CN105278239A - Stereo-lithography rapid-prototyping polysiloxane photosensitive resin composition and preparation method and application thereof - Google Patents

Abstract

The invention relates to a stereolithography rapid prototyping polysiloxane-based photosensitive resin composition and its preparation method and application, which mainly includes the following raw material components in mass ratio: double-ended acrylate-based polysiloxane 10-85 %; multi-acrylic polysiloxane 3-21%; acrylate polysiloxane diluent 10-60%; acrylate diluent 10-60%; free radical initiator 1.0-4.0%. According to the above ratio, the raw materials are mixed, stirred and heated to a transparent liquid, and the stereolithography rapid prototyping polysiloxane-based photosensitive resin is obtained. A stereolithography rapid prototyping polysiloxane-based photosensitive resin composition according to the present invention has not only the characteristics of rapid prototyping of photosensitive resins, but also the high and low temperature resistance characteristics of polysiloxane after being formed by stereolithography . The parts formed by using the photosensitive resin have the advantages of high precision, good heat resistance and the like.

Description

A stereolithography rapid prototyping polysiloxane-based photosensitive resin composition and its preparation method and application

technical field

The invention belongs to the technical field of 3D printing rapid prototyping manufacturing, and in particular relates to a stereolithography rapid prototyping free radical polysiloxane-based photosensitive resin composition and a preparation method thereof.

Background technique

3D printing technology is based on the computer three-dimensional design model, through the software layered discrete and numerical control forming system, using laser beams, hot-melt nozzles, etc. to accumulate metal powder, ceramic powder, plastic, cell tissue and other special materials layer by layer Bonding, and finally overlaying and molding to create a solid product. Unlike the traditional manufacturing industry, which shapes and cuts raw materials through mechanical processing methods such as moulds, turning and milling to finally produce finished products, 3D printing transforms a three-dimensional entity into several two-dimensional planes. The manufacturing complexity is reduced. This digital manufacturing mode does not require complex processes, huge machine tools, or a lot of manpower. Parts of any shape can be generated directly from computer graphics data, enabling manufacturing to extend to a wider range of production groups.

As a new generation of 3D printing, liquid photosensitive resin is used to form parts and cured with ultraviolet light. There is no need for expensive laser systems, so the equipment is cheap, the operation and maintenance costs are also very low, and it can work at lower temperatures (up to 50°C); moreover, it also has the advantages of simple operation, fast forming speed, and seamless forming process. Pollution, high precision of formed parts, and can be used in office environment, etc. Therefore, the application prospect is very promising.

The photosensitive resin suitable for 3D printing requires the glue system to have low viscosity, good fluidity, fast curing rate, low curing shrinkage, no prying of the product, and excellent heat resistance. At present, there are few domestic reports on the preparation methods of high-precision, high-heat-resistant stereolithography rapid prototyping materials. Specific to stereolithography rapid prototyping free radical polysiloxane-based photosensitive resin and its preparation have not been reported.

Contents of the invention

The purpose of the present invention is to provide a high-precision, high-heat-resistant stereolithography rapid prototyping polysiloxane-based photosensitive resin. The photosensitive glue prepared by this technology has the advantages of low system viscosity and good fluidity. Under the irradiation of ultraviolet light, it has the characteristics of fast glue curing rate, low curing shrinkage rate, and no prying of the product. Due to its polysiloxane main body structure, which endows the cured product with excellent high and low temperature resistance characteristics. Parts formed by using the polysiloxane-based photosensitive resin have the advantages of high precision, good heat resistance, excellent low-temperature performance, enhanced toughness, and the like.

The object of the present invention is also to provide a method for manufacturing the free-radical polysiloxane-based photosensitive resin for stereolithography rapid prototyping.

The present invention is achieved through the following technical solutions:

A stereolithography rapid prototyping polysiloxane-based photosensitive resin composition, comprising the following raw material components in mass ratio:

Double-ended acrylate-based polysiloxane 10-85%;

Multi-acrylate polysiloxane 3-21%;

Thinner 10-60%;

Free radical initiator 1.0-4.0%.

