CN114044888A

CN114044888A - Hydrolytically degradable polymers, method for the production thereof and use thereof

Info

Publication number: CN114044888A
Application number: CN202111487976.2A
Authority: CN
Inventors: 张小琴; 董云霄; 胡晗; 樊林; 王静刚; 朱锦
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2021-12-07
Filing date: 2021-12-07
Publication date: 2022-02-15
Anticipated expiration: 2041-12-07
Also published as: CN114044888B

Abstract

The invention discloses a polymer capable of being hydrolyzed and degraded, a preparation method and application thereof. The preparation method comprises the following steps: the carbonate diester, aromatic dibasic acid and/or ester thereof, diglycolic acid and/or ester thereof and dihydric alcohol are copolymerized to prepare the polymer capable of being hydrolyzed and degraded, wherein the dihydric alcohol comprises cyclic dihydric alcohol or the combination of the cyclic dihydric alcohol and aliphatic dihydric alcohol. The ether bond contained in the diglycolic acid molecular structure selected by the invention has good hydrophilic performance, and the hydrophilicity of the polyester can be obviously improved by introducing the diglycolic acid into the molecular chain segment of the polyester, so that the polyester can be subjected to biodegradation and hydrolytic degradation; the invention introduces carbonate bonds into the copolymer, can also improve the gas barrier property of the copolymer, and improves the ester bond density of polymer molecular chain segments, which is beneficial to the degradation process, thereby improving the degradation rate. The invention also introduces cyclic diol into the copolymer, which can improve the mechanical property and heat resistance of the polymer.

Description

Hydrolytically degradable polymers, method for the production thereof and use thereof

Technical Field

The invention relates to a polymer, in particular to a polymer capable of being hydrolyzed and degraded, a preparation method and application thereof, and belongs to the technical field of high molecular materials.

Background

Common degradable polyesters such as polyglycolic acid (PGA), polylactic acid (PLA), Polycaprolactone (PCL), Polyhydroxyalkanoate (PHA), and the like all belong to aliphatic polyesters, and although the degradation performance of these polyesters is good, the mechanical properties, gas barrier properties, heat resistance, and the like are poor. Polybutylene terephthalate adipate (PBAT) is also a well-known degradable polyester, and the structure of the PBAT not only contains a flexible aliphatic chain segment, but also contains a rigid aromatic chain segment, so that the mechanical property, the gas barrier property and the heat resistance of the PBAT are all improved compared with those of the aliphatic degradable polyester, but the PBAT can be biodegraded only under the violent conditions of enzyme, bacteria and the like, and cannot be hydrolytically degraded under the mild aqueous condition.

Disclosure of Invention

The invention mainly aims to provide a polymer capable of being hydrolyzed and degraded, a preparation method and application thereof, so as to overcome the defect that the existing degradable polyester can be biodegraded under severe conditions of enzyme, bacteria and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

some embodiments of the present invention provide a method of preparing a hydrolytically degradable polymer comprising:

(1) carrying out an ester exchange reaction on a first mixture reaction system containing a carbonic diester, a dihydric alcohol and a first ester exchange catalyst at 90-220 ℃ in a protective atmosphere, reducing the temperature to room temperature after the ester exchange reaction is finished, and then maintaining the reaction system in the protective atmosphere to form a first intermediate product;

(2) carrying out esterification or ester exchange reaction on a second mixed reaction system containing aromatic dibasic acid and/or an ester thereof, diglycolic acid and/or an ester thereof, dihydric alcohol and a second esterification or ester exchange catalyst at 140-250 ℃ in a protective atmosphere, reducing the temperature to room temperature after the reaction is finished, and then keeping the reaction in the protective atmosphere to obtain a second intermediate product;

(3) vacuumizing a third mixed reaction system containing the first intermediate product, the second intermediate product, a polycondensation catalyst and a stabilizer to below 50Pa, and gradually heating to 210-300 ℃ to perform polycondensation reaction to obtain a polymer capable of being hydrolyzed and degraded;

alternatively, the preparation method comprises:

(i) carrying out an ester exchange reaction on a first mixture reaction system containing a carbonic diester, a dihydric alcohol and a first ester exchange catalyst at 90-220 ℃ in a protective atmosphere, reducing the temperature to room temperature after the ester exchange reaction is finished, and then maintaining the reaction system in the protective atmosphere to form a first intermediate product;

(ii) carrying out esterification or ester exchange reaction on a fourth mixed reaction system containing aromatic dibasic acid and/or an ester thereof, diglycolic acid and/or an ester thereof, dihydric alcohol, a first intermediate product and a second esterification or ester exchange catalyst at 140-250 ℃ in a protective atmosphere, reducing the temperature to room temperature after the esterification or ester exchange reaction is finished, and then keeping the reaction system in the protective atmosphere to obtain a third intermediate product;

(iii) vacuumizing a fifth mixed reaction system containing a third intermediate product, a polycondensation catalyst and a stabilizer to below 50Pa, and gradually heating to 210-300 ℃ to perform polycondensation reaction to obtain a polymer capable of being hydrolyzed and degraded;

wherein, the aromatic dibasic acid and/or the ester thereof comprises one or the combination of more than two of terephthalic acid and/or the ester thereof, isophthalic acid and/or the ester thereof, phthalic acid and/or the ester thereof, and naphthalenedicarboxylic acid and/or the ester thereof;

the first dihydric alcohol and the second dihydric alcohol both comprise cyclic dihydric alcohol, or the combination of the cyclic dihydric alcohol and aliphatic dihydric alcohol, and the cyclic dihydric alcohol comprises any one or the combination of more than two of tricyclodecane dimethanol, tricyclodecane diol and tetracyclo-diol; the aliphatic diol comprises any one or the combination of more than two of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, octanediol and decanediol.

Some embodiments of the present invention also provide hydrolytically degradable polymers synthesized by the foregoing methods of preparation, which polymers are both biodegradable and hydrolytically degradable.

Some embodiments of the present invention also provide a composition for synthesizing a hydrolytically degradable polymer, comprising:

component (a) comprising an aromatic dibasic acid and/or an esterified product thereof;

component (b) comprising diglycolic acid and/or an esterified product thereof;

component (c), comprising a carbonic acid diester;

component (d) comprising a glycol;

the carbonic diester comprises any one or the combination of more than two of dimethyl carbonate, diethyl carbonate and diphenyl carbonate;

the dihydric alcohol comprises cyclic dihydric alcohol or the combination of the cyclic dihydric alcohol and aliphatic dihydric alcohol, and the cyclic dihydric alcohol comprises any one or the combination of more than two of tricyclodecane dimethanol, tricyclodecane diol and tetracyclic diol; the aliphatic diol comprises any one or the combination of more than two of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, octanediol and decanediol.

Some embodiments of the invention also provide uses of the hydrolytically degradable polymers, for example in the field of making packaging materials (e.g., packaging bags, packaging films, etc.), containers (e.g., shopping bags), geomembranes, structural members, body implants, and the like.

Compared with the prior art, the invention has the beneficial effects that:

(1) the diglycolic acid selected by the invention is derived from biomass raw materials and can be prepared in a green way, and the ether bond contained in the molecular structure of the diglycolic acid has good hydrophilic property, so that the hydrophilicity of the polyester can be obviously improved by introducing the diglycolic acid into the molecular chain segment of the polyester, and the polyester can be subjected to biodegradation and hydrolytic degradation;

(2) the invention introduces carbonate into the copolymer, so that the content of the aliphatic chain in the copolymer can be reduced, and the lower tensile modulus, tensile strength, glass transition temperature (Tg) and melting point (Tm) caused by the existence of the aliphatic chain can be compensated. In addition, the introduction of the carbonate can also improve the gas barrier property of the copolymer, and improve the ester bond density of the polymer molecular chain segment, which is beneficial to the degradation process, thereby improving the degradation rate;

(3) the invention also introduces aliphatic diol or cyclic diol into the copolymer, different cyclic diols can play different roles, and different diols can be introduced according to requirements to adjust the mechanical property, the heat resistance and the like of the copolymer so as to obtain a final polymer product with excellent comprehensive properties.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a stress-strain plot of a hydrolytically degradable polymer prepared according to example 1 of the present invention;

FIG. 2 is a DSC plot of a hydrolytically degradable polymer prepared according to example 1 of the present invention.

