinone, phenanthrene, naphthacene, naphthacenedione, pyridine, quinoline, isoquinoline, indole, isoindole, pyrrole, imidazole,>thiazole, pyrazole, pyrazine, pyrimidine, purine, benzimidazole, furan, benzofuran, dibenzofuran, carbazole, acridine, acridone, phenanthridine, thiophene, benzothiophene, dibenzothiophene, xanthene, xanthone, flavone, coumarin, azulene, or anthracyclines. As used herein, groups corresponding to the groups listed above expressly include aromatic or heterocyclic aromatic groups listed herein, including monovalent, divalent, and more polyvalent groups, provided in covalently bonded configurations at any suitable point of attachment in compounds of the present disclosure. In some embodiments, aryl groups contain 5 to 30 carbon atoms. In some embodiments, the aryl group contains one aromatic or heteroaromatic six-membered ring and one or more additional five-or six-membered aromatic or heteroaromatic rings. In embodiments, aryl groups contain 5 to 18 carbon atoms in the ring. The aryl group optionally has one or more aromatic or heterocyclic aromatic rings with one or more electron donating groups, electron withdrawing groups, and/or targeting ligands provided as substituents.

Arylalkyl is an alkyl group substituted with one or more aryl groups, wherein the alkyl group optionally carries additional substituents and the aryl group is optionally substituted. A particular alkylaryl group is a phenyl substituted alkyl group, such as phenylmethyl. Alkylaryl groups may alternatively be described as aryl groups substituted with one or more alkyl groups, wherein the alkyl groups optionally bear additional substituents, and the aryl groups are optionally substituted. Specific alkylaryl groups are alkyl substituted phenyl groups, such as methylphenyl. Substituted arylalkyl groups include fully halogenated or semi-halogenated arylalkyl groups, such as arylalkyl groups having one or more alkyl groups and/or aryl groups having one or more hydrogens substituted with one or more fluorine, chlorine, bromine and/or iodine atoms.

As used herein, the terms "alkylene" and "alkylene group" are used synonymously and refer to the divalent group "-CH" derived from an alkyl group as defined herein ₂ - ". The present disclosure includes compounds having one or more alkylene groups. The alkylene groups in some compounds act as linking groups and/or spacer groups. The compounds of the present disclosure may have substituted and/or unsubstituted C ₁ -C ₂₀ Alkylene, C ₁ -C ₁₀ Alkylene and C ₁ -C ₆ An alkylene group.

As used herein, the terms "cycloalkylene" and "cycloalkylene group" are used synonymously and refer to a divalent group derived from a cycloalkyl group as defined herein. The present disclosure includes compounds having one or more cycloalkylene groups. Cycloalkyl groups in some compounds act as linking groups and/or spacer groups. The compounds of the present disclosure may have substituted and/or unsubstituted C ₃ -C ₂₀ Cycloalkylene, C ₃ -C ₁₀ Cycloalkylene and C ₃ -C ₅ Cycloalkylene radicals.

As used herein, the terms "arylene" and "arylene group" are used synonymously and refer to a divalent group derived from an aryl group as defined herein. The present disclosure includes compounds having one or more arylene groups. In some embodiments, arylene is a divalent group derived from an aryl group and removing a hydrogen atom from two ring carbon atoms of the aryl ring of the aryl group. Arylene groups in some compounds act as linking groups and/or spacer groups. Arylene groups in some compounds act as chromophores, fluorophores, aromatic tentacles, dyes, and/or imaging groups. The compounds of the present disclosure include substituted and/or unsubstituted C ₃ -C ₃₀ Arylene group, C ₃ -C ₂₀ Arylene group, C ₃ -C ₁₀ Arylene groupC ₁ -C ₅ Arylene groups.

As used herein, the terms "heteroarylene" and "heteroarylene group" are used synonymously and refer to a divalent group derived from a heteroaryl group as defined herein. The present disclosure includes compounds having one or more heteroarylenes. In some embodiments, a heteroaryl group is a divalent group derived from a heteroaryl group and removing a hydrogen atom from two ring carbon atoms or ring nitrogen atoms of a heteroaromatic or aromatic ring of the heteroaryl group. The heteroarylene group in some compounds acts as a linking group and/or a spacer group. The heteroarylene group in some compounds acts as a chromophore, aromatic tentacle, fluorophore, dye, and/or imaging group. The compounds of the present disclosure include substituted and/or unsubstituted C ₃ -C ₃₀ Heteroarylene, C ₃ -C ₂₀ Heteroarylene, C ₁ -C ₁₀ Heteroarylene and C ₃ -C ₅ Heteroaryl groups.

As used herein, the terms "alkenylene" and "alkenylene group" are used synonymously and refer to a divalent group derived from an alkenyl group as defined herein. The present invention includes compounds having one or more alkenylene groups. Alkenylene groups in some compounds act as linking groups and/or spacer groups. The compounds of the present disclosure include substituted and/or unsubstituted C ₂ -C ₂₀ Alkenylene, C ₂ -C ₁₀ Alkenylene and C ₂ -C ₅ Alkenylene radicals.

As used herein, the terms "cycloalkenyl" and "cycloalkenyl group" are used synonymously and refer to a divalent group derived from a cycloalkenyl group as defined herein. The present disclosure includes compounds having one or more cycloalkenyl groups. The cycloalkenyl groups in some compounds act as linking and/or spacer groups. The compounds of the present disclosure include substituted and/or unsubstituted C ₃ -C ₂₀ Cycloalkenyl, C ₃ -C ₁₀ Cycloalkenyl and C ₃ -C ₅ Cycloalkenyl groups.

As used herein, the terms "alkynylene" and "alkynylene group" are used synonymously and refer to a divalent group derived from an alkynyl group as defined herein.The present disclosure includes compounds having one or more alkynylene groups. Alkynylene groups in some compounds act as linking groups and/or spacer groups. The compounds of the present disclosure include substituted and/or unsubstituted C ₂ -C ₂₀ Alkynylene, C ₂ -C ₁₀ Alkynylene and C ₂ -C ₅ Alkynylene groups.

As used herein, the terms "halo" and "halogen" are used interchangeably and refer to a halogen group, such as fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I)

The term "heterocycle" refers to a ring structure that contains at least one other atom in the ring in addition to carbon. Examples of such heteroatoms include nitrogen, oxygen, and sulfur. Heterocyclic rings include heterocyclic alicyclic rings and heterocyclic aromatic rings. Examples of heterocyclic rings include, but are not limited to, pyrrolidinyl, piperidinyl, imidazolidinyl, tetrahydrofuranyl, tetrahydrothienyl, furanyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl, Radicals, thiazolyl, pyrazolyl, pyridinyl, and benzoOxazolyl, benzothiadiazolyl, triazolyl, and tetrazolyl. The atoms of the heterocyclic ring may be combined with a wide variety of other atoms and functional groups, for example provided as substituents.

The term "carbocycle" refers to a ring structure that contains only carbon atoms in the ring. Carbon atoms of the carbocycle may be bonded to a variety of other atoms and functional groups, for example, provided as substituents.

The term "cycloaliphatic ring" refers to a ring or condensed rings that are not aromatic. Alicyclic rings include carbocyclic and heterocyclic rings.

The term "aromatic ring" refers to a ring or multiple condensed rings comprising at least one aromatic ring group. The term aromatic ring includes aromatic rings comprising carbon, hydrogen and heteroatoms. Aromatic rings include carbocyclic and heterocyclic aromatic rings. An aromatic ring is a component of an aryl group.

The term "fused ring" or "fused ring structure" refers to a plurality of cycloaliphatic and/or aromatic rings provided in a fused ring configuration, such as fused rings that share at least two ring carbon atoms and/or heteroatoms.

As used herein, the term "alkoxyalkyl" refers to a substituent of the formula alkyl-O-alkyl.

As used herein, the term "polyhydroxyalkyl" refers to substituents having 2 to 12 carbon atoms and 2 to 5 hydroxyl groups, such as 2, 3-dihydroxypropyl, 2,3, 4-trihydroxybutyl, or 2,3,4, 5-tetrahydroxypentyl residues.

As used herein, the term "polyalkoxyalkyl" refers to a formula alkyl- (alkoxy) _n -substituents of alkoxy groups, wherein n is an integer from 1 to 10, such as 1-4, and in some embodiments from 1 to 3.

As used herein, the term "heteroalkyl" generally refers to an alkyl, alkenyl, or alkynyl group as defined herein, wherein at least one carbon atom of the alkyl group is replaced with a heteroatom. In some examples, the heteroalkyl group may contain 1 to 18 non-hydrogen atoms (carbon and heteroatoms), or 1 to 12 non-hydrogen atoms, or 1 to 6 non-hydrogen atoms, or 1 to 4 non-hydrogen atoms in the chain. Heteroalkyl groups may be straight or branched chain and may be saturated or unsaturated. Unsaturated heteroalkyl groups have one or more double bonds and/or one or more triple bonds. Heteroalkyl groups may be unsubstituted or substituted. Exemplary heteroalkyl groups include, but are not limited to, alkoxyalkyl groups (e.g., methoxymethyl) and aminoalkyl groups (e.g., alkylaminoalkyl groups and dialkylaminoalkyl groups). Heteroalkyl groups may be optionally substituted with one or more substituents.

As used herein, the term "carbonyl", e.g., at C _1-6 In the context of carbonyl substituents, generally refers to carbon chains of a given length (e.g., C _1-6 ) Wherein each carbon atom of a given carbon chain may form a carbonyl bond, provided that it is chemically feasible in terms of the valence of that carbon atom. Thus, in some examples, "C _1-6 Carbonyl "substituent means a carbon chain of 1 to 6 carbon atoms and the terminal carbon contains a carbonyl function, or the internal carbon contains a carbonyl function, in which case the substituent may beDescribed as ketones. As used herein, the term "carboxy", e.g., at C _1-6 In the context of carboxyl substituents, generally refers to carbon chains of a given length (e.g., C _1-6 ) Wherein the terminal carbon contains a carboxyl functionality unless otherwise defined herein.

For any of the groups described herein that contain one or more substituents, it is to be understood that these groups do not contain any substitution or pattern of substitution that is sterically impractical and/or synthetically infeasible. Furthermore, the compounds of the present disclosure include all stereochemical isomers resulting from the substitution of these compounds.

Unless otherwise defined herein, any optional substituents of alkyl, alkenyl, and aryl groups include substitution with one or more of the following substituents, and the like:

halogen, including fluorine, chlorine, bromine or iodine;

pseudohalides, including-CN, -OCN (cyanate), -NCO (isocyanate), -SCN (thiocyanate), and-NCS (isothiocyanate);

-COOR, wherein R is hydrogen or alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which groups are optionally substituted;

-COR, wherein R is hydrogen or alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which groups are optionally substituted;

-CON(R) ₂ wherein each R is independently of each other R is hydrogen or alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; and wherein R and R may form a ring, which may contain one or more double bonds and may contain one or more additional carbon atoms;

-OCON(R) ₂ wherein each R is independently of each other R is hydrogen or alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; and wherein R and R may form a ring which may contain one or more double bonds and may contain one or more additional carbon atoms；

-N(R) ₂ Wherein each R is independently of each other R is hydrogen or alkyl or acyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl, phenyl or acetyl, all of which are optionally substituted; and wherein R and R may form a ring, which may contain one or more double bonds and may contain one or more additional carbon atoms;

-SR, wherein R is hydrogen or alkyl or aryl, more particularly wherein R is hydrogen, methyl, ethyl, propyl, butyl or phenyl, which is optionally substituted;

-SO ₂ r or-SOR, wherein R is alkyl or aryl, more specifically wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted;

-OCOOR, wherein R is alkyl or aryl;

-SO ₂ N(R) ₂ wherein each R is independently of each other R is hydrogen or alkyl or aryl, all of which are optionally substituted, and wherein R and R may form a ring which may contain one or more double bonds and may contain one or more additional carbon atoms; and

-OR, wherein R is H, alkyl, aryl OR acyl, all of which are optionally substituted. In one particular example, R may be an acyl-generating-OCOR ", wherein R" is hydrogen or alkyl or aryl, more particularly wherein R "is methyl, ethyl, propyl, butyl or phenyl, all of which groups are optionally substituted.

Specific substituted alkyl groups include haloalkyl groups, particularly trihalomethyl groups and particularly trifluoromethyl groups. Specific substituted aryl groups include mono-, di-, tri-, tetra-and pentahalo-substituted phenyl groups; mono-, di-, tri-, tetra-, penta-, hexa-, and heptahalo-substituted naphthyl; 3-or 4-halo-substituted phenyl, 3-or 4-alkyl-substituted phenyl, 3-or 4-alkoxy-substituted phenyl, 3-or 4-RCO-substituted phenyl, 5-or 6-halo-substituted naphthyl. More specifically, substituted aryl groups include acetylphenyl, especially 4-acetylphenyl; fluorophenyl, in particular 3-fluorophenyl and 4-fluorophenyl; chlorophenyl, in particular 3-chlorophenyl and 4-chlorophenyl; methylphenyl, in particular 4-methylphenyl; and methoxyphenyl, in particular 4-methoxyphenyl.

With respect to any of the above groups containing one or more substituents, it is to be understood that these groups do not contain any substitution or pattern of substitution that is sterically impractical and/or synthetically infeasible. Furthermore, the compounds of the present disclosure include all stereochemical isomers resulting from the substitution of these compounds.

Polymerizable monomers

The present disclosure provides polymerizable monomers. The polymerizable monomers of the present disclosure can be used as part of a polymerizable composition (e.g., a photocurable resin). As described herein, polymerizable monomers according to the present disclosure can be used as reactive diluents for, for example, high viscosity curable resins, and in some embodiments, crosslinked polymers can also be provided that can have useful thermo-mechanical properties for use in devices such as medical appliances (e.g., orthodontic appliances).

In various embodiments, the polymerizable monomers herein may be compounds according to formula (I):

(I)

wherein:

x is O, S, NR ⁶ Or SiR ⁷ R ⁸ ；

R ¹ Is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ² is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _3-6 Carbonyl, substituted or unsubstituted C _3-6 Carboxyl, substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

R ³ 、R ⁴ and R is ⁵ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y- (CH) ₂ ) _n -R ⁹ Or R is ⁴ And R is ⁵ Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

wherein Y is O, S, NH or C (O) O;

n is an integer from 0 to 6;

(I)

wherein:

x is O, S, NR ⁶ Or SiR ⁷ R ⁸ ；

R ¹ Is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ² is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _3-6 Carbonyl, substituted or unsubstituted C _3-6 Carboxyl, substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted orUnsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

R ³ is H, substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y- (CH) ₂ ) _n -R ⁹ The method comprises the steps of carrying out a first treatment on the surface of the Or R is ⁴ And R is ⁵ Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

R ⁴ and R is ⁵ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y- (CH) ₂ ) _n -R ⁹ The method comprises the steps of carrying out a first treatment on the surface of the Or R is ⁴ And R is ⁵ Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

wherein Y is O, S, NH or C (O) O;

n is an integer from 0 to 6;

R ⁹ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

In some examples, R ³ H. In some examples, R ³ Is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y- (CH) ₂ ) _n -R ⁹ . In some examples, R ³ Is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 An alkoxy group. In some examples, R ³ Is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _3-6 An alkoxy group. In some examples, R ³ Is substituted or unsubstituted C _4-6 Alkyl or substituted or unsubstituted C _4-6 An alkoxy group.

In some examples, R ⁴ H. In some cases, R ⁴ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y- (CH) ₂ ) _n -R ⁹ . In some cases, R ⁴ Is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _3-6 Alkoxy, substituted or unsubstituted C _3-6 Thioalkoxy groups. In some cases, R ⁴ Is substituted or unsubstituted C _3-6 Alkyl or substituted or unsubstituted C _3-6 An alkoxy group. In some cases, R ⁴ Is substituted or unsubstituted C _4-6 Alkyl or substituted or unsubstituted C _4-6 An alkoxy group.

In each case, R ¹ Is H or methyl. In some examples, X is O. In some cases, R ³ 、R ⁴ And R is ⁵ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y- (CH) ₂ ) _n -R ⁹ . In some cases, R ³ 、R ⁴ And R is ⁵ Each independently is H, substituted or unsubstituted C _1-6 Alkyl or substituted or unsubstituted C _1-6 An alkoxy group. In some cases, R ³ 、R ⁴ And R is ⁵ At least one of which is substituted or unsubstituted C _1-6 An alkoxy group.

In some examples, R ⁵ H. In some cases, R ⁵ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y- (CH) ₂ ) _n -R ⁹ . In some cases, R ⁵ Is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _3-6 Alkoxy, substituted or unsubstituted C _3-6 Thioalkoxy groups. In some cases, R ⁵ Is substituted or unsubstituted C _3-6 Alkyl or substituted or unsubstituted C _3-6 An alkoxy group. In some cases, R ⁵ Is substituted or unsubstituted C _4-6 Alkyl or substituted or unsubstituted C _4-6 An alkoxy group.

In some embodiments, R ² Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In some cases, R ² Is an unsubstituted ring (C _3-8 ) Alkyl, not takenSubstituted ring (C) _3-8 ) Heteroalkyl, unsubstituted aryl, or unsubstituted heteroaryl. In some cases, R ² Is a substituted or unsubstituted ring (C _3-8 ) Alkyl or substituted or unsubstituted aryl. In some cases, R ² Is an unsubstituted ring (C _3-8 ) Alkyl or unsubstituted aryl. In some cases, R ² Is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _3-6 Carbonyl, substituted or unsubstituted C _3-6 And (3) carboxyl. In some cases, R ² Is unsubstituted C _3-6 Alkyl, unsubstituted C _3-6 Heteroalkyl, unsubstituted C _3-6 Carbonyl or unsubstituted C _3-6 And (3) carboxyl. In some cases, R ² Is substituted or unsubstituted C _3-6 Alkyl or substituted or unsubstituted C _3-6 A heteroalkyl group. In some cases, R ² Is unsubstituted C _3-6 Alkyl or unsubstituted C _3-6 A heteroalkyl group.

In such a case, the polymerizable monomer may be selected from:

in some embodiments, R ⁵ Is substituted or unsubstituted C _1-6 An alkoxy group. In such a case, the polymerizable monomer may be:

in some embodiments, X is S or SiR ⁷ R ⁸ And R is ⁵ Is substituted or unsubstituted C _1-6 An alkyl group. In such a case, the polymerizable monomer may be:

in various embodiments, the polymerizable monomer herein may be a compound according to formula (II):

(II)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ¹¹ and R is ¹² Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X- (CH) ₂ ) _n -R ¹³ Or R is ¹¹ And R is ¹² Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

wherein X is O, S, NH or C (O) O;

n is an integer from 0 to 6; and is also provided with

R ¹³ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, orSubstituted or unsubstituted heteroaryl.

In some examples, R ¹¹ H. In some examples, R ¹² H. In each case R ¹ Is H or methyl. In some examples, R ¹¹ And R is ¹² Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X- (CH) ₂ ) _n -R ¹³ . In some examples, R ¹¹ And R is ¹² Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Alkoxy or substituted or unsubstituted C _1-6 Thioalkoxy groups. In some examples, R ¹¹ And R is ¹² Each independently is H, substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Alkoxy or substituted or unsubstituted C _3-6 Thioalkoxy groups. In some examples, R ¹¹ And R is ¹² Each independently is H, substituted or unsubstituted C _3-6 An alkyl group. In some examples, R ¹¹ And R is ¹² Each independently is H, substituted or unsubstituted C _3-6 An alkoxy group. In some examples, R ¹¹ And R is ¹² At least one of which is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X- (CH) ₂ ) _n -R ¹³ 。

In some examples, R ¹⁰ Is substituted or unsubstituted C _1-6 An alkoxy group. In such a case, the polymerizable monomer may be:

in various embodiments, the polymerizable monomer herein may be a compound according to formula (III):

(III)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ¹⁴ is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted ring (C) _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

R ¹⁵ and R is ¹⁶ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X- (CH) ₂ ) _n -R ¹⁷ Or R is ¹⁵ And R is ¹⁶ Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

wherein X is O, S, NH or C (O) O;

n is an integer from 0 to 6; and is also provided with

(III)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ¹⁵ and R is ¹⁶ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X- (CH) ₂ ) _n -R ¹⁷ Wherein R is ¹⁵ And R is ¹⁶ At most one of (a) is H;

wherein X is O, S, NH or C (O) O;

n is an integer from 0 to 6; and is also provided with

In some examples, R ¹ Is H or methyl. In some cases, where R ¹⁴ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In such a case, wherein R ¹⁴ May be substituted or unsubstituted aryl.

In some examples, R ¹⁴ Is substituted or unsubstituted C _3-6 Alkyl or substituted or unsubstituted C _3-6 A heteroalkyl group. In some examples, R ¹⁴ Is substituted or unsubstituted C _3-4 Alkyl, substituted or unsubstituted C _3-4 Heteroalkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl or substituted or unsubstituted heteroaryl. In some examples, R ¹⁴ Is substituted or unsubstituted C _3-6 An alkyl group. In some examples, R ¹⁴ Is unsubstituted C _3-6 An alkyl group.

In some examples, R ¹⁵ And R is ¹⁶ At most one of which is H. In some examples, R ¹⁵ And R is ¹⁶ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X- (CH) ₂ ) _n -R ¹⁷ . In some examples, R ¹⁵ And R is ¹⁶ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Alkoxy or substituted or unsubstituted C _1-6 Thioalkoxy groups. In some examples, R ¹⁵ And R is ¹⁶ Each independently is H, substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Alkoxy or substituted or unsubstituted C _3-6 Thioalkoxy groups. In some examples, R ¹⁵ And R is ¹⁶ Each independently is H, substituted or unsubstituted C _3-6 An alkyl group. In some examples, R ¹⁵ And R is ¹⁶ Each independently is H, substituted or unsubstituted C _3-6 An alkoxy group.

In some examples, R ¹⁵ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstitutedC _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X- (CH) ₂ ) _n -R ¹⁷ . In some examples, R ¹⁶ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X- (CH) ₂ ) _n -R ¹⁷ . In some examples, R ¹⁵ And R is ¹⁶ At least one of which is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy or substituted or unsubstituted C _1-6 Thioalkoxy groups. In some examples, R ¹⁵ And R is ¹⁶ Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl group.

In such a case, the polymerizable monomer may be:

in some cases, the compound according to formula (III) has a structure according to formula (IIIa) below:

wherein:

R ⁸² is hydrogen, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, OR ⁸³ 、-NR ⁸³ R ⁸⁴ 、SR ⁸³ Or halogen; and is also provided with

R ⁸³ And R is ⁸⁴ Each occurrence of (a) is independently selected from hydrogen and C _1-3 Alkyl, or wherein R ⁸³ And R is ⁸⁴ Together form a 4-, 5-, 6-, 7-or 8-membered ring substituted or unsubstituted heterocycle. In some examples, R ⁸² -R ⁸⁴ One or more of them being halogen, OH, NH ₂ 、NH(C _1-6 Alkyl), N (C) _1-6 Alkyl) (C) _1-6 Alkyl) or C _1-3 Alkyl substitution. In some examples, R ⁸² -R ⁸⁴ One or more of them being halogen, OH or NH ₂ And (3) substitution.

In various embodiments, the polymerizable monomer herein may be a compound according to formula (IV):

(IV)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

(IV)

wherein:

R ¹ is H, substituted or unsubstitutedSubstituted C _1-3 Alkyl or halogen;

R ¹⁸ is substituted C _3-6 Alkyl, unsubstituted C _4-6 Alkyl or substituted or unsubstituted C _3-6 A heteroalkyl group; and is also provided with

In some examples, R ¹ Is H or methyl. In some examples, R ¹⁸ Is substituted C _3-6 Alkyl or unsubstituted C _4-6 An alkyl group. In some examples, R ¹⁸ Is unsubstituted C _4-6 An alkyl group. In some examples, R ¹⁹ Is substituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl or substituted or unsubstituted C _1-6 And (3) carboxyl. In some examples, R ¹⁹ Is substituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl or substituted or unsubstituted C _1-6 An alkoxy group. In some examples, R ¹⁸ Is substituted or unsubstituted C _3-6 Alkyl and R ¹⁹ Is substituted or unsubstituted C _1-6 An alkoxy group. In some examples, R ¹⁸ Is substituted or unsubstituted C _3-6 Alkyl and R ¹⁹ Is substituted or unsubstituted C _1-6 An alkyl group. In some examples, R ¹⁸ Is substituted or unsubstituted C _3-6 Alkyl and R ¹⁹ Is substituted or unsubstituted C _1-6 A heteroalkyl group. In some examples, R ¹⁸ Is substituted or unsubstituted C _3-4 Alkyl and R ¹⁹ Is substituted or unsubstituted C _1-3 An alkoxy group. In some examples, R ¹⁸ Is substituted or unsubstituted C _3-4 Alkyl and R ¹⁹ Is substituted or unsubstituted C _1-3 An alkyl group. In some examples, R ¹⁸ Is substituted or unsubstituted C _3-4 Alkyl and R ¹⁹ Is substituted or unsubstituted C _1-3 A heteroalkyl group. In some examples, R ¹⁸ Is substituted C _2-6 Alkyl and R ¹⁹ Is unsubstituted C _1-6 An alkyl group. In such a case, the polymerizable monomer may be:

in various embodiments, the polymerizable monomer herein may be a compound according to formula (V):

(V)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ²⁰ and R is ²² Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ¹ -(CH ₂ ) _a -R ²⁸ ；

X ¹ 、X ² 、X ³ And X ⁴ Each independently is a bond, O or S;

(V)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ²⁰ and R is ²² Each independently is substituted or unsubstituted C _4-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl group,Substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ¹ -(CH ₂ ) _a -R ²⁸ ；

R ²⁴ And R is ²⁶ Each independently is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _2-6 Carboxyl or-X ³ -(CH ₂ ) _c -R ³⁰ ；

X ¹ 、X ² 、X ³ And X ⁴ Each independently is a bond, O or S;

R ²⁸ 、R ²⁹ 、R ³⁰ And R is ³¹ Each independently is a substituted ring (C) _3-8 ) Alkyl, substituted ring (C) _3-8 ) Heteroalkyl, substituted aryl, or substituted or unsubstituted heteroaryl.

In some examples, R ²⁰ And R is ²² At least one of them is-X ¹ -(CH ₂ ) _a -R ²⁸ ；R ²¹ And R is ²³ At least one of them is-X ² -(CH ₂ ) _b -R ²⁹ ；R ²⁴ And R is ²⁶ At least one of them is-X ³ -(CH ₂ ) _c -R ³⁰ ；R ²⁵ And R is ²⁷ At least one of them is-X ⁴ -(CH ₂ ) _d -R ³¹ The method comprises the steps of carrying out a first treatment on the surface of the Or a combination thereof.

In some examples, cy isIn some examples, R ²⁰ 、R ²¹ 、R ²² And R is ²³ At least one of which is substituted or unsubstituted C _1-6 An alkoxy group.

In some examples, cy isIn some examples, R ²⁴ 、R ²⁵ 、R ²⁶ And R is ²⁷ At least one of which is substituted or unsubstituted C _1-6 An alkoxy group.

