CN110713577A - Expansion monomer modified light-cured resin and preparation method thereof - Google Patents

Abstract

An expansion monomer modified light-cured resin and a preparation method thereof, aiming at providing an expansion monomer modified light-cured resin and a preparation method thereof. The light-cured resin plays a very key role in a light-cured rapid prototyping technology (SLA), the prototyping technology has the characteristics of low energy consumption, low cost, high prototyping precision and the like, and the emergence of the technology promotes great change in the manufacturing field. The volume of the light-cured resin shrinks in the curing process, so that the formed product has large shrinkage and warpage, small precision and poor mechanical property, and the performance of the final product is influenced. According to the invention, the expansion monomer is introduced into the resin curing system, and the volume shrinkage of the photocuring resin during polymerization is counteracted by utilizing the polymerization expansion characteristic of the expansion monomer, so that the prepared photocuring composite resin has the advantages of low shrinkage characteristic, good physical and chemical properties and thermodynamic properties, can be formed by adopting direct photocuring rapid forming, 3D printing forming and other modes, and has wide application prospect.

Description

Expansion monomer modified light-cured resin and preparation method thereof

Technical Field

The invention relates to the field of high-molecular light-cured resin, in particular to expansion monomer modified light-cured resin and a preparation method thereof.

Background

The united states, at the end of the 20 th century 70 s, proposed the concept of rapid prototyping, the idea of producing three-dimensional entities using selective curing of successive layers. Among the rapid prototyping technologies, the photocuring rapid prototyping technology is the most deeply researched, rapidly developed and widely applied, and is the most mature rapid prototyping technology at present. After 30 years of development, the technology of rapid photo-curing molding has been developed for a long time, and more enterprises and institutions are engaged in the research of the rapid photo-curing molding method, such as 3D Systems, EOC, CMET, etc. At present, the application of laser scanning improves the forming speed by about 4 times, greatly improves the forming efficiency, correspondingly improves the printing forming precision by one time, and is widely applied to industries such as aviation, automobiles, electric appliances, consumer goods, medical treatment and the like.

The material used earlier in the rapid prototyping technology was a photocurable resin, of which the radical type is the most. The free radical type light-cured resin has the advantages of high mechanical strength, high curing speed and low cost, but has large shrinkage rate and low material forming precision. The cationic photocurable resin has the advantages of low viscosity and small warpage, but has the disadvantages of large critical exposure, low curing speed and the like. The free radical type light-cured resin and the cationic type light-cured resin are mixed to prepare the hybrid light-cured resin, and the advantages of the free radical type light-cured resin and the cationic type light-cured resin are combined. This type of photocurable resin can compensate for the slow curing of cationic resins and increase the curing speed. However, the hybrid light-cured resin still has the problem of curing volume shrinkage, namely, the conventional pouring molding and extrusion molding. In the photocuring molding, not only the shrinkage caused by thermal expansion and contraction but also the shrinkage caused by intermolecular reaction occur. As is well known, a photocurable resin consists of an oligomer and a reactive diluent, and when the photocurable resin is not reacted, the intermolecular existence is van der waals force, and the intermolecular distance is van der waals distance; when the photoinitiator decomposes, the diluent and oligomer polymerize and the intermolecular distance changes from van der Waals to covalent bond.

The volume shrinkage affects the mechanical properties, physical and chemical properties and the like of the final photocuring resin material in the rapid molding process of the photocuring resin. Researchers have been working on solving the problem of volume shrinkage of photocurable resins in rapid prototyping. Scientists discovered expansion monomers in the 70's of the 20 th century and continually explored many of their particular applications. The swelling monomer is a monomer substance which can generate swelling volume in the polymerization process, and the volume of the substance is obviously increased compared with the monomer state after the polymerization reaction is finished, so that the swelling monomer can meet the requirements of certain industrial applications. At present, the swelling monomer and swelling polymerization reaction are used for preparing high-strength composite materials, high-performance adhesives, biodegradable high polymer materials and medical high polymer materials, and are also used in the fields of modification of general high polymers, synthesis of oligomers with functional groups and the like.

The main purpose of developing such monomers is to modify commercial resins with them to improve their performance and thus to make them high-tech, high value-added products. The invention aims to prepare a high-performance light-cured resin material, an acrylic acid-epoxy composite resin system is used as a matrix, a spiro orthocarbonate expansion monomer is introduced, the volume shrinkage of the light-cured resin during polymerization is counteracted by utilizing the polymerization expansion characteristic of the spiro orthocarbonate expansion monomer, and the prepared light-cured composite resin has the advantages of low shrinkage characteristic, good physical and chemical properties and thermodynamic properties, can be formed by adopting direct light-cured rapid forming, 3D printing forming and other modes, and has wide application prospect.