Detailed Description

As described above, in view of the defects of the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose a technical solution of the present invention. The present invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.

The technical solution, its implementation and principles, etc. will be further explained as follows.

One aspect of the embodiments of the present invention provides a method for preparing a hydrolytically degradable polymer, comprising:

(3) and vacuumizing a third mixed reaction system containing the first intermediate product, the second intermediate product, the polycondensation catalyst and the stabilizer to below 50Pa, and gradually heating to 210-300 ℃ to perform polycondensation reaction to obtain the polymer capable of being hydrolyzed and degraded.

Another aspect of an embodiment of the present invention provides a method for preparing the hydrolytically degradable polymer, comprising:

(iii) and vacuumizing a fifth mixed reaction system containing the third intermediate product, the polycondensation catalyst and the stabilizer to below 50Pa, and gradually heating to 210-300 ℃ to perform polycondensation reaction to obtain the polymer capable of being hydrolyzed and degraded.

The diglycolic acid selected by the invention is derived from biomass raw materials and can be prepared in a green way, and the hydrophilicity of the polyester can be obviously improved by introducing the diglycolic acid into a molecular chain segment of the copolyester because ether bonds contained in the molecular structure of the diglycolic acid have good hydrophilic performance. Therefore, the diglycolic acid-based polyester can be subjected to biodegradation and hydrolytic degradation without adding other substances such as enzyme, bacteria and the like.

The preparation mechanism of the invention is as follows: the diglycolic acid is introduced into the molecular chain segment of the copolyester, so that the hydrophilicity of the polyester can be obviously improved, and the carbonate bond (-OCOO-) is introduced into the copolymer, so that the content of the aliphatic chain in the copolymer can be reduced, and the lower tensile modulus, tensile strength, glass transition temperature (Tg) and melting point (Tm) caused by the existence of the aliphatic chain are compensated. In addition, the introduction of the carbonate can also improve the gas barrier property of the copolymer, and improve the ester bond density of polymer molecular chain segments, which is beneficial to the degradation process, thereby improving the degradation rate. In addition, different dihydric alcohols can play different roles, and different dihydric alcohols can be introduced according to requirements to adjust the mechanical property, the heat resistance and the like of the copolymer so as to obtain a final polymer product with excellent comprehensive properties.

In some embodiments, the aromatic dibasic acid and/or the ester thereof includes any one or a combination of two or more of terephthalic acid and/or an ester thereof, isophthalic acid and/or an ester thereof, phthalic acid and/or an ester thereof, and naphthalenedicarboxylic acid and/or an ester thereof, but is not limited thereto.

In some more specific embodiments, the aromatic dibasic acid and/or the ester thereof includes any one or two or more structures represented by the following formulae:

wherein R is a hydrogen atom or a carbon chain with the carbon number not more than 4.

In some embodiments, the diol comprises a cyclic diol, or a combination of a cyclic diol and a fatty diol.

Further, the aliphatic diol includes any one or a combination of two or more of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, 2-methyl-1, 3-propanediol, neopentyl glycol, octanediol, decanediol, and the like, but is not limited thereto.

In some embodiments, the cyclic diol includes any one or a combination of two of tricyclodecane dimethanol, tricyclodecane diol, tetracyclic diol, and the like, but is not limited thereto, and the specific structure may be as shown in the following formula:

the invention introduces the cyclic diol or the combination of the aliphatic diol and the cyclic diol into the copolymer, and different cyclic diols can play different roles, for example, the tricyclodecanedimethanol and the tricyclodecanediol can improve the heat resistance of the polymer by improving the rigidity of a polymer chain segment, and the tetracyclodiol contains four aliphatic rings, has more rings than the tricyclodecanedimethanol and the tricyclodecanediol, and can better realize the adjustment of the comprehensive properties of the polymer, such as heat resistance, crystallization property, mechanical property and the like. Specifically, different cyclic diols can be introduced according to the needs, and the mechanical properties, heat resistance and the like of the copolymer can be adjusted to obtain a final polymer product with excellent comprehensive properties.

In some embodiments, the carbonic acid diester includes any one or a combination of two or more of dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like, but is not limited thereto. The carbonic acid diester selected by the invention has low price, and can obviously reduce the production cost by introducing the carbonic acid diester into the copolymer structure in a copolymerization mode.

In some embodiments, in step (1) or step (i), the molar weight ratio of the carbonic acid diester to the glycol is 1: 0.2 to 3.0.

In some embodiments, the first transesterification catalyst is added in an amount of 0.01 to 0.5% of the theoretical mass of the first intermediate product.

In some embodiments, in step (2) or step (ii), the molar ratio of the combination of the aromatic dibasic acid and/or the ester thereof and the diglycolic acid and/or the ester thereof to the glycol is 1: 1.2 to 3.0.

In some embodiments, the second esterification or transesterification catalyst is added in an amount of 0.01 to 0.5% of the theoretical mass of the second intermediate product or the third intermediate product.

Further, in the step (ii), the mass ratio of the first intermediate product to the total mass of the aromatic dibasic acid and/or the ester thereof, the diglycolic acid and/or the ester thereof and the dihydric alcohol reacted in the polymer is 1-80: 99-20.

In some embodiments, in step (3), the mass ratio of the first intermediate product to the second intermediate product is 1-80: 99-20.

In some embodiments, in step (3) or step (iii), the mass of the polycondensation catalyst added is 0.01 to 0.5% of the theoretical mass of the hydrolytically degradable polymer, and the mass of the stabilizer is 0.01 to 0.5% of the theoretical mass of the hydrolytically degradable polymer.

In some embodiments, the method of making comprises: and carrying out ester exchange reaction on the first mixed reaction system at 90-220 ℃ for 4.0-36.0 h in a protective atmosphere, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the reaction is finished, and then keeping the reaction system in the protective atmosphere to form a first intermediate product.

In some embodiments, the method of making comprises: in the step (2), the second mixed reaction system is subjected to esterification or ester exchange reaction for 1.5-6.0 h at 140-250 ℃ in a protective atmosphere, the temperature is reduced to room temperature at a cooling rate of 1-50 ℃/min after the esterification or ester exchange reaction is finished, and then the second mixed reaction system is maintained in the protective atmosphere to form a second intermediate product.

In some embodiments, the method of making comprises: in the step (3), the third mixed reaction system is vacuumized to below 50Pa, and then gradually heated to 210-300 ℃ to carry out polycondensation reaction for 2.0-10.0 h, so as to obtain the polymer capable of being hydrolyzed and degraded.

In some embodiments, the method of making comprises: in the step (ii), the fourth mixed reaction system is subjected to esterification or ester exchange reaction for 1.5-6.0 h at 140-250 ℃ in a protective atmosphere, and the temperature is reduced to room temperature at a cooling rate of 1-50 ℃/min after the reaction is finished, and then the reaction is maintained in the protective atmosphere to form a third intermediate product.

In some embodiments, the method of making comprises: in the step (iii), the fifth mixed reaction system is vacuumized to below 50Pa, and then gradually heated to 210-300 ℃ to carry out polycondensation reaction for 2.0-10.0 h, so as to obtain the polymer capable of being hydrolyzed and degraded.

As a more preferable embodiment, each of the step (1), the step (2), the step (i), and the step (ii) further includes: and after the reaction is finished, reducing the temperature to room temperature, and then keeping the temperature in a protective atmosphere for 1.0-5.0 h. Further, step (3) and step (iii) each further include: starting to vacuumize to below 50Pa at room temperature, then gradually heating to the polycondensation temperature of 210-300 ℃ to perform polycondensation reaction, and continuously vacuumizing to keep the vacuum not to exceed 50Pa in the whole polycondensation process. According to the preparation method, after the esterification or ester exchange reaction is finished, the temperature is reduced to room temperature under the action of protective atmosphere and is kept for a period of time, and the room temperature is vacuumized to below 50Pa and then is heated to the polycondensation temperature, compared with the traditional process without a cooling step and high-temperature vacuumization, the cooling rate is 1-50 ℃/min to be reduced to the room temperature, the lower the cooling rate is, the more perfect the crystallization of the product can be, in addition, the side reactions of high-temperature oxidation and the like of the product can be avoided, and the colorless or white high-quality product can be obtained.