In some examples, R ²⁰ And R is ²² Each independently is substituted or unsubstituted C _4-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy or-X ¹ -(CH ₂ ) _a -R ²⁸ . In some examples, R ²⁰ And R is ²² Each independently is substituted or unsubstituted C _4-6 Alkyl, substituted or unsubstituted C _1-6 Alkoxy or-X ¹ -(CH ₂ ) _a -R ²⁸ . In some examples, R ²⁰ And R is ²² Each independently is substituted or unsubstituted C _4-6 Alkyl or unsubstituted C _1-6 An alkoxy group.

In some examples, R ²¹ And R is ²³ At least one of which is substituted or unsubstitutedC _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ² -(CH ₂ ) _b -R ²⁹ . In some examples, R ²¹ And R is ²³ At least one of which is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy or-X ² -(CH ₂ ) _b -R ²⁹ . In some examples, R ²⁸ 、R ²⁹ 、R ³⁰ And R is ³¹ Each independently is a substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. In some examples, R ²¹ And R is ²³ At least one of them is-X ² -(CH ₂ ) _b -R ²⁹ And each R ²⁹ Independently a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In some cases, each instance of a is independently 2-6. In some cases, each instance of a is 0.

In some examples, R ²⁴ And R is ²⁶ Each independently is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _1-6 Alkoxy or-X ³ -(CH ₂ ) _c -R ³⁰ . In some examples, R ²⁴ And R is ²⁶ Each independently is substituted or unsubstituted C _3-6 Alkyl or unsubstituted C _1-6 An alkoxy group.

In some cases, R ²⁵ And R is ²⁷ At least one of which is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl group,Substituted or unsubstituted C _1-6 Carboxyl or-X ⁴ -(CH ₂ ) _d -R ³¹ . In some cases, R ²⁵ And R is ²⁷ At least one of which is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy or-X ⁴ -(CH ₂ ) _d -R ³¹ . In some cases, R ²⁵ And R is ²⁷ At least one of which is substituted or unsubstituted C _1-3 Alkyl or unsubstituted C _1-3 An alkoxy group. In some cases, each instance of c is independently 2-6. In some cases, each instance of c is 0.

In such a case, the polymerizable monomer may be selected from:

in various embodiments, the polymerizable monomer herein may be a compound according to formula (VI):

(VI)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ³³ And R is ³⁵ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstitutedSubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁶ -(CH ₂ ) _f -R ⁴³ ；

R ³⁶ And R is ³⁸ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁷ -CH ₂ ) _g -R ⁴⁴ ；

In some cases, cy isIn some cases, cy isIn some cases, R ³² 、R ³³ 、R ³⁴ And R is ³⁵ At least one of which is substituted or unsubstituted C _1-6 Alkoxy or substituted or unsubstituted C _1-6 Thioalkoxy groups. In some cases, cy is +.>In some cases, R ³⁶ 、R ³⁷ 、R ³⁸ And R is ³⁹ At least one of which is substituted or unsubstituted C _1-6 Alkoxy or substituted or unsubstituted C _1-6 Thioalkoxy groups. In some cases, cy is +.>In some cases, R ⁴¹ Is substituted or unsubstituted C _1-6 Alkoxy or substituted or unsubstituted C _1-6 Thioalkoxy groups. In some cases, R ⁴⁰ Is substituted or unsubstituted C _3-6 Alkoxy or substituted or unsubstituted C _3-6 Thioalkoxy groups.

In some cases, R ³³ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁶ -(CH ₂ ) _f -R ⁴³ . In some cases, R ³³ And R is ³⁵ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁶ -(CH ₂ ) _f -R ⁴³ . In some cases, R ³⁷ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁶ -(CH ₂ ) _f -R ⁴³ . In some cases, R ³⁷ And R is ³⁹ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁶ -(CH ₂ ) _f -R ⁴³ 。

In various embodiments, the polymerizable monomer may be a compound according to formula (VI):

(VI)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ³² and R is ³⁴ Each independently is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁵ -(CH ₂ ) _e -R ⁴² ；

R ³⁶ And R is ³⁸ Each independently is substituted or unsubstituted C _3-6 Alkyl, substituted C _4-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ⁷ -CH ₂ ) _g -R ⁴⁴ ；

X ⁵ 、X ⁶ 、X ⁷ And X ⁸ Each independently is a bond, O or S;

e. f, g and h are each independently integers from 0 to 6;

R ⁴² and R is ⁴³ Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and is also provided with

R ⁴⁴ And R is ⁴⁵ Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted aryl, or substituted or unsubstituted heteroaryl.

In some examples, R ¹ Is H or methyl. In such a case, the polymerizable monomer may be selected from:

in some cases, the polymerizable monomer may be selected from:

in some embodiments, R ¹ -R ⁸⁴ Any one or more of which may be halogen, OH, NH ₂ 、NH(C _1-6 Alkyl), N (C) _1-6 Alkyl) (C) _1-6 Alkyl) or C _1-3 Alkyl substitution. In some cases, R ¹ -R ⁸⁴ Can be halogen, OH, NH ₂ Or C _1-3 Alkyl substitution. In some cases, R ¹ -R ⁸⁴ Can be fluorine, chlorine, bromine, OH or C _1-3 Alkyl substitution. In some cases, R ¹ -R ⁸⁴ Can be halogen, OH or NH ₃ And (3) substitution.

In some embodiments, provided herein are polymerizable monomers according to formula (IX):

(IX)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ⁷⁹ and R is ⁸⁰ Each independently H, C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and is also provided with

R ⁸¹ Is substituted or unsubstituted C _1-6 An alkoxy group.

In some cases, R ⁷⁷ Is nitrile or substituted or unsubstituted C _1-6 Alkyl cyanide. In some cases, R ⁷⁹ And R is ⁸⁰ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substitutedOr unsubstituted C _1-6 Carboxyl, substituted or unsubstituted ring (C _3-8 ) Alkyl or substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group. In some cases, R ⁷⁹ And R is ⁸⁰ Each independently is H, unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted ring (C) _3-8 ) Alkyl or substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group. In some cases, R ⁷⁹ And R is ⁸⁰ Each independently is H, unsubstituted C _1-4 Alkyl or unsubstituted C _1-4 An alkoxy group. In some cases, R ⁸¹ Is unsubstituted C _1-6 An alkoxy group.

In some embodiments, the polymerizable monomer according to formula (IX) may be vanillin, such as o-vanillin or a derivative thereof. In such a case, R ⁷⁷ Is a nitrile. In such a case, R ⁷⁷ Is carbonyl or aldehyde. In any such case, R ⁸¹ Can be methoxy and R ¹ Is H or methyl. In such a case, the polymerizable monomer according to formula (IX) may have the following structure:

in some embodiments, provided herein are polymeric materials comprising a polymer comprising a monomer in its polymerized form according to formula (VII):

(VII)

wherein:

x is N or CR ⁵⁹ ；

R ¹ Is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ⁴⁸ 、R ⁴⁹ and R is ⁵⁰ Each independently is H, nitrile, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y groups ¹ -(CH ₂ ) _a -R ⁶⁰ Or R is ⁴⁸ And R is ⁴⁹ Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

Y ¹ 、Y ² 、Y ³ And Y ⁴ Each independently is a bond, O or S;

In some examples, and with reference to formula (VII),

wherein:

x is N or CR ⁵⁹ ；

R ¹ Is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

Y ¹ And Y ⁴ Each independently is a bond, O or S;

a and d are each independently integers from 0 to 6; and is also provided with

R ⁶⁰ And R is ⁶³ Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

(VII)

wherein:

x is N or CH;

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ⁴⁸ 、R ⁴⁹ And R is ⁵⁰ Each independently is H, nitrile, substituted or unsubstituted C _1-6 Alkyl cyanide, substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _3-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y groups ¹ -(CH ₂ ) _a -R ⁶⁰ The method comprises the steps of carrying out a first treatment on the surface of the Or R is ⁴⁸ And R is ⁴⁹ Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl group, wherein R ⁴⁸ 、R ⁴⁹ And R is ⁵⁰ At most one of (a) is H;

Y ¹ 、Y ² 、Y ³ And Y ⁴ Each independently is a bond, O or S;

a. b, c and d are each independently integers from 0 to 6;

R ⁶⁰ and R is ⁶² Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and is also provided with

R ⁶¹ Is a substituted ring (C) _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some cases, R ¹ Is H or methyl. In such a case, X is N or CR ⁵⁹ ，R ⁴⁹ H, R of a shape of H, R ⁴⁸ And R is ⁵⁰ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy or-Y ¹ -(CH ₂ ) _a -R ⁶⁰ Wherein Y is ¹ Is a bond, O or S, a is an integer from 0 to 6, R ⁵⁹ Is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, and R ⁶⁰ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, or alternatively, R ⁴⁸ And R is ⁴⁹ Taken together to form a ring (C) selected from substituted or unsubstituted _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A 4-, 5-, 6-, 7-or 8-membered ring of a heteroalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl group. In some examples, X is N or CH, R ⁴⁹ Is H, R ⁴⁸ And R is ⁵⁰ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy or-Y ¹ -(CH ₂ ) _a -R ⁶⁰ Wherein Y is ¹ Is a bond or O, a is 0, 1 or 2, and R ⁶⁰ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In other cases, X is N or CH, R ⁴⁹ Is H, R ⁴⁸ And R is ⁵⁰ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Alkoxy or-Y ¹ -(CH ₂ ) _a -R ⁶⁰ Wherein Y is ¹ Is a bond or O, a is 0, 1 or 2, and R ⁶⁰ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some examples, and with reference to formula (VII),

wherein:

R ¹ Is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

Y ² Is bond, O or S;

b is an integer from 0 to 6; and is also provided with

R ⁶¹ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some cases, R ¹ Is H or methyl. In such a case, R ⁵¹ 、R ⁵² 、R ⁵³ And R is ⁵⁴ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy or-Y ² -(CH ₂ ) _b -R ⁶¹ Wherein Y is ² Is a bond, O or S, b is an integer from 0 to 6, and R ⁶¹ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In some cases, R ⁵² And R is ⁵⁴ Is H, and R ⁵¹ And R is ⁵³ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy or-Y ² -(CH ₂ ) _b -R ⁶¹ Wherein Y is ² Is a bond, O or S, b is an integer from 0 to 6, and R ⁶¹ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In other cases, R ⁵² And R is ⁵⁴ Is H, and R ⁵¹ And R is ⁵³ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy or-Y ² -(CH ₂ ) _b -R ⁶¹ Wherein Y is ² Is a bond or O, b is an integer from 0 to 3, and R ⁶¹ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some examples, and with reference to formula (VII),

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

Y ³ Is bond, O or S;

c is an integer from 0 to 6; and is also provided with

R ⁶² Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some cases, R ¹ Is H or methyl. In such a case, R ⁵⁵ 、R ⁵⁶ 、R ⁵⁷ And R is ⁵⁸ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y groups ³ -(CH ₂ ) _c -R ⁶² Wherein Y is ³ Is a bond, O or S, c is an integer from 0 to 6, and R ⁶² Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In some aspects, in some cases, R ⁵⁶ And R is ⁵⁸ Is H, and R ⁵⁵ And R is ⁵⁷ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-Y groups ³ -(CH ₂ ) _c -R ⁶² Wherein Y is ³ Is a bond, O or S, c is an integer from 0 to 6, and R ⁶² Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In other cases, R ⁵⁶ And R is ⁵⁸ Is H, and R ⁵⁵ And R is ⁵⁷ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy or-Y ³ -(CH ₂ ) _c -R ⁶² Wherein Y is ³ Is a bond or O, c is an integer from 0 to 3, and R ⁶² Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some embodiments, provided herein are polymeric materials comprising a polymer comprising a monomer in its polymerized form according to formula (VIII):

(VIII)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ⁷² And R is ⁷³ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstitutedC _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ³ -(CH ₂ ) _c -R ⁷⁶ ；

X ¹ 、X ² And X ³ Each independently is a bond, O or S;

(VIII)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ⁶⁴ 、R ⁶⁵ 、R ⁶⁶ And R is ⁶⁷ Each independently is H, substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ¹ -(CH ₂ ) _a -R ⁷⁴ Wherein R is ⁶⁴ 、R ⁶⁵ 、R ⁶⁶ And R is ⁶⁷ At most two of (a) are H;

R ⁶⁸ 、R ⁶⁹ 、R ⁷⁰ and R is ⁷¹ Each independently is H, substituted or unsubstituted C _3-6 Alkyl, takeSubstituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ² -(CH ₂ ) _b -R ⁷⁵ Wherein R is ⁶⁸ 、R ⁶⁹ 、R ⁷⁰ And R is ⁷¹ At most two of (a) are H;

R ⁷² and R is ⁷³ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ³ -(CH ₂ ) _c -R ⁷⁶ ；

X ¹ 、X ² And X ³ Each independently is a bond, O or S;

R ⁷⁴ 、R ⁷⁵ And R is ⁷⁶ Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted aryl, or substituted or unsubstituted heteroaryl.

In some examples, and with reference to formula (VIII),

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ⁶⁴ 、R ⁶⁵ 、R ⁶⁶ and R is ⁶⁷ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstitutedC _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ¹ -(CH ₂ ) _a -R ⁷⁴ ；

X ¹ Is bond, O or S;

a is an integer from 0 to 6; and is also provided with

R ⁷⁴ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some cases, R ¹ Is H or methyl. In such a case, R ⁶⁵ And R is ⁶⁷ Is H, R ⁶⁴ And R is ⁶⁶ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ¹ -(CH ₂ ) _a -R ⁷⁴ ，X ¹ Is a bond or O, a is an integer from 0 to 3, and R ⁷⁴ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some examples, and with reference to formula (VIII),

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ⁶⁸ 、R ⁶⁹ 、R ⁷⁰ and R is ⁷¹ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy radicalRadicals, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ² -(CH ₂ ) _b -R ⁷⁵ ；

X ² Is bond, O or S;

b is an integer from 0 to 6; and is also provided with

R ⁷⁵ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some cases, R ¹ Is H or methyl. In such a case, R ⁶⁹ And R is ⁷¹ Is H, R ⁶⁸ And R is ⁷⁰ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ² -(CH ₂ ) _b -R ⁷⁵ ，X ² Is a bond or O, b is an integer from 0 to 3, and R ⁷⁵ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some examples, and with reference to formula (VIII),

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ⁷² and R is ⁷³ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy groupSubstituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl or-X ³ -(CH ₂ ) _c -R ⁷⁶ ；

X ³ Is bond, O or S;

c is an integer from 0 to 6; and is also provided with

R ⁷⁶ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some cases, R ¹ Is H or methyl. In such a case, R ⁷² And R is ⁷³ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy or-X ³ -(CH ₂ ) _c -R ⁷⁶ ，X ³ Is a bond or O, c is an integer from 0 to 3, and R ⁷⁵ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In other examples, R ⁷² Is H, and R ⁷³ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy or-X ³ -(CH ₂ ) _c -R ⁷⁶ ，X ³ Is a bond or O, c is an integer from 0 to 3, and R ⁷⁵ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some examples, and with reference to formulas (VII) and (VIII), R ¹ Or R is ⁴⁸ -R ⁸¹ One or more of them being halogen, OH, NH ₂ 、NH(C _1-6 Alkyl), N (C) _1-6 Alkyl) (C) _1-6 Alkyl) or C _1-3 Alkyl substitution.

In some embodiments, the polymerizable monomers of the present disclosure can have a low vapor pressure at elevated temperatures and high boiling points. Such low vapor pressures are particularly advantageous for use of such monomers in curable (e.g., photocurable) compositions and additive manufacturing where elevated temperatures (e.g., 60 ℃, 80 ℃,90 ℃ or higher) can be used. In each case, the polymerizable monomer may have a vapor pressure of up to about 12Pa at 60 ℃. In each case, the polymerizable monomer may have a vapor pressure of up to about 2Pa to 10Pa at 60 ℃. In each case, the polymerizable monomer may have a vapor pressure of up to about 2Pa to 5Pa at 60 ℃. Thus, in some embodiments, the polymerizable monomers of the present disclosure can have low mass loss at elevated temperatures. As used herein, mass loss of a compound at a particular temperature (e.g., 90 ℃) for a particular time (e.g., 2 hours) can be used as a measure of the volatility of such a compound. Herein, "substantially free of volatility" may refer to a mass loss of <1wt% at the corresponding temperature (e.g., at 90 ℃) for 2 hours. In each case, the mass loss of the polymerizable monomers of the present disclosure may be <1wt% after heating at a corresponding temperature of 90 ℃ for 2 hours. In some embodiments, the mass loss of the polymerizable monomer after heating at 90 ℃ for 2 hours may be less than about 0.5%. In some embodiments, the mass loss of the polymerizable monomer after heating at 90 ℃ for 2 hours may be about 0.1% to about 0.45%. In some embodiments, the mass loss of the polymerizable monomer after heating at 90 ℃ for 2 hours may be about 0.05% to about 0.25%.

In some embodiments, the polymerizable monomers of the present disclosure can have a molecular weight of at least about 150Da, 200Da, 250Da, 300Da, 350Da, 400Da, or at least about 450 Da. In some cases, the polymerizable monomer has a molecular weight of 190 daltons to 320 daltons. In some cases, the polymerizable monomer has a molecular weight of 200 daltons to 280 daltons.

In some embodiments, the polymerizable monomers of the present disclosure can have a melting point of at least about 20 ℃, 30 ℃, 40 ℃, 50 ℃ or higher. The polymerizable monomers according to the present disclosure, for example, according to any of formulas (I) - (VI) and (IX), insofar as their possible use as reactive diluents in curable compositions, include having a melting point below the processing temperature currently used in the high Wen Guangke-based photopolymerization process, which is typically in the range of 50-120 ℃, for example 90-120 ℃. Thus, the polymerizable monomers provided herein that can be used as reactive diluents can have a melting point of <120 ℃, <90 ℃, <70 ℃ or even <50 ℃ or <30 ℃, which provides a low viscosity of the melt, thus providing a more pronounced viscosity reducing effect when they are used as reactive diluents for resins to be cured by high Wen Guangke-based polymerization. In some cases, they are liquid at room temperature, which facilitates their handling in addition to the advantages described above.

In various embodiments, any of the polymerizable monomers described herein, e.g., compounds according to any of formulas (I) - (VI) and (IX), may be photopolymerizable monomers. In various cases, the photopolymerizable monomers of the present disclosure may be components of a photopolymerizable composition (e.g., a photocurable resin), which may be capable of 3D printing as described herein.

In some embodiments, the photopolymerizable monomers of the present disclosure may be added to the photocurable resins described herein, for example, to alter (e.g., reduce) the viscosity of the resin, promote crosslinking between telechelic polymers during polymerization (e.g., during curing), lengthen polymer chains during polymerization, initiate and/or enhance polymerization-induced phase separation during curing (e.g., photocuring), control the size of the phases or domains formed during phase separation, increase the toughness of polymeric materials made from the resin, alter the glass transition temperature (T) of amorphous domains (e.g., amorphous polymer phases) of polymeric materials made from the resin _g ) Modifying the melting point temperature (T) of crystalline domains (e.g., crystalline polymer phases) of a polymeric material prepared from a resin _m ) Or to adjust the refractive index of amorphous domains of a polymeric material prepared from the resin.

III photo-curable resins

The present disclosure provides curable resins that may include one or more polymerizable monomers described herein. In various embodiments, the curable resin herein is a photocurable resin that may include one or more photopolymerizable monomers, such as one or more compounds according to any of formulas (I) - (VI) and (IX).

Resin component

The photocurable resins of the present disclosure may comprise one or more components. One or more of such components may be photopolymerizable components. In such examples, the photocurable resins herein may comprise 1, 2, 3, 4, 5, or more of the different types of photopolymerizable monomers described herein. In some cases, each monomer species may be a compound according to any one of formulas (I) - (VI) and (IX).

In some cases, the photocurable resin comprises 10-80wt% of a compound according to any one of formulas (I) - (VI) and (IX). In some cases, the photocurable resin comprises 15-45wt% of a compound according to any one of formulas (I) - (VI) and (IX). In some cases, the photocurable resin comprises 25-35wt% of a compound according to any one of formulas (I) - (VI) and (IX). In some cases, the photocurable resin comprises 10-50wt% of the second acrylate or methacrylate monomer. In some cases, the second acrylate or methacrylate monomer is an alkyl acrylate, an alkyl methacrylate, an acrylic acid homosalicylate (homosalicyclic), a methacrylic acid homosalicylate, or a combination thereof. In some cases, the second acrylate or methacrylate monomer is an acrylic acid homosalicylate, a methacrylic acid homosalicylate, or a combination thereof.

In addition to the one or more photopolymerizable monomers, the photocurable resins of the present disclosure may also include one or more photopolymerizable components. Such one or more photopolymerizable components may include one or more telechelic oligomers, one or more telechelic polymers, or a combination thereof. In such an example, the telechelic oligomer may have a number average molecular weight greater than 500Da (0.5 kDa) but less than 5 kDa. The telechelic polymer may have a number average molecular weight greater than 10kDa but less than 50 kDa. The telechelic polymer may have a number average molecular weight greater than 5kDa but less than 50 kDa. The telechelic polymer may have a number average molecular weight greater than 5kDa but less than 300 kDa. The telechelic oligomer and/or polymer may contain a photoreactive moiety at its terminus. In some cases, the photoreactive moiety may be an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, silicon carbene, alkynyl, alkenyl, vinyl ether, maleimide, fumarate, maleate, itaconate, or styryl moiety. In some cases, the photoreactive moiety may be an acrylate or methacrylate. Telechelic polymers herein may include polyurethanes, polyesters, block copolymers, or any other commercial polymer having reactive (e.g., photoreactive) end groups.

In certain aspects, the photopolymerizable monomer of the present disclosure and another second photopolymerizable component (e.g., a telechelic polymer) that may be present in the resin may be miscible with each other. In some aspects, the polymerizable monomers herein may be partially or completely immiscible in the second polymerizable component.

The photocurable resins disclosed herein may comprise from about 0.5 to 99.5wt%, from about 1 to 99wt%, from about 10 to 95wt%, from about 20 to 90wt%, from about 25 to 60wt%, or from about 35 to 50wt% of one or more polymerizable monomers, telechelic polymers, and/or oligomers according to any of formulas (I) - (VI) and (IX), or any combination thereof.

The photocurable resins described herein may further comprise one or more photoinitiators. Such photoinitiators, when activated with light of an appropriate wavelength (e.g., UV/VIS), can initiate polymerization reactions (e.g., during photocuring) between the telechelic polymer, monomer, and other potentially polymerizable components that may be present in the photocurable resin to form a polymeric material as further described herein. Generally, photoinitiators described in the present disclosure can include those that can be activated with light and initiate polymerization of the polymerizable components of the formulation. As used herein, "photoinitiator" generally refers to a compound that is capable of generating free radical species and/or promoting a free radical reaction upon exposure to radiation (e.g., UV or visible light).

In some embodiments, the photocurable resins herein further comprise 0.05wt% to 1wt%, 0.05wt% to 2wt%, 0.05wt% to 3wt%, 0.05wt% to 4wt%, 0.05wt% to 5wt%, 0.1wt% to 1wt%, 0.1wt% to 2wt%, 0.1wt% to 3wt%, 0.1wt% to 4wt%, 0.1wt% to 5wt%, 0.1wt% to 6wt%, 0.1wt% to 7wt%, 0.1wt% to 8wt%, 0.1wt% to 9wt% or 0.1wt% to 10wt% of a photoinitiator, based on the total weight of the composition. In some embodiments, the photoinitiator is a free radical photoinitiator. In certain embodiments, the free radical photoinitiator comprises an alpha-hydroxy ketone moiety (e.g., 2-hydroxy-2-methylbenzophenone or 1-hydroxycyclohexylphenyl ketone), an alpha-amino ketone (e.g., 2-benzyl-2- (dimethylamino) -4' -morpholinophenone or 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one), 4-methylbenzophenone, an azo compound (e.g., 4' -azobis (4-cyanovaleric acid), 1' -azobis (cyclohexanecarbonitrile, azobisisobutyronitrile, 2' -azobis (2-methylpropanenitrile) or 2,2' -azobis (2-methylpropanenitrile)), an inorganic peroxide, an organic peroxide, or any combination thereof, in some embodiments, the composition comprises a photoinitiator comprising speedcube TPO-L ((2, 4, 6-trimethylbenzoyl) phenylphosphinate). In some embodiments, the photocurable composition comprises a mixture selected from benzophenone, and an aromatic-containing at least one direct bond to a tertiary amine such as Irgare, a photoinitiator of Irgacure907 (2-methyl-1- [4- (methylthio) -phenyl ] -2-morpholino-propanone-1) or Irgacure651 (2, 2-dimethoxy-1, 2-diphenylethan-1-one). In some embodiments, the photoinitiator comprises an acetophenone photoinitiator (e.g., 4' -hydroxyacetophenone, 4'0 phenoxyacetophenone, 4' -ethoxyacetophenone), benzoin derivatives, benzil derivatives, benzophenone (e.g., 4-benzoylbiphenyl, 3,4- (dimethylamino) benzophenone, 2-methylbenzophenone), a cationic photoinitiator (e.g., diphenyliodonitrate.(4-iodophenyl) diphenylsulfonium triflate, triphenylsulfonium triflate), anthraquinone, quinone (e.g., camphorquinone), phosphine oxide, phosphinate, 9, 10-phenanthrenequinone, thioxanthone, any combination thereof, or any derivative thereof.

In some embodiments, the photoinitiator may have a maximum wavelength absorbance of 200nm to 300nm, 300nm to 400nm, 400nm to 500nm, 500nm to 600nm, 600nm to 700nm, 700nm to 800nm, 800nm to 900nm, 150nm to 200nm, 200nm to 250nm, 250nm to 300nm, 300nm to 350nm, 350nm to 400nm, 400nm to 450nm, 450nm to 500nm, 500nm to 550nm, 550nm to 600nm, 600nm to 650nm, 650nm to 700nm, or 700nm to 750 nm. In some embodiments, the photoinitiator has a maximum wavelength absorbance of 300nm to 500 nm.

In some embodiments, the photocurable resins of the present disclosure may include a crosslinking modifier (e.g., in addition to or without a polymerizable monomer that may act as a crosslinking agent), a light blocking agent, a solvent, a glass transition temperature modifier, or a combination thereof. In some aspects, the photocurable resin comprises 0-25wt% of a crosslinking modifier having a number average molecular weight equal to or less than 1,500 da. In some aspects, the photocurable resin comprises from 0wt% to 10wt%, from 0wt% to 9wt%, from 0wt% to 8wt%, from 0wt% to 7wt%, from 0 to 6wt%, from 0wt% to 5wt%, from 0wt% to 4wt%, from 0 to 3wt%, from 0wt% to 2wt%, from 0wt% to 1wt%, or from 0wt% to 0.5wt% of the light blocker. In some embodiments, the photocurable resin comprises a solvent. In some embodiments, the solvent comprises a non-polar solvent. In certain embodiments, the non-polar solvent comprises pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1, 4-dioxane, chloroform, diethyl ether, dichloromethane, derivatives thereof, or combinations thereof. In some embodiments, the solvent comprises a polar aprotic solvent. In certain embodiments, the polar aprotic solvent comprises tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, DMSO, propylene carbonate, derivatives thereof, or combinations thereof. In some embodiments, the solvent comprises a polar protic solvent. In certain embodiments, the polar protic solvent comprises formic acid, n-butanol, isopropanol, n-propanol, t-butanol, ethanol, methanol, acetic acid, water, derivatives thereof, or combinations thereof. In some embodiments, the photocurable resin comprises less than 90wt% solvent.