Preferably, the double-ended acrylate-based polysiloxane is a polysiloxane main chain, an acrylate polysiloxane resin containing (meth)acryloyloxypropyl groups at both ends, and the molecular weight is between 1000-50000 , using one or more molecular weight polymers in combination.

Preferably, the polyacrylate-based polysiloxane is a polysiloxane acrylate resin with polysiloxane as the main chain and side groups or (and) terminal groups containing (meth)acryloyloxypropyl groups , also known as acryloxypropyl modified polysiloxane, the molecular weight is between 300-50000.

Preferably, the so-called diluent is an acrylate polysiloxane diluent, an acrylate diluent or a mixture thereof.

More preferably, the so-called acrylate polysiloxane diluents are bis(acryloyloxypropyl)tetramethyldisiloxane, bis(acryloyloxypropyl)hexamethyltrisiloxane, bis(acryloxypropyl) Oxypropyl) octamethyltetrasiloxane, bis(acryloxypropyl) decamethylpentasiloxane, bis(methacryloxypropyl) tetramethyldisiloxane, bis(methyl Acryloxypropyl) hexamethyltrisiloxane, bis(methacryloxypropyl) octamethyltetrasiloxane, bis(methacryloxypropyl) decamethylpentasiloxane, Tetrakis(acryloxypropyl)tetramethylcyclotetrasiloxane, tetrakis(methacryloxypropyl)tetramethylcyclotetrasiloxane or a mixture of the above substances.

More preferably, the so-called acrylate diluent is lauryl acrylate, ethoxyethyl acrylate, ethoxyethoxyethyl acrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, Ethoxylated nonylphenol acrylate, isooctyl acrylate, beta-hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(methyl) Acrylates, trimethylol tetra(meth)acrylates or mixtures thereof.

Preferably, the so-called free-radical initiator is a free-radical initiator that initiates acrylate-based polymerization.

More preferably, the so-called free radical initiators are methyl benzoylformate, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2-di Methylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2, 4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 1-Hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylacetone, poly[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)benzene Base] acetone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 4-phenylbenzophenone, methyl o-benzoylbenzoate, 4-(dimethylamino )-(2-ethyl)hexyl benzoate, ethyl 4-dimethylaminobenzoate, 2,2-dimethoxy-1,2-benzophenone, 4-methylbenzophenone Ketone, benzophenone, 4,4'-bis(diethylamino)benzophenone, polyethylene glycol phthaloylbenzoate, polyethylene glycol bis(β-4-[p-(2- Dimethylamine-2-benzyl)butyrylphenyl]piperazine) propionate, polyethylene glycol di(β-4-p-acetylphenyl-piperazine) propionate, polyethylene glycol Alcohol di-(p-dimethylaminobenzoate) ester, polytetramethylene glycol 250 di-(2-carboxymethoxythioxanthone) ester, polytetramethylene glycol 250-(4-benzoylphenoxyacetic acid ) ester, polytetramethylene glycol bisbenzoate or a mixture of two or more of them.

The present invention also provides a preparation method of the stereolithography rapid prototyping photosensitive resin, the method is to mix the raw material components according to the mass ratio, heat the mixed material, and stir until it becomes a transparent uniform liquid So far, the obtained product is stereolithography rapid prototyping photosensitive resin.

The stereolithography rapid prototyping photosensitive resin mentioned above is used as a photocuring material in the field of stereolithography rapid prototyping technology, and the curing light source is preferably ultraviolet light with a wavelength of 355nm-385nm.

detailed description

The present invention will be described in further detail below in conjunction with the embodiments, but the implementation of the present invention is not limited thereto.

Example 1

In a 5000 ml glass three-neck flask equipped with a stirrer and a condenser tube, add 1700 g of double-ended acrylate-based polysiloxane (molecular weight is about 1000), polyacryloxypropyl modified polysiloxane (molecular weight: 50000 or so) 420.0g, diluent bis(acryloxypropyl)tetramethyldisiloxane 60g and lauryl acrylate 600g, methyl benzoylformate and 2-hydroxy-2-methyl-1-[4 40 g each of -(2-hydroxyethoxy)phenyl]-1-propanone. Heat and stir until it becomes a transparent light yellow homogeneous liquid, which is a prepared photosensitive resin.