In some more specific embodiments, the preparation method of the hydrolytically degradable polymer specifically comprises the following steps:

(1) under the protection of nitrogen or inert atmosphere, uniformly mixing carbonic acid diester, dihydric alcohol and a first ester exchange catalyst to form a first mixture reaction system, carrying out ester exchange reaction for 4.0-36.0 hours at 90-220 ℃, reducing the temperature to room temperature at the rate of 1-50 ℃/min after finishing the reaction, and keeping the temperature for 1.0-5.0 hours under the protection of nitrogen or inert atmosphere to obtain a first intermediate product;

(2) under the protection of nitrogen or inert atmosphere, uniformly mixing aromatic dibasic acid and/or an esterified product thereof, diglycolic acid and/or an esterified product thereof, dihydric alcohol and a second esterification or ester exchange catalyst to form a second mixed reaction system, carrying out esterification or ester exchange reaction for 1.5-6.0 hours at 140-250 ℃, reducing the temperature to room temperature at the cooling rate of 1-50 ℃/min after the reaction is finished, and keeping the temperature for 1.0-5.0 hours under the protection of nitrogen or inert atmosphere to obtain a second intermediate product;

(3) uniformly mixing the first intermediate product, the second intermediate product, a polycondensation catalyst and a stabilizer to form a third mixed reaction system, vacuumizing to below 50Pa, gradually heating to 210-300 ℃ to perform polycondensation for 2.0-10.0 hours, and obtaining the polymer capable of being hydrolyzed and degraded.

(i) under the protection of nitrogen or inert atmosphere, uniformly mixing carbonic acid diester, dihydric alcohol and a first ester exchange catalyst to form a first mixture reaction system, carrying out ester exchange reaction for 4.0-36.0 hours at 90-220 ℃, reducing the temperature to room temperature at the rate of 1-50 ℃/min after finishing the reaction, and keeping the temperature for 1.0-5.0 hours under the protection of nitrogen or inert atmosphere to obtain a first intermediate product;

(ii) uniformly mixing aromatic dibasic acid and/or an esterified product thereof, diglycolic acid and/or an esterified product thereof, dihydric alcohol, a first intermediate product and a second esterification or transesterification catalyst under the protection of nitrogen or inert atmosphere to form a fourth mixture reaction system, carrying out esterification or transesterification reaction for 1.5-6.0 hours at 140-250 ℃, reducing the temperature to room temperature at the cooling rate of 1-50 ℃/min after the reaction is finished, and keeping the temperature for 1.0-5.0 hours under the protection of nitrogen or inert atmosphere to obtain a third intermediate product;

(iii) and uniformly mixing the third intermediate product, the polycondensation catalyst and the stabilizer to form a fifth mixed reaction system, vacuumizing to below 50Pa, gradually heating to 210-300 ℃ to perform polycondensation for 2.0-10.0 hours, and obtaining the polymer capable of being hydrolyzed and degraded.

The diol used in step (1) and step (2) may be the same type or different types, and is not particularly limited.

In some embodiments, the first transesterification catalyst is selected from a combination of one or more of a titanium-based catalyst, a tin-based catalyst, a germanium-based catalyst, and the like, but is not limited thereto.

Further, the titanium-based catalyst includes any one or a combination of two or more of tetrabutyl titanate, isopropyl titanate, titanium dioxide, an inorganic supported titanium catalyst, and the like, but is not limited thereto.

Further, the tin-based catalyst includes any one or a combination of two or more of dibutyltin oxide, stannous isooctanoate, monobutyl triisooctanoate, dioctyltin oxide, and the like, but is not limited thereto.

Further, the germanium-based catalyst includes any one or a combination of two or more of germanium dioxide, germanium acetate, germanium tetraethoxide, and the like, but is not limited thereto.

In some embodiments, the second esterification or transesterification catalyst is selected from a combination of one or more of a titanium-based catalyst, a tin-based catalyst, a germanium-based catalyst, and the like, but is not limited thereto.

In some embodiments, the polycondensation catalyst is selected from the group consisting of one or more combinations of titanium-based catalysts, tin-based catalysts, germanium-based catalysts, and the like, but is not limited thereto.

In some embodiments, the stabilizer is selected from the group consisting of phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium dihydrogen phosphate, and the like, without limitation.

Another aspect of an embodiment of the present invention provides a hydrolytically degradable polymer that may be formed by the method of any of the preceding embodiments.

Yet another aspect of an embodiment of the present invention provides a composition for preparing the hydrolytically degradable polymer of the preceding embodiments, comprising:

component (b) comprising diglycolic acid and/or an esterified product thereof;

component (c), comprising a carbonic acid diester;

component (d) comprising a glycol;

the first dihydric alcohol and the second dihydric alcohol both comprise cyclic dihydric alcohol or the combination of the cyclic dihydric alcohol and aliphatic dihydric alcohol, and the cyclic dihydric alcohol comprises any one or the combination of more than two of tricyclodecane dimethanol, tricyclodecane diol and tetracyclodiol; the aliphatic diol comprises any one or the combination of more than two of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, octanediol and decanediol.

Further, the terephthalate may be dimethyl terephthalate, but is not limited thereto.

Further, the diglycolic acid and/or the esterified product thereof may be dimethyl diglycolate, but is not limited thereto.

Another aspect of embodiments of the invention also provides uses of the hydrolytically degradable polymers, for example in the field of making packaging materials (e.g., packaging bags, packaging films, etc.), containers (e.g., shopping bags), mulching films, structural members, body implants, and the like.

The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.

In the following examples, thermal transition performance tests were carried out using a differential scanning calorimeter (Mettler Toledo DSC), N₂The temperature range of the atmosphere is-100-300 ℃, and the heating rate is 10 ℃/min.

In the following examples, mechanical properties were measured in a Zwick i 1kN type universal material tester, and the specimens were 20.0mm in length, 2.0mm in width, 1.0mm in thickness and 20mm/min in tensile speed.

In the following examples, Labthink VAC-V2 was used to determine the barrier properties for oxygen and carbon dioxide, respectively as CO₂And O₂Is used as air source, and is tested under the conditions of 23 deg.C and 50% RH, sample size phi is 97mm, and permeation area is 38.5cm²。

In the following examples, hydrolytic degradation and biodegradation tests were carried out using a phosphate buffer solution and a phosphate buffer solution containing 0.2mg/ml of lipase as degradation solvents, respectively, at a constant temperature of 37 ℃ and samples 20mm in length, 20mm in width and 0.5mm in thickness.

Example 1

315.3g (3.5mol) of dimethyl carbonate, 19.6g (0.1mol) of tricyclodecane dimethanol, 54.1g (0.6mol) of 1, 4-butanediol and 0.14g of tetrabutyl titanate are put into a reactor, the temperature is gradually increased to 90 ℃ under the protection of nitrogen, the reaction is carried out for 36.0h, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 10 ℃/min under the protection of nitrogen, and the temperature is maintained for 3.0h, thus obtaining the poly-tricyclodecane dimethanol butanediol ester oligomer.

Putting 37.4g (0.225mol) of terephthalic acid, 36.9g (0.275mol) of diglycolic acid, 19.6g (0.1mol) of tricyclodecane dimethanol, 72.1g (0.8mol) of 1, 4-butanediol and 0.1g of tetrabutyl titanate into a reactor, gradually heating to 250 ℃ under the protection of nitrogen, reacting for 4.0h, then closing the heating, cooling to room temperature at the cooling rate of 10 ℃/min under the protection of nitrogen, and keeping for 2.0h to obtain the tricyclodecane dimethanol butanediol terephthalate.

Putting 15g of poly-tricyclodecane dimethanol butylene carbonate oligomer, 35g of poly-tricyclodecane dimethanol diglycol terephthalate oligomer, 0.05g of tetrabutyl titanate and 0.1g of triphenyl phosphate into a reactor, vacuumizing to 30Pa under the condition of room temperature, gradually heating to 255 ℃, continuously vacuumizing to maintain the vacuum degree of a reaction system to be lower than 30Pa, reacting for 6.0h, and obtaining the polymer capable of being hydrolyzed and degraded after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 188.5MPa, a tensile strength of 21.1MPa, an elongation at break of 446%, a glass transition temperature of 26.2 ℃ and CO₂Permeability coefficient of 5.95barrer, O₂The permeability coefficient is 5.81barrer, and the biodegradable film can be both biodegraded and hydrolytically degraded.