In some embodiments, the added resin component (e.g., crosslinking modifier, polymerization catalyst, polymerization inhibitor, glass transition temperature modifier, light blocker, plasticizer, solvent, surface energy modifier, pigment, dye, filler, or biologically significant chemical) is functionalized so that it can be incorporated into the polymeric material such that it cannot be easily extracted from the final cured material. In certain embodiments, polymerization catalysts, polymerization inhibitors, light blockers, plasticizers, surface energy modifiers, pigments, dyes, and/or fillers are functionalized to facilitate their incorporation into the cured polymeric material.

In some embodiments, the resins herein comprise, in addition to the polymerizable monomers described herein, components capable of changing the glass transition temperature of the cured polymeric material. In this case, the glass transition temperature modifier (also referred to herein as T _g Modifiers or glass transition modifiers) may be present in the photocurable composition at about 0wt% to 50 wt%. T (T) _g The modifier may have a high glass transition temperature, which results in a high heat distortion temperature, which is necessary for using the material at elevated temperatures. In some embodiments, the curable composition comprises 0wt% to 80wt%, 0wt% to 75wt%, 0wt% to 70wt%, 0wt% to 65wt%, 0wt% to 60wt%, 0wt% to 55wt%, 0wt% to 50wt%, 1wt% to 50wt%, 2wt% to 50wt%, 3wt% to 50wt%, 4wt% to 50wt%, 5wt% to 50wt%, 10wt% to 50wt%, 15wt% to 50wt%, 20wt% to 50wt%, 25wt% to 50wt%, 30wt% to 50wt%, 35wt% to 50wt%, 0wt% to 40wt%, 1wt% to 40wt%, 2wt% to 40wt%, 3wt% to 40wt%, 4wt% to 40wt%, 5wt% to 40wt%, 10wt% to 40wt%, 15wt% to 40wt%, or T of 20wt% to 40wt% _g And (3) a modifying agent. In certain embodiments, the curable composition comprises 0 to 50wt% glass transition modifier. In some examples, T _g The number average molecular weight of the modifier is from 0.4kDa to 5kDa. In some embodiments, T _g The number average molecular weight of the modifier is0.1kDa to 5kDa, 0.2kDa to 5kDa, 0.3kDa to 5kDa, 0.4kDa to 5kDa, 0.5kDa to 5kDa, 0.6kDa to 5kDa, 0.7kDa to 5kDa, 0.8kDa to 5kDa, 0.9kDa to 5kDa, 1.0kDa to 5kDa, 0.1kDa to 4kDa, 0.2kDa to 4kDa, 0.3kDa to 4kDa, 0.4kDa to 4kDa, 0.5kDa to 4kDa, 0.6kDa to 4kDa, 0.7kDa to 4kDa, 0.8kDa to 4kDa, 0.9kDa to 4kDa, 1kDa to 4kDa, 0.1kDa to 3kDa, 0.2kDa to 3kDa, 0.3kDa to 3kDa, 0.4kDa to 3kDa, 0.5kDa to 3kDa, 0.7kDa to 3kDa, 0.8kDa to 3kDa, 0.9kDa to 3kDa or 1kDa to 3kDa. The polymerizable monomers of the present disclosure (which themselves may act as T _g Modifier) and T alone _g The modifier compounds can be miscible and compatible in the methods described herein. When used in the compositions of the present subject matter, T _g The modifier can provide a high T _g And strength values, sometimes at the expense of elongation at break. In some cases, the toughness modifiers can provide high elongation at break and toughness through reinforcement effects, and the polymerizable monomers described herein can improve the processability of the formulation, for example, by acting as reactive diluents, particularly those compositions containing substantial amounts of toughness modifiers, while maintaining high strength and T _g Values.

Resin Properties

The photocurable resins herein may be characterized by having one or more properties. In some embodiments, photopolymerizable monomers of the present disclosure, such as compounds according to any of formulas (I) - (VI) and (IX), may be used as reactive diluents in the curable resins disclosed herein. Thus, in some examples, the photopolymerizable monomer may reduce the viscosity of the curable resin (e.g., photocurable resin). In this case, the photopolymerizable monomer may reduce the viscosity of the curable resin by at least about 5% as compared to a resin that does not include the polymerizable monomer. In some examples, the photopolymerizable monomer may reduce the viscosity of the photocurable resin by at least about 5%, 10%, 20%, 30%, 40%, or 50%. In some examples, the photocurable resins of the present disclosure may have a viscosity of about 30cP to about 50,000cP at the printing temperature. In some embodiments, the photocurable resin has a viscosity of less than or equal to 30,000cp, less than or equal to 25,000cp, less than or equal to 20,000cp, less than or equal to 19,000cp, less than or equal to 18,000cp, less than or equal to 17,000cp, less than or equal to 16,000cp, less than or equal to 15,000cp, less than or equal to 14,000cp, less than or equal to 13,000cp, less than or equal to 12,000cp, less than or equal to 11,000cp, less than or equal to 10,000cp, less than or equal to 9,000cp, less than or equal to 8,000cp, less than or equal to 7,000cp, less than or equal to 6,000cp, or less than or equal to 5,000cp at 25 ℃. In some embodiments, the resin has a viscosity of less than 15,000cp at 25 ℃. In some embodiments, the photocurable resin has a viscosity of less than or equal to 100,000cP, less than or equal to 90,000cP, less than or equal to 80,000cP, less than or equal to 70,000cP, less than or equal to 60,000cP, less than or equal to 50,000cP, less than or equal to 40,000cP, less than or equal to 35,000cP, less than or equal to 30,000cP, less than or equal to 25,000cP, less than or equal to 20,000cP, less than or equal to 15,000cP, less than or equal to 10,000cP, less than or equal to 5,000cP, less than or equal to 4,000cP, less than or equal to 3,000cP, less than or equal to 2,000cP, less than or equal to 1,000cP, less than or equal to 750cP, less than or equal to 500cP, less than or equal to 250cP, less than or equal to 100cP, less than or equal to 90cP, less than or equal to 80cP, less than or equal to 70cP, less than or equal to 60cP, less than or equal to 50, less than or equal to 40cP, less than or equal to 30 cP. In some embodiments, the photocurable resin has a viscosity of 50,000cP to 30cP, 40,000cP to 30cP, 30,000cP to 30cP, 20,000cP to 30cP, 10,000cP to 30cP, or 5,000cP to 30cP at the printing temperature. In some embodiments, the printing temperature is from 0 ℃ to 25 ℃, from 25 ℃ to 40 ℃, from 40 ℃ to 100 ℃, or from 20 ℃ to 150 ℃. In some embodiments, the photocurable resin has a viscosity of 30cP to 50,000cP at a printing temperature, wherein the printing temperature is 20 ℃ to 150 ℃. In other embodiments, the photocurable resin has a viscosity of less than 20,000cp at the printing temperature. In some embodiments, the printing temperature is 10 ℃ to 200 ℃, 15 ℃ to 175 ℃, 20 ℃ to 150 ℃, 25 ℃ to 125 ℃, or 30 ℃ to 100 ℃. In a preferred embodiment, the printing temperature is 20 ℃ to 150 ℃.

The photocurable resins of the present disclosure are capable of 3D printing at temperatures greater than 25 ℃. In some cases, the printing temperature is at least about 30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃, or 100 ℃. As described herein, the photopolymerizable monomers of the present disclosure, which may be part of the photocurable resin, may have a low vapor pressure and/or mass loss at the printing temperature, thereby providing improved printing conditions compared to conventional resins used in additive manufacturing.

In some embodiments, the photocurable resins herein have a melting temperature greater than room temperature. In some embodiments, the photocurable resin has a melting temperature greater than 20 ℃, greater than 25 ℃, greater than 30 ℃, greater than 35 ℃, greater than 40 ℃, greater than 45 ℃, greater than 50 ℃, greater than 55 ℃, greater than 60 ℃, greater than 65 ℃, greater than 70 ℃, greater than 75 ℃, or greater than 80 ℃. In some embodiments, the melting temperature of the photocurable resin is from 20 ℃ to 250 ℃, from 30 ℃ to 180 ℃, from 40 ℃ to 160 ℃, or from 50 ℃ to 140 ℃. In some embodiments, the photocurable resin has a melting temperature greater than 60 ℃. In other embodiments, the photocurable resin has a melting temperature of 80 ℃ to 110 ℃. In some examples, the photocurable resin may have a melting temperature of about 80 ℃ prior to polymerization, and the resulting polymeric material may have a melting temperature of about 100 ℃ after polymerization.

In some instances, it may be advantageous for the photocurable resin to be in the liquid phase at elevated temperatures. For example, conventional photocurable resins may contain polymerizable components that may be tacky at process temperatures and thus may be difficult to use in the manufacture of objects (e.g., using 3D printing). As a solution to this technical problem, the present disclosure provides photocurable resins comprising a photopolymerizable component, such as the monomers described herein, which can melt at elevated temperatures (e.g., at manufacturing temperatures) (e.g., during 3D printing) and can have reduced viscosity at elevated temperatures, which can make such resins more suitable and useful for applications such as 3D printing. Thus, in some embodiments, provided herein are photocurable liquids at elevated temperaturesAnd (5) resin melting. In some embodiments, the elevated temperature is equal to or greater than Yu Keguang the melting temperature (T _m ). In certain embodiments, the elevated temperature is a temperature in the range of about 40 ℃ to about 100 ℃, about 60 ℃ to about 100 ℃, about 80 ℃ to about 100 ℃, about 40 ℃ to about 150 ℃, or about 150 ℃ to about 350 ℃. In some embodiments, the elevated temperature is a temperature greater than about 40 ℃, greater than about 60 ℃, greater than about 80 ℃, or greater than about 100 ℃. In some embodiments, the photocurable resins herein are liquids having a viscosity of less than about 50PaS, less than about 2 about 0PaS, less than about 10PaS, less than about 5PaS, or less than about 1PaS at elevated temperatures. In some embodiments, the photocurable resins herein are liquids having a viscosity of less than about 20PaS at elevated temperatures above about 40 ℃. In other embodiments, the photocurable resins herein are liquids having a viscosity of less than about 1PaS at elevated temperatures above about 40 ℃.

In some embodiments, at least a portion of the photocurable resins herein have a melting temperature of less than about 100 ℃, less than about 90 ℃, less than about 80 ℃, less than about 70 ℃, or less than about 60 ℃. In some embodiments, at least a portion of the photocurable resins herein melt at an elevated temperature of about 100 ℃ to about 20 ℃, about 90 ℃ to about 20 ℃, about 80 ℃ to about 20 ℃, about 70 ℃ to about 20 ℃, about 60 ℃ to about 10 ℃, or about 60 ℃ to about 0 ℃.

In various embodiments, the photocurable resins herein and the photopolymerizable components thereof may be biocompatible, bioinert, or a combination thereof. In various cases, the photopolymerizable monomers of the resins herein may have biocompatible and/or bioinert metabolic (e.g., hydrolysis) products.

The photocurable resins of the present disclosure may contain less than about 20wt% or less than about 10wt% hydrogen bond units. In some aspects, the photocurable resins herein comprise less than about 15wt%, less than about 10wt%, less than about 9wt%, less than about 8wt%, less than about 7wt%, less than about 6wt%, less than about 5wt%, less than about 4wt%, less than about 3wt%, less than about 2wt%, or less than about 1wt% hydrogen bond units, wherein wt% is the weight percent of the substance comprising monomer units in polymerized, oligomeric, and monomeric forms capable of forming at least one hydrogen bond.

Polymeric materials

The present disclosure provides polymeric materials. Such polymeric materials may be produced by curing the curable compositions or resins described herein. The polymeric materials provided herein may be biocompatible, bioinert, or a combination thereof. In various examples, the polymeric materials herein are produced by photocuring the photocurable compositions described herein. Such photocurable compositions may comprise one or more photopolymerizable monomers of the present disclosure.

Phase separation in polymeric materials

In some aspects herein, the photocurable compositions or resins herein may be cured by exposing such compositions or resins to electromagnetic radiation of an appropriate wavelength. Such curing or polymerization may cause phase separation in the photocurable composition and/or in the formation of the polymeric material. Such polymerization-induced phase separation may occur along one or more of the lateral and vertical directions (see, e.g., fig. 8). Polymerization-induced phase separation may produce one or more polymer phases in the resulting polymer material. The photocurable composition that undergoes polymerization and polymerization-induced phase separation may comprise one or more photopolymerizable monomers of the present disclosure. Thus, in some cases, at least one of the one or more polymer phases generated during the curing process and present in the resulting polymeric material may comprise at least one of the one or more photopolymerizable monomers in polymerized form. In one example, a photocurable resin comprising one photopolymerizable monomer species (e.g., a compound according to any one of formulas (I) - (VI) and (IX)) is cured by exposure to electromagnetic radiation of an appropriate wavelength. The cured polymeric material contained 2 polymer phases a and B. In some cases, at least one of phases a or B may comprise a photopolymerizable monomer as a component in its polymer structure. In some cases, both phase a and phase B may comprise a photopolymerizable monomer as a component in their polymer structure. Phases a and B may contain different amounts or concentrations of photopolymerizable monomers. Thus, in some cases herein, two or more phases comprising a photopolymerizable monomer may be separated by a concentration gradient of such monomer.

The polymer phase of the polymeric materials of the present disclosure may have a certain size or volume. In some embodiments, the polymer phase is three-dimensional and may have at least one dimension less than 1000 μm, less than 500 μm, less than 250 μm, less than 200 μm, less than 150 μm, less than 100 μm, less than 90 μm, less than 80 μm, less than 70 μm, less than 60 μm, less than 50 μm, less than 40 μm, less than 30 μm, less than 20 μm, or less than 10 μm. In certain embodiments, the polymer phase may have at least two dimensions of less than 1000 μm, less than 500 μm, less than 250 μm, less than 200 μm, less than 150 μm, less than 100 μm, less than 90 μm, less than 80 μm, less than 70 μm, less than 60 μm, less than 50 μm, less than 40 μm, less than 30 μm, less than 20 μm, or less than 10 μm. In certain embodiments, the polymer phase may have three dimensions of less than 1000 μm, less than 500 μm, less than 250 μm, less than 200 μm, less than 150 μm, less than 100 μm, less than 90 μm, less than 80 μm, less than 70 μm, less than 60 μm, less than 50 μm, less than 40 μm, less than 30 μm, less than 20 μm, or less than 10 μm. In some aspects, the polymeric material comprises an average polymeric phase size of less than about 5 μm in at least one spatial dimension.

In various aspects, the present disclosure provides a polymeric material that may include one or more polymeric phases, wherein at least one of the one or more polymeric phases is a crystalline phase. In various aspects, the present disclosure provides a polymeric material that may include one or more polymeric phases, wherein at least one of the one or more polymeric phases is amorphous. In some examples, provided herein is a polymeric material that may include two or more polymeric phases, wherein at least one of the one or more polymeric phases is a crystalline phase and at least one of the one or more polymeric phases is an amorphous phase.

Accordingly, in some examples, provided herein is a polymeric material comprising: (i) At least one crystalline phase comprising at least one polymer crystal having a melting temperature above 20 ℃; and (ii) at least one amorphous phase comprising at least one amorphous polymer having a glass transition temperature greater than 40 ℃. In some cases, the at least one crystalline phase may comprise a photopolymerizable monomer according to any of formulas (I) - (VI) and (IX) in polymerized form. In some cases, at least one amorphous phase may comprise a photopolymerizable monomer according to any of formulas (I) - (VI) and (IX) in polymerized form. In some aspects, such an amorphous phase has a glass transition temperature greater than 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, or greater than 110 ℃. In some examples, such an amorphous phase may comprise, in polymerized form, a photopolymerizable monomer according to any of formulas (I) - (VI) and (IX). In some aspects, at least one polymer crystal has a melting temperature above 30 ℃, 40 ℃, 50 ℃, 60 ℃, or above 70 ℃. In some examples, such crystalline phase may comprise a photopolymerizable monomer according to any of formulas (I) - (VI) and (IX) in polymerized form.

Amorphous polymer phase

The present disclosure provides polymeric materials comprising one or more amorphous phases, e.g., produced by polymerization-induced phase separation. Such polymeric materials, or regions of such materials comprising a polymeric phase, may provide a fast response time to external stimuli, which may impart advantageous properties to polymeric materials comprising crystalline and/or amorphous phases, for example, for use in medical devices (e.g., orthodontic appliances). In some cases, a polymeric material comprising one or more amorphous polymeric phases may, for example, provide flexibility to the cured polymeric material, which may increase its durability (e.g., the material may be stretched or bent while maintaining its structure, while a similar material without an amorphous phase may fracture). In certain embodiments, the amorphous phase may be characterized by randomly oriented polymer chains (e.g., stacked not in parallel or in a crystalline structure). In some embodiments, such amorphous polymer phase of the polymeric material may have a glass transition temperature greater than about 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, or greater than about 110 ℃. In some embodiments, the amorphous polymer phase may have a glass transition temperature of about 40 ℃ to about 60 ℃, about 50 ℃ to about 70 ℃, about 60 ℃ to about 80 ℃, or about 80 ℃ to about 110 ℃. In some embodiments, the amorphous phase has a glass transition temperature of less than 10 ℃, 0 ℃, -10 ℃, -30 ℃, -50 ℃. In some preferred aspects, the glass transition temperature of one or more phases is less than 0 ℃. In some embodiments, two or more phases have a glass transition temperature above 60 ℃ and below 10 ℃.

In some embodiments, an amorphous phase (also referred to herein as amorphous domains) herein may comprise at least about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or at least about 90% of an amorphous polymeric material in an amorphous state. The percentage of amorphous polymer material in the amorphous phase generally refers to the total volume percentage.

In some embodiments, the amorphous polymer phase may comprise one or more polymer types, which may be formed during curing from polymerizable monomers, telechelic polymers and/or oligomers, and any other polymerizable components that may be present in the curable composition used to prepare the polymeric material containing the amorphous polymer phase. In some examples, such one or more polymer types may include one or more of homopolymers, linear copolymers, block copolymers, alternating copolymers, periodic copolymers, statistical copolymers, random copolymers, gradient copolymers, branched copolymers, brush copolymers, comb copolymers, dendritic polymers, or any combination thereof. In some cases, the amorphous polymeric material comprises a random copolymer. In some embodiments, the amorphous polymeric material may comprise polyethylene glycol (PEG), polyethylene glycol diacrylate, PEG-THF, polytetrahydrofuran, poly-t-butyl acrylate, poly (ethylene-co-maleic anhydride), any derivative thereof, or any combination thereof.

In some cases, the polymerizable component of the resin that can form the crystalline material can instead form an amorphous phase when exposed to conditions that prevent crystallization thereof. Thus, in some cases, a material that can be conventionally regarded as crystalline may be used as an amorphous material. As a non-limiting example, polycaprolactone can be a crystalline polymer, but when mixed with other polymerizable monomers and telechelic polymers, can prevent crystal formation, and can form an amorphous phase.

The amorphous phase may comprise, in polymerized form, one or more polymerizable monomers according to any of formulas (I) - (VI) and (IX), and may additionally comprise one or more of the following moieties: acrylic acid monomers, acrylamide, methacrylamide, acrylonitrile, bisphenol acrylic acid, carbohydrates, fluorinated acrylic acid, maleimide, acrylic acid esters, 4-acetoxyphenethyl acrylic acid esters, acrylic acid chloride, 4-acryloylmorpholine, 2- (acryloyloxy) ethyl ] trimethylammonium chloride, ethyl 2- (4-benzoyl-3-hydroxyphenoxy) acrylate, benzyl 2-propyl acrylate, butyl acrylate, t-butyl acrylate, ethyl 2[ [ (butylamino) carbonyl ] oxy ] acrylate, t-butyl 2-bromoacrylate, ethyl 2-carboxyacrylate, ethyl 2-chloroacrylate, ethyl 2- (diethylamino) acrylate, diethyl glycol) diethyl ether acrylate ethyl 2- (dimethylamino) acrylate, propyl 3- (dimethylamino) acrylate, dipentaerythritol penta-/hexa-acrylate, ethyl acrylate, 2-ethyl acryloyl chloride, ethyl 2- (bromomethyl) acrylate, cis- (. Beta. -cyano) ethyl acrylate, ethylene glycol dicyclopentene ether acrylate, ethylene glycol methyl ether acrylate, ethylene glycol phenyl ether acrylate, ethyl 2-ethylacrylate, 2-ethylhexyl acrylate, 2-propyl acrylate, ethyl 2- (trimethylsilyl methyl) acrylate, hexyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxypropyl acrylate, isobornyl acrylate, isobutyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, methyl 2-acetamido acrylate, methyl acrylate, methylene malonate (e.g., dibutyl, dihexyl or dicyclohexyl methylene malonate), methylene malonate macromers (e.g., polyesters of 2-methylene malonate, for example, forza B3000 XP), methyl-bromoacrylate, methyl 2- (bromomethyl) acrylate, methyl 2- (chloromethyl) acrylate, methyl 3-hydroxy-2-methylenebutyrate, methyl 2- (trifluoromethyl) acrylate, octadecyl acrylate, pentabromobenzyl acrylate, pentabromophenyl acrylate, pentafluorophenyl acrylate, poly (ethylene glycol) diacrylate, poly (ethylene glycol) methyl ether acrylate, poly (propylene glycol) acrylate, epoxidized soybean oil acrylate, 3-sulfopropyl acrylate, tetrahydrofurfuryl acrylate, 2-tetrahydropyranyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 3, 5-trimethylhexyl acrylate, 10-undecylenate acrylate, urethane acrylate methacrylate, tricyclodecane diacrylate, isobornyl acrylate, methacrylate, allyl methacrylate, benzyl methacrylate, (2-boc-amino) ethyl methacrylate, t-butyl methacrylate, 9H-carbazole-9-ethyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, cyclohexyl methacrylate, 1, 10-decanediol dimethacrylate, ethylene glycol dicyclopentenyl ether methacrylate, ethylene glycol methyl ether methacrylate, 2-ethylhexyl methacrylate, furfuryl methacrylate, glycidyl methacrylate, glycoxyethyl methacrylate, hexyl methacrylate, hydroxybutyl methacrylate, 2-hydroxy-5-N-methacrylamidobenzoic acid, isobutyl methacrylate, methacryloyl chloride, methyl methacrylate, mono-2-methacryloyloxy) ethyl succinate, 2-N-morpholinoethyl methacrylate, 1-naphthalene methacrylate, pentabromophenyl methacrylate, phenyl methacrylate, pentabromophenyl methacrylate, TEMPO methacrylate, 3-sulfopropyl methacrylate, triethylene glycol methyl ether methacrylate, 2- [ (1 ',1',1 '-trifluoro-2' - (trifluoromethyl) -2'0 hydroxy) propyl ] -3-methyl methacrylate norbornyl ester, 3, 5-trimethyl cyclohexyl methacrylate, (trimethylsilyl) methacrylate, vinyl methacrylate, isobornyl methacrylate, bisphenol A dimethacrylate, omnilaneOC, t-butyl acrylate, isodecyl acrylate, tricyclodecane diacrylate, multifunctional acrylate, N' -methylenebisacrylamide, 3- (acryloyloxy) -2-hydroxypropyl) methacrylate, bis [2- (methacryloyloxy) ethyl ] phosphate, 1, 3-butanediol diacrylate, 1, 4-butanediol diacrylate, di-polyurethane dimethacrylate, N' -ethylenebis (acrylamide), glycerol 1, 3-glycerolate diacrylate, 1, 6-hexanediol diacrylate, hydroxypivalyl hydroxypivalate bis [6- (acryloyloxy) hexanoate ], neopentyl glycol diacrylate, pentaerythritol diacrylate, 1,3, 6-triacryloylhexahydro-1, 3, 5-triazine, trimethylolpropane ethoxylate, tris [2- (acryloyloxy) ethyl ] isocyanurate, any derivative thereof, or a combination thereof.

The phase (e.g., amorphous or crystalline phase) of the polymeric material herein may include one or more reactive functional groups, which may allow for further modification of the polymeric material, such as addition polymerization (e.g., post-cure). In some embodiments, the amorphous polymeric material comprises a plurality of reactive functional groups, and the reactive functional groups may be located at one or both ends of the amorphous material, in a chain, at a side chain (e.g., a side group attached to the polymeric backbone), or any combination thereof. Non-limiting examples of reactive functional groups include free radical polymerizable functional groups, photoactive groups, groups that promote step-growth polymerization, thermally reactive groups, and/or groups that promote bond formation (e.g., covalent bond formation). In some embodiments, the functional groups include acrylates, methacrylates, acrylamides, vinyl ethers, thiols, allyl ethers, norbornenes, vinyl acetates, maleates, fumarates, maleimides, epoxides, ring strained cyclic ethers, ring strained thioethers, cyclic esters, cyclic carbonates, cyclic silanes, cyclic siloxanes, hydroxyl groups, amines, isocyanates, blocked isocyanates, acid chlorides, activated esters, oxetanes, diels-Alder reactive groups, furans, cyclopentadiene, anhydrides, groups that facilitate photodimerization (e.g., anthracene, acenaphthylene, or coumarin), groups that photodegradation to reactive species (e.g., norrish type 1 and type 2 materials), azides, derivatives thereof, or combinations thereof.

Crystalline polymer phase

As further described herein, the polymeric materials of the present disclosure may include one or more crystalline phases, such as crystalline phases generated by polymerization-induced phase separation during curing. As described herein, the crystalline phase is a polymeric phase of a cured polymeric material comprising at least one polymeric crystal. As disclosed herein, the crystalline phase may consist of a single polymer crystal, or may comprise multiple polymer crystals.

In some embodiments, the crystalline polymer phase may have a melting temperature equal to or greater than about 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, or equal to or greater than 150 ℃. In some cases, at least two of the plurality of crystalline phases may have different melting temperatures due to differences in, for example, crystalline phase size, impurities, degree of crosslinking, chain length, thermal history, rate at which polymerization occurs, degree of phase separation, or any combination thereof. In some aspects, at least two crystalline phases of the polymeric material may each have a polymer crystal melting temperature that differs from each other by within about 5 ℃. In some examples, this difference in melting temperature may be less than about 5 ℃. In other examples, this difference in melting temperature may be greater than about 5 ℃. In some aspects, each polymer crystal of the polymeric material may have a melting temperature of about 40 ℃ to about 100 ℃. In some aspects, at least about 80% of the crystalline domains of the polymeric material may comprise polymer crystals having a melting temperature of about 40 ℃ to about 100 ℃.