Example 2

In a 5000 ml glass three-neck flask equipped with a stirrer and a condenser tube, add 1000 grams of double-ended acrylate-based polysiloxane (molecular weight is about 50,000), polyacryloxypropyl modified polysiloxane (molecular weight about 300) 300 grams, 500 grams of diluent bis(methacryloxypropyl) hexamethyltrisiloxane and 500 grams of 1,6-hexanediol diacrylate, 2-isopropylthia Anthrone 40g and methyl phthaloylbenzoate 40g. Heat and stir until it becomes a transparent light yellow homogeneous liquid, which is a prepared photosensitive resin.

Example 3

In a 5000 ml glass three-neck flask equipped with a stirrer and a condenser tube, add 1000 grams of double-ended acrylate-based polysiloxane (molecular weight is about 22000), polyacryloxypropyl modified polysiloxane (molecular weight 24000 or so) 300 grams, diluent two (acryloxypropyl) octamethyltetrasiloxane 1000 grams and pentaerythritol tri (meth) acrylate 1000 grams, polytetramethylene glycol 250 two - (2- carboxymethyl Oxythioxanthone) ester 60g and 2,2-dimethoxy-1,2-benzophenone 60g. Heat and stir until it becomes a transparent light yellow homogeneous liquid, which is a prepared photosensitive resin.

Example 4

In a 5000 ml glass three-neck flask equipped with a stirrer and a condenser, add 1000 grams of double-ended methacrylate polysiloxane (molecular weight is about 20000), polymethacryloxypropyl modified polysiloxane Oxane (molecular weight is about 18000) 300 grams, diluent bis(methacryloxypropyl) octamethyltetrasiloxane 600 grams and diethylene glycol diacrylate 600 grams, polytetramethylene glycol 250 40 g of bis-(2-carboxymethoxythioxanthone) ester and 60 g of 2,2-dimethoxy-1,2-benzophenone. Heat and stir until it becomes a transparent light yellow homogeneous liquid, which is a prepared photosensitive resin.

Example 5

In a 5000 ml glass three-neck flask equipped with a stirrer and a condenser tube, add 800 grams of double-ended methacrylate-based polysiloxane (molecular weight is about 50,000), polymethacryloxypropyl modified polysiloxane Oxane (molecular weight is about 300) 500 grams, diluent bis(methacryloxypropyl) decamethylpentasiloxane 600 grams and ethoxy nonylphenol acrylate 400 grams, o-benzoyl benzoic acid 40 grams of methyl ester and 50 grams of 4-(dimethylamino)-benzoic acid-(2-ethyl)hexyl ester. Heat and stir until it becomes a transparent light yellow homogeneous liquid, which is a prepared photosensitive resin.

Example 6

In a 5000 ml glass three-neck flask equipped with a stirrer and a condenser, add 1000 grams of double-ended methacrylate polysiloxane (molecular weight is about 30000), polyacryloxypropyl modified polysiloxane (Molecular weight is about 10000) 400 grams, diluent tetrakis (acryloyloxypropyl) tetramethylcyclotetrasiloxane 500 grams and tetrakis (methacryloyloxypropyl) tetramethylcyclotetrasiloxane 600 grams , 2,4,6-trimethylbenzoyl-diphenylphosphine oxide 30 g and 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl] - 1-acetone 40 g. Heat and stir until it becomes a transparent light yellow homogeneous liquid, which is a prepared photosensitive resin.

Claims (9)

1. a stereolithography rapid prototyping polysiloxane group photosensitive resin composition, is characterized in that: the material component comprising following quality proportioning:

Both-end acrylate based polysiloxane 10 ~ 85%;

Many acrylate based polysiloxane 3-21%;

Thinning agent 10-60%;

Radical initiator 1.0 ~ 4.0%.