Of the hydrolytically degradable Polymer obtained in this example¹An H-NMR spectrum showed that the peak at 7.90ppm was an H peak (4H) on the benzene ring, the peaks at 4.30ppm, 4.24ppm and 4.08ppm were an H peak (4H) on the methylene group near the ester bond in 1, 4-butanediol, the peak at 4.14ppm was an H peak (4H) on diglycolic acid, the peak at 3.09-3.25 ppm was an H peak (4H) on tricyclodecanedimethanol linked to the hydroxyl group, the peak at 0.77-2.35 ppm was an H peak (14H) on the aliphatic ring of tricyclodecanedimethanol, and the peaks at 1.83ppm, 1.70ppm and 1.56ppm were an H peak (4H) on the middle two methylene groups of 1, 4-butanediol.

The stress-strain curve of the hydrolytically degradable polymer obtained in this example is shown in FIG. 1.

The DSC curve of the hydrolytically degradable polymer obtained in this example is shown in FIG. 2.

Example 2

191.3g (2.1mol) of dimethyl carbonate, 19.6g (0.1mol) of tricyclodecane dimethanol, 54.1g (0.6mol) of 1, 4-butanediol and 0.08g of tetrabutyl titanate are put into a reactor, the temperature is gradually increased to 90 ℃ under the protection of nitrogen, the reaction is carried out for 32.0h, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 15 ℃/min under the protection of nitrogen, and the temperature is maintained for 1.0 h, thus obtaining the poly-tricyclodecane dimethanol butanediol ester oligomer.

41.5g (0.25mol) of terephthalic acid, 33.5g (0.25mol) of diglycolic acid, 19.6g (0.1mol) of tricyclodecanedimethanol, 72.1g (0.8mol) of 1, 4-butanediol and 0.1g of tetrabutyl titanate are put into a reactor, gradually heated to 240 ℃ under the protection of nitrogen, reacted for 4.0h, then the heating is closed, and the temperature is reduced to room temperature at the cooling rate of 15 ℃/min under the protection of nitrogen and kept for 4.0h, thus obtaining the tricyclodecanedimethanol butanediol terephthalate oligomer.

Putting 40g of poly-tricyclodecane dimethanol butanediol oligomer, 20g of poly-tricyclodecane dimethanol butanediol diglycolate butanediol oligomer, 0.05g of tetrabutyl titanate and 0.05g of triphenyl phosphate into a reactor, vacuumizing to 20Pa at room temperature, gradually heating to 260 ℃, continuously vacuumizing to maintain the vacuum degree of a reaction system to be lower than 20Pa, reacting for 5.0h, and obtaining the polymer capable of being hydrolyzed and degraded after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 430.1MPa, a tensile strength of 29.9MPa, an elongation at break of 150%, a glass transition temperature of 38.2 ℃ and CO₂Permeability coefficient of 1.64barrer, O₂The permeability coefficient is 2.47barrer, and the biodegradable film can be biodegraded and can also be hydrolytically degraded.

Example 3

212.2g (2.33mol) of dimethyl carbonate, 117.8g (0.6mol) of tricyclodecanediol, 9.0g (0.1mol) of 1, 4-butanediol and 0.16g of tetrabutyl titanate are put into a reactor, the temperature is gradually increased to 90 ℃ under the protection of nitrogen, the reaction is carried out for 36.0h, then the heating is closed, the temperature is reduced to room temperature at the cooling rate of 20 ℃/min under the protection of nitrogen, and the temperature is kept for 5.0h, thus obtaining the poly-tricyclodecanediol butanediol ester oligomer.

Putting 48.5g (0.25mol) of dimethyl terephthalate, 33.5g (0.25mol) of diglycolic acid, 58.9g (0.3mol) of tricyclodecanediol, 54.1g (0.6mol) of 1, 4-butanediol and 0.20g of tetrabutyl titanate into a reactor, gradually heating to 170 ℃ under the protection of nitrogen, reacting for 5.5 hours, then closing the heating, cooling to room temperature at the cooling rate of 20 ℃/min under the protection of nitrogen, keeping for 2.0 hours, and obtaining the tricyclodecanediol butanediol terephthalate oligomer after the reaction.

10g of poly-tricyclodecanediol butylene terephthalate oligomer, 90g of poly-tricyclodecanediol butylene terephthalate diglycolate oligomer, 0.01g of tetrabutyl titanate and 0.25g of triphenyl phosphate are put into a reactor, the reactor is vacuumized to 25Pa at room temperature, the temperature is gradually raised to 210 ℃, the vacuum degree of the reaction system is kept to be lower than 25Pa by continuous vacuum pumping, the reaction lasts for 10.0h, and the polymer capable of being hydrolyzed and degraded is obtained after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 357.2MPa, a tensile strength of 23.0MPa, an elongation at break of 190%, a glass transition temperature of 34.6 ℃ and a CO content₂Permeability coefficient of 5.25barrer, O₂The permeability coefficient is 4.46barrer, and the biodegradable plastic can be both biodegraded and hydrolytically degraded.

Example 4

191.3g (2.1mol) of dimethyl carbonate, 98.1g (0.5mol) of tricyclodecanediol, 18.0g (0.2mol) of 1, 4-butanediol and 0.41g of tetrabutyl titanate are put into a reactor, the temperature is gradually increased to 90 ℃ under the protection of nitrogen, the reaction is carried out for 30.0h, then the heating is closed, the temperature is reduced to room temperature at the cooling rate of 5 ℃/min under the protection of nitrogen, and the temperature is maintained for 4.0h, thus obtaining the poly-tricyclodecanediol butanediol ester oligomer.

Putting 48.5g (0.25mol) of dimethyl terephthalate, 40.5g (0.25mol) of dimethyl diglycolate, 78.5g (0.4mol) of tricyclodecanediol, 52.1g (0.5mol) of neopentyl glycol and 0.16g of tetrabutyl titanate into a reactor, gradually raising the temperature to 150 ℃ under the protection of nitrogen, reacting for 6.0h, then closing the heating, reducing the temperature to room temperature at the cooling rate of 5 ℃/min under the protection of nitrogen, keeping the temperature for 2.0h, and obtaining the tricyclodecanediol neopentyl glycol terephthalate oligomer of the poly (diethylene glycol terephthalate).

Putting 20g of poly-tricyclodecane diol butanediol oligomer, 80g of poly-tricyclodecane diol diglycol neopentyl glycol terephthalate oligomer, 0.2g of tetrabutyl titanate and 0.35g of triphenyl phosphate into a reactor, vacuumizing to 40Pa under the condition of room temperature, gradually heating to 225 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 40Pa, reacting for 3.0h, and obtaining the polymer capable of being hydrolyzed and degraded after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 683.5MPa, a tensile strength of 36.6MPa, an elongation at break of 143%, a glass transition temperature of 35.9 ℃ and a CO content of₂Permeability coefficient of 4.84barrer, O₂The permeability coefficient is 5.17barrer, and the biodegradable film can be biodegraded and can also be hydrolytically degraded.

Example 5

147.7g (1.25mol) of diethyl carbonate, 19.6g (0.1mol) of tricyclodecanediol, 45.1g (0.5mol) of 1, 4-butanediol and 0.12g of tetrabutyl titanate are put into a reactor, the temperature is gradually increased to 125 ℃ under the protection of nitrogen, the reaction is carried out for 18.0h, then the heating is closed, the temperature is reduced to room temperature at the cooling rate of 1 ℃/min under the protection of nitrogen, and the temperature is maintained for 4.0h, thus obtaining the poly-tricyclodecanediol butanediol ester oligomer.