In some embodiments, at least 80% of the crystalline phase has a crystalline melting point at a temperature of 0 ℃ to 100 ℃. In some embodiments, at least 80% of the crystalline phase has a crystalline melting point at a temperature of 40 ℃ to 60 ℃, 40 ℃ to 80 ℃, 40 ℃ to 100 ℃, 60 ℃ to 80 ℃, 60 ℃ to 100 ℃, 80 ℃ to 100 ℃, or greater than 100 ℃. In some embodiments, at least 90% of the crystalline phase has a crystalline melting point at a temperature of 0 ℃ to 100 ℃. In some embodiments, at least 90% of the crystalline phase has a crystalline melting point at a temperature of 40 ℃ to 60 ℃, 40 ℃ to 80 ℃, 40 ℃ to 100 ℃, 60 ℃ to 80 ℃, 60 ℃ to 100 ℃, 80 ℃ to 100 ℃, or greater than 100 ℃. In some embodiments, at least 95% of the crystalline phase has a crystalline melting point at a temperature of 0 ℃ to 100 ℃. In some embodiments, at least 95% of the crystalline phase has a crystalline melting point at a temperature of 40 ℃ to 60 ℃, 40 ℃ to 80 ℃, 40 ℃ to 100 ℃, 60 ℃ to 80 ℃, 60 ℃ to 100 ℃, 80 ℃ to 100 ℃, or greater than 100 ℃.

In certain embodiments, the temperature at which the crystalline phase of the cured polymeric material melts may be controlled, for example, by using different amounts and types of polymerizable components in the curable resin, e.g., different amounts and types of polymerizable monomers described herein (e.g., those compounds according to any of formulas (I) - (VI) and (IX)), different amounts and types of telechelic polymers and/or oligomers, and/or by using polymer blocks having different crystalline melting points (i.e., in the copolymer).

In some embodiments, curing of the resin may occur at an elevated temperature (e.g., at about 90 ℃) and when the cured polymeric material cools to room temperature (e.g., 25 ℃), the cooling may trigger the formation and/or growth of polymer crystals in the polymeric material. In some examples, the polymeric material may be solid at room temperature and may be non-crystalline, but may form a crystalline phase over time. In this case, the crystalline phase may be formed within 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 18 hours, 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, or 7 days after cooling. In some embodiments, when the solidified polymeric material is in a cooled environment, a crystalline phase may form, for example, in an environment having a temperature of about 40 ℃ to about 30 ℃, about 30 ℃ to about 20 ℃, about 20 ℃ to about 10 ℃, about 10 ℃ to about 0 ℃, about 0 ℃ to about-10 ℃, about-10 ℃ to about-20 ℃, about-20 ℃ to about-30 ℃, or less than about-30 ℃. In some examples, the polymeric material may be heated to an elevated temperature to induce crystallization or form a crystalline phase. As a non-limiting example, a polymeric material near its glass transition temperature may contain polymer chains that may not be sufficiently mobile to organize into crystals, so further heating the material may increase chain mobility and induce crystal formation.

In some embodiments, the formation, and/or growth of the polymer phase is spontaneous. In some embodiments, the formation, and/or growth of polymer crystals is promoted by triggering. In some embodiments, triggering includes adding seeding particles (also referred to herein as "seeds") that can induce crystallization. For example, such seeds may include finely ground solid material having at least some properties similar to crystals formed. In some embodiments, the trigger comprises a decrease in temperature. In certain embodiments, the lowering of the temperature may include cooling the solidified material to a temperature of 40 ℃ to 30 ℃, 30 ℃ to 20 ℃, 20 ℃ to 10 ℃, 10 ℃ to 0 ℃, 0 ℃ to-10 ℃, 10 ℃ to-20 ℃, 20 ℃ to-30 ℃, or below-30 ℃. In some embodiments, the trigger may include an increase in temperature. In certain embodiments, the raising of the temperature may include heating the polymer cured material to a temperature of 20 ℃ to 40 ℃, 40 ℃ to 60 ℃, 60 ℃ to 80 ℃, 80 ℃ to 100 ℃, or above 100 ℃. In some embodiments, triggering includes a force exerted on the cured polymeric material. In certain embodiments, the force comprises pressing, compacting, pulling, twisting, or providing any other physical force to the material. In some embodiments, the trigger includes an electrical charge and/or an electrical field applied to the material. In some embodiments, the formation of one or more crystalline phases may be induced by more than one trigger (i.e., more than one type of trigger may promote the generation, formation, and/or growth of crystals). In some embodiments, the polymeric material comprises a plurality of crystalline phases, and at least two crystalline phases may be induced by different triggers.

In some embodiments, the polymeric materials herein comprise a crystalline phase having a discontinuous phase transition (e.g., a first order phase transition). In some cases, the polymeric material has a discontinuous phase change due at least in part to the presence of one or more crystalline domains. As a non-limiting example, a solidified polymeric material comprising one or more crystalline domains may have one or more portions that melt at an elevated temperature when heated to such elevated temperature, and one or more portions that remain solid.

In some embodiments, the cured polymeric material comprises a crystalline phase that is a continuous and/or discontinuous phase. The continuous phase may be a phase that is traceable or linked from one side of the polymeric material to the other side of the material; for example, closed cell foam materials contain foam that can be traced throughout the sample, while closed cells (bubbles) represent the discontinuous phase of air pockets. In some embodiments, at least one crystalline phase forms a continuous phase, while at least one amorphous phase is discontinuous throughout the material. In another embodiment, at least one crystalline phase is discontinuous and at least one amorphous phase is continuous throughout the material. In another embodiment, the at least one crystalline phase and the at least one amorphous phase are continuous throughout the material. In some embodiments, the polymeric material comprises a plurality of crystalline phases, wherein one or more of the plurality of crystalline phases has a high melting point (e.g., at least about 50 ℃, 70 ℃, or 90 ℃) and is in the discontinuous phase, and another one or more of the plurality of crystalline phases has a low melting point (e.g., at less than about 50 ℃, 70 ℃, or 90 ℃) and is in the continuous phase. In some embodiments, there are two consecutive amorphous phases. In other embodiments, there is one continuous and one discontinuous amorphous phase

In some aspects, the polymeric material comprises an average crystalline phase size of less than about 100 μm, 50 μm, 20 μm, 10 μm, or less than about 5 μm in at least one spatial dimension.

In some aspects, the polymer crystals of the crystalline phase can comprise greater than about 40wt%, greater than about 50wt%, greater than about 60wt%, greater than about 70wt%, greater than about 80wt%, or greater than about 90wt% linear polymer and/or linear oligomer.

In some aspects, the polymeric materials described herein can have a crystalline phase content of about 10% to about 90%, about 20% to about 80%, about 30% to about 70%, about 40% to about 95%, or about 50% to about 95%, as measured by X-ray diffraction. In some aspects, the polymeric materials herein may comprise crystalline and amorphous phases in a weight ratio of about 1:99 to about 99:1.

In various aspects, the present disclosure provides a polymeric material comprising: an amorphous phase; and a crystalline phase comprising a polymer having stereoregular properties. In some aspects, the stereotactic property includes isotactic, syndiotactic, having multiple meso-divalent radicals, having multiple racemic-divalent radicals, having multiple isotactic trivalent radicals, having multiple syndiotactic trivalent radicals, or having multiple hetero-syndiotactic trivalent radicals. In some aspects, a polymeric material comprising a crystalline phase comprising a polymer having stereoregular properties has increased crystallinity compared to a comparable polymeric material comprising a comparable atactic polymer. In some aspects, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, greater than 95%, or greater than 99% of the crystalline phase comprises a stereoregular property. In some aspects, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, greater than 95%, or greater than 99% of the polymeric material comprises stereoregular properties. In some aspects, a polymeric material comprising a polymer having stereoregular properties is characterized by at least one of: elongation at break greater than or equal to 5%; a storage modulus greater than or equal to 500MPa; a tensile modulus greater than or equal to 500MPa; and a residual bending stress greater than or equal to 0.01MPa. In some aspects, a comparable polymeric material comprising a comparable atactic polymer with a polymer having stereoregular properties is characterized by at least one of: elongation at break less than 5%; storage modulus less than 500MPa; a tensile modulus of less than 500MPa; and residual bending stress less than 0.01MPa. In some aspects, the polymeric material is at least partially crosslinked. In some aspects, the polymeric material is thermoset or thermoplastic. In some aspects, the polymeric material comprises a semi-crystalline segment.

In some embodiments, the cured polymer (e.g., crosslinked polymer) may be characterized by a tensile stress-strain curve that exhibits a yield point after which the specimen continues to elongate, but without (detectable) or with only a very low increase in stress. Such yield point behavior may occur "near" the glass transition temperature, where the material is between glassy and rubbery, and may be characterized as having a viscoelastic behaviorSexual behavior. In some embodiments, viscoelastic behavior is observed over a temperature range of about 20 ℃ to about 40 ℃. The yield stress is determined at the yield point. In some embodiments, the modulus is determined from the initial slope of the stress-strain curve, or as a secant modulus at 1% strain (e.g., when the stress-strain curve has no linear portion). The elongation at yield is determined by the strain of the yield point. When the yield point occurs at the maximum of the stress, the ultimate tensile strength is less than the yield strength. For tensile test specimens, the strain is defined by ln (l/l ₀ ) Definition, which can be approximated as (l-l) at small strains (e.g., less than about 10%) ₀ )/l ₀ And elongation is l/l ₀ Wherein l is the gauge length after a certain deformation, and l ₀ Is the initial gauge length. The mechanical properties may depend on the temperature at which they are measured. The test temperature may be lower than the intended use temperature of the dental appliance, for example 35 ℃ to 40 ℃. In some embodiments, the test temperature is 23±2 ℃.

As further provided herein, polymeric materials comprising crystalline phases (also referred to herein as crystalline domains) and amorphous phases (also referred to herein as amorphous domains) may have improved properties, such as the ability to act rapidly (e.g., vibrate rapidly and react upon application of strain, from the elastic characteristics of the amorphous domains), and the ability to provide a strong modulus (e.g., be hard and provide strength from the crystalline domains). The polymer crystals disclosed herein may comprise tightly stacked and/or filled polymer chains. In some embodiments, the polymer crystals comprise long oligomers or long polymer chains stacked in an organized manner, overlapping in parallel. In some cases, the polymer crystals may be pulled from the crystalline phase, thereby producing elongation as the polymer chains of the polymer crystals are pulled (e.g., application of force may pull long polymer chains of the polymer crystals, thereby introducing disorder to the stacked chains, pulling at least a portion out of its crystalline state without damaging the polymer chains). This is in contrast to fillers conventionally used to form resins for materials having a high flexural modulus, which can simply slide through an amorphous phase when a force is applied to the polymeric material, or when the filler is covalently bonded to the polymer, resulting in a reduced elongation at break of the material. Thus, the use of polymer crystals in the resulting polymeric material provides a less brittle product that retains more of the original physical properties (i.e., is more durable) after use and retains elastic characteristics through a combination of amorphous and crystalline phases.

In some embodiments, the polymeric materials herein include a ratio (wt/wt) of crystalline to amorphous polymeric phase of greater than about 1:10, greater than about 1:9, greater than about 1:8, greater than about 1:7, greater than about 1:6, greater than about 1:5, greater than about 1:4, greater than about 1:3, greater than about 1:2, greater than about 1:1, greater than about 2:1, greater than about 3:1, greater than about 4:1, greater than about 5:1, greater than about 6:1, greater than about 7:1, greater than about 8:1, greater than about 9:1, greater than about 10:1, greater than about 20:1, greater than about 30:1, greater than about 40:1, greater than about 50:1, or greater than about 99:1. In some embodiments, the polymeric material comprises a ratio of crystallizable polymeric material to amorphous polymeric material (wt/wt) of at least 1:10, at least 1:9, at least 1:8, at least 1:7, at least 1:6, at least 1:5, at least 1:4, at least 1:3, at least 1:2, at least 1:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 99:1. In certain embodiments, the polymeric material comprises a crystalline to amorphous polymeric phase ratio (wt/wt) of from 1:9 to 99:1, from 1:9 to 9:1, from 1:4 to 4:1, from 1:4 to 1:1, from 3:5 to 1:1, from 1:1 to 5:3, or from 1:1 to 4:1.

In some embodiments, the polymeric materials of the present disclosure include a ratio (vol/vol) of crystalline to amorphous polymeric phase of greater than about 1:10, greater than about 1:9, greater than about 1:8, greater than about 1:7, greater than about 1:6, greater than about 1:5, greater than about 1:4, greater than about 1:3, greater than about 1:2, greater than about 1:1, greater than about 2:1, greater than about 3:1, greater than about 4:1, greater than about 5:1, greater than about 6:1, greater than about 7:1, greater than about 8:1, greater than about 9:1, greater than about 10:1, greater than about 20:1, greater than about 30:1, greater than about 40:1, greater than about 50:1, or greater than about 99:1. In some embodiments, the polymeric material comprises a ratio (vol/vol) of crystalline to amorphous polymeric phase of at least 1:10, at least 1:9, at least 1:8, at least 1:7, at least 1:6, at least 1:5, at least 1:4, at least 1:3, at least 1:2, at least 1:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 99:1. In certain embodiments, the polymeric material comprises a ratio (vol/vol) of crystalline to amorphous polymer phase of from 1:9 to 99:1, from 1:9 to 9:1, from 1:4 to 4:1, from 1:4 to 1:1, from 3:5 to 1:1, from 1:1 to 5:3, or from 1:1 to 4:1.

Properties of the Polymer Material

Polymeric materials of the present disclosure formed from polymerization of the curable resins disclosed herein may provide advantageous properties compared to conventional polymeric materials. In some examples, the polymeric material may contain a percentage of crystallinity, as described herein, which may impart increased toughness and high modulus to the polymeric material while being a 3D printable material in some cases. In addition, the polymeric materials herein may further comprise one or more amorphous phases, which may provide increased durability, prevent crack formation, and prevent crack propagation. In some examples, the polymeric material may also have a lower water absorption and may be solvent resistant. In some cases, the polymeric material may be characterized by one or more properties selected from elongation at break, storage modulus, tensile modulus, residual bending stress, glass transition temperature, water absorption, hardness, color, transparency, hydrophobicity, lubricity, surface texture, percent crystallinity, phase composition ratio, domain size, and domain size and morphology. Furthermore, as described herein, the polymeric materials provided herein can be used in a variety of applications, including 3D printing, to form materials with advantageous elastic and stiffness properties.

In some embodiments, the polymeric materials of the present disclosure may have one or more of the following features: (A) storage modulus greater than or equal to 200MPa; (B) Residual bending stress and/or bending modulus after 24 hours in a humid environment at 37 ℃ is greater than or equal to 1.5MPa; (C) Elongation at break greater than or equal to about 24 hours in a wet environment at 37 DEG C5%; (D) The water absorption is less than 25wt% when measured after 24 hours in a humid environment at 37 ℃; (E) After 24 hours in a humid environment at 37 ℃, the visible light transmission through the polymeric material is at least 30%; and (F) comprises a plurality of polymer phases, wherein T of at least one of the one or more polymer phases _g At least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃. In some examples, the polymeric materials herein have at least two, three, four, five, or all of the characteristics of (a), (B), (C), (D), (E), and (F).

In some examples, the polymeric material may be characterized by a storage modulus of 0.1MPa to 4000MPa, a storage modulus of 300MPa to 3000MPa, or a storage modulus of 750MPa to 3000MPa after 24 hours in a humid environment at 37 ℃. In some examples, the polymeric material is characterized by a residual flexural stress and/or flexural modulus of greater than or equal to 5MPa, greater than or equal to 10MPa, greater than or equal to 20MPa, greater than or equal to 30MPa, greater than or equal to 40MPa, greater than or equal to 50MPa, greater than or equal to 60MPa, greater than or equal to 80MPa, or greater than or equal to 100MPa after 24 hours in a humid environment at 37 ℃.

In some examples, the flexural stress and/or flexural modulus of the polymeric materials herein can be 400MPa or greater, 300MPa or greater, 200MPa or greater, 180MPa or greater, 160MPa or greater, 120MPa or greater, 100MPa or greater, 80MPa or greater, 70MPa or greater, 60MPa or greater after 24 hours in a humid environment at 37 ℃.

In some examples, the polymeric material may be characterized by an elongation at break of greater than 10%, an elongation at break of greater than 20%, an elongation at break of greater than 30%, an elongation at break of 5% to 250%, an elongation at break of 20% to 250%, or an elongation at break value of 40% to 250% before and after 24 hours in a humid environment at 37 ℃.

The polymeric material may be characterized by a water absorption of less than 20wt%, less than 15wt%, less than 10wt%, less than 5wt%, less than 4wt%, less than 3wt%, less than 2wt%, less than 1wt%, less than 0.5wt%, less than 0.25wt%, or less than 0.1wt%, when measured after 24 hours in a humid environment at 37 ℃. In some cases, the polymeric material may have a double bond to single bond conversion of greater than 50%, 60%, or 70% as compared to the photocurable resin, as measured by FTIR.

In some examples, the ultimate tensile strength of the polymeric material may be 10MPa to 100MPa, 15MPa to 80MPa, 20MPa to 60MPa, 10MPa to 50MPa, 10MPa to 45MPa, 25MPa to 40MPa, 30MPa to 45MPa, or 30MPa to 40MPa after 24 hours in a humid environment at 37 ℃.

In some examples, the polymeric material may have a lower amount of hydrogen bonds than conventional polymeric materials having a greater amount of hydrogen bonds, which may facilitate a reduction in water absorption. Thus, in some examples, the polymeric materials herein may comprise less than about 10wt%, less than about 9wt%, less than about 8wt%, less than about 7wt%, less than about 6wt%, less than about 5wt%, less than about 4wt%, less than about 3wt%, less than about 2wt%, less than about 1wt%, or less than about 0.5wt% water when fully saturated at the use temperature (e.g., about 20 ℃, 25 ℃, 30 ℃, or 35 ℃). In some examples, the use temperature may include a temperature of a person's mouth (e.g., about 35-40 ℃). The application temperature can be selected from-100-250deg.C, 0-90deg.C, 0-80deg.C, 0-70 deg.C, 0-60 deg.C, 0-50deg.C, 0-40 deg.C, 0-30 deg.C, 0-20 deg.C, 0-10 deg.C, 20-90 deg.C, 20-80 deg.C, 20-70 deg.C, 20-60 deg.C, 20-50 deg.C, 20-40 deg.C, 20-30 deg.C or below 0deg.C.

In some embodiments, the polymeric materials herein comprise at least one crystalline phase and at least one amorphous phase, wherein the at least one crystalline phase, the at least one amorphous phase, or both contain a polymerizable monomer of the present disclosure, which may be a compound according to any one of formulas (I) - (VI) and (IX). In some examples, a combination of these two types of phases or domains may produce a polymeric material having a high modulus phase (e.g., a crystalline polymeric material may provide a high modulus) and a low modulus phase (e.g., provided by the presence of an amorphous polymeric material). By having these two phases, the polymeric material can have a high modulus and high elongation, as well as a high residual bending stress after stress relaxation.

In various examples, one or more amorphous phases of the polymeric material may have a glass transition temperature of at least about 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, or at least about 110 ℃. In this case, at least one of the one or more amorphous phases having a glass transition temperature of at least about 50 ℃ comprises the polymerizable monomers of the present disclosure incorporated in their polymer structure, e.g., a compound according to any one of formulas (I) - (VI) and (IX).

In some cases, the polymeric material may include polymer crystals attached to an amorphous polymer. As non-limiting examples, the polymer crystals may be covalently bonded to, entangled with, crosslinked to, and/or otherwise associated with the amorphous polymer material (e.g., by hydrophobic interactions, pi stacking, or hydrogen bonding interactions).

In some embodiments, the polymeric materials herein may comprise crystalline and/or amorphous phases having smaller dimensions (e.g., less than about 5 μm). The smaller polymer phase in the polymeric material may facilitate the passage of light and provide a polymeric material that appears transparent. Conversely, a larger polymer phase (e.g., a polymer phase greater than about 1 μm) may scatter light, for example, when the refractive index of the polymer crystal differs from the refractive index of an amorphous phase (e.g., amorphous material) adjacent to the polymer crystal. In some cases, at least 40%, 50%, 60% or 70% of the visible light passes through the polymeric material after 24 hours in a humid environment at 37 ℃.

Thus, in some cases, it may be advantageous to have a polymeric material that contains a small polymeric phase (e.g., crystalline or amorphous phase), as measured by the longest length of the phase. In some embodiments, such polymeric materials comprise an average polymeric phase size of less than 5 μm. In some cases, the maximum polymer phase size of the polymeric material may be about 5 μm. In some embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the polymer phase of the polymeric material has a size of less than about 5 μm. In other embodiments, the polymeric material comprises an average polymeric phase size of less than about 1 μm. In some embodiments, the cured polymeric material has a maximum polymer phase size of 1 μm. In some embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the polymer phase of the polymeric material has a size of less than about 1 μm. In other embodiments, the polymeric material comprises an average polymer phase size of less than about 500nm. In some embodiments, the cured polymeric material has a maximum polymer phase size of about 500nm. In some embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the polymer phase of the polymeric material has a size less than 500nm.

In some embodiments, the size of at least one or more polymer phases (e.g., crystalline and amorphous phases) of the polymeric material may be controlled. Non-limiting examples of ways in which the size of the polymer phase may be controlled include: rapidly cooling the solidified polymeric material, annealing the solidified polymeric material at an elevated temperature (i.e., above room temperature), annealing the solidified polymeric material at a temperature below room temperature, controlling the rate of polymerization, controlling the intensity of light during the solidification step using light, controlling and/or adjusting the polymerization temperature, exposing the solidified polymeric material to acoustic vibrations, and/or controlling the presence and amount of impurities, particularly for crystalline phases, adding crystallization inducing chemicals or particles (e.g., crystallization seeds).

In some embodiments, the refractive index of one or more crystalline phases and/or one or more amorphous phases of the polymeric materials herein may be controlled. A decrease in the index of refraction difference between the different phases (e.g., a decrease in the index of refraction difference between the crystalline polymer and the amorphous polymer) may increase the transparency of the cured polymeric material, thereby providing a transparent or near transparent material. Light scattering can be reduced by minimizing the polymer crystal size, and by reducing the refractive index difference at the interface between the amorphous and crystalline phases of the polymer. In some embodiments, the refractive index difference between a given polymer phase and an adjacent phase (e.g., crystalline phase and adjacent amorphous phase) may be less than about 0.1, less than about 0.01, or less than about 0.001.

Further provided herein are polymeric films comprising the polymeric materials of the present disclosure. In some cases, the thickness of such polymer films may be at least about 50 μm, 100 μm, 250 μm, 500 μm, 1mm, 2mm, and no greater than 3mm.

Polymeric materials in medical devices

The present disclosure provides an apparatus comprising the polymeric material of the present disclosure. As described herein, such polymeric materials may comprise and incorporate in their polymeric structure one or more polymerizable monomers of the present disclosure, such as compounds according to formulas (I) - (VI) and (IX). In some embodiments, such polymeric materials may comprise a polymer comprising a monomer according to formulas (VII) or (VIII) described herein. In various cases, the device may be a medical instrument. The medical device may be an orthodontic appliance. The orthodontic appliance may be a dental appliance, a dental expander, or a dental spacer.

V. method of use

The present disclosure provides methods for synthesizing the polymerizable monomers of the present disclosure, methods of using compositions (e.g., resins and polymeric materials) comprising such monomers, and methods of using them in devices such as medical devices. Photopolymerizable monomers of the present disclosure, such as those according to any of formulas (I) - (VIII), can be used as components in materials used in many different industries, such as transportation (e.g., aircraft, trains, boats, automobiles, etc.), hobbyist, prototyping, medical, artistic and design, microfluidics, molds, and the like. In various embodiments herein, such medical devices comprise orthodontic appliances.

Synthesis method

The present disclosure provides synthetic methods for producing the polymerizable monomers described herein. In some embodiments, the polymerizable monomers of formula (I) according to the present disclosure can be prepared as shown in the following exemplary scheme 1:

wherein:

x is O, S, NR ⁶ Or SiR ⁷ R ⁸ ；

R ¹ Is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

Wherein Y is O, S, NH or C (O) O;

n is an integer from 0 to 6;

In some embodiments, the polymerizable monomer of formula (II) according to the present disclosure can be prepared as shown in the following exemplary scheme 2:

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

wherein X is O, S, NH or C (O) O;

n is an integer from 0 to 6; and is also provided with

In some embodiments, the polymerizable monomer of formula (III) according to the present disclosure can be prepared as shown in the following exemplary scheme 3:

wherein:

PG is a suitable phenolic alcohol protecting group;

LG is a suitable leaving group, e.g., hydroxy, chloro, bromo, and the like.

R ¹ Is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

wherein X is O, S, NH or C (O) O;

n is an integer from 0 to 6; and is also provided with

In some embodiments, the polymerizable monomer of formula (IV) according to the present disclosure may be prepared as shown in the following exemplary scheme 4:

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

In some embodiments, the polymerizable monomer of formula (V) according to the present disclosure may be prepared as shown in the following exemplary scheme 5:

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

X ¹ And X ² Each independently is a bond, O or S;

a and b are each independently integers from 0 to 6; and is also provided with

R ²⁸ And R is ²⁹ Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some embodiments, the polymerizable monomer of formula (VI) according to the present disclosure can be prepared as shown in the following exemplary scheme 6:

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

X ⁵ And X ⁶ Each independently is a bond, O or S;

e and f are each independently integers from 0 to 6; and is also provided with

R ⁴² And R is ⁴³ Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In some embodiments, any of such methods may include isolating the polymerizable monomer in a chemical yield of at least about 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or at least about 95%, and a chemical purity of at least about 90%, 95%, or 99%.

Those skilled in the art will appreciate that substituents (e.g., R ¹ -R ²³ 、R ²⁸ -R ²⁹ 、R ³² -R ³⁵ And R is ⁴² -R ⁴³ ) Changes may be made before, during, or after preparation of the phenyl acrylate scaffold, and exemplary conditions (e.g., temperature, solvents, etc.) may be appropriately adjusted. Furthermore, one skilled in the art will recognize that protecting groups may be necessary to prepare certain compounds, and will recognize those conditions that are compatible with the protecting group selected.

Method for forming polymer material

Further provided herein is a method of polymerizing (e.g., photocuring) a curable composition (e.g., a photocurable resin) comprising at least one polymerizable monomer described herein (e.g., those according to formulas (I) - (VI) and (IX)) and optionally selected from telechelic polymers, telechelic oligomers, polymerization initiators, polymerization inhibitors, solvents, fillers, antioxidants, pigments, colorants, surface modifying agents, and mixtures thereof to obtain an optionally crosslinked polymer, the method comprising the steps of mixing the curable composition with a reactive diluent, optionally after heating, and then initiating polymerization by heating and/or irradiating the composition; wherein the reactive diluent is selected from polymerizable monomers, such as those of any of formulas (I) - (VI) and (IX) according to the first aspect of the disclosure, and mixtures thereof.