Disclosure of Invention

The invention aims to provide a light-cured resin material, in particular to an expansion monomer modified light-cured resin and a preparation method thereof.

The invention relates to an expansion monomer modified light-cured resin which comprises the following components: the composite material comprises matrix resin, an expansion monomer, a reactive diluent, a cationic photoinitiator, a free radical photoinitiator, a photosensitive auxiliary agent, nano particles and pigment; calculated according to the mass portion, relative to 100 portions of matrix resin, 8 to 25 portions of reactive diluent, 2 to 20 portions of expansion monomer, 0.8 to 12 portions of cationic photoinitiator, 0.8 to 10 portions of free radical photoinitiator, 0.1 to 2 portions of photosensitizer, 25 to 70 portions of nano-particles and 0 to 1 portion of pigment.

The matrix resin comprises a composition of acrylic resin and epoxy resin;

the acrylic resin includes, but is not limited to, one or more of methacrylic acid, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobornyl acrylate, n-butyl acrylate, butyl methylacrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, 2-hydroxy-3-phenoxypropyl 2-acrylate, hydroxypentyl acrylate, and hydroxyhexyl acrylate.

The epoxy resin includes, but is not limited to, one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin, and alicyclic epoxy resin.

The reactive diluent is a monomer containing a carbon-carbon double bond, and comprises a monomer containing an acryloyloxy group, a methacryloyloxy group and a vinyl group, and comprises but is not limited to one or more of the following compositions: tripropylene glycol diacrylate, triethylene glycol divinyl, dipropylene glycol diacrylate, glyceryl carbonate propenyl ether, triethylene glycol divinyl ether, polyoxypropylene polyoxyethylene glyceryl ether, dodecyl vinyl ether, dodecyl glycidyl ether, silicone-modified polysiloxane, butyl glycidyl ether, and benzyl glycidyl ether 692, 1, 6-ethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolpropane diacrylate.

The cationic photoinitiator is one or more of xanthone phenyl iodonium salt, fluorenone phenyl iodonium salt, cumene metallocene (II) hexafluorophosphate, dialkyl benzoyl sulfide salt, triaryl (1-pyrene) bismuth salt, dialkyl benzoyl sulfide salt, bis (5-fluorothiophene-2-yl) iodonium formate, S-dialkyl-S- (dimethyl hydroxyphenyl) sulfide salt and thiophenyl phenyl diphenyl sulfonium salt.

The free radical photoinitiator is one or more than one of (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 2-isopropyl thioxanthone, 4-ethyl dimethylaminobenzoate, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzoin dimethyl ether, methyl o-benzoylbenzoate, tetramethylMichler's ketone, 2, 4-diethyl thioxanthone and 1-chloro-4-propoxy thioxanthone;

the photosensitive auxiliary agent comprises one or more of camphorquinone, naphthalene, anthracene, pyrene, perylene, carbazole with an N-unsaturated double bond, benzophenone, dibenzoyl, 3, 5-diphenyl dithieno [3,2-b:2,3-a ] anthracene, coumarin and curcumin.

The pigment is a conventional reagent, and specific colors are selected according to products.

The expansion monomer is prepared by heating a dihydroxy compound or a trihydroxy compound and orthocarbonate in a corresponding solvent for chemical reaction; the molar ratio of the hydroxy compound to the orthocarbonate is: 2: 1-3: 1, the dosage of the solvent is 15 to 30 times of the mass of the hydroxyl compound.

The dihydroxy compound and the trihydroxy compound are as follows: one or more of ethylene glycol, trimethylolpropane monoallyl ether, propane allyl ether diol, allyl propane-1, 3-diol, phenyl-2-hydroxymethyl propanediol, 6, 8-dihydroxy-1-anylene and glycol-forming oxetane.

The above orthocarbonates are tetraethyl orthocarbonate and tetrapropyl orthocarbonate.

The above solvent is selected from toluene, xylene and diethyl ether.

The preparation method of the expansion monomer comprises the following steps: adding a dihydroxy compound or a trihydroxy compound and orthocarbonate into a solvent, stirring and heating to 100-120 ℃, and simultaneously carrying out reflux and water diversion; adding p-toluenesulfonic acid, reacting for 15-24h, and cooling to room temperature. The product is decompressed and compressed, and then the expanded monomer is separated and purified by column chromatography.

The nano-particles are surface-modified by adopting a silane coupling agent, and the ratio of the silane coupling agent to the nano-particles is 1: 3-1: 10 in parts by mass.