41.5g (0.25mol) of terephthalic acid, 40.5g (0.25mol) of dimethyl diglycolate, 88.3g (0.45mol) of tricyclodecanediol, 54.1g (0.6mol) of 1, 4-butanediol and 0.15g of tetrabutyl titanate are put into a reactor, the temperature is gradually increased to 230 ℃ under the protection of nitrogen, the reaction is carried out for 1.5h, then the heating is closed, the temperature is reduced to room temperature at the cooling rate of 1 ℃/min under the protection of nitrogen, the reaction is kept for 4.0h, and the poly (trimethylene terephthalate) diglycolate tricyclodecanediol butylene glycol oligomer is obtained after the reaction is finished.

30g of poly-tricyclodecanediol butylene terephthalate oligomer, 70g of poly-tricyclodecanediol diglycolate butylene terephthalate oligomer, 0.15g of tetrabutyl titanate and 0.5g of triphenyl phosphate are put into a reactor, the reactor is vacuumized to 50Pa at room temperature, then the temperature is gradually raised to 225 ℃, the vacuum degree of the reaction system is kept to be lower than 50Pa by continuous vacuum pumping, the reaction lasts for 3.5h, and the polymer capable of being hydrolyzed and degraded is obtained after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 207.2MPa, a tensile strength of 20.7MPa, an elongation at break of 277%, a glass transition temperature of 20.2 ℃ and a CO content of₂Permeability coefficient of 4.08barrer, O₂The permeability coefficient is 4.56barrer, and the biodegradable film can be biodegraded and also can be hydrolytically degraded.

Example 6

118.1g (1.0mol) of diethyl carbonate, 98.1g (0.5mol) of tricyclodecanedimethanol, 52.1g (0.5mol) of neopentyl glycol and 0.12g of tetrabutyl titanate are put into a reactor, the temperature is gradually increased to 125 ℃ under the protection of nitrogen, the reaction is carried out for 24.0h, then the heating is closed, the temperature is decreased to room temperature at the temperature decreasing rate of 10 ℃/min under the protection of nitrogen, and the reaction is kept for 1.0 h, thus obtaining the poly-tricyclodecanedimethanol neopentyl glycol ester oligomer.

Putting 48.5g (0.25mol) of dimethyl terephthalate, 40.5g (0.25mol) of dimethyl diglycolate, 196.29g (1mol) of tricyclodecane dimethanol, 18.0g (0.2mol) of 1, 4-butanediol and 0.2g of tetrabutyl titanate into a reactor, gradually heating to 210 ℃ under the protection of nitrogen, reacting for 2.5h, then closing the heating, cooling to room temperature at the cooling rate of 10 ℃/min under the protection of nitrogen, keeping for 3.0h, and obtaining the tricyclodecane dimethanol butanediol terephthalate oligomer after the reaction is finished.

Putting 40g of poly (tricyclodecane dimethanol neopentyl glycol carbonate) oligomer, 60g of poly (tricyclodecane dimethanol diglycol succinate) oligomer, 0.25g of tetrabutyl titanate and 0.05g of triphenyl phosphate into a reactor, vacuumizing to 10Pa at room temperature, then gradually heating to 225 ℃, continuously vacuumizing to maintain the vacuum degree of a reaction system to be lower than 10Pa, reacting for 3.0h, and obtaining the polymer capable of being hydrolyzed and degraded after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 370.3MPa, a tensile strength of 32.8MPa, an elongation at break of 245%, a glass transition temperature of 18.5 ℃ and a CO content₂Penetration ofCoefficient of 3.31barrer, O₂The permeability coefficient is 4.28barrer, and the biodegradable film can be biodegraded and can also be hydrolytically degraded.

Example 7

Putting 118.1g (1mol) of diethyl carbonate, 125.2g (0.5mol) of tetracyclo-diol, 38.1g (0.5mol) of 1, 3-propylene glycol and 0.16g of dibutyltin oxide into a reactor, gradually heating to 125 ℃ under the protection of nitrogen, reacting for 16h, then closing the reactor, cooling to room temperature at the cooling rate of 30 ℃/min under the protection of nitrogen, and keeping for 3.0h to obtain the poly (tetracyclo-1, 3-propylene glycol carbonate) oligomer.

19.4g (0.1mol) of dimethyl terephthalate, 53.6g (0.4mol) of diglycolic acid, 75.1g (0.3mol) of tetracyclic glycol, 74.5g (1.2mol) of ethylene glycol and 0.41g of dibutyltin oxide are put into a reactor, the temperature is gradually increased to 190 ℃ under the protection of nitrogen, the reaction is carried out for 3.5 hours, then the heating is closed, the temperature is reduced to room temperature at the cooling rate of 30 ℃/min under the protection of nitrogen, the reaction is kept for 2.0 hours, and the poly (ethylene terephthalate) diglycolic acid tetracyclic glycol oligomer is obtained after the reaction is finished.

50g of poly (1, 3-propylene carbonate) oligomer, 50g of poly (tetracycloethylene terephthalate) oligomer, 0.5g of dibutyltin oxide and 0.01g of phosphorous acid are put into a reactor, the reactor is vacuumized to 7.5Pa at room temperature, then the temperature is gradually raised to 225 ℃, the vacuum degree of the reaction system is kept to be lower than 7.5Pa by continuous vacuum pumping, the reaction is carried out for 2.0h, and the polymer capable of being hydrolyzed and degraded is obtained after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 414.6MPa, a tensile strength of 35.2MPa, an elongation at break of 262%, a glass transition temperature of 26.4 ℃ and CO₂Permeability coefficient of 4.49barrer, O₂The permeability coefficient is 4.82barrer, and the biodegradable film can be both biodegraded and hydrolytically degraded.

Example 8

107.1g (0.5mol) of diphenyl carbonate, 125.2g (0.5mol) of tetracyclo-diol, 90.1g (1.0mol) of 1, 4-butanediol and 0.24g of isopropyl titanate are put into a reactor, the temperature is gradually increased to 220 ℃ under the protection of nitrogen, the reaction is carried out for 4.0h, then the heating is closed, the temperature is reduced to room temperature under the protection of nitrogen at the temperature reduction rate of 15 ℃/min, and the reaction is kept for 2.0h, thus obtaining the poly (tetracyclo-1, 4-butanediol carbonate) oligomer.

Putting 48.5g (0.25mol) of dimethyl terephthalate, 33.5g (0.25mol) of diglycolic acid, 1.3g (0.005mol) of tetracyclic glycol, 90.1g (1.0mol) of 1, 4-butanediol and 0.08g of isopropyl titanate into a reactor, gradually raising the temperature to 180 ℃ under the condition of nitrogen protection, reacting for 4.5 hours, then closing the heating, reducing the temperature to room temperature at the cooling rate of 15 ℃/min under the condition of nitrogen protection, and keeping for 2.0 hours to obtain the poly (terephthalic acid) diglycolic acid tetracyclic glycol 1, 4-butanediol ester oligomer.

60g of poly (1, 4-butylene carbonate) oligomer, 40g of poly (ethylene glycol terephthalate) oligomer, 0.12g of isopropyl titanate and 0.15g of pyrophosphoric acid are put into a reactor, vacuum pumping is carried out to 10Pa at room temperature, then the temperature is gradually increased to 230 ℃, vacuum pumping is continuously carried out to maintain the vacuum degree of the reaction system to be lower than 10Pa, the reaction is carried out for 6.0h, and then the polymer capable of being hydrolyzed and degraded is obtained.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 362.5MPa, a tensile strength of 27.8MPa, an elongation at break of 117%, a glass transition temperature of 45.7 ℃ and a CO content of₂Permeability coefficient of 3.49barrer, O₂The permeability coefficient is 4.18barrer, and the biodegradable film can be both biodegraded and hydrolytically degraded.

Example 9

107.1g (0.5mol) of diphenyl carbonate, 98.1g (0.5mol) of tricyclodecane dimethanol and 0.01g of stannous isooctanoate are put into a reactor, the temperature is gradually increased to 220 ℃ under the protection of nitrogen, the reaction is carried out for 4.0h, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 5 ℃/min under the protection of nitrogen, and the temperature is maintained for 5.0h, thus obtaining the poly-tricyclodecane dimethanol ester oligomer.

Putting 48.5g (0.25mol) of dimethyl terephthalate, 33.5g (0.25mol) of diglycolic acid, 117.8g (0.6mol) of tricyclodecane dimethanol and 0.01g of stannous isooctanoate into a reactor, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 6.0h, then closing the reactor, cooling to room temperature at the cooling rate of 5 ℃/min under the protection of nitrogen, keeping for 2.0h, and obtaining the tricyclodecane dimethanol terephthalate oligomer after the reaction is finished.