The present disclosure provides methods of producing polymeric materials using the curable resins described herein. In various embodiments, provided herein are methods for photocuring a photocurable resin. Accordingly, in various examples, provided herein is a method of forming a polymeric material, the method comprising: (i) providing a photocurable resin of the present disclosure; (ii) exposing the photocurable resin to a light source; and curing the photocurable resin to form a polymeric material.

In some embodiments, the photo-curing comprises a single curing step. In some embodiments, the photo-curing includes multiple curing steps. In other embodiments, the photo-curing includes at least one curing step of exposing the curable resin to light. Exposure of the curable resin to light may initiate and/or promote photopolymerization. In some examples, a photoinitiator may be used as part of the resin to accelerate and/or initiate photopolymerization. In some embodiments, the resin is exposed to UV (ultraviolet) light, visible light, IR (infrared) light, or any combination thereof. In some embodiments, the cured polymeric material is formed from a photocurable resin using at least one step that includes exposure to a light source, wherein the light source includes UV light, visible light, and/or IR light. In some embodiments, the light source comprises a wavelength of 10nm to 200nm, 200nm to 350nm, 350nm to 450nm, 450nm to 550nm, 550nm to 650nm, 650nm to 750nm, 750nm to 850nm, 850nm to 1000nm, or 1000nm to 1500 nm.

In some embodiments, the method of forming a polymeric material from the photopolymerizable resins described herein may further comprise inducing phase separation in the formation of the polymeric material (i.e., during photocuring), wherein such phase separation may be polymerization-induced. The polymerization-induced phase separation may include generating one or more polymer phases in the polymer material during photocuring. In some cases, at least one of the one or more polymer phases is an amorphous polymer phase. Such at least one amorphous polymer phase may haveAt least about 40 ℃, 50 ℃, 60 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, or at least about 120 ℃ (T) _g ). In some cases, at least 25%, 50%, or 75% of the polymer phase produced during photocuring has a glass transition temperature (T) of at least about 40 ℃, 50 ℃, 60 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, or at least about 120 DEG _g ). In some examples, the glass transition temperature (T _g ) At least one polymer phase of at least about 40 ℃, 50 ℃, 60 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, or at least about 120 ℃ comprises a polymerizable monomer according to any one of formulas (i) - (VI) and (IX) and is incorporated into its polymer structure (i.e., is present in polymerized form). In some examples, the glass transition temperature (T _g ) At least one polymer phase of at least about 40 ℃, 50 ℃, 60 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or at least about 120 ℃ comprises a polymer comprising a monomer according to formula (VII) or formula (VIII). In various cases, at least one of the one or more polymer phases generated during the photo-curing comprises a crystalline polymer material. Thus, in some cases, at least one of the one or more polymer phases is a crystalline polymer phase. The crystalline polymeric material (e.g., as part of a crystalline phase) may have a melting point of at least about 40 ℃, 50 ℃, 60 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, or at least about 120 ℃.

In some embodiments, the method of forming a polymeric material from the photopolymerizable resins described herein may further comprise initiating and/or enhancing the formation of crystalline phases in the formed polymeric material. In certain embodiments, triggering includes cooling the solidified material, adding seeding particles to the resin, providing a force to the solidified material, providing an electrical charge to the resin, or any combination thereof. In some cases, the polymer crystals may yield upon application of strain (e.g., physical strain, such as twisting or stretching the material). Yield may include unwinding, dislocation, coarse slip, and/or fine slip of the crystalline polymer. In some embodiments, the methods disclosed herein further comprise the step of growing the polymer crystals. As further described herein, the polymer crystals comprise a crystallizable polymeric material.

Thus, in various embodiments, the methods of forming a polymeric material from the photopolymerizable resins described herein may include inducing phase separation in forming the polymeric material (i.e., during photocuring), wherein such phase separation may result in a polymeric material comprising one or more amorphous phases, one or more crystalline phases, or both one or more amorphous phases and one or more crystalline phases.

As described herein, the polymeric materials produced by the methods provided herein may be characterized by one or more of the following: (i) a storage modulus greater than or equal to 200MPa; (ii) Residual flexural stress and/or flexural modulus after 24 hours in a humid environment at 37 ℃ is greater than or equal to 1.5MPa; (iii) Elongation at break greater than or equal to 5% before and after 24 hours in a humid environment at 37 ℃; (iv) The water absorption is less than 25wt% when measured after 24 hours in a humid environment at 37 ℃; and (v) at least 30% of visible light is transmitted through the polymeric material after 24 hours in a humid environment at 37 ℃. In each case, the characteristics of such polymeric materials may lie in at least 2, 3, 4 or all of these properties.

Manufacture and use of orthodontic appliances

Provided herein are methods of making medical devices, such as orthodontic appliances (e.g., dental appliances, dental dilators, or dental spacers), using polymerizable monomers, curable resins, and compositions comprising such monomers, and polymeric materials prepared from such resins and compositions.

Thus, in some embodiments, the methods herein further comprise the step of manufacturing the device or object using an additive manufacturing device, wherein the additive manufacturing device facilitates curing. In some embodiments, curing of the polymerizable resin produces a cured polymeric material. In certain embodiments, the polymerizable resin is cured using an additive manufacturing apparatus to produce a cured polymeric material. In some embodiments, the method further comprises the step of cleaning the cured polymeric material. In certain embodiments, the cleaning of the cured polymeric material includes washing and/or rinsing the cured polymeric material with a solvent that can remove uncured resin and undesirable impurities from the cured polymeric material.

In some embodiments, the polymerizable resins herein may be curable and have a melting point of < 100 ℃ so as to be liquid and thus processable at temperatures typically employed in currently available additive manufacturing techniques. As described herein, the polymerizable monomers of the present disclosure used as components in the curable resin may have a low vapor pressure at elevated temperatures compared to conventional reactive diluents or other polymerizable components used in curable resins. This low vapor pressure of the monomers described herein is particularly advantageous for use of such monomers in curable (e.g., photocurable) compositions and additive manufacturing where elevated temperatures (e.g., 60 ℃, 80 ℃, 90 ℃ or higher) can be used. In various examples, the polymerizable monomer can have a vapor pressure of up to about 12Pa at a temperature of 60 ℃ or less, as further described herein.

In some embodiments, the curable resin herein may comprise at least one photopolymerization initiator (i.e., photoinitiator), and may be heated to a predefined elevated process temperature in the range of about 50 ℃ to about 120 ℃, e.g., about 90 ℃ to 120 ℃, prior to light irradiation of the appropriate wavelength absorbed by the photoinitiator, thereby causing activation of the photoinitiator to induce polymerization of the curable resin, resulting in a cured polymeric material that is optionally crosslinked. In some embodiments, the curable resin may include at least one multivalent polymerizable monomer that can provide a crosslinked polymer.

In some embodiments, the methods disclosed herein for forming polymeric materials are part of a high Wen Guangke-based photopolymerization process in which a curable composition (e.g., a photocurable resin), which may include at least one photopolymerization initiator, is heated to an elevated process temperature (e.g., about 50 ℃ to about 120 ℃, such as from about 90 ℃ to about 120 ℃). Thus, the method for forming a polymeric material according to the present disclosure may provide the possibility of fast and convenient production of devices (e.g. orthodontic appliances) by additive manufacturing (e.g. 3D printing) using the curable resins disclosed herein. In various embodiments, such a curable resin is a photocurable resin comprising one or more photopolymerizable monomers according to any one of formulas (I) - (VI) and (IX).

Photopolymerization may occur when the photocurable resins herein are exposed to radiation (e.g., UV or visible light) of a wavelength sufficient to initiate polymerization. The wavelength of the radiation used to initiate the polymerization may depend on the photoinitiator used. As used herein, "light" includes any wavelength and power capable of initiating polymerization. Some wavelengths of light include Ultraviolet (UV) light or visible light. The UV light source includes UVA (wavelength from about 400 nanometers (nm) to about 320 nm), UVB (about 320nm to about 290 nm), or UVC (about 290nm to about 100 nm). Any suitable source may be used, including a laser source. The source may be broadband or narrowband or a combination thereof. The light source may provide continuous or pulsed light during the process. The length of time the system is exposed to UV light and the intensity of UV light can be varied to determine the desired reaction conditions.

In some embodiments, the methods disclosed herein include using additive manufacturing to produce an apparatus comprising a cured polymeric material. Such a device may be an orthodontic appliance. The orthodontic appliance may be a dental appliance, a dental expander, or a dental spacer. In certain embodiments, the methods disclosed herein use additive manufacturing to produce a device comprising, consisting essentially of, or consisting of a cured polymeric material. Additive manufacturing includes various techniques for manufacturing three-dimensional objects directly from digital models through additive processes. In some aspects, successive layers of material are deposited and "cured in place". Various techniques for additive manufacturing are known in the art, including Selective Laser Sintering (SLS), fused Deposition Modeling (FDM), and jetting or extrusion. In many embodiments, selective laser sintering involves the use of a laser beam to selectively melt and fuse layers of powder material according to a desired cross-sectional shape in order to establish an object geometry. In many embodiments, fused deposition modeling involves fusing and selectively depositing filaments of thermoplastic polymer in a layer-by-layer fashion to form an object. In yet another example, 3D printing may be used to manufacture orthodontic appliances herein. In many embodiments, 3D printing involves jetting or extruding one or more materials (e.g., the crystallizable resins disclosed herein) onto a build surface to form a continuous layer of object geometry. In some embodiments, the photocurable resins described herein can be used in inkjet or coating applications. The cured polymeric material may also be manufactured by a "barrel" process in which light is used to selectively cure barrels or reservoirs of curable resin. Each layer of curable resin may be selectively exposed to light in a single exposure or by scanning a light beam across the layers. Specific techniques that may be used herein may include Stereolithography (SLA), digital Light Processing (DLP), and two-photon induced photopolymerization (TPIP).

In some embodiments, the methods disclosed herein use continuous direct manufacturing to produce an apparatus comprising a cured polymeric material. Such a device may be an orthodontic appliance as described herein. In certain embodiments, the methods disclosed herein can include using continuous direct manufacturing to produce a device (e.g., an orthodontic appliance) comprising, consisting essentially of, or consisting of a cured polymeric material. A non-limiting exemplary direct fabrication process may enable continuous build of an object geometry by continuous motion of the build platform (e.g., along a vertical or Z-direction) during the irradiation phase such that the depth of hardening of the irradiated photopolymer (e.g., irradiated photocurable resin, hardened during formation of the cured polymeric material) is controlled by the speed of motion. Thus, continuous polymerization of the material on the build surface (e.g., polymerization of the photocurable resin into a cured polymeric material) may be achieved. Such a method is described in U.S. Pat. No. 7,892,474, the disclosure of which is incorporated herein by reference in its entirety. In yet another example, a continuous direct fabrication method utilizes a "solar lithography" method in which a liquid resin (e.g., a photocurable resin) is cured with focused radiation while continuously rotating and raising a build platform. Thus, the object geometry can be continuously built along the spiral build path. Such methods are described in U.S. patent publication No. 2014/0265034, the disclosure of which is incorporated herein by reference in its entirety. Continuous liquid interface production of 3D objects has also been reported (j. Tuneston et al, science,2015,347 (6228), pp 1349-1352), the entire contents of which are incorporated herein by reference to describe the method. Another example of a continuous direct manufacturing method may include extruding a material composed of a curable liquid material or resin surrounding a solid strand. The material may be extruded along a continuous three-dimensional path to form the object. Such a process is described in U.S. patent publication No. 2014/0061974, the disclosure of which is incorporated herein by reference in its entirety.

In some embodiments, the methods disclosed herein can include using high Wen Guangke to produce an apparatus comprising a cured polymeric material. Such a device may be an orthodontic appliance as described herein. In certain embodiments, the methods disclosed herein use high Wen Guangke to produce an apparatus comprising, consisting essentially of, or consisting of a cured polymeric material. As used herein, "high temperature lithography" may refer to any lithography-based photopolymerization process that involves heating a photopolymerizable material (e.g., the photocurable resins disclosed herein). The heating may reduce the viscosity of the photocurable resin prior to and/or during curing. Non-limiting examples of high temperature lithographic processes include those described in WO2015/075094, WO2016/078838 and WO 2018/03022. In some implementations, the high Wen Guangke can involve applying heat to the material to a temperature of about 50 ℃ to about 120 ℃, such as about 90 ℃ to about 120 ℃, about 100 ℃ to about 120 ℃, about 105 ℃ to about 115 ℃, about 108 ℃ to about 110 ℃, and the like. The material may be heated to greater than about 120 ℃. Note that other temperature ranges may be used without departing from the scope and spirit of the inventive concepts described herein.

In some cases, since the polymerizable monomers of the present disclosure as part of the photocurable resin may become copolymerized during polymerization in accordance with the methods of the present disclosure, the result may be an optionally crosslinked polymer comprising one or more polymerizable monomer moieties as repeating units. In some cases, such polymers are crosslinked polymers, which may be generally suitable and useful for applications in orthodontic appliances.

In further embodiments, the methods herein may include polymerizing a curable composition comprising at least one multivalent monomer, which upon polymerization may provide a crosslinked polymer, which may comprise as repeating units a moiety derived from the polymerizable monomers of the present disclosure. In order to obtain a crosslinked polymer that is particularly suitable for use as an orthodontic appliance, at least one polymerizable substance used in the method according to the present disclosure may be selected according to several thermo-mechanical properties of the resulting polymer. In some examples, the curable resins of the present disclosure may comprise one or more multivalent polymerizable monomers. In some cases, the polymerizable monomers of the present disclosure may also have crosslinking functionality, thus not only acting as a reactive diluent for low vapor pressure, but also as a crosslinking agent during polymerization of the curable resins described herein. In other embodiments, the resin comprises a polymerizable monomer and a crosslinking monomer as described herein, wherein both monomers are different substances (i.e., chemical entities).

VI orthodontic appliance and use thereof

Polymerizable monomers according to the present disclosure (e.g., those according to any of formulas (I) - (VI) and (IX)) may be used as components of adhesive or highly adhesive photocurable resins, and may result in polymeric materials that may have advantageous thermo-mechanical properties (e.g., stiffness, residual bending stress, etc.) as described herein for orthodontic appliances, e.g., for moving one or more teeth of a patient.

As described herein, the present disclosure provides a method of repositioning teeth of a patient, the method comprising: (i) Generating a treatment plan for the patient, the plan including a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial tooth arrangement to a final tooth arrangement; (ii) Producing a dental appliance comprising a polymeric material as described herein, e.g. a polymeric material comprising monomers according to formulas (VII) - (VIII); and moving at least one tooth of the patient toward the intermediate tooth arrangement or the final tooth arrangement as planned using the dental appliance. Such dental appliances may be produced using processes that include 3D printing, as further described herein. The method of repositioning the patient's teeth may further include tracking the progression of the patient's teeth along the treatment path after the dental appliance is applied to the patient, the tracking including comparing the current arrangement of the patient's teeth to the planned arrangement of the patient's teeth. In such an example, greater than 60% of the patient's teeth may develop on a treatment plan after 2 weeks of treatment. In some examples, the dental appliance has a retained repositioning force on at least one tooth of the patient after 2 days that is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% of the repositioning force originally provided to the at least one tooth of the patient.

As used herein, the terms "stiffness" and "stiffness" are used interchangeably, as are the corresponding terms "stiffness" and "stiffness". As used herein, "plurality of teeth" includes two or more teeth.

In many embodiments, the one or more posterior teeth comprise one or more of molar teeth, premolars, or canine teeth, and the one or more anterior teeth comprise one or more of a middle incisor, a side incisor, a cuspid, a first bicuspid, or a second bicuspid.

In some embodiments, the compositions and methods described herein can be used to couple one or more sets of teeth to each other. The one or more sets of teeth may include a first set of one or more anterior teeth and a second set of one or more posterior teeth. The first set of teeth may be coupled to the second set of teeth by a polymeric shell appliance as disclosed herein.

The embodiments disclosed herein are well suited for moving one or more teeth of a first set of one or more teeth or moving one or more teeth of a second set of one or more teeth, and combinations thereof.

The embodiments disclosed herein are well suited for combination with one or more known commercially available tooth movement assemblies (e.g., attachments and polymeric shell appliances). In many embodiments, the appliance and the one or more attachments are configured to move one or more teeth along a tooth motion vector comprising six degrees of freedom, wherein three degrees of freedom are rotational and three degrees of freedom are translational.

The present disclosure provides orthodontic systems and related methods for designing and providing improved or more efficient tooth movement systems for causing desired tooth movement and/or repositioning of teeth in a desired arrangement.

Although references are made to appliances comprising polymeric shell appliances, the embodiments disclosed herein are well suited for use with many tooth-receiving appliances, such as appliances that do not have one or more polymers or shells. The appliance may be manufactured using one or more of a number of materials, such as, for example, metal, glass, reinforcing fibers, carbon fibers, composites, reinforced composites, aluminum, biological materials, and combinations thereof. In some cases, the reinforced composite may include a polymer matrix reinforced with, for example, ceramic or metal particles. The appliance may be shaped in a variety of ways, such as, for example, thermoforming or direct manufacturing as described herein. Alternatively or in combination, the appliance may be manufactured by machining, for example by computer numerical control machining, from a block of material. In some cases, the polymerizable monomers according to the present disclosure are used to make the appliance, for example, using the monomers as reactive diluents for the curable resin.

Turning now to the drawings, wherein like numerals denote like elements throughout the various views, FIG. 1A illustrates an exemplary tooth repositioning appliance or appliance 100 that a patient may wear in order to effect incremental repositioning of individual teeth 102 in the mandible. The appliance may include a shell (e.g., a continuous polymer shell or a segmented shell) having a tooth receiving cavity that receives and resiliently repositions the teeth. The appliance or portion thereof may be indirectly manufactured using a physical model of the tooth. For example, a physical model of a tooth and a sheet of suitable polymer material layer may be used to form an appliance (e.g., a polymer appliance). In some embodiments, the physical appliance is fabricated directly from a digital model of the appliance, for example using rapid prototyping techniques. The appliance can fit all, or less than all, of the teeth of the upper or lower jaw. The appliance may be specifically designed to receive a patient's teeth (e.g., the topography of the tooth receiving cavity matches the topography of the patient's teeth), and may be manufactured based on a positive or negative model of the patient's teeth produced by impression, scanning, or the like. Alternatively, the appliance may be a universal appliance configured to receive teeth, and it need not be shaped to match the topography of the patient's teeth. In some cases, only the particular tooth that the appliance accommodates is repositioned by the appliance, while other teeth may provide a base or anchor area for securing the appliance in place when the appliance applies a force to one or more teeth to be repositioned. In some cases, some, most, or even all of the teeth are repositioned at some point during treatment. The moved teeth may also act as a base or anchor for the appliance to be secured while the appliance is worn by the patient. Typically, no wires or other means for securing the appliance in place over the teeth are provided. However, in some instances, it may be desirable or necessary to provide a separate attachment or other anchoring element 104 on the tooth 102 and a corresponding socket or aperture 106 in the appliance 100 so that the appliance can apply a selected force on the tooth. The inclusion is described in various patents and patent applications assigned to Align Technology, inc Exemplary appliances for use in the system include, for example, U.S. Pat. nos. 6,450,807 and 5,975,893, and the company's website, which is accessible on the world wide web (see, for example, url "invisalign. Com"). Examples of dental mounting attachments suitable for use with orthodontic appliances are also described in patents and patent applications assigned to Align Technology, inc, including, for example, U.S. patent nos. 6,309,215 and 6,830,450.

Fig. 1B illustrates a tooth repositioning system 110 that includes a plurality of appliances 112, 114, 116. Any of the appliances described herein may be designed and/or provided as part of a set of multiple appliances for use in a tooth repositioning system. Each appliance may be configured such that the tooth receiving cavity has a geometry corresponding to the intermediate or final tooth arrangement intended for the appliance. The patient's teeth may be gradually repositioned from the initial tooth arrangement to the target tooth arrangement by placing a series of incremental position adjustment appliances over the patient's teeth. For example, the tooth repositioning system 110 may include a first appliance 112 corresponding to an initial tooth arrangement, one or more intermediate appliances 114 corresponding to one or more intermediate arrangements, and a final appliance 116 corresponding to a target arrangement. The target tooth arrangement may be a planned final tooth arrangement selected for the patient's teeth at the end of all planned orthodontic treatments. Alternatively, the target arrangement may be one of some intermediate arrangements of the patient's teeth during orthodontic treatment, which may include a variety of different treatment scenarios including, but not limited to, cases where surgery is recommended, cases where interproximal reduction (IPR) is appropriate, cases where progress checking is planned, cases where the anchor location is optimal, cases where palate expansion is required, cases involving restorative dentistry (e.g., inlays, onlays, crowns, bridges, implants, veneers, etc.). Thus, it will be appreciated that the target tooth arrangement may be any planned resulting arrangement of the patient's teeth after one or more incremental repositioning phases. Likewise, the initial tooth arrangement may be any initial arrangement of the patient's teeth followed by one or more incremental repositioning stages.

Fig. 1C illustrates an orthodontic treatment method 150 using a plurality of appliances, according to an embodiment. Method 150 may be implemented using any of the appliances or appliance components described herein. In step 160, a first orthodontic appliance is applied to the teeth of the patient to reposition the teeth from the first tooth arrangement to the second tooth arrangement. In step 170, a second orthodontic appliance is applied to the teeth of the patient to reposition the teeth from the second tooth arrangement to the third tooth arrangement. Method 150 may be repeated as necessary using any suitable number and combination of successive appliances to incrementally reposition the patient's teeth from the initial arrangement to the target arrangement. The appliances may be produced all at the same stage, may be produced in sets or batches (e.g. at the beginning of a stage of treatment), or the appliances may be produced one at a time, the patient may wear each appliance until the pressure of each appliance against the teeth is no longer felt, or until the maximum tooth movement is reached for a given stage of compression. A plurality of different appliances (e.g., a set of appliances) may be designed and even manufactured before any of the plurality of appliances is worn by a patient. After wearing the appliances for an appropriate period of time, the patient may replace the current appliance with the next appliance in the series until no more appliances remain. The appliance is not typically fixed to the teeth and the patient can place and replace the appliance at any time during the procedure (e.g., the patient may remove the appliance). The final appliance or appliances in the series may have one or more geometries selected to overcorrect the dental arrangement. For example, the geometry of one or more appliances may (if fully realized) move individual teeth out of a selected "final" tooth arrangement. Such overcorrection may be desirable in order to counteract potential recurrence after the repositioning method has terminated (e.g., to allow individual teeth to move back to their pre-corrected positions). Overcorrection may also help to increase the speed of correction (e.g., appliances having geometries beyond the desired intermediate or final position may move individual teeth toward that position at a greater rate). In this case, the use of the appliance may be terminated before the teeth reach the defined position of the appliance. In addition, to compensate for any inaccuracy or limitation of the appliance, an overcorrection may be deliberately made.

The various embodiments of orthodontic appliances presented herein may be manufactured in a variety of ways. In some embodiments, orthodontic appliances (or portions thereof) herein may be produced using direct manufacturing, such as additive manufacturing techniques (also referred to herein as "3D printing") or subtractive manufacturing techniques (e.g., milling). In some embodiments, direct manufacturing involves forming an object (e.g., an orthodontic appliance or portion thereof) without using a physical template (e.g., a mold, mask, etc.) to define the geometry of the object. Additive manufacturing techniques may be categorized as follows: (1) Barrel photopolymerization (e.g., stereolithography), in which an object is composed of a barrel of liquid photopolymer resin layer by layer; (2) Material jetting, wherein the material is jetted onto a build platform using a continuous or Drop On Demand (DOD) method; (3) Adhesive jetting, in which alternating layers of build material (e.g., powder-based material) and bond material (e.g., liquid adhesive) are deposited by a printhead; (4) Fused Deposition Modeling (FDM), wherein a material is stretched through a nozzle, heated, and deposited layer by layer; (5) Powder bed melting including, but not limited to, direct Metal Laser Sintering (DMLS), electron Beam Melting (EBM), selective thermal sintering (SHS), selective Laser Melting (SLM), and Selective Laser Sintering (SLS); (6) Sheet lamination, including but not limited to layered solid fabrication (LOM) and ultrasonic additive fabrication (UAM); and (7) directed energy deposition including, but not limited to, laser near-shape fabrication, directed light fabrication, direct metal deposition, and 3D laser cladding. For example, stereolithography may be used to directly fabricate one or more of the tools herein. In some embodiments, stereolithography involves selectively polymerizing a photosensitive resin (e.g., a photopolymer) according to a desired cross-sectional shape using light (e.g., ultraviolet light). By sequentially aggregating a plurality of object cross sections, the object geometry can be built up in a layer-by-layer manner. As another example, the devices herein may be directly manufactured using selective laser sintering. In some embodiments, selective laser sintering involves selectively melting and fusing layers of powder material according to a desired cross-sectional shape using a laser beam in order to establish an object geometry. As yet another example, the devices herein may be directly manufactured by fused deposition modeling. In some embodiments, fused deposition modeling involves fusing and selectively depositing filaments of thermoplastic polymer in a layer-by-layer fashion to form an object. In yet another example, material jetting may be used to directly manufacture the appliances herein. In some embodiments, material jetting involves jetting or extruding one or more materials onto a build surface to form a continuous layer of object geometry.

Alternatively or in combination, some embodiments of the appliances (or portions thereof) herein may be produced using indirect manufacturing techniques, for example by thermoforming on a male or female mold. Indirect fabrication of orthodontic appliances may involve producing a male or female mold of a patient's dentition in a target arrangement (e.g., by rapid prototyping, milling, etc.), and thermoforming one or more sheets of material over a mold to create an appliance shell.

In some embodiments, the direct fabrication methods provided herein build object geometry in a layer-by-layer fashion, forming continuous layers in discrete build steps. Alternatively or in combination, a direct fabrication method may be used that allows for continuous build of the object geometry, referred to herein as "continuous direct fabrication". Various types of continuous direct manufacturing processes may be used. As an example, in some embodiments, the devices herein are fabricated using "continuous liquid phase printing" in which an object is continuously built from a reservoir of photopolymerizable resin by forming a gradient of partially cured resin between the build surface of the object and a "dead zone" of polymerization inhibition. In some embodiments, a semi-permeable membrane is used to control the transport of photopolymerization inhibitors (e.g., oxygen) into the dead zone to form a polymerization gradient. Continuous liquid phase-to-phase printing can achieve manufacturing speeds of about 25 to about 100 times faster than other direct manufacturing methods, and speeds of about 1000 times faster can be achieved by incorporating a cooling system. Continuous liquid phase printing is described in U.S. patent publication nos. 2015/0097315, 2015/0097316, and 2015/0102532, the respective disclosures of which are incorporated herein by reference in their entirety.

As another example, a continuous direct fabrication method may enable continuous build of an object geometry by continuous movement of a build platform (e.g., along a vertical or Z-direction) during a radiation phase such that the depth of hardening of the irradiated photopolymer is controlled by the speed of movement. Thus, a continuous polymerization of the material on the build surface can be achieved. Such a method is described in U.S. Pat. No. 7,892,474, the disclosure of which is incorporated herein by reference in its entirety.