The nano particles are one or more of fumed silica, talcum powder and mica powder, wherein the specific surface area of the fumed silica, the talcum powder and the mica powder is more than 1000 meshes.

The silane coupling agent is a siloxane containing unsaturated double bonds, and includes but is not limited to one or more of gamma-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, allyltriethoxysilane, 5-hexenyltrimethoxysilane, 11-acetoxyundecyltriethoxysilane, 10-alkenylundecyltrimethoxysilane, unsaturated double-bonded trimethoxysilane, unsaturated double-bonded triethoxysilane, methyl unsaturated double-bonded diethoxysilane, methyl unsaturated double-bonded dimethoxysilane and tetramethyl di-unsaturated double-bonded siloxane.

The preparation method of the nano-particles comprises the following steps:

⑴ respectively weighing silane coupling agent and nanoparticles;

⑵ adding the nanometer particles into the reaction kettle, adding the silane coupling agent while stirring, and stirring at constant speed for 1-2 hours for standby.

The preparation method of the expansion monomer modified light-cured resin comprises the following steps:

⑴ the swelling monomer and the nanoparticles are prepared separately and are ready for use.

⑵ adding the matrix resin, the expansion monomer and the nano filler into the active diluent, and stirring uniformly;

⑶ adding cationic photoinitiator, free radical photoinitiator, photosensitive assistant and pigment into the mixture, stirring, and vacuum degassing to obtain the final product.

The method of making an intumescent monomer modified photocurable resin according to the present invention does not represent the only form in which the present invention may be made or utilized. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The volume of the light-cured resin prepared by the invention is reduced, the precision of the molding process is improved, and the deformation and cracking of the cured product are greatly reduced. Meanwhile, the use of a composite photo-initiation system improves the curing rate and the curing completion rate, and simultaneously improves the storage stability of the product.

Detailed Description

Example 1

Preparing an expansion monomer: weighing 55g of trimethylolpropane monoallyl ether, adding the trimethylolpropane monoallyl ether into 800 mL of toluene, magnetically stirring and heating to 110 ℃, refluxing and dividing water, adding 1g of p-toluenesulfonic acid, adding 31mL of tetraethyl orthocarbonate, reacting for 24h, cooling to room temperature, decompressing and concentrating a product, and separating and purifying by column chromatography (ethyl acetate: petroleum ether = l: 30) to obtain an expanded monomer for later use.

Preparing nano particles: respectively weighing 10g of silicon gamma-methacryloxypropyl trimethoxy silane and 30g of talcum powder; adding the nano particles into a reaction kettle, adding the silane coupling agent while stirring under the stirring state, and stirring at a constant speed for 1-2 hours for later use.

Preparing a light-cured resin: 23g of methyl methacrylate, 36g of butyl acrylate, 41g of glycidyl ether epoxy resin, 8g of expansion monomer and 40g of nano particles are weighed and added into a mixture of 5g of tripropylene glycol diacrylate and 8g of triethylene glycol divinyl, and the mixture is stirred uniformly. Weighing 4g of dialkyl benzoylsulfide salt, 5g of dialkyl benzoylsulfide salt, 0.8g of 2-isopropyl thioxanthone and 1g of camphorquinone, uniformly mixing, adding into the mixture, and uniformly stirring; adding 0.5g of blue color, mixing until the color is uniform, and vacuum degassing to obtain the expanded monomer modified light-cured resin.

Example 2

Preparing an expansion monomer: weighing 25g of allyl propane-1, 3-diol, adding the allyl propane-1, 3-diol into 650 mL of toluene, heating the mixture to 100 ℃ under magnetic stirring, refluxing and water dividing, adding 0.65 g of p-toluenesulfonic acid, adding 43mL of tetrapropyl orthocarbonate, cooling the mixture to room temperature after reacting for 24h, concentrating the product under reduced pressure, and separating and purifying the product by column chromatography (ethyl acetate: petroleum ether = l: 30) to obtain an expanded monomer for later use.

Preparing nano particles: respectively weighing 10g of silicon gamma-methacryloxypropyl trimethoxy silane, 5g of 3-methacryloxypropyl methyldiethoxy silane, 20g of talcum powder and 40g of mica powder; adding the nano particles into a reaction kettle, adding the silane coupling agent while stirring under the stirring state, and stirring at a constant speed for 1-2 hours for later use.