70g of tricyclodecane dimethyl carbonate oligomer, 30g of tricyclodecane dimethyl terephthalate oligomer, 0.10g of germanium dioxide ester and 0.12g of ammonium phosphate are put into a reactor, the reactor is vacuumized to 10Pa at room temperature, then the temperature is gradually increased to 230 ℃, the vacuum degree of the reaction system is kept to be lower than 10Pa by continuous vacuumization, the reaction lasts for 4.0h, and the polymer capable of being hydrolyzed and degraded is obtained after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 705.4MPa, a tensile strength of 50.7MPa, an elongation at break of 86%, a glass transition temperature of 67.0 ℃ and a CO content of₂Permeability coefficient of 2.66barrer, O₂The permeability coefficient is 3.57barrer, and the biodegradable film can be biodegraded and can also be hydrolytically degraded.

Example 10

107.1g (0.5mol) of diphenyl carbonate, 84.1g (0.5mol) of tricyclodecanediol, 90.1g (1.0mol) of 2-methyl-1, 3-propanediol and 0.18g of titanium dioxide are put into a reactor, the temperature is gradually increased to 220 ℃ under the protection of nitrogen, the reaction is carried out for 6.0h, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 50 ℃/min under the protection of nitrogen, and the reaction is kept for 5.0h, thus obtaining the poly-tricyclodecanediol 2-methyl-1, 3-propanediol oligomer.

48.5g (0.25mol) of dimethyl terephthalate, 33.5g (0.25mol) of diglycolic acid, 16.8g (0.1mol) of tricyclodecanediol, 62.5g (0.693mol) of 2-methyl-1, 3-propanediol and 0.06g of germanium acetate are put into a reactor, gradually heated to 185 ℃ under the protection of nitrogen, reacted for 4.0h, then the heating is closed, cooled to room temperature at the cooling rate of 50 ℃/min under the protection of nitrogen, kept for 2.5h, and the poly (terephthalic acid) diglycolic acid tricyclodecanediol 2-methyl-1, 3-propanediol ester oligomer is obtained after the reaction is finished.

80g of poly-tricyclodecane diol 2-methyl-1, 3-propylene glycol oligomer, 20g of poly-tricyclodecane diol diglycolate 2-methyl-1, 3-propylene glycol oligomer, 0.13g of germanium acetate and 0.11g of trimethyl phosphate are put into a reactor, the reactor is vacuumized to 5Pa at room temperature, then the temperature is gradually raised to 250 ℃, the vacuum degree of the reaction system is continuously vacuumized to be kept lower than 5Pa, the reaction is carried out for 3.5h, and the polymer capable of being hydrolyzed and degraded is obtained after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 422.6MPa, a tensile strength of 33.6MPa, an elongation at break of 138%, a glass transition temperature of 36.4 ℃ and a CO content₂Permeability coefficient of 2.16barrer, O₂The permeability coefficient is 3.05barrer, and the biodegradable film can be biodegraded and can also be hydrolytically degraded.

Example 11

107.1g (0.5mol) of diphenyl carbonate, 103.1g (0.99mol) of 1, 5-pentanediol, 2.5g (0.01mol) of tetracyclic diol and 0.14g of inorganic supported titanium catalyst are put into a reactor, the temperature is gradually increased to 220 ℃ under the protection of nitrogen, the reaction is carried out for 4 hours, then the heating is closed, the temperature is reduced to room temperature at the cooling rate of 10 ℃/min under the protection of nitrogen, and the reaction is kept for 2.5 hours, so that the 1, 5-pentanediol tetracyclic diol oligomer is obtained.

Putting 48.5g (0.25mol) of dimethyl terephthalate, 33.5g (0.25mol) of diglycolic acid, 53.1g (0.51mol) of 1, 5-pentanediol, 122.7g (0.49mol) of tetracyclic glycol and 0.35g of inorganic supported titanium catalyst into a reactor, gradually raising the temperature to 175 ℃ under the protection of nitrogen, reacting for 4.0h, then closing the heating, reducing the temperature to room temperature at the cooling rate of 10 ℃/min under the protection of nitrogen, keeping for 2.5h, and obtaining the 1, 5-pentanediol tetracyclic glycol oligomer of the polydiglycolic acid terephthalate after the reaction is finished.

Putting 15g of 1, 5-pentanediol tetracyclodiol polycarbonate oligomer, 85g of 1, 5-pentanediol tetracyclodiol polyterephthalate oligomer, 0.22g of inorganic supported titanium catalyst and 0.11g of dimethyl phosphate into a reactor, vacuumizing to 15Pa at room temperature, then gradually heating to 235 ℃, continuously vacuumizing to maintain the vacuum degree of a reaction system to be lower than 15Pa, reacting for 4.5h, and obtaining the polymer capable of being hydrolyzed and degraded after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 485.9MPa, a tensile strength of 37.5MPa, an elongation at break of 119%, a glass transition temperature of 49.4 ℃ and a CO content of₂Permeability coefficient of 3.92barrer, O₂The permeability coefficient is 3.54barrer, and the biodegradable film can be both biodegraded and hydrolytically degraded.

Example 12

150.4g (1.67mol) of dimethyl carbonate, 29.5g (0.25mol) of 1, 6-hexanediol, 49.1g (0.25mol) of tricyclodecane dimethanol and 0.16g of tetrabutyl titanate are put into a reactor, the temperature is gradually increased to 90 ℃ under the protection of nitrogen, the reaction is carried out for 34.0h, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 30 ℃/min under the protection of nitrogen, and the temperature is maintained for 1.0 h, thus obtaining the poly (1, 6-hexanediol tricyclodecane dimethanol ester) oligomer.

Putting 48.5g (0.25mol) of dimethyl terephthalate, 33.5g (0.25mol) of diglycolic acid, 117.8g (0.6mol) of tricyclodecanedimethanol and 0.35g of tetrabutyl titanate into a reactor, gradually heating to 175 ℃ under the protection of nitrogen, reacting for 4.0h, then closing the reactor, cooling to room temperature at the cooling rate of 30 ℃/min under the protection of nitrogen, keeping for 2.5h, and obtaining the tricyclodecanedimethanol terephthalate oligomer after the reaction is finished.

25g of poly (1, 6-hexanediol tricyclodecane dimethyl ester) oligomer, 75g of poly (terephthalic acid) tricyclodecane dimethyl ester oligomer, 0.19g of tetrabutyl titanate and 0.07g of triphenyl phosphate are put into a reactor, the reactor is vacuumized to 25Pa at room temperature, then the temperature is gradually raised to 230 ℃, the vacuum degree of the reaction system is kept to be lower than 25Pa by continuous vacuum pumping, the reaction is carried out for 6.0h, and the polymer capable of being hydrolyzed and degraded is obtained after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 415.3MPa, a tensile strength of 43.1MPa, an elongation at break of 68%, a glass transition temperature of 45.6 ℃ and a CO content of₂Permeability coefficient of 4.55barrer, O₂The permeability coefficient is 4.97barrer, and the biodegradable film can be biodegraded and can also be hydrolytically degraded.

Example 13

127.5g (1.4mol) of dimethyl carbonate, 81.9g (0.47mol) of 1, 10-decanediol, 5.9g (0.03mol) of tricyclodecanedimethanol and 0.26g of tetrabutyl titanate are put into a reactor, the temperature is gradually increased to 90 ℃ under the protection of nitrogen, the reaction is carried out for 36.0h, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 15 ℃/min under the protection of nitrogen, and the reaction is kept for 1.5h, thus obtaining the poly (1, 10-decanediol tricyclodecanedimethanol ester) oligomer.

Putting 29.1g (0.15mol) of dimethyl terephthalate, 46.9g (0.35mol) of diglycolic acid, 109.7g (0.75mol) of 1, 8-octanediol, 12.5g (0.05mol) of tetracyclodiol and 0.22g of tetrabutyl titanate into a reactor, gradually raising the temperature to 210 ℃ under the condition of nitrogen protection, reacting for 4.5 hours, then closing the heating, reducing the temperature to room temperature at the cooling rate of 15 ℃/min under the condition of nitrogen protection, and keeping for 2.5 hours to obtain the 1, 8-octanediol tetracyclodiol terephthalate oligomer.