In another example, a continuous direct manufacturing method may include extruding a composite material composed of a curable liquid material surrounding a solid strand. The composite material may be extruded along a continuous three-dimensional path to form an object. Such a process is described in U.S. patent publication No. 2014/0061974, the disclosure of which is incorporated herein by reference in its entirety.

In yet another example, a continuous direct fabrication method utilizes a "solar lithography" method in which focused radiation is utilized to cure a liquid photopolymer while continuously rotating and raising a build platform. Thus, the object geometry can be continuously built along the spiral build path. Such a method is described in U.S. patent publication No. 2014/0265034, the disclosure of which is incorporated herein by reference in its entirety.

The direct fabrication methods provided herein are compatible with a variety of materials, including but not limited to one or more of the following: polyesters, copolyesters, polycarbonates, thermoplastic polyurethanes, polypropylene, polyethylene, polypropylene and polyethylene copolymers, acrylic, cyclic block copolymers, polyetheretherketones, polyamides, polyethylene terephthalates, polybutylene terephthalates, polyetherimides, polyethersulfones, polytrimethylene terephthalates, styrene Block Copolymers (SBC), silicone rubbers, elastomeric alloys, thermoplastic elastomers (TPE), thermoplastic vulcanizate (TPV) elastomers, polyurethane elastomers, block copolymer elastomers, polyolefin blend elastomers, thermoplastic copolyester elastomers, thermoplastic polyamide elastomers, thermosets, or combinations thereof. The material for direct fabrication may be provided in uncured form (e.g., liquid, resin, powder, etc.) and may be cured (e.g., by photopolymerization, photo-curing, gas curing, laser curing, cross-linking, etc.) to form the orthodontic appliance or a portion thereof. The properties of the material before curing may be different from the properties of the material after curing. Once cured, the materials herein may exhibit sufficient strength, rigidity, durability, biocompatibility, etc., for use in orthodontic appliances. The post-cure characteristics of the materials used may be selected according to the desired characteristics of the corresponding portion of the appliance.

In some embodiments, the relatively rigid portion of the orthodontic appliance may be formed by direct fabrication using one or more of the following materials: polyesters, copolyesters, polycarbonates, thermoplastic polyurethanes, polypropylene, polyethylene, polypropylene and polyethylene copolymers, acrylic acid, cyclic block copolymers, polyetheretherketones, polyamides, polyethylene terephthalates, polybutylene terephthalates, polyetherimides, polyethersulfones and/or polytrimethylene terephthalates.

In some embodiments, the relatively resilient portion of the orthodontic appliance may be formed by direct manufacture using one or more of the following materials: styrene Block Copolymers (SBC), silicone rubber, elastomer alloys, thermoplastic elastomers (TPE), thermoplastic vulcanizate (TPV) elastomers, polyurethane elastomers, block copolymer elastomers, polyolefin blend elastomers, thermoplastic copolyester elastomers and/or thermoplastic polyamide elastomers.

The machine parameters may include curing parameters. For Digital Light Processing (DLP) based curing systems, the curing parameters may include power, curing time, and/or grayscale of the complete image. For laser-based curing systems, the curing parameters may include power, speed, beam size, beam shape, and/or power distribution of the beam. For printing systems, curing parameters may include material drop size, viscosity, and/or curing power. These machine parameters may be monitored and adjusted periodically (e.g., some parameters per 1-x layer and some parameters after each build) as part of the process control of the manufacturing machine. Process control may be achieved by including sensors on the machine that measure power and other beam parameters at each layer or every few seconds and automatically adjust them through a feedback loop. For DLP machines, depending on the stability of the system, the grey scale may be measured and calibrated before, during and/or at the end of each build and/or at predetermined time intervals (e.g., once per n builds, once per hour, once per day, once per week, etc.). In addition, material properties and/or photographic characteristics may be provided to the manufacturing machine, which may be used by the machine process control module to adjust machine parameters (e.g., power, time, grayscale, etc.) to compensate for variations in material properties. By implementing process control over the manufacturing machine, reduced variation in fixture accuracy and residual stress can be achieved.

Optionally, the direct fabrication methods described herein allow for fabrication of devices comprising multiple materials, referred to herein as "multi-material direct fabrication". In some embodiments, the multi-material direct fabrication method involves simultaneously forming objects from multiple materials in a single fabrication step. For example, a multi-tipped extrusion device may be used to selectively dispense multiple types of materials from different material supplies in order to manufacture objects from multiple different materials. Such a method is described in U.S. patent No. 6,749,414, the entire disclosure of which is incorporated herein by reference. Alternatively or in combination, the multi-material direct fabrication method may involve forming an object from multiple materials in multiple sequential fabrication steps. For example, a first portion of an object may be formed from a first material according to any direct manufacturing method herein, then a second portion of an object may be formed from a second material according to the methods herein, and so on until the entirety of the object has been formed.

Direct manufacturing may provide various advantages over other manufacturing methods. For example, direct manufacturing allows orthodontic appliances to be produced without using any mold or template to shape the appliance, thereby reducing the number of manufacturing steps involved and improving the resolution and accuracy of the final appliance geometry, as compared to indirect manufacturing. Furthermore, direct manufacturing allows for precise control of the three-dimensional geometry of the appliance, such as the appliance thickness. The complex structure and/or ancillary components may be integrally formed as one piece with the appliance housing in a single manufacturing step rather than added to the housing in a separate manufacturing step. In some embodiments, the devices used to produce the device geometries that are difficult to create using alternative manufacturing techniques are manufactured directly, such as devices with very small or fine features, complex geometries, undercuts, adjoining structures, shells with variable thickness, and/or internal structures (e.g., to increase strength by reducing weight and material usage). For example, in some embodiments, the direct fabrication methods herein allow for the fabrication of orthodontic appliances having feature sizes less than or equal to about 5 μm, or in the range of about 5 μm to about 50 μm, or in the range of about 20 μm to about 50 μm.

The direct fabrication techniques described herein may be used to produce devices having substantially isotropic material properties, e.g., substantially the same or similar strength in all directions. In some embodiments, the direct manufacturing methods herein allow for the production of orthodontic appliances having a strength that varies by no more than about 25%, about 20%, about 15%, about 10%, about 5%, about 1%, or about 0.5% in all directions. Furthermore, the direct manufacturing methods herein may be used to produce orthodontic appliances at a faster rate than other manufacturing techniques. In some embodiments, the direct manufacturing methods herein allow orthodontic appliances to be produced in a time interval of less than or equal to about 1 hour, about 30 minutes, about 25 minutes, about 20 minutes, about 15 minutes, about 10 minutes, about 5 minutes, about 4 minutes, about 3 minutes, about 2 minutes, about 1 minute, or about 30 seconds. Such manufacturing speeds allow for rapid "chair-side" production of custom appliances, for example, during routine reservations or inspections.

In some embodiments, the direct manufacturing methods described herein enable process control over various machine parameters of a direct manufacturing system or apparatus to ensure that the resulting appliance is manufactured with high accuracy. Such precision can help ensure that the required force system is accurately transferred to the tooth, effectively causing tooth movement. Process control may be implemented to account for process variability caused by a variety of sources, such as material properties, machine parameters, environmental variables, and/or aftertreatment parameters.

The material properties may vary depending on the nature of the raw materials, the purity of the raw materials, and/or process variables during the mixing of the raw materials. In many embodiments, the resins or other materials used in direct fabrication should be fabricated under stringent process control to ensure that there is little variation in optical properties, material properties (e.g., viscosity, surface tension), physical properties (e.g., modulus, strength, elongation), and/or thermal properties (e.g., glass transition temperature, heat distortion temperature). Process control of the material manufacturing process may be achieved by physical property screening and/or control of temperature, humidity and/or other process parameters of the raw materials during the mixing process. By implementing process control over the material manufacturing process, reduced variability in process parameters can be achieved and material properties of each batch of material can be made more uniform. As discussed further herein, residual variations in material properties may be compensated for by process control on the machine.

The machine parameters may include curing parameters. For Digital Light Processing (DLP) based curing systems, the curing parameters may include power, curing time, and/or grayscale of the complete image. For laser-based curing systems, the curing parameters may include power, speed, beam size, beam shape, and/or power distribution of the beam. For printing systems, curing parameters may include material titer, viscosity, and/or curing power. These machine parameters may be monitored and adjusted periodically (e.g., some parameters per 1-x layer and some parameters after each build) as part of process control on the manufacturing machine. Process control may be achieved by including sensors on the machine that measure power and other beam parameters at each layer or every few seconds and automatically adjust them through a feedback loop. For DLP machines, the grayscale can be measured and calibrated at the end of each build. In addition, material properties and/or photo features may be provided to the manufacturing machine, which may be used by the machine process control module to adjust machine parameters (e.g., power, time, grayscale, etc.) to compensate for variations in material properties. By implementing process control over the manufacturing machine, reduced variation in fixture accuracy and residual stress can be achieved.

In many embodiments, environmental variables (e.g., temperature, humidity, sunlight, or exposure to other energy/curing sources) are kept within narrow limits that reduce variability in appliance thickness and/or other properties. Optionally, machine parameters may be adjusted to compensate for environmental variables.

In many embodiments, the post-treatment of the appliance includes washing, post-curing, and/or support removal processes. Related post-treatment parameters may include purity of the detergent, wash pressure and/or temperature, wash time, post-cure energy and/or time, and/or consistency of the support removal process. These parameters may be measured and adjusted as part of a process control scheme. Furthermore, the physical properties of the appliance may be changed by modifying the post-processing parameters. Adjusting the aftertreatment machine parameters may provide another method to compensate for variability in material properties and/or machine properties.

The configuration of orthodontic appliances herein may be determined according to a treatment plan for a patient, for example, a treatment plan involving the sequential application of multiple appliances to incrementally reposition teeth. Computer-based treatment planning and/or appliance manufacturing methods may be used to facilitate the design and manufacture of appliances. For example, one or more of the appliance assemblies described herein may be digitally designed and manufactured by means of computer-controlled manufacturing equipment (e.g., computer Numerical Control (CNC) milling, computer controlled rapid prototyping, such as 3D printing, etc.). The computer-based methods presented herein may improve the accuracy, flexibility, and convenience of appliance manufacturing.

Fig. 2 illustrates a method 200 for designing an orthodontic appliance produced by direct manufacturing, according to an embodiment. The method 200 may be applied to any of the embodiments of orthodontic appliances described herein. Some or all of the steps of method 200 may be performed by any suitable data processing system or device, such as one or more processors configured with suitable instructions.

In step 210, a path of movement is determined for moving one or more teeth from an initial arrangement to a target arrangement. The initial alignment may be determined by molding or scanning of the patient's teeth or oral tissue, for example, using wax biting, direct contact scanning, x-ray imaging, tomographic imaging, ultrasound imaging, and other techniques, to obtain information about the position and structure of the teeth, jaw, gums, and other orthodontic related tissue. From the obtained data, a digital data set may be derived that represents an initial (e.g., pre-processed) arrangement of the patient's teeth and other tissue. Optionally, the initial digital data set is processed to segment the tissue elements from one another. For example, a data structure may be generated that digitally represents a single crown. Advantageously, a digital model of the entire tooth can be generated, including the measured or extrapolated hidden surface and root structure, as well as surrounding bone and soft tissue.

The target arrangement of teeth (e.g., desired and expected end result of orthodontic treatment) may be received from a clinician in the form of a prescription, may be calculated according to basic orthodontic principles, and/or may be computationally inferred from a clinical prescription. By way of illustration of the desired final position of the teeth and the digital representation of the teeth themselves, the final position and surface geometry of each tooth can be specified to form a complete model of the tooth arrangement at the end of the intended treatment.

Each tooth has an initial position and a target position, and a path of movement is defined for each tooth's movement. In some embodiments, the movement path is configured to move the tooth in the fastest manner with the least number of round trips to move the tooth from its initial position to its desired target position. The tooth path may optionally be segmented, and the segments may be calculated such that the motion of each tooth within one segment remains within the threshold limits of linear and rotational translation. In this way, the endpoints of each path segment may constitute a clinically viable repositioning, and the collection of segment endpoints may constitute a sequence of clinically viable tooth positions such that moving from one point to the next in the sequence does not result in tooth collision.

In step 220, a force system that produces movement of one or more teeth along a movement path is determined. The force system may include one or more forces and/or one or more torques. Different force systems may result in different types of tooth movement (e.g., tilting, translating, rotating, squeezing, intrusion, root movement, etc.). Biomechanical principles, modeling techniques, force calculation/measurement techniques, etc., including knowledge and methods commonly used in orthodontic, may be used to determine an appropriate force system to apply to the teeth to accomplish tooth movement. Sources may be considered in determining the force system to be applied, including literature, force systems determined through experimental or virtual modeling, computer-based modeling, clinical experience, minimizing unwanted forces, and the like.

The determination of the force system may include constraints on the allowable force, such as allowable direction and magnitude, and the desired movement caused by the applied force. For example, in the manufacture of a palatal expander, different patients may require different movement strategies. For example, the amount of force required to separate the palate may depend on the age of the patient, as very young patients may not have a fully developed bone suture. Thus, in adolescent patients and other patients without a fully occluded palate suture, palate expansion can be accomplished with a lower force level. Slower palate movements also contribute to bone growth to fill the expanded bone slot. For other patients, a faster expansion may be required, which may be achieved by applying a greater force. These requirements can be incorporated as desired to select the construction and materials of the appliance; for example, by selecting a palate expander that can apply a large force to break the palate suture and/or cause rapid expansion of the palate. Subsequent appliance stages may be designed to apply different amounts of force, such as first applying a greater force to fracture the bone slot and then applying a lesser force to keep the bone slot separate or gradually expand the palate and/or dental arch.

The determination of the force system may also include modeling of patient facial structures, such as skeletal structures of the jaw and palate. Scan data (e.g., X-ray data or 3D optical scan data) of the palate and dental arch, for example, can be used to determine parameters of the skeletal and muscular system of the patient's mouth, thereby determining a force sufficient to provide a desired expansion of the palate and/or dental arch. In some embodiments, the thickness and/or density of the bone slots in the palate can be measured or entered by a treatment professional. In other embodiments, the treatment professional may select an appropriate treatment based on the physiological characteristics of the patient. For example, the characteristics of the palate can also be assessed based on factors such as the age of the patient, e.g., young adolescent patients often require lower force to dilate the suture than older patients because the suture has not yet developed sufficiently.

In step 230, a dental arch or palate expander design of an orthodontic appliance configured to produce a force system is determined. The treatment or force modeling environment may be used to determine the design, appliance geometry, material composition, and/or performance of the dental arch or palate expander. The simulation environment may include, for example, a computer modeling system, a biomechanical system or device, and the like. Optionally, a digital model of the appliance and/or tooth may be produced, such as a finite element model. The finite element model may be created using various vendor-supplied computer program applications. For creating the solid geometry model, computer Aided Engineering (CAE) or Computer Aided Design (CAD) programs, such as those provided by Autodesk, inc. Of san-fei, california A software product. To create and analyze the finite element model, program products from multiple suppliers may be used, including the finite element analysis software package of ANSYS, inc. Of kanrsburg, pennsylvania, and the SIMULIA (Abaqus) software product of Dassault sysmes of waltham, ma.

Optionally, one or more dental arch or palate expander designs may be selected for testing or force modeling. As described above, the desired tooth movement can be identified, as well as the force system needed or desired to cause the desired tooth movement. Using the simulated environment, the candidate dental arch or palate expander designs can be analyzed or modeled to determine the actual force system generated using the candidate appliance. Optionally, one or more modifications may be made to the candidate instrument, and the force modeling may be further analyzed as described, for example, in order to iteratively determine an instrument design that yields a desired force system.

In step 240, a manufacturing specification for an orthodontic appliance incorporating the design of the dental arch or palate expander is generated. The instructions may be configured to control the manufacturing system or apparatus to produce an orthodontic appliance having a specified arch or palate expander design. In some embodiments, the instructions are configured to manufacture the orthodontic appliance using direct fabrication (e.g., stereolithography, selective laser sintering, fused deposition modeling, 3D printing, continuous direct fabrication, multi-material direct fabrication, etc.), according to the various methods provided herein. In alternative embodiments, the instructions may be configured to indirectly fabricate the appliance, such as by thermoforming.

The method 200 may include the additional steps of: 1) Intraoral scanning of the patient's upper arch and palate to generate three-dimensional data of the palate and upper arch; 2) The three-dimensional shape of the implement is contoured to provide the clearance and tooth engaging structure as described herein.

While the above steps illustrate a method 200 of designing an orthodontic appliance according to some embodiments, one of ordinary skill in the art will recognize some variations based on the teachings described herein. Some steps may include sub-steps. Some of these steps may be repeated as desired. One or more steps of method 200 may be performed using any suitable manufacturing system or apparatus (e.g., embodiments described herein). Some steps may be optional and the order of the steps may be changed as desired.

Fig. 3 illustrates a method 300 for digitally planning orthodontic treatment and/or designing or manufacturing appliances, according to an embodiment. The method 300 may be applied to any of the therapeutic procedures described herein and may be performed by any suitable data processing system.

In step 310, a digitized representation of a patient's teeth is received. The digitized representation may include surface topography data within the patient's mouth (including teeth, gingival tissue, etc.). The surface topography data may be generated by directly scanning the intraoral groove, a physical model of the intraoral groove (male or female), or an impression of the intraoral groove using a suitable scanning device (e.g., a handheld scanner, a desktop scanner, etc.).

In step 320, one or more treatment phases are generated based on the digitized representation of the tooth. The treatment phase may be an incremental repositioning phase of an orthodontic treatment program designed to move one or more teeth of a patient from an initial tooth arrangement to a target arrangement. For example, the treatment phase may be generated by determining an initial tooth arrangement indicated by the digital representation, determining a target tooth arrangement, and determining a path of movement of one or more teeth in the initial arrangement required to achieve the target tooth arrangement. The movement path may be optimized based on minimizing the total distance moved, preventing interdental collisions, avoiding more difficult tooth movement, or any other suitable criteria.

In step 330, at least one orthodontic appliance is manufactured based on the generated treatment phase. For example, a set of appliances may be manufactured, each appliance being shaped according to a tooth arrangement specified for one treatment session, such that the appliances may be worn sequentially by a patient to incrementally reposition teeth from an initial arrangement to a target arrangement. The appliance assembly may include one or more orthodontic appliances described herein. Manufacturing of the appliance may involve creating a digitized model of the appliance for use as input to a computer controlled manufacturing system. The appliance may be formed using direct manufacturing methods, indirect manufacturing methods, or a combination thereof, as desired.

In some instances, various arrangements or phasing of treatment phases may not be necessary for the design and/or manufacture of the appliance. As shown in dashed lines in fig. 3, the design and/or manufacture of an orthodontic appliance, and possibly a particular orthodontic treatment, may include using a representation of a patient's teeth (e.g., a digital representation of the received patient's teeth 310) followed by the design and/or manufacture of an orthodontic appliance based on the representation of the patient's teeth in the arrangement represented by the received representation.

Treatment according to a schedule

Referring to fig. 4, a method 400 according to the present disclosure is shown. Various aspects of the method are discussed in further detail below. The process includes receiving information about an orthodontic condition of a patient (402), generating a case assessment (404), and generating a treatment plan for repositioning teeth of the patient (406). Briefly, patient/treatment information includes data comprising an initial arrangement of patient's teeth, including obtaining an impression or scan of the patient's teeth prior to initiating treatment, and may also include identification of one or more treatment targets selected by the practitioner and/or patient. A case estimate may be generated (404) to estimate the complexity or difficulty of moving a particular patient's teeth, generally or specifically corresponding to the identified treatment objective, and may also include practitioner experience and/or comfort of delivering the desired orthodontic treatment. However, in some cases, the assessment may include simply identifying particular treatment options of interest to the patient and/or practitioner (e.g., appointment planning, progress tracking, etc.). The information and/or corresponding treatment plan includes identifying a desired final or target arrangement of the patient's teeth, and a plurality of planned successive or intermediate tooth arrangements for moving the teeth along the treatment path from the initial arrangement to the selected final or target arrangement.

The method also includes generating a customized therapy guideline (408). The treatment plan may include a plurality of treatment phases and a set of customized treatment guidelines corresponding to one phase of the treatment plan are generated. The guidelines may include detailed information about the time and/or content (e.g., specific tasks) to be completed at a given treatment stage, and may guide practitioners in sufficient detail during the treatment stage, including less experienced practitioners or practitioners relatively unfamiliar with a particular orthodontic treatment procedure. The guideline is said to be customized because it is designed to correspond specifically to the treatment plan and is provided with respect to treatment information and/or well-defined activities in the generated treatment plan. The practitioner is then provided with customized treatment guidelines to help guide the practitioner how to provide a given treatment session. As described above, the appliance may be generated based on the planned schedule and may be provided to the practitioner and ultimately administered to the patient (410). The device may be provided and/or applied in a kit or batch, such as 2, 3, 4, 5, 6, 7, 8, 9 or more devices, but is not limited to any particular application regimen. The appliance may be provided to the practitioner concurrently with a given set of guidelines, or the appliance and guidelines may be provided separately.

After treatment is initiated according to the plan, and after the appliance is applied to the patient, treatment progress tracking (412) is performed, for example by tooth matching, to assess the current and actual arrangement of the patient's teeth as compared to the planned arrangement. If it is determined that the patient's teeth are "on schedule" and progress in accordance with the treatment plan, then treatment will be on schedule and treatment will proceed to the next treatment stage (414). If the patient's teeth substantially reach the final arrangement of the initial plan, then treatment will enter the final treatment phase (414). If it is determined that the patient's teeth are tracked according to the treatment plan, but the final arrangement has not been reached, the next set of appliances may be administered to the patient.

Table 1 below gives the threshold difference between the planned and actual positions of the teeth, which is selected as an indication that the patient's teeth have been planned to develop. If the patient's tooth development reaches or is within a threshold, the progress is considered as planned. If the patient's tooth development exceeds a threshold, the development is deemed to deviate from the plan.

TABLE 1

The patient's teeth were determined to be planned by comparing the teeth at their current positions to the teeth at their expected or planned positions and by confirming that the teeth were within the parameter variance ranges disclosed in table 1. If the patient's teeth are determined to be on schedule, the treatment may progress in accordance with the existing or initial treatment plan. For example, according to a treatment plan, a patient determined to progress in accordance with the treatment plan may administer one or more subsequent appliances, such as a next set of appliances. The treatment may progress to a final stage and/or may reach a point in the treatment plan at which bite matching is repeated to determine whether the patient's teeth are progressing as planned or whether the teeth deviate from the treatment plan.

In some embodiments, as further disclosed herein, the present disclosure provides methods of treating a patient using a 3D printed orthodontic appliance. As one non-limiting example, orthodontic appliances including crystalline domains, polymer crystals, and/or materials that may form crystalline domains or polymer crystals may be 3D printed and used to reposition a patient's teeth. In certain embodiments, a method of repositioning a patient's teeth (or in some embodiments, a single tooth) includes: generating a treatment plan for the patient, the plan including a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial arrangement to a final arrangement; producing a 3D printing orthodontic appliance; and moving at least one tooth of the patient in a plan using the orthodontic appliance toward the intermediate or final tooth arrangement. In some embodiments, producing 3D printed orthodontic appliances uses the crystallizable resins further disclosed herein. The per-schedule performance may be determined, for example, according to table 1 above.

In some embodiments, the method further comprises tracking the progression of the patient's teeth along the treatment path after the orthodontic appliance is applied. In some embodiments, tracking includes comparing the current arrangement of the patient's teeth to a planned arrangement of teeth. As one non-limiting example, after a period of time (e.g., two weeks) has elapsed after the first application of the orthodontic appliance, the current arrangement of the patient's teeth (i.e., two weeks of treatment) may be compared to the arrangement of the teeth of the treatment plan. In some embodiments, progress may also be tracked by comparing the current arrangement of the patient's teeth to the initial arrangement of the patient's teeth. For example, the time period may be greater than 3 days, greater than 4 days, greater than 5 days, greater than 6 days, greater than 7 days, greater than 8 days, greater than 9 days, greater than 10 days, greater than 11 days, greater than 12 days, greater than 13 days, greater than 2 weeks, greater than 3 weeks, greater than 4 weeks, or greater than 2 months. In some embodiments, the period of time may be from at least 3 days to at most 4 weeks, from at least 3 days to at most 3 weeks, from at least 3 days to at most 2 weeks, from at least 4 days to at most 4 weeks, from at least 4 days to at most 3 weeks, or from at least 4 days to at most 2 weeks. In certain embodiments, the time period may be restarted after the application of a new orthodontic appliance.

In some embodiments, after a period of treatment using the orthodontic appliance further disclosed herein, the patient is greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, greater than 91%, greater than 92%, greater than 93%, greater than 94%, greater than 95%, greater than 96%, greater than 97%, greater than 98%, or greater than 99% of the teeth are consistent with the treatment plan. In some embodiments, the period of time is 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 2 weeks, 3 weeks, 4 weeks, or greater than 4 weeks.

As further disclosed herein, the orthodontic appliances disclosed herein have advantageous properties, such as increased durability, and are capable of retaining a spring force on a patient's teeth for an extended period of time. In some embodiments of the above disclosed methods, the 3D printed orthodontic appliance has a retained repositioning force (i.e., the orthodontic appliance has been applied to the patient or after the patient has been worn for a period of time) and after the period of time, has a retained repositioning force on at least one tooth of the patient that is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% of the repositioning force initially provided to at least one tooth of the patient (i.e., the orthodontic appliance first applied). In some embodiments, the period of time is 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 2 weeks, 3 weeks, 4 weeks, or greater than 4 weeks. In some embodiments, the repositioning force applied to at least one tooth of the patient is present for a period of time of less than 24 hours, about 24 hours to about 2 months, about 24 hours to about 1 month, about 24 hours to about 3 weeks, about 24 hours to about 14 days, about 24 hours to about 7 days, about 24 hours to about 3 days, about 3 days to about 2 months, about 3 days to about 1 month, about 3 days to about 3 weeks, about 3 days to about 14 days, about 3 days to about 7 days, about 7 days to about 2 months, about 7 days to about 1 month, about 7 days to about 3 weeks, about 7 days to about 2 weeks, or greater than 2 months. In some embodiments, the repositioning force applied to the at least one tooth of the patient is present for about 24 hours, about 3 days, about 7 days, about 14 days, about 2 months, or greater than 2 months.

In some embodiments, the orthodontic appliance disclosed herein may move at least one tooth of a patient as planned. The planned movement is further described herein, as shown in table 1. In some embodiments, the orthodontic appliances disclosed herein may be used to effect a planned movement of at least one tooth of a patient toward an intermediate tooth arrangement. In some embodiments, the orthodontic appliances disclosed herein may be used to effect a planned movement of at least one tooth of a patient toward a final tooth arrangement.