Preparing a light-cured resin: 33g of methyl acrylate, 13g of 2-acrylic acid-2-hydroxy-3-phenoxypropyl ester, 57g of glycidyl ester epoxy resin, 2g of expansion monomer and 70g of nano particles are weighed and added into a mixture of 15g of tripropylene glycol diacrylate, 5g of dodecyl vinyl ether and 5g of triethylene glycol divinyl, and the mixture is stirred uniformly. Weighing 5g of triaryl (1-pyrene) bismuth onium salt, 2g of dialkyl benzoyl sulfide salt, 5g of dialkyl benzoyl sulfide salt, 0.1g of 4-dimethyl ethyl aminobenzoate and 2g of camphorquinone, uniformly mixing, adding into the mixture, and uniformly stirring; adding 0.2g of white color, mixing until the color is uniform, and vacuum degassing to obtain the expanded monomer modified light-cured resin.

Example 3

Preparing an expansion monomer: adding 12.3g of 6, 8-dihydroxy-1-anylene into 600 mL of toluene, heating to 110 ℃ under magnetic stirring, refluxing, separating water, adding 0.98 g of p-toluenesulfonic acid, adding 6.2mL of tetraethyl orthocarbonate, reacting for 20 h, cooling to room temperature, decompressing and concentrating a product, and separating and purifying by column chromatography (ethyl acetate: petroleum ether = l: 30) to obtain an expanded monomer for later use.

Preparing nano particles: respectively weighing 5g of silicon gamma-methacryloxypropyl trimethoxysilane, 5g of allyl triethoxysilane, 20g of talcum powder and 40g of gas phase white carbon black; adding the nano particles into a reaction kettle, adding the silane coupling agent while stirring under the stirring state, and stirring at a constant speed for 1-2 hours for later use.

Preparing a light-cured resin: 13g of methyl acrylate, 17g of hydroxybutyl acrylate, 16g of hydroxyethyl methacrylate, 51g of glycidyl ester epoxy resin, 20g of expansion monomer and 25g of nanoparticles are weighed and added to a mixture of 10g of tripropylene glycol diacrylate and 5g of dodecyl vinyl ether, and the mixture is stirred uniformly. Weighing 4g of thiophenyl phenyl diphenyl sulfonium salt, 3g of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 0.2g of 4-dimethyl ethyl benzoate and 0.1g of camphorquinone, uniformly mixing, adding into the mixture, and uniformly stirring; adding gray color 0.8g, mixing until the color is uniform, and vacuum degassing to obtain the expanded monomer modified light-cured resin.

Example 4

Preparing an expansion monomer: adding 5.3g of propane allyl ether diol and 4.5g of allyl propane-1, 3-diol into 350 mL of toluene and 400mL of diethyl ether, heating to 120 ℃ under magnetic stirring, refluxing for water separation, adding 0.88 g of p-toluenesulfonic acid, adding 5.5mL of tetraethyl orthocarbonate, reacting for 15 hours, cooling to room temperature, concentrating the product under reduced pressure, and separating and purifying by column chromatography (ethyl acetate: petroleum ether = l: 30) to obtain an expanded monomer for later use.

Preparing nano particles: respectively weighing 5g of silicon 3-methacryloxypropyl methyldiethoxysilane, 5g of allyl triethoxysilane, 30g of talcum powder, 40g of fumed silica and 30g of mica powder; adding the nano particles into a reaction kettle, adding the silane coupling agent while stirring under the stirring state, and stirring at a constant speed for 1-2 hours for later use.

Preparing a light-cured resin: 27g of hydroxybutyl acrylate, 19g of hydroxyethyl methacrylate, 8g of isobornyl acrylate, 46g of glycidyl ester epoxy resin, 10g of expansion monomer and 55g of nanoparticles are weighed and added into a mixture of 12g of tripropylene glycol diacrylate and 8g of 1, 6-ethylene glycol diacrylate and stirred uniformly. Weighing 0.8g xanthone-based phenyliodonium salt, 5g 2-isopropyl thioxanthone, 5g 4-dimethyl amino ethyl benzoate, 1g camphorquinone and 0.5g coumarin, mixing, adding into the mixture, and stirring; adding 1g of blue color, mixing until the color is uniform, and vacuum degassing to obtain the expanded monomer modified light-cured resin.

Example 5

Preparing an expansion monomer: see example 4.

Preparing nano particles: respectively weighing 15g of silicon gamma-methacryloxypropyl trimethoxy silane, 10g of allyl triethoxy silane, 20g of talcum powder and 30g of mica powder; adding the nano particles into a reaction kettle, adding the silane coupling agent while stirring under the stirring state, and stirring at a constant speed for 1-2 hours for later use.