2. a kind of stereolithography rapid prototyping polysiloxane group photosensitive resin composition according to claim 1, it is characterized in that: described both-end acrylate based polysiloxane is polysiloxane backbone, the acrylate polysiloxane resin of two ends are contained (methyl) acryloxypropyl, molecular weight is between 1000-50000.

3. a kind of stereolithography rapid prototyping polysiloxane group photosensitive resin composition according to claim 1, it is characterized in that: described many acrylate based polysiloxane is polysiloxane is main chain, side base or (with) end group contains the silicone acrylates resin of (methyl) acryloxypropyl group, also be referred to as meaning acryloxypropyl modified polyorganosiloxane, molecular weight is between 100-50000.

4. a kind of stereolithography rapid prototyping polysiloxane group photosensitive resin composition according to claim 1, is characterized in that: described thinning agent is acrylate polysiloxane thinning agent, acrylate diluent or their potpourri.

5. a kind of stereolithography rapid prototyping polysiloxane group photosensitive resin composition according to claim 4, it is characterized in that: described acrylate polysiloxane thinning agent is: two (acryloxypropyl) tetramethyl disiloxane, two (acryloxypropyl) hexam ethylcyclotrisiloxane, two (acryloxypropyl) octamethylcyclotetrasiloxane, two (acryloxypropyl) decamethyl five siloxane, two (methacryloxypropyl) tetramethyl disiloxane, two (methacryloxypropyl) hexam ethylcyclotrisiloxane, two (methacryloxypropyl) octamethylcyclotetrasiloxane, two (methacryloxypropyl) decamethyl five siloxane, four (acryloxypropyl) tetramethyl-ring tetrasiloxane, the potpourri of four (methacryloxypropyl) tetramethyl-ring tetrasiloxane or more material.

6. a kind of stereolithography rapid prototyping polysiloxane group photosensitive resin composition according to claim 4, it is characterized in that: described acrylate diluent is lauryl acrylate, ethoxyethyl acrylate, ethoxyethoxy ethyl acrylate, diacrylate diglycol ester, trimethyol propane triacrylate, Nonyl phenol ethoxylate acrylate, Isooctyl acrylate monomer, methacrylic acid-beta-hydroxy ethyl ester, 1, 6-hexanediyl ester, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, two contracting trihydroxy methyl four (methyl) acrylate or their potpourris.

7. a kind of stereolithography rapid prototyping polysiloxane group photosensitive resin composition according to claim 1, is characterized in that: described radical initiator is methyl benzoylformate, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl) phenyl]-1-fourth, 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester, 2,4,6-trimethylbenzoy-dipheny phosphine oxide, 2-methyl-2-(4-morpholinyl)-1-[4-(methyl mercapto) phenyl]-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylacetone, polymerization [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 4-phenyl benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-(dimethylamino)-benzoic acid-(2-ethyl) own ester, EDMAB, 2,2-dimethoxy-1,2-benzyl phenyl ketone, 4-methyl benzophenone, benzophenone, 4,4 '-two (lignocaine) benzophenone, o-benzoyl yl benzoic acid macrogol ester, polyglycol two (β-4-[to (2-dimethyl amine 2-benzyl) bytyry phenyl] piperazine) propionic ester, polyglycol two (β-4-is to acetylphenyl-piperazine) propionic ester, polyglycol two-(p-dimethylaminobenzoic acid) ester, polytetramethylene glycol 250 2-(2-carboxymethoxyl thioxanthones) ester, polytetramethylene glycol 250-(4-benzoyl phenoxy acetic acid) ester, the two benzoyl formiate of polytetramethylene glycol or two or more potpourri in them.

8. the preparation method of a kind of stereolithography rapid prototyping polysiloxane group photosensitive resin composition according to claim 1-8 is: by described material component by the mixing of described quality proportioning, stirs lower heating, until become transparent uniform liquid.

9. the shaping feature of a kind of stereolithography rapid prototyping polysiloxane group photosensitive resin composition described in claim 1-8 is: curing light source adopts wavelength to be the ultraviolet light of 355nm ~ 385nmnm.