In some embodiments, the orthodontic appliance has features that remain after use of the orthodontic appliance prior to moving at least one tooth of a patient toward an intermediate or final tooth arrangement. In some embodiments, the orthodontic appliance includes a first flexural modulus prior to the moving step. In certain embodiments, after the moving step, the orthodontic appliance includes a second flexural modulus. In some embodiments, the second flexural modulus is at least 99%, at least 98%, at least 97%, at least 96%, at least 95%, at least 94%, at least 93%, at least 92%, at least 91%, at least 90%, at least 85%, at least 80%, at least 75%, at least 70%, at least 65%, at least 60%, at least 50%, or at least 40% of the first flexural modulus. In some embodiments, the second flexural modulus is greater than 50% of the first flexural modulus. In some embodiments, the comparison is performed after a period of time after the appliance is applied. In some embodiments, the period of time is 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 2 weeks, 3 weeks, 4 weeks, or greater than 4 weeks.

In some embodiments, the orthodontic appliance includes a first elongation at break prior to the moving step. In some embodiments, after the moving step, the orthodontic appliance includes a second elongation at break. In some embodiments, the second elongation at break is at least 99%, at least 98%, at least 97%, at least 96%, at least 95%, at least 94%, at least 93%, at least 92%, at least 91%, at least 90%, at least 85%, at least 80%, at least 75%, at least 70%, at least 65%, at least 60%, at least 50%, or at least 40% of the first elongation at break. In some embodiments, the second elongation at break is greater than 50% of the first elongation at break. In some embodiments, the comparison is performed after a period of time after the appliance is applied. In some embodiments, the period of time is 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 2 weeks, 3 weeks, 4 weeks, or greater than 4 weeks.

As provided herein, the methods of the present disclosure may use orthodontic appliances as further disclosed herein. The orthodontic appliance may be directly manufactured using, for example, the crystallizable resins disclosed herein. In certain embodiments, the direct fabrication includes crosslinking the crystallizable resin.

The devices formed from the crystallizable resins disclosed herein provide improved durability, strength, and flexibility, which in turn increases the proportion of planned progress in the treatment plan. In some embodiments, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95% of patients treated using the orthodontic appliances (e.g., appliances) disclosed herein are classified as being planned in a given treatment stage. In certain embodiments, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95% of patients treated using the orthodontic appliances (e.g., appliances) disclosed herein, greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, or greater than 95% of the teeth are classified as planned tooth movement.

As further disclosed herein, the cured polymeric material has advantageous properties that result, at least in part, from the presence of polymer crystals. These cured polymeric materials have increased resistance to failure, may be tough, and may have reduced water absorption when compared to similar polymeric materials. The cured polymeric materials may be used in the orthodontic field as well as in devices outside the orthodontic field. For example, the cured polymeric materials disclosed herein may be used to manufacture equipment for aerospace applications, automotive manufacturing, prototype manufacturing, and/or equipment for durable part production.

VII Experimental methods

Unless otherwise indicated, all chemicals were purchased from commercial sources and used without further purification.

Recording on BRUKER AC-E-200FT-NMR spectrometer or BRUKER Avance DRX-400FT-NMR spectrometer ¹ H NMR ¹³ C NMR spectrum. Chemical shifts are in ppm (s: singlet, d: doublet, t: triplet, q: quadruple, m: multiplet). The solvent used was deuterated chloroform (CDCl) ₃ 99.5% deuteration) and deuterated DMSO (d) ₆ DMSO,99.8% deuterated).

In some embodiments, stress relaxation of a material or device may be measured by monitoring time-dependent stress caused by a stable strain. The degree of stress relaxation may also depend on temperature, relative humidity, and other applicable conditions (e.g., the presence of water). In an embodiment, the test conditions for stress relaxation are a temperature of 37±2 ℃ at 100% relative humidity or a temperature of 37±2 ℃ in water.

Dynamic viscosity of fluidIndicating its resistance to shear flow. The SI unit of dynamic viscosity is Poisson's leaf (Pa.s). Dynamic viscosity is typically given in centipoise, where 1 centipoise (cP) equals 1 mpa·s. Kinematic viscosity is the ratio of dynamic viscosity to fluid density; SI unit is m ² And/s. Devices for measuring viscosity include viscometers and rheometers. For example, a MCR 301 rheometer from An Dongpa can be used for rheometry in rotary mode (PP-25, 50s-1, 50-115 ℃, 3 ℃ C./min).

Determining the moisture content at full saturation at the use temperature may include exposing the polymeric material to 100% humidity at the use temperature (e.g., 40 ℃) for a period of 24 hours, and then determining the moisture content by methods known in the art, such as by weight.

In some embodiments, the presence of crystalline and amorphous phases provides advantageous material properties for the polymeric material. For example, the property values of the cured polymeric material may be determined by using the following method:

flexural modulus, residual flexural stress and stress relaxation properties can be evaluated by three-point bending using a TA Instruments RSA-G2 instrument according to ASTM D790; for example, stress relaxation can be measured at 30 ℃ and immersed in water and reported as residual load after 24 hours, expressed as a percentage (%) of initial load and/or in MPa;

storage modulus can be measured at 37 ℃ and reported in MPa;

t of cured polymeric material can be evaluated using Dynamic Mechanical Analysis (DMA) _g And provided herein as tan delta peaks;

tensile modulus, tensile strength, elongation at yield and elongation at break can be assessed according to ISO 527-2 5 b; tensile strength at yield, elongation at break, tensile strength and young's modulus can be evaluated according to ASTM D1708;

molecular weight may be measured by size exclusion chromatography or gel permeation chromatography.

Additive manufacturing or 3D printing methods for generating the devices herein (e.g., orthodontic appliances) may be performed using a thermal lithographic apparatus prototype from Cubicure (Vienna, austria), which may be configured substantially as shown in fig. 9. In this case, the photocurable composition (e.g., resin) according to the present disclosure may be filled into a transparent material barrel of the apparatus shown in fig. 9, which barrel may be heated to 90-110 ℃. The build platform can also be heated to 90-110 ℃ and lowered to establish full contact with the upper surface of the curable composition. By irradiating the composition with 375nm UV radiation using a diode laser from the Soliton, which may have an output power of 70mW, which may be controlled to track a predetermined prototype design and alternately raise the build platform, the composition may be cured layer by a photopolymerization process according to the present disclosure, resulting in a polymeric material according to the present disclosure.

Examples

The following examples are given to illustrate various embodiments of the invention and are not meant to limit the disclosure in any way. The present examples, as well as the methods described herein, are presently representative of certain embodiments, are exemplary, and are not intended as limitations on the scope of the invention. Variations therein and other uses within the spirit of the invention as defined by the scope of the claims will occur to those skilled in the art.

Example 1

Synthesis of guaiacyl methacrylate (2)

This example describes the synthesis of guaiacyl methacrylate 2, giving a chemical yield of the final product of at least 25%.

Guaiacol (1, 1 equivalent) and dimethylaminopyridine (0.02 equivalent) were added to a round bottom flask and treated with N ₂ Bubbling for 1 hour. The flask was cooled in an ice-water bath and methacrylic anhydride (1.2 eq) was added to the mixture. The reaction was stirred at 45 ℃ overnight. The cooled mixture was then diluted with dichloromethane and washed with saturated sodium bicarbonate solution, then with 1M NaOH solution. The organic layer was dried and concentrated to give methacrylic acid in 29% yieldAnd (3) a guaranyl ester 2.

Example 2

Synthesis of eugenol methacrylate (4)

This example describes the synthesis of eugenol (meth) acrylate 4, resulting in a chemical yield of the final product of at least about 25%.

Eugenol (3.1 eq.) was dissolved in chloroform in a round bottom flask. Lithium carbonate (1.1 eq.) was added followed by methacrylic anhydride (1.1 eq.). The reaction mixture was stirred at 50℃or 60℃overnight. Then, the solids were removed by filtration, and the filtrate was washed with saturated sodium bicarbonate solution and brine, dried over sodium sulfate and concentrated. Column chromatography of the crude product (eluting with 80% dichloromethane in hexanes) afforded product 4 in >95% yield.

An alternative synthetic route involves the addition of 4-dimethyl-aminopyridine DMAP in >95% yield. In this procedure, eugenol (3, 1 equivalent), methacrylic anhydride (1.3 equivalent), triethylamine (1 equivalent) and butylated hydroxytoluene BHT (total mass: 1 wt%) were added with equivalent amounts of DMAP corresponding to the addition amount of BHT. The resulting mixture was dissolved in chloroform and reacted at 60C overnight. The next day, the solids were removed by filtration and the filtrate was washed with saturated sodium bicarbonate solution and brine, dried over sodium sulfate and concentrated. Dichloromethane column chromatography of the crude product gave product 4 in >95% yield.

Example 3

Melting point measurement of polymerizable monomers

As described herein, the polymerizable monomers of the present disclosure can be in a liquid state at the processing temperature, for example for 3D printing. This means that the lower limit of the processing window of the polymerizable monomer is defined by the viscosity (if still liquid) or melting point of the substance.

Thus, polymerizable monomers that were solid at room temperature were analyzed using an OptiMelt melting point device from Stanford Research Systems at a heating rate of 1K/min. The melting point interval is determined by an optical sensor. In addition, STA (synchronous thermal analyser) measurements were performed on a DSC apparatus of Netzsch, STA 449F1 Jupiter, comprising a temperature range of-50℃to 400℃using a heating rate of 10K/min. For purposes herein, DSC data is used to determine the melting point of a synthetic compound. Since the heating rate is quite high, the melting start point is used as a reference point.

The results of this study showed that at least some of the compounds tested in this example were solid at room temperature.

Example 4

Volatility and thermal stability of polymerizable monomers

The selected polymerizable monomers were tested for volatility and thermal stability by Simultaneous Thermal Analysis (STA), which represents a combination of thermogravimetric analysis (TG) and differential scanning calorimetric analysis (DSC). To determine the volatility and thermal stability of the compounds, STA measurements were performed on a Netzsch STA 449F1 Jupiter, including temperatures ranging from-50℃to 400℃with a heating rate of 10K/min. For the monomers, temperatures of 5% mass loss or 10% mass loss, respectively, were detected as a measure of volatility. The thermal stability is derived from the recorded DSC data, i.e. the temperature at which the energy release initiated by thermal polymerization of the monomers is detected. Herein, the temperature at the beginning of exothermic thermal polymerization is taken as a measure of thermal stability. Furthermore, at a constant temperature of 90 ℃, a loss of mass of the reactive diluent was observed over a period of 2 hours. In this case, less than 1% mass loss was determined to determine the monomer most suitable as a reactive diluent for high temperature applications.

Example 5

Viscosity experiment

This example describes experiments to determine the viscosity of exemplary photopolymerizable monomers, as well as resin formulations comprising such monomers, as described herein. For this purpose, the rheology measurements are carried out on the pure monomers in a temperature range comprising 25℃to 100 ℃. The measurements were carried out on an Anton Paar MCR301 instrument equipped with a CTD 450 oven and a CP-25-1 measuring system, with a gap distance between the punch (cone) and the base plate of 48 μm, a constant shear rate of 50s ^-1 。

Example 6

Homopolymerization and photoreactivity

To determine the photoreactivity of the polymerizable monomers described herein, light differential scanning calorimetry (photo-DSC) measurements were performed on some of the synthetic substances. To this end, the monomers were mixed with 1 wt.% of a commercially available photoinitiator (TPO-L, (2, 4, 6-trimethylbenzoyl) ethyl phenylphosphinate) in an ultrasonic bath at 50℃or above the melting temperature for 15 minutes. Then, 10.+ -.1 mg of each monomer was weighed into a DSC aluminum pan and placed into a DSC 204F1 apparatus from Netzsch using an auto-sampler that was similar to that from Exfo OmniCure ^TM A series 2000 broadband UV light source (320-500 nm) is coupled. Sample at N ₂ Atmosphere (N) ₂ Flow rate: 20 mL/min) at the exit of the light guide using 1W/cm ² Corresponding to about 20mW/cm on the sample surface ² For 5 minutes. After measurement, some of the cured sample was dissolved in CDCl ₃ And recorded by BRUKER Avance DRX-400FT-NMR spectrometer ¹ H NMR spectrum. The double bond conversion (DBC; in%) of each monomer is calculated based on the corresponding integrated double bond peak area.

Example 7

Tensile Strength, stress relaxation and dynamic mechanical analysis

This example describes experiments and results obtained for tensile strength, stress relaxation and dynamic mechanical analysis of a photocurable composition comprising one of monomers 5, 2 or 4 in polymerized form:

table 3 below shows the composition and curing conditions of three photocurable resins R1-R3, which each contain polymerizable monomers 5, 2 and 4 and methacrylic acid Homosalicylate (HSMA).

TABLE 3 composition of photocurable resins R1-R3

The experimental results of tensile strength of the cured polymeric materials P1-P3 produced from the photocurable resins R1-R3, respectively, were studied, as shown in fig. 5, and summarized in table 4 below.

TABLE 4 tensile Strength data for Polymer materials P1-P3

Fig. 6 shows the Dynamic Mechanical Analysis (DMA) results obtained for the polymeric materials P1-P3. The storage modulus and tan delta are shown as a function of the temperature to which the polymer composition is exposed. Glass transition temperature (T) _g ) Is determined as the peak of the tan delta curve and calculated as 133.94 ℃ (P1), 127.05 ℃ (P2) and 142.14 ℃ (P3). Since the glass transition temperature may depend on the segment mobility in the amorphous phase (which in turn may be reduced by polymer chain stiffness and/or steric hindrance between monomers and within monomer structures (e.g., monomer side chains)), it is shown that by increasing steric hindrance and reducing rotational freedom of the side chains attached to the polymer backbone (e.g., by introducing more bulky substituents at one or both ortho-positions of the cyclic side groups, e.g., R in formula (I)) ² And R is ⁵ And methoxy groups of compounds 2 and 4 as compared to hydrogen in compound 5 of this example), can produce a compound having higher rigidity and higher T _g Such polymeric materials may be useful components of a variety of devices, such as medical appliances (e.g., orthodontic appliances).

In addition, stress relaxation experiments were performed using the polymer materials P1 to P3. The results are shown in fig. 7 and summarized in table 5 below.

TABLE 5 stress relaxation data for Polymer materials P1-P3

Taken together, these results demonstrate that the photopolymerizable monomers of the present disclosure (e.g., compounds 2 and 4 shown in the present example) can not only allow 3D printing at elevated temperatures due to the relatively low vapor pressure of the compounds described herein, but can also provide polymeric materials with advantageous mechanical and physical properties.

Example 8

Polymerizable monomers as reactive diluents

This example demonstrates that the polymerizable monomers of the present disclosure can be used as reactive diluents in photocurable resins. For this purpose, compounds 5, 2 and 4 were mixed with commercially available resins of high viscosity, and then the viscosity of the resins with and without these compounds was measured. The results show that in particular compound 4, which has a reduced degree of rotational freedom around the C-O bond connecting the aryl moiety and the methacrylate moiety, 4 reduces the viscosity of the resin compared to compounds 2 and 5, while having a relatively low vapor pressure at elevated temperatures (e.g., >80 ℃).

Example 9

Treatment using orthodontic appliances

This embodiment describes the use of a direct 3D printed orthodontic appliance to move a patient's teeth according to a treatment plan. This embodiment also describes features that an orthodontic appliance may have after use, in contrast to features prior to use.

Patients who need or want therapeutic treatment to rearrange at least one tooth should evaluate their tooth arrangement. An orthodontic treatment plan is generated for the patient. Orthodontic treatment plans include a plurality of intermediate tooth arrangements for moving teeth along a treatment path to move from an initial arrangement (e.g., an initially assessed arrangement) to a final arrangement. Treatment planning includes the use of orthodontic appliances (which are made using the photocurable resins and methods further disclosed herein) to provide orthodontic appliances with low levels of hydrogen bonding units. In some embodiments, a plurality of orthodontic appliances are used, each of which may be made using the photocurable resins and methods further disclosed herein that comprise one or more polymerizable monomers.

Orthodontic appliances are provided and applied repeatedly to the patient's teeth to move the teeth through each intermediate tooth arrangement toward the final arrangement. The tooth movement of the patient is tracked. The actual tooth arrangement of the patient is compared to the planned intermediate arrangement. If it is determined that the patient's teeth are evolving according to the treatment plan, but the final arrangement has not been reached, the next set of appliances may be administered to the patient. Table 1 above provides threshold differences in the planned tooth position from the actual position selected, which indicates that the patient's teeth are developing as planned. If the patient's tooth development reaches a threshold or is within a threshold range, the development is deemed to be planned. Advantageously, use of the appliance disclosed herein increases the likelihood that teeth will move as planned.

For example, it may be assessed and determined whether treatment is planned after a period of 1 week (7 days) of first application of the orthodontic appliance. Additional parameters related to the durability of the orthodontic appliance may also be evaluated after the period of time is applied. For example, the relative repositioning force (as compared to the force initially provided by the instrument), the residual bending stress, the relative bending modulus, and the relative elongation at break may be determined.

Furthermore, the terms and expressions which have been employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Therefore, it is to be understood that although the present invention has been specifically disclosed by some embodiments, exemplary embodiments and optional features, modification and variation of the inventive concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims. The specific embodiments provided herein are examples of useful embodiments of the invention, and it will be apparent to those skilled in the art that the invention may be practiced with numerous variations of the apparatus, apparatus assemblies, method steps set forth in the present specification. As will be apparent to those of skill in the art, the methods and apparatus useful in the present methods may include a wide variety of optional components and processing elements and steps.

Claims

1. A polymerizable monomer according to formula (I):

(I)

wherein:

x is O, S, NR ⁶ Or SiR ⁷ R ⁸ ；

R ¹ Is H, substituted or unsubstituted C _1-3 Alkyl, or halogen;

R ² is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _3-6 Carbonyl, substituted or unsubstituted C _3-6 Carboxyl, substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl;

R ³ is H;

R ⁴ and R is ⁵ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-Y- (CH) ₂ ) _n -R ⁹ The method comprises the steps of carrying out a first treatment on the surface of the Or R is ⁴ And R is ⁵ Taken together form a 4-, 5-, 6-, 7-or 8-membered ring, said 4-, 5-, 6-, 7-or 8-membered ring being selected from substituted or unsubstituted rings (C _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl;

wherein Y is O, S, NH or C (O) O;

n is an integer from 0 to 6;

2. A polymerizable monomer according to formula (I):

(I)

wherein:

x is O, S, NR ⁶ Or SiR ⁷ R ⁸ ；

R ¹ Is H, substituted or unsubstituted C _1-3 Alkyl, or halogen;

R ³ is H, substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-Y- (CH) ₂ ) _n -R ⁹ ；

R ⁴ And R is ⁵ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or notSubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-Y- (CH) ₂ ) _n -R ⁹ The method comprises the steps of carrying out a first treatment on the surface of the Or R is ⁴ And R is ⁵ Taken together form a 4-, 5-, 6-, 7-or 8-membered ring, said 4-, 5-, 6-, 7-or 8-membered ring being selected from substituted or unsubstituted rings (C _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

wherein Y is O, S, NH or C (O) O;

n is an integer from 0 to 6;

3. The polymerizable monomer of claim 2 wherein R ³ H.

4. The polymerizable monomer of claim 2 wherein R ³ Is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-Y- (CH) ₂ ) _n -R ⁹ 。

5. The polymerizable monomer of any one of claims 1-4 wherein R ⁴ H.

6. The polymerizable monomer of any one of claims 1-4 wherein R ⁴ Is substituted byOr unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-Y- (CH) ₂ ) _n -R ⁹ 。

7. The polymerizable monomer of any one of claims 1-6 wherein R ¹ Is H or methyl.

8. The polymerizable monomer of any one of claims 1-7 wherein X is O.

9. The polymerizable monomer of any one of claims 1-8 wherein R ⁵ H.

10. The polymerizable monomer of any one of claims 1-8 wherein R ⁵ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-Y- (CH) ₂ ) _n -R ⁹ 。

11. The polymerizable monomer of any one of claims 2, 4, 6-8, or 10 wherein R ³ 、R ⁴ And R is ⁵ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, or substituted or unsubstituted C _1-6 An alkoxy group.

12. The polymerizable monomer of any one of claims 1-11 wherein R ³ 、R ⁴ And R is ⁵ At least one of which is substituted or unsubstituted C _1-6 An alkoxy group.

13. The polymerizable monomer of any one of claims 1-12 wherein R ³ 、R ⁴ And R is ⁵ At least one of which is unsubstituted C _1-3 An alkoxy group.

14. The polymerizable monomer of any one of claims 1-13 wherein R ² Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

15. The polymerizable monomer of any one of claims 1-14 wherein R ² Is an unsubstituted ring (C _3-8 ) Alkyl, unsubstituted Ring (C) _3-8 ) Heteroalkyl, unsubstituted aryl, or unsubstituted heteroaryl.

16. The polymerizable monomer of any one of claims 1-15 wherein R ² Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, or substituted or unsubstituted aryl.

17. The polymerizable monomer of any one of claims 1-16 wherein R ² Is an unsubstituted ring (C _3-8 ) Alkyl or unsubstituted aryl.

18. The polymerizable monomer of any one of claims 1-13 wherein R ² Is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _3-6 Carbonyl, substituted or unsubstituted C _3-6 And (3) carboxyl.

19. The polymerizable monomer of any one of claims 1-13 or 18 wherein R ² Is unsubstituted C _3-6 Alkyl, unsubstituted C _3-6 Heteroalkyl, unsubstituted C _3-6 Carbonyl or unsubstituted C _3-6 Carboxyl group。

20. The polymerizable monomer of any one of claims 1-13 or 18-19 wherein R ² Is substituted or unsubstituted C _3-6 Alkyl, or substituted or unsubstituted C _3-6 A heteroalkyl group.

21. The polymerizable monomer of any one of claims 1-13 or 18-20 wherein R ² Is unsubstituted C _3-6 Alkyl or unsubstituted C _3-6 A heteroalkyl group.

22. The polymerizable monomer of any one of claims 1-11 wherein the polymerizable monomer is selected from the group consisting of:

23. the polymerizable monomer of any one of claims 1-21 wherein R ⁵ Is substituted or unsubstituted C _1-6 An alkoxy group.

24. The polymerizable monomer of claim 23 wherein the polymerizable monomer is:

25. the polymerizable monomer of any one of claims 1-7 or 14-21 wherein X is S or SiR ⁷ R ⁸ And R is ⁵ Is substituted or unsubstituted C _1-6 An alkyl group.

26. The polymerizable monomer of claim 25 wherein the polymerizable monomer is:

27. a polymerizable monomer according to formula (II):

(II)

Wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl, or halogen;

R ¹⁰ is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl;

R ¹¹ and R is ¹² Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X- (CH) ₂ ) _n -R ¹³ The method comprises the steps of carrying out a first treatment on the surface of the Or R is ¹¹ And R is ¹² Taken together form a 4-, 5-, 6-, 7-or 8-membered ring, said 4-, 5-, 6-, 7-or 8-membered ring being selected from substituted or unsubstituted rings (C _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

wherein X is O, S, NH or C (O) O;

n is an integer from 0 to 6; and is also provided with

28. The polymerizable monomer of claim 27 wherein R ¹¹ H.

29. The polymerizable monomer of claim 27 or 28 wherein R ¹² H.

30. The polymerizable monomer of any one of claims 27-29 wherein R ¹ Is H or methyl.

31. The polymerizable monomer of any one of claims 27-30 wherein R ¹⁰ Is substituted or unsubstituted C _1-6 An alkoxy group.

32. The polymerizable monomer of any one of claims 27-31 wherein R ¹¹ And R is ¹² Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X- (CH) ₂ ) _n -R ¹³ 。

33. The polymerizable monomer of any one of claims 27-32 wherein R ¹¹ And R is ¹² At least one of which is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl group,or-X- (CH) ₂ ) _n -R ¹³ 。

34. The polymerizable monomer of any one of claims 27-32 wherein the polymerizable monomer is:

35. a polymerizable monomer according to formula (III):

(III)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl, or halogen;

R ¹⁴ is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted ring (C) _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl;

R ¹⁵ and R is ¹⁶ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X- (CH) ₂ ) _n -R ¹⁷ Wherein R is ¹⁵ And R is ¹⁶ At most one of (a) is H;

wherein X is O, S, NH or C (O) O;

n is an integer from 0 to 6; and is also provided with

R ¹⁷ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstitutedSubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

36. The polymerizable monomer of claim 35 wherein R ¹ Is H or methyl.

37. The polymerizable monomer of claim 35 or 36 wherein R ¹⁴ Is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

38. The polymerizable monomer of any one of claims 35-37 wherein R ¹⁴ Is a substituted or unsubstituted aryl group.

39. The polymerizable monomer of any one of claims 35-38 wherein R ¹⁵ And R is ¹⁶ Together form a 4-, 5-, 6-, 7-, or 8-membered ring; the 4-, 5-, 6-, 7-or 8-membered ring is selected from the group consisting of substituted or unsubstituted rings (C _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

40. The polymerizable monomer of any one of claims 35-38 wherein R ¹⁵ And R is ¹⁶ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X- (CH) ₂ ) _n -R ¹⁷ 。

41. The polymerizable monomer of any one of claims 35-38 or 40 wherein R ¹⁵ Is substituted or unsubstitutedC of (2) _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X- (CH) ₂ ) _n -R ¹⁷ 。

42. The polymerizable monomer of any one of claims 35-38 or 40-41 wherein R ¹⁶ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X- (CH) ₂ ) _n -R ¹⁷ 。

43. The polymerizable monomer of any one of claims 35-38 or 40-42 wherein R ¹⁵ And R is ¹⁶ At least one of which is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, or substituted or unsubstituted C _1-6 Thioalkoxy groups.

44. The polymerizable monomer of any one of claims 35-43 wherein R ¹⁴ Is substituted or unsubstituted C _3-6 Alkyl or substituted or unsubstituted C _3-6 A heteroalkyl group.

45. The polymerizable monomer of any one of claims 35-43 wherein R ¹⁴ Is substituted or unsubstituted C _3-4 Alkyl, substituted or unsubstituted C _3-4 Heteroalkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, or substituted or unsubstituted heteroaryl.

46. The polymerizable monomer of any one of claims 35-38 or 40-45 wherein the polymerizable monomer comprises a structure according to formula (IIIa):

wherein:

R ⁸³ And R is ⁸⁴ Independently at each occurrence selected from hydrogen and C _1-3 Alkyl, or wherein R ⁸³ And R is ⁸⁴ Together form a 4-, 5-, 6-, 7-or 8-membered ring substituted or unsubstituted heterocycle.

47. The polymerizable monomer of claim 46 wherein R ⁸² -R ⁸⁴ One or more of them being halogen, OH, NH ₂ 、NH(C _1-6 Alkyl), N (C) _1-6 Alkyl) (C) _1-6 Alkyl) or C _1-3 Alkyl substitution.

48. The polymerizable monomer of claim 46 or 47 wherein R ⁸² -R ⁸⁴ One or more of them being halogen, OH or NH ₂ And (3) substitution.