55g of poly (1, 10-decanediol tricyclodecanedimethanol) oligomer, 45g of poly (1, 8-octanediol diglycolic acid) tetracyclodiol oligomer, 0.45g of tetrabutyl titanate and 0.27g of triphenyl phosphate are put into a reactor, the reactor is vacuumized to 35Pa at room temperature, then the temperature is gradually increased to 265 ℃, the vacuum degree of the reaction system is continuously vacuumized to maintain the vacuum degree of the reaction system to be lower than 35Pa, the reaction is carried out for 2.0h, and the polymer capable of being hydrolyzed and degraded is obtained after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 391.9MPa, a tensile strength of 40.1MPa, an elongation at break of 122%, a glass transition temperature of 35.4 ℃ and a CO content of₂Permeability coefficient of 5.08barrer, O₂The permeability coefficient is 4.64barrer, and the biodegradable film can be both biodegraded and hydrolytically degraded.

Example 14

147.66g (1.25mol) of diethyl carbonate, 81.9g (0.40mol) of ethylene glycol, 16.8g (0.10mol) of tricyclodecane diol and 0.38g of dioctyltin oxide are put into a reactor, the temperature is gradually increased to 120 ℃ under the protection of nitrogen, the reaction is carried out for 12.0h, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 20 ℃/min under the protection of nitrogen, and the reaction is kept for 2.0h, thus obtaining the poly ethylene carbonate tricyclodecane diol oligomer.

58.3g (0.30mol) of dimethyl terephthalate, 26.8g (0.20mol) of diglycolic acid, 45.7g (0.6mol) of 1, 3-propylene glycol, 84g (0.5mol) of tricyclodecane diol, 10g of polyethylene carbonate tricyclodecane diol oligomer and 0.15g of dioctyltin oxide are put into a reactor, gradually heated to 205 ℃ under the protection of nitrogen, reacted for 3.5h, then the heating is closed, the temperature is reduced to room temperature at the cooling rate of 20 ℃/min under the protection of nitrogen, and the intermediate product is obtained after the reaction is maintained for 3.5 h.

Putting 90g of the intermediate product, 0.12g of germanium acetate and 0.10g of triphenyl phosphite into a reactor, vacuumizing to 5Pa at room temperature, then gradually heating to 280 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 5Pa, reacting for 2.5h, and obtaining the polymer capable of being hydrolyzed and degraded after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 261.8MPa, a tensile strength of 16.6MPa, an elongation at break of 357%, a glass transition temperature of 20.5 ℃ and CO₂Permeability coefficient of 4.99barrer, O₂The permeability coefficient is 5.17barrer, and the biodegradable film can be biodegraded and can also be hydrolytically degraded.

Example 15

118.1g (1mol) of diethyl carbonate, 12.4g (0.20mol) of ethylene glycol, 16.8g (0.10mol) of tricyclodecanediol, 25.0g (0.10mol) of tetracyclodiol and 0.38g of dioctyltin oxide are put into a reactor, the temperature is gradually increased to 150 ℃ under the protection of nitrogen, the reaction is carried out for 14.0h, then the heating is closed, the temperature is reduced to room temperature at the cooling rate of 10 ℃/min under the protection of nitrogen, and the reaction is kept for 3.0h, thus obtaining the tetracyclo-glycol oligomer of poly (ethylene carbonate) tricyclodecanediol.

Putting 64.9g (0.30mol) of naphthalenedicarboxylic acid, 26.8g (0.20mol) of diglycolic acid, 37.2g (0.6mol) of ethylene glycol, 100.2g (0.4mol) of tetracyclic glycol and 0.15g of dioctyltin oxide into a reactor, gradually raising the temperature to 140 ℃ under the protection of nitrogen, reacting for 6 hours, then closing the heating, reducing the temperature to room temperature at the cooling rate of 15 ℃/min under the protection of nitrogen, keeping the temperature for 3.5 hours, and obtaining the ethanediol tetracyclic glycol oligomer of the naphthalenedicarboxylic acid diglycolic acid.

Putting 1g of poly (ethylene carbonate) tricyclodecanediol tetracyclodiol oligomer, 99g of ethylene glycol tetracyclodiol oligomer naphthalene dicarboxylate, 0.50g of germanium acetate and 0.10g of triphenyl phosphite into a reactor, vacuumizing to 5Pa at room temperature, then gradually heating to 300 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 5Pa, reacting for 2h, and obtaining the polymer capable of being hydrolyzed and degraded after the reaction is finished.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 801MPa, a tensile strength of 65.2MPa, an elongation at break of 54%, a glass transition temperature of 66.4 ℃ and a CO content of₂Permeability coefficient of 2.39barrer, O₂The permeability coefficient is 2.81barrer, and the biodegradable film can be biodegraded and also can be hydrolytically degraded.

Example 16

This embodiment is substantially the same as embodiment 3 except that: dimethyl terephthalate was replaced with diethyl phthalate.

The hydrolyzable degradable polymer obtained in this example was found to be white, and to have a tensile modulus of 592.4MPa, a tensile strength of 37.8MPa, an elongation at break of 83%, a glass transition temperature of 48.5 ℃ and a CO content of₂Permeability coefficient of 2.62barrer, O₂The permeability coefficient is 1.87barrer, and the biodegradable film can be biodegraded and also can be hydrolytically degraded.

Example 17

This embodiment is substantially the same as embodiment 3 except that: dimethyl terephthalate was replaced with dipropyl isophthalate.

The hydrolytically degradable polymer obtained in this example was found to be white, to have a tensile modulus of 520.0MPa, a tensile strength of 34.7MPa, an elongation at break of 153%, a glass transition temperature of 43.8 ℃ and a CO content of₂Permeability coefficient of 3.17barrer, O₂The permeability coefficient is 2.06barrer, and the biodegradable film can be both biodegraded and hydrolytically degraded.

Example 18

This example is substantially the same as example 15 except that: the naphthalene dicarboxylic acid was replaced with dimethyl 2, 6-naphthalenedicarboxylate.

Example 19

This example is substantially the same as example 15 except that: the naphthalene diacid is replaced by 1, 4-dibutyl naphthalene dicarboxylate.

Example 20

This example is substantially the same as example 15 except that: the naphthalene diacid is replaced by diethyl 2, 3-naphthalene dicarboxylate.

The products obtained in examples 18 to 20 were also found to have desirable properties.

Comparative example 1

Putting 97.1g (0.5mol) of dimethyl terephthalate, 72.1g (0.8mol) of 1, 4-butanediol and 0.11g of tetrabutyl titanate into a reactor, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, adding 0.11g of triphenyl phosphate into the reactor after the reaction is finished, vacuumizing to 15Pa, gradually heating to 250 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 15Pa, and reacting for 3.5h to obtain the polymer capable of being hydrolyzed and degraded.

The tensile modulus of the hydrolytically degradable polymer obtained in this example was 1200MPa, the tensile strength was 71.0MPa, the elongation at break was 352%, the glass transition temperature was 40.7 ℃ and the CO temperature was determined to be₂Permeability coefficient of 0.38barrer, O₂The permeability coefficient is 0.46barrer, and the biodegradable film can not be biodegraded and can not be hydrolytically degraded.

Comparative example 2

Putting 43.7g (0.225mol) of dimethyl terephthalate, 47.9g (0.275mol) of dimethyl adipate, 72.1g (0.8mol) of 1, 4-butanediol and 0.11g of tetrabutyl titanate into a reactor, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0 hours, then vacuumizing to 30Pa, gradually heating to 230 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 30Pa, and finishing the reaction after 4.0 hours to obtain the polybutylene terephthalate adipate.

The polybutylene terephthalate adipate obtained in the comparative example is detected to be orange, and the tensile modulus is 93.5MPa, tensile strength of 16.6MPa, elongation at break of 917%, glass transition temperature of-25.2 deg.C, CO₂Permeability coefficient of 4.33barrer, O₂The permeability coefficient is 6.73barrer, and the biodegradable material can be biodegraded but can not be hydrolytically degraded.