49. The polymerizable monomer of claim 35 wherein the polymerizable monomer is:

50. a polymerizable monomer according to formula (IV):

(IV)

Wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl, or halogen;

R ¹⁸ is substituted C _2-6 Alkyl and R ¹⁹ Is unsubstituted C _1-6 An alkyl group.

51. A polymerizable monomer according to formula (IV):

(IV)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl, or halogen;

R ¹⁸ is substituted C _3-6 Alkyl, unsubstituted C _4-6 Alkyl, or substituted or unsubstituted C _3-6 A heteroalkyl group; and is also provided with

R ¹⁹ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, or substituted or unsubstituted C _1-6 And (3) carboxyl.

52. The polymerizable monomer of claim 50 or 51 wherein R ¹ Is H or methyl.

53. The polymerizable monomer of claim 51 or 52 wherein R ¹⁸ Is substituted C _3-6 Alkyl or unsubstituted C _4-6 An alkyl group.

54. The polymerizable monomer of any one of claims 51-53 wherein R ¹⁸ Is unsubstituted C _4-6 An alkyl group.

55. The polymerizable monomer of any one of claims 51-54 wherein R ¹⁹ Is substituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, or substituted or unsubstituted C _1-6 And (3) carboxyl.

56. The polymerizable monomer of any one of claims 51-53 or 55 wherein R ¹⁹ Is substituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, or substituted or unsubstituted C _1-6 An alkoxy group.

57. The polymerizable monomer of claim 51 or 52 wherein R ¹⁸ Is substituted or unsubstituted C _3-6 Alkyl and R ¹⁹ Is substituted or unsubstituted C _1-6 An alkoxy group.

58. The polymerizable monomer of claim 51 or 52 wherein R ¹⁸ Is substituted or unsubstituted C _3-6 Alkyl and R ¹⁹ Is substituted or unsubstituted C _1-6 An alkyl group.

59. The polymerizable monomer of claim 51 or 52 wherein R ¹⁸ Is substituted or unsubstituted C _3-6 Alkyl and R ¹⁹ Is substituted or unsubstituted C _1-6 A heteroalkyl group.

60. The polymerizable monomer of claim 51 or 52 wherein the polymerizable monomer is:

61. a polymerizable monomer according to formula (V):

(V)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl, or halogen;

R ²⁰ and R is ²² Each independently is substituted or unsubstituted C _4-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ¹ -(CH ₂ ) _a -R ²⁸ ；

R ²¹ And R is ²³ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ² -(CH ₂ ) _b -R ²⁹ ；

R ²⁴ And R is ²⁶ Each independently is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _2-6 Carboxyl, or-X ³ -(CH ₂ ) _c -R ³⁰ ；

R ²⁵ And R is ²⁷ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ⁴ -(CH ₂ ) _d -R ³¹ ；

X ¹ 、X ² 、X ³ And X ⁴ Each independently is a bond, O or S;

R ²⁸ 、R ²⁹ 、R ³⁰ And R is ³¹ Each independently is a substituted ring (C) _3-8 ) Alkyl, substituted ring (C) _3-8 ) Heteroalkyl, substituted aryl, or substituted heteroaryl.

62. The polymerizable monomer of claim 61, wherein:

R ²⁰ and R is ²² At least one of them is-X ¹ -(CH ₂ ) _a -R ²⁸ ；

R ²¹ And R is ²³ At least one of them is-X ² -(CH ₂ ) _b -R ²⁹ ；

R ²⁴ And R is ²⁶ At least one of them is-X ³ -(CH ₂ ) _c -R ³⁰ ；

R ²⁵ And R is ²⁷ At least one of them is-X ⁴ -(CH ₂ ) _d -R ³¹ The method comprises the steps of carrying out a first treatment on the surface of the Or (b)

A combination thereof.

63. The polymerizable monomer of claim 61 or 62 wherein Cy is

64. The polymerizable monomer of any one of claims 61-63 wherein R ²⁰ 、R ²¹ 、R ²² And R is ²³ At least one of which is substituted or unsubstituted C _1-6 An alkoxy group.

65. The polymerizable monomer of claim 61 or 62 wherein Cy is

66. The polymerizable monomer of any one of claims 61, 62, or 65 wherein R ²⁴ 、R ²⁵ 、R ²⁶ And R is ²⁷ At least one of which is substituted or unsubstituted C _1-6 An alkoxy group.

67. The polymerizable monomer of any one of claims 61-66 wherein R ²¹ And R is ²³ At least one of which is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ² -(CH ₂ ) _b -R ²⁹ 。

68. The polymerizable monomer of any one of claims 61-67 wherein R ²⁸ 、R ²⁹ 、R ³⁰ And R is ³¹ Each independently is a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

69. The polymerizable monomer of claims 61-68 wherein R ²¹ And R is ²³ At least one of them is-X ² -(CH ₂ ) _b -R ²⁹ And each R ²⁹ Independently a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

70. The polymerizable monomer of claims 61-69 wherein each instance of a is independently 2-6.

71. The polymerizable monomer of claims 61-69 wherein each instance of a is independently 0.

72. The polymerizable monomer of claims 61-71 wherein R ²⁵ And R is ²⁷ At least one of which is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ⁴ -(CH ₂ ) _d -R ³¹ 。

73. The polymerizable monomer of claims 61-72 wherein each instance of c is independently 2-6.

74. The polymerizable monomer of claims 61-72 wherein each instance of c is independently 0.

75. The polymerizable monomer of claim 61 wherein the polymerizable monomer is selected from the group consisting of:

76. A polymerizable monomer according to formula (VI):

(VI)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl, or halogen;

R ³² and R is ³⁴ Each independently is substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ⁵ -(CH ₂ ) _e -R ⁴² ；

R ³³ And R is ³⁵ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ⁶ -(CH ₂ ) _f -R ⁴³ ；

R ³⁶ And R is ³⁸ Each independently is substituted or unsubstituted C _3-6 Alkyl, substituted C _4-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ⁷ -CH ₂ ) _g -R ⁴⁴ ；

R ³⁷ And R is ³⁹ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ⁸ -(CH ₂ ) _h -R ⁴⁵ ；

X ⁵ 、X ⁶ 、X ⁷ And X ⁸ Each independently is a bond, O or S;

e、f. g and h are each independently integers from 0 to 6; r is R ⁴² And R is ⁴³ Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl; and is also provided with

77. The polymerizable monomer of claim 76 wherein Cy is

78. The polymerizable monomer of claim 76 or 77 wherein R ³² 、R ³³ 、R ³⁴ And R is ³⁵ At least one of which is substituted or unsubstituted C _1-6 Alkoxy, or substituted or unsubstituted C _1-6 Thioalkoxy groups.

79. The polymerizable monomer of claim 76 wherein Cy is

80. The polymerizable monomer of claim 76 or 79 wherein R ³⁶ 、R ³⁷ 、R ³⁸ And R is ³⁹ At least one of which is substituted or unsubstituted C _1-6 Alkoxy, or substituted or unsubstituted C _1-6 Thioalkoxy groups.

81. The polymerizable monomer of claim 76 wherein Cy is

82. The polymerizable monomer of claim 76 or 81 wherein R ⁴¹ Is substituted or unsubstituted C _1-6 Alkoxy, or substituted or unsubstituted C _1-6 Thioalkoxy groups.

83. The polymerizable monomer of any one of claims 76-82 wherein R ¹ Is H or methyl.

84. The polymerizable monomer of any one of claims 76, 77, or 83, wherein R ³³ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ⁶ -(CH ₂ ) _f -R ⁴³ 。

85. The polymerizable monomer of any one of claims 76-77 or 83-84, wherein R ³³ And R is ³⁵ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ⁶ -(CH ₂ ) _f -R ⁴³ 。

86. The polymerizable monomer of claim 76, 80, or 83-85 wherein R ³⁷ Is substituted or unsubstituted C _1-6 Alkyl, substituted orUnsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ⁶ -(CH ₂ ) _f -R ⁴³ 。

87. The polymerizable monomer of claim 76, 80, or 83-86 wherein R ³⁷ And R is ³⁹ Each independently is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ⁶ -(CH ₂ ) _f -R ⁴³ 。

88. The polymerizable monomer of claim 76 wherein the polymerizable monomer is selected from the group consisting of:

89. a polymerizable monomer according to formula (IX):

(IX)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl, or halogen;

R ⁷⁷ is nitrile, substituted or unsubstituted C _1-6 Alkyl cyanide, or substituted or unsubstituted C _1-6 A carbonyl group;

R ⁷⁸ is substituted or unsubstituted C _1-6 Alkyl groupSubstituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl;

R ⁷⁹ And R is ⁸⁰ Each independently H, C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl; and is also provided with

R ⁸¹ Is substituted or unsubstituted C _1-6 An alkoxy group.

90. The polymerizable monomer of claim 89, wherein R ⁷⁷ Is nitrile, or substituted or unsubstituted C _1-6 Alkyl cyanide.

91. The polymerizable monomer of claim 89 or 90 wherein R ⁷⁹ And R is ⁸⁰ Each independently H, C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, substituted or unsubstituted ring (C _3-8 ) Alkyl, or substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group.

92. The polymerizable monomer of claims 89-91, itsR in (B) ⁸¹ Is unsubstituted C _1-6 An alkoxy group.

93. The polymerizable monomer of any one of claims 1-92 wherein the polymerizable monomer has a vapor pressure of up to 12Pa at 60 ℃.

94. The polymerizable monomer of any one of claims 1-93 wherein the polymerizable monomer has a vapor pressure of from 2Pa to 10Pa at 60 ℃.

95. The polymerizable monomer of any one of claims 1-94 wherein the polymerizable monomer has a vapor pressure of from 2Pa to 5Pa at 60 ℃.

96. The polymerizable monomer of any one of claims 1-95 wherein the polymerizable monomer has a mass loss of less than 0.5% after heating at 90 ℃ for 2 hours.

97. The polymerizable monomer of any one of claims 1-96 wherein the polymerizable monomer has a mass loss of 0.1% to 0.45% after heating at 90 ℃ for 2 hours.

98. The polymerizable monomer of any one of claims 1-97 wherein the polymerizable monomer has a mass loss of 0.05% to 0.25% after heating at 90 ℃ for 2 hours.

99. The polymerizable monomer of any one of claims 1-98 wherein the polymerizable monomer has a melting point of at least 30 ℃.

100. The polymerizable monomer of any one of claims 1-99 wherein the polymerizable monomer has a molecular weight of 190 to 300 daltons (Da).

101. The polymerizable monomer of any one of claims 1-100 wherein R ¹ -R ⁴⁷ Or R is ⁷⁷ -R ⁸¹ One or more of them being halogen, OH, NH ₂ 、NH(C _1-6 Alkyl), N (C) _1-6 Alkyl) (C) _1-6 Alkyl) or C _1-3 Alkyl substitution.

102. The polymerizable monomer of any one of claims 1-101 wherein R ¹ -R ⁴⁷ Or R is ⁷⁷ -R ⁸¹ One or more of them being halogen, OH or NH ₂ And (3) substitution.

103. A polymer comprising the polymerizable monomer of any one of claims 1-102.

104. The polymer of claim 103, comprising 10-80wt% of the polymerizable monomer.

105. The polymer of claim 103 or 104, comprising 15-45wt% of the polymerizable monomer.

106. The polymer of any one of claims 103-105, comprising 25-35wt% of the polymerizable monomer.

107. A photocurable resin comprising:

the polymerizable monomer of any one of claims 1-102; and

a photoinitiator.

108. The photocurable resin of claim 107, wherein the polymerizable monomer reduces the viscosity of the photocurable resin by at least 5% as compared to the resin that does not comprise the polymerizable monomer.

109. The photocurable resin of claim 107 or 108, wherein the polymerizable monomer reduces the viscosity of the photocurable resin by at least 10%, 20%, 30%, 40%, or 50%.

110. The photocurable resin of any one of claims 107-109, further comprising a telechelic oligomer, a telechelic polymer, or a combination thereof.

111. The photocurable resin of claim 110, wherein the telechelic oligomer has a number average molecular weight greater than 500Da but less than 3 kDa.

112. The photocurable resin of claim 110, wherein the telechelic polymer has a number average molecular weight greater than 5kDa but less than 50 kDa.

113. The photocurable resin of any one of claims 110-112, wherein the telechelic oligomer and the telechelic polymer comprise photoreactive moieties at both ends thereof.

114. The photocurable resin of claim 113, wherein the photoreactive moiety is an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, silicon carbene, alkynyl, alkenyl, vinyl ether, maleimide, fumarate, maleate, itaconate, or styryl moiety.

115. The photocurable resin of claim 114, wherein the photoreactive moiety is an acrylate or methacrylate.

116. The photocurable resin of any one of claims 107-115 which is capable of being 3D printed at a temperature greater than 25 ℃.

117. The photocurable resin of claim 116, wherein the temperature is at least 30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃ or 100 ℃.

118. The photocurable resin of any one of claims 107-117, which has a viscosity of 30cP to 50,000cP at printing temperature.

119. The photocurable resin of claim 118, wherein the printing temperature is from 20 ℃ to 150 ℃.

120. The photocurable resin of any one of claims 107-119, comprising less than 20wt% hydrogen bond units.

121. The photocurable resin of any one of claims 107-120, further comprising a crosslinking modifier, a light blocker, a solvent, a glass transition temperature modifier, or a combination thereof.

122. The photocurable resin of any one of claims 107-121, comprising 0.5-99.5wt%, 1-99wt%, 10-95wt%, 20-90wt%, 25-60wt%, or 35-50wt% of the polymerizable monomer, the oligomer, or a combination thereof.

123. The photocurable resin of any one of claims 107-122, comprising 10-80wt% of the polymerizable monomer.

124. The photocurable resin of any one of claims 107-123, comprising 15-45wt% of the polymerizable monomer.

125. The photocurable resin of any one of claims 107-124, comprising 25-35wt% of the polymerizable monomer.

126. The photocurable resin of any one of claims 107-125, comprising from 10-50wt% of a second acrylate or methacrylate monomer.

127. The photocurable resin of any one of claims 107-126, wherein the second acrylate or methacrylate monomer is an acrylic or methacrylic acid homosalicylate.

128. The photocurable resin of any one of claims 107-127, wherein the photocurable resin is capable of polymerization-induced phase separation during photocuring.

129. The photocurable resin of claim 128, wherein the photocurable resin comprises one or more polymeric phases upon polymerization.

130. The photocurable resin of claim 129, wherein at least one of said one or more polymer phases is a glass transition temperature (T _g ) An amorphous phase of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃ or at least 110 ℃.

131. The photocurable resin of claim 130, wherein the polymerizable monomer in polymerized form is T _g At least one amorphous phase component at least 60 ℃, 80 ℃, 90 ℃, 100 ℃ or at least 110 ℃.

132. The photocurable resin of any one of claims 129-131, wherein at least one of the one or more polymeric phases is a crystalline phase comprising a polymeric material.

133. The photocurable resin of claim 132, wherein the crystalline polymeric material has a melting point of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃.

134. The photocurable resin of any of claims 129-133, wherein at least one of the one or more polymer phases is three-dimensional and has at least one dimension that is less than 1000 μιη, less than 500 μιη, greater than 250 μιη, or less than 200 μιη in length.

135. A polymeric material formed from the photocurable resin of any one of claims 107-134.

136. The polymeric material of claim 135, wherein the polymeric material has one or more of the following characteristics:

(A) Storage modulus greater than or equal to 200MPa;

(B) Residual flexural stress and/or flexural modulus after 24 hours in a humid environment at 37 ℃ is greater than or equal to 1.5MPa;

(C) Elongation at break greater than or equal to 5% before and after 24 hours in a humid environment at 37 ℃;

(D) The water absorption is less than 25wt% when measured after 24 hours in a humid environment at 37 ℃;

(E) At least 30% of the visible light is transmitted through the polymeric material after 24 hours in a humid environment at 37 ℃; and is also provided with

(F) Comprising a plurality of polymer phases, wherein at least one of the one or more polymer phases has a T of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 DEG C _g 。

137. The polymeric material of claim 136, wherein the polymeric material has at least two features of (a), (B), (C), (D), (E), and (F).

138. The polymeric material of any of claims 136-137, wherein the polymeric material has at least three features of (a), (B), (C), (D), (E), and (F).

139. The polymeric material of any of claims 136-138, wherein the polymeric material has at least four features of (a), (B), (C), (D), (E), and (F).

140. The polymeric material of any of claims 136-139, wherein the polymeric material has at least five features of (a), (B), (C), (D), (E), and (F).

141. The polymeric material of any of claims 136-140, wherein the polymeric material has all of the features of (a), (B), (C), (D), (E), and (F).

142. The polymeric material of any of claims 135-141, wherein the polymeric material is characterized by a water absorption of less than 20wt%, less than 15wt%, less than 10wt%, less than 5wt%, less than 4wt%, less than 3wt%, less than 2wt%, less than 1wt%, less than 0.5wt%, less than 0.25wt%, or less than 0.1wt%, when measured after 24 hours in a humid environment at 37 ℃.

143. The polymeric material of any of claims 135-142, wherein the polymeric material has a double bond to single bond conversion of greater than 60% compared to the photocurable resin as measured by FTIR.

144. The polymeric material of any of claims 135-143, wherein the ultimate tensile strength of the polymeric material is 10MPa to 100MPa, 15MPa to 80MPa, 20MPa to 60MPa, 10MPa to 50MPa, 10MPa to 45MPa, 25MPa to 40MPa, 30MPa to 45MPa, or 30MPa to 40MPa after 24 hours in a humid environment at 37 ℃.

145. The polymeric material of any of claims 135-144, wherein the polymeric material is characterized by an elongation at break of greater than 10%, an elongation at break of greater than 20%, an elongation at break of greater than 30%, an elongation at break of 5% to 250%, an elongation at break of 20% to 250%, or an elongation at break value of 40% to 250% before and after 24 hours in a humid environment at 37 ℃.

146. The polymeric material of any of claims 135-145, wherein the polymeric material is characterized by a storage modulus of 0.1MPa to 4000MPa, a storage modulus of 300MPa to 3000MPa, or a storage modulus of 750MPa to 3000MPa after 24 hours in a humid environment at 37 ℃.

147. The polymeric material of any of claims 135-146, wherein after 24 hours in a humid environment at 37 ℃, the polymeric material has a flexural stress and/or flexural modulus of 400MPa or greater, 300MPa or greater, 200MPa or greater, 180MPa or greater, 160MPa or greater, 120MPa or greater, 100MPa or greater, 80MPa or greater, 70MPa or greater, 60MPa or greater.

148. The polymeric material of any of claims 135-147, wherein at least 40%, 50%, 60%, or 70% of visible light passes through the polymeric material after 24 hours in a humid environment at 37 ℃.

149. The polymeric material of any of claims 135-148, wherein the polymeric material is biocompatible, bioinert, or a combination thereof.

150. The polymeric material of any of claims 135-149, wherein the polymeric material is capable of being 3D printed.

151. A polymeric film comprising the polymeric material of any one of claims 135-150.

152. The polymer film of claim 151, wherein the film has a thickness of at least 100 μιη and no greater than 3mm.

153. An apparatus comprising the polymeric material of any one of claims 135-150 or the polymeric film of any one of claims 151-152.

154. A medical device comprising the polymeric material of any one of claims 135-150 or the polymeric film of any one of claims 151-152.

155. A medical device comprising a polymer, wherein the polymer comprises a monomer of formula (VII):

(VII)

wherein:

x is N or CR ⁵⁹ ；

R ¹ Is H, substituted or unsubstituted C _1-3 Alkyl, or halogen;

R ⁴⁸ 、R ⁴⁹ and R is ⁵⁰ Each independently is H, nitrile, substituted or unsubstituted C _1-6 Alkyl cyanide, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-Y ¹ -(CH ₂ ) _a -R ⁶⁰ The method comprises the steps of carrying out a first treatment on the surface of the Or R is ⁴⁸ And R is ⁴⁹ Taken together form a 4-, 5-, 6-, 7-or 8-membered ring, said 4-, 5-, 6-, 7-or 8-membered ring being selected from substituted or unsubstituted rings (C _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl;

R ⁵¹ 、R ⁵² 、R ⁵³ and R is ⁵⁴ Each independently is H, substituted or unsubstituted C _4-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-Y ² -(CH ₂ ) _b -R ⁶¹ ；

R ⁵⁵ 、R ⁵⁶ 、R ⁵⁷ And R is ⁵⁸ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-Y ³ -(CH ₂ ) _c -R ⁶² ；

R ⁵⁹ Is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-Y ⁴ -(CH ₂ ) _d -R ⁶³ ；

Y ¹ 、Y ² 、Y ³ And Y ⁴ Each independently is a bond, O or S;

156. A medical device comprising a polymer, wherein the polymer comprises a monomer of formula (VII):

(VII)

wherein:

x is N or CH;

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl, or halogen;

R ⁴⁸ 、R ⁴⁹ and R is ⁵⁰ Each independently is H, nitrile, substituted or unsubstituted C _1-6 Alkyl cyanide, substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _3-6 Heteroalkyl, substituted or unsubstituted C _3-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-Y ¹ -(CH ₂ ) _a -R ⁶⁰ The method comprises the steps of carrying out a first treatment on the surface of the Or R is ⁴⁸ And R is ⁴⁹ Taken together form a 4-, 5-, 6-, 7-or 8-membered ring, said 4-, 5-, 6-, 7-or 8-membered ring being selected from substituted or unsubstituted rings (C _4-8 ) Alkyl, substituted or unsubstituted ring (C) _4-8 ) Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, wherein R ⁴⁸ 、R ⁴⁹ And R is ⁵⁰ At most one of (a) is H;

R ⁵¹ 、R ⁵² 、R ⁵³ and R is ⁵⁴ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-Y ² -(CH ₂ ) _b -R ⁶¹ ；

Y ¹ 、Y ² 、Y ³ And Y ⁴ Each independently is a bond, O or S;

a. b, c and d are each independently integers from 0 to 6;

R ⁶⁰ and R is ⁶² Each independently is a substituted or unsubstituted ring (C _3-8 ) Alkyl, substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl; and is also provided with

157. A medical device comprising a polymer, wherein the polymer comprises a monomer of formula (VIII):

(VIII)

wherein:

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl, or halogen;

R ⁶⁸ 、R ⁶⁹ 、R ⁷⁰ and R is ⁷¹ Each independently is H, substituted or unsubstituted C _3-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ² -(CH ₂ ) _b -R ⁷⁵ Wherein R is ⁶⁸ 、R ⁶⁹ 、R ⁷⁰ And R is ⁷¹ At most two of (a) are H;

R ⁷² and R is ⁷³ Each independently is H, substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted C _1-6 Alkoxy, substituted or unsubstituted C _1-6 Thioalkoxy, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted C _1-6 Carboxyl, or-X ³ -(CH ₂ ) _c -R ⁷⁶ ；

X ¹ 、X ² And X ³ Each independently is a bond, O or S;

158. The medical instrument of any one of claims 155-157, wherein R ¹ Or R is ⁴⁸ -R ⁷⁶ One or more of them being halogen, OH, NH ₂ 、NH(C _1-6 Alkyl), N (C) _1-6 Alkyl) (C) _1-6 Alkyl) or C _1-3 Alkyl substitution.

159. The medical instrument of any of claims 155-158, wherein R ¹ Or R is ⁴⁸ -R ⁷⁶ One or more of them being halogen, OH or NH ₂ And (3) substitution.

160. The medical instrument of any of claims 155-159, wherein R ¹ Or R is ⁴⁸ -R ⁷⁶ Is substituted with OH.

161. The medical instrument of any one of claims 155-160, wherein the medical instrument is a dental instrument.

162. The medical instrument of claim 161, wherein the dental instrument is a dental appliance, a dental expander, or a dental spacer.

163. The medical instrument of any one of claims 155-162, wherein the medical instrument is producible by 3D printing.

164. A method of synthesizing a polymerizable monomer according to any one of formulas (I) - (VI) and (IX), the method comprising isolating the polymerizable monomer in a chemical yield of at least 25%.

165. A method of forming a polymeric material, the method comprising:

providing the photocurable resin of any one of claims 107-134;

exposing the photocurable resin to a light source; and

curing the photocurable resin to form the polymeric material.

166. The method of claim 165, further comprising inducing phase separation during photocuring.

167. The method of claim 166, wherein inducing phase separation comprises generating one or more polymer phases in the polymer material during photocuring.

168. The method of claim 167, wherein at least one of the one or more polymer phases is a glass transition temperature (T _g ) An amorphous phase of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃ or at least 110 ℃.

169. The method of claim 168, wherein at least 25%, 50%, or 75% of the polymer phase produced during the photocuring has a glass transition temperature (T) of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 °c _g )。

170. The method of claim 168, wherein the glass transition temperature (T _g ) At least one amorphous phase that is at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃ comprises a polymerizable monomer incorporated into its polymer structure.

171. The method of claim 167, wherein at least one of the one or more polymer phases is a crystalline phase comprising a crystalline polymer material.

172. The method of claim 171, wherein the crystalline polymeric material has a melting point of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃.

173. The method of any of claims 165-172, wherein at least one of the one or more polymer phases is three-dimensional and has at least one dimension that is less than 1000 μιη, less than 500 μιη, less than 250 μιη, or less than 200 μιη in length.

174. The method of any of claims 165-173, wherein the polymeric material is characterized by one or more of:

a storage modulus greater than or equal to 200 MPa;

a residual flexural modulus after 24 hours in a humid environment at 37 ℃ of greater than or equal to 1.5M Pa;

elongation at break greater than or equal to 5% before and after 24 hours in a humid environment at 37 ℃;

the water absorption is less than 25wt% when measured after 24 hours in a humid environment at 37 ℃; and is also provided with

At least 30% of visible light is transmitted through the polymeric material after 24 hours in a humid environment at 37 ℃.

175. The method of any of claims 165-174, further comprising manufacturing a medical device from the polymeric material.

176. The method of claim 175, wherein the medical instrument is a dental instrument.

177. The method of claim 176, wherein the dental appliance is a dental appliance, a dental dilator, or a dental spacer.

178. A method of repositioning teeth of a patient, the method comprising:

generating a treatment plan for the patient, the plan including a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial tooth arrangement toward a final tooth arrangement;

producing a dental appliance according to claim 89 or comprising a polymeric material according to any one of claims 66-81; and

the dental appliance is used to move at least one tooth of the patient as planned to face the intermediate tooth arrangement or the final tooth arrangement.

179. The method of claim 178, wherein producing the dental appliance comprises 3D printing of the dental appliance.

180. The method of claim 178 or 179, further comprising tracking progress of the patient's teeth along the treatment path after the dental appliance is applied to the patient, the tracking comprising comparing a current arrangement of the patient's teeth to a planned arrangement of the patient's teeth.

181. The method of any of claims 178-180, wherein after 2 weeks of treatment, greater than 60% of the patient's teeth conform to the treatment plan.

182. The method of any of claims 178-181, wherein the dental appliance has a retained repositioning force on at least one tooth of the patient after 2 days that is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% of the repositioning force originally provided to the at least one tooth of the patient.