Comparative example 3

This comparative example differs from example 1 in that: after the transesterification reaction, the temperature was not lowered to room temperature, and the reaction was not maintained under nitrogen. Adding poly tricyclodecane dimethanol butanediol ester oligomer at the temperature of 250 ℃ of ester exchange reaction, directly vacuumizing, and gradually heating to 255 ℃.

The comparative example adopts the traditional process without temperature reduction step and high-temperature vacuum pumping, the obtained product can generate side reactions such as high-temperature oxidation and the like, and the obtained product is yellow in color.

Example 21

Some embodiments of the invention also provide for the use of the hydrolytically degradable polymers, for example, in the preparation of packaging materials, containers, geomembranes, structural members, body implants, and the like.

In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.

While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims

1. a preparation method of a hydrolytically degradable polymer is characterized in that comprising:

(1) Under a protective atmosphere, the first mixture reaction system containing carbonic acid diester, diol, and the first transesterification catalyst is subjected to transesterification at 90 to 220° C. After the end, the temperature is lowered to room temperature, and then protected maintained in a sexual atmosphere to form the first intermediate product;

(2) Under a protective atmosphere, a second mixture containing an aromatic dibasic acid and/or its ester product, diglycolic acid and/or its ester product, a diol, a second esterification or transesterification catalyst is made The reaction system is subjected to esterification or transesterification at 140-250°C, and the temperature is lowered to room temperature after the end, and then kept in a protective atmosphere to obtain a second intermediate product;

(3) the third mixed reaction system comprising the first intermediate product, the second intermediate product, the polycondensation catalyst and the stabilizer is evacuated to below 50Pa, and then gradually heated to 210～300 ℃ to carry out the polycondensation reaction to obtain a hydrolytically degradable polymerization thing;

Alternatively, the preparation method includes:

(i) Under a protective atmosphere, the first mixture reaction system containing carbonic acid diester, diol, and the first transesterification catalyst is subjected to transesterification at 90-220°C, and the temperature is lowered to room temperature after completion, and then protected maintained in a sexual atmosphere to form the first intermediate product;

(ii) under a protective atmosphere, esterification or transesterification comprising aromatic diacids and/or their esters, diglycolic acid and/or their esters, diols, first intermediates, second The fourth mixed reaction system of the catalyst is subjected to esterification or transesterification reaction at 140-250°C, the temperature is lowered to room temperature after completion, and then maintained in a protective atmosphere to obtain a third intermediate product;

(iii) evacuate the fifth mixed reaction system comprising the third intermediate product, polycondensation catalyst and stabilizer to below 50Pa, and then gradually heat up to 210～300°C to carry out polycondensation reaction to obtain a hydrolytically degradable polymer;

Wherein, the aromatic dibasic acid and/or its esters include terephthalic acid and/or its esters, isophthalic acid and/or its esters, phthalic acid and/or its esters, naphthalene Any one or a combination of two or more of dicarboxylic acid and/or its esters;

The dihydric alcohol includes cyclic dihydric alcohol, or a combination of cyclic dihydric alcohol and aliphatic dihydric alcohol, and the cyclic dihydric alcohol includes tricyclodecane dimethanol, tricyclodecanediol, tetracyclic Any one or a combination of two or more diols; the fatty diols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2-methyl-1,3-propanediol, Any one or a combination of two or more of neopentyl glycol, octanediol, and decanediol.

2. preparation method according to claim 1 is characterized in that, described aromatic dibasic acid and/or its ester compound comprise any one or two or more structures shown in following formula:

Wherein, R is a hydrogen atom or a carbon chain with no more than 4 carbon atoms;

And/or, described carbonic acid diester comprises any one or the combination of more than two in dimethyl carbonate, diethyl carbonate, diphenyl carbonate; And/or, in step (1) or step (i) , the molar ratio of the carbonic acid diester to the diol is 1:0.2-3.0; and/or, the addition amount of the first transesterification catalyst is 0.01-0.5% of the theoretical mass of the first intermediate product.

3. preparation method according to claim 1 is characterized in that: in step (2) or step (ii), described aromatic dibasic acid and/or its ester compound and diglycolic acid and/or its ester The molar ratio of the combination of the compound and the dihydric alcohol is 1:1.2～3.0; and/or, the addition amount of the second esterification or transesterification catalyst is 0.01～0.5 of the theoretical mass of the second intermediate product or the third intermediate product %; and/or, in step (ii), the quality of the first intermediate product reacts with aromatic dibasic acid and/or its esters, diglycolic acid and/or its esters and dihydric alcohols The ratio of the total mass to the polymer is 1-80:99-20.

4. preparation method according to claim 1 is characterized in that: in step (3), the mass ratio of described first intermediate product and second intermediate product is 1～80: 99～20; And/or, step (3) or step (iii), the mass of the polycondensation catalyst is 0.01-0.5% of the theoretical mass of the hydrolytically degradable polymer, and the mass of the stabilizer is 0.01-0.5% of the theoretical mass of the hydrolytically degradable polymer %.

5. The preparation method according to claim 1, characterized by comprising: in a protective atmosphere, the first mixed reaction system is subjected to a transesterification reaction at 90-220° C. for 4.0-36.0 h, and after the end, the transesterification reaction is performed at a temperature of 1- A cooling rate of 50°C/min lowers the temperature to room temperature and then maintains it in a protective atmosphere to form the first intermediate product;

And/or, in step (2), in a protective atmosphere, the second mixed reaction system is subjected to an esterification or transesterification reaction at 140-250° C. for 1.5-6.0 h, and after completion, the temperature is 1-50° C./min. The temperature is lowered to room temperature at a cooling rate of 100 , and then maintained in a protective atmosphere to form a second intermediate product;

And/or, in step (3), the third mixed reaction system is evacuated to below 50 Pa, and then gradually heated to 210-300° C. to carry out a polycondensation reaction for 2.0-10.0 h to obtain the hydrolytically degradable polymer. ;

And/or, in step (ii), in a protective atmosphere, the fourth mixed reaction system is subjected to an esterification or transesterification reaction at 140-250° C. for 1.5-6.0 h, and after completion, the reaction rate is 1-50° C./min. The temperature is lowered to room temperature at a cooling rate of 100, and then maintained in a protective atmosphere to form a third intermediate product;

And/or, in step (iii), the fifth mixed reaction system is evacuated to below 50Pa, and then gradually heated to 210～300°C to carry out a polycondensation reaction for 2.0～10.0h to obtain the hydrolytically degradable polymer ;

And/or, in step (3) or step (iii), vacuumize to below 50Pa at room temperature, then gradually heat up to 210～300℃ to carry out polycondensation reaction, and continue to vacuumize to keep the vacuum not more than 50Pa in the whole polycondensation process. 50Pa.

6. The preparation method according to claim 1, wherein the first transesterification catalyst comprises any one or a combination of two or more of titanium-based catalysts, tin-based catalysts, and germanium-based catalysts; and/or , the second esterification or transesterification catalyst includes any one or a combination of two or more of titanium-based catalysts, tin-based catalysts, and germanium-based catalysts;

And/or, the polycondensation catalyst includes any one or a combination of two or more of titanium-based catalysts, tin-based catalysts, and germanium-based catalysts;

And/or, the stabilizer includes phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, phosphorous acid Any one or a combination of two or more of diphenyl ester, ammonium phosphite and ammonium dihydrogen phosphate.

7. preparation method according to claim 1 or 5 is characterized in that: comprise in step (1), step (2), step (i), step (ii): after the reaction finishes, the temperature is reduced to room temperature, After that, it was kept in a protective atmosphere for 1.0 to 5.0 h.

8. A hydrolytically degradable polymer prepared by the method of any one of claims 1-7.

9. A composition for synthesizing a hydrolytically degradable polymer, characterized in that it comprises:

Component (a), including aromatic dibasic acids and/or esters thereof;

Component (b), including diglycolic acid and/or its esters;

component (c), including carbonic acid diesters;

component (d), including glycols;

Described carbonic acid diester comprises any one or the combination of two or more in dimethyl carbonate, diethyl carbonate, diphenyl carbonate;

10. Use of the hydrolytically degradable polymer of claim 8 in the field of preparing packaging materials, containers, mulching films, structural parts or human implants.