Preparing a light-cured resin: 26g of hydroxybutyl acrylate, 15g of methacrylic acid, 14g of isobornyl acrylate, 25g of glycidyl ester epoxy resin, 20g of linear aliphatic epoxy resin, 12g of swelling monomer and 50g of nanoparticles were weighed and added to a mixture of 10g of tripropylene glycol diacrylate and 10g of glyceryl carbonate propenyl ether, and the mixture was stirred uniformly. Weighing 1g of dialkyl benzoyl sulfide salt, 2g of triaryl (1-pyrene) bismuth onium salt, 2.0g of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 0.5g of camphorquinone and 0.3g of coumarin, uniformly mixing, adding into the mixture, uniformly stirring, and vacuum degassing to obtain the expanded monomer modified photocuring resin.

Example 6

Preparing an expansion monomer: see example 4.

Preparing nano particles: see example 5.

Preparing a light-cured resin: 16g of polyethylene glycol monoacrylate, 15g of methyl acrylate, 14g of hydroxypropyl acrylate, 29g of glycidyl ester epoxy resin, 26g of alicyclic epoxy resin, 13g of swelling monomer and 63g of nanoparticles were weighed and added to a mixture of 5g of polyoxypropylene polyoxyethylene glycerol ether, 10g of tripropylene glycol diacrylate and 10g of glyceryl carbonate propenyl ether, and the mixture was stirred uniformly. Weighing 1.5g of dialkyl benzoyl sulfide salt, 1.5g of triaryl (1-pyrene) bismuth onium salt, 1.5g of 4-dimethyl ethyl aminobenzoate, 2.0g of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 0.5g of camphorquinone, 0.3g of coumarin and 0.8g of blue pigment, uniformly mixing, adding into the mixture, uniformly stirring, and vacuum degassing to obtain the expanded monomer modified light-cured resin.

Claims (10)

1. An expansion monomer modified light-cured resin and a preparation method thereof are characterized in that the expansion monomer modified light-cured resin is provided, and the main components of the expansion monomer modified light-cured resin comprise: the composite material comprises matrix resin, an expansion monomer, a reactive diluent, a cationic photoinitiator, a free radical photoinitiator, a photosensitive auxiliary agent, nano particles and pigment; calculated according to the mass portion, relative to 100 portions of matrix resin, 8 to 25 portions of reactive diluent, 2 to 20 portions of expansion monomer, 0.8 to 12 portions of cationic photoinitiator, 0.8 to 10 portions of free radical photoinitiator, 0.1 to 2 portions of photosensitizer, 25 to 70 portions of nano-particles and 0 to 1 portion of pigment.

2. The expanded monomer-modified photocurable resin according to claim 1, wherein the matrix resin comprises a combination of an acrylic resin and an epoxy resin;

the acrylic resin includes but is not limited to one or more of methacrylic acid, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobornyl acrylate, n-butyl acrylate, butyl methylacrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, 2-hydroxy-3-phenoxypropyl 2-acrylate, hydroxypentyl acrylate, and hydroxyhexyl acrylate;

the epoxy resin includes, but is not limited to, one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin, and alicyclic epoxy resin.

3. The expanded monomer-modified photocurable resin of claim 1, wherein the reactive diluent is a monomer containing a carbon-carbon double bond, including monomers containing acryloxy, methacryloxy and vinyl groups, including but not limited to one or more of the following combinations: tripropylene glycol diacrylate, triethylene glycol divinyl, dipropylene glycol diacrylate, glyceryl carbonate propenyl ether, triethylene glycol divinyl ether, polyoxypropylene polyoxyethylene glyceryl ether, dodecyl vinyl ether, dodecyl glycidyl ether, silicone-modified polysiloxane, butyl glycidyl ether, and benzyl glycidyl ether 692, 1, 6-ethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolpropane diacrylate.

4. The expanded monomer-modified photocurable resin according to claim 1, wherein the cationic photoinitiator is one or more of xanthone-based phenyliodonium salt, fluorenone-based phenyliodonium salt, cumen (II) hexafluorophosphate, dialkyl benzoylsulfide salt, triaryl (1-pyrene) bismuth salt, dialkyl benzoylsulfide salt, bis (5-fluorothien-2-yl) iodonium formate salt, S-dialkyl-S- (dimethylhydroxyphenyl) sulfide salt and phenylthiophenyl diphenylsulfonium salt.

5. The expandable monomer-modified photocurable resin according to claim 1, wherein the radical photoinitiator is one or more selected from the group consisting of (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, 2-isopropylthioxanthone, ethyl 4-dimethylaminobenzoate, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, methyl o-benzoylbenzoate, tetramethylmichler's ketone, 2, 4-diethylthioxanthone and 1-chloro-4-propoxythioxanthone.

6. The expandable monomer-modified photocurable resin of claim 1, wherein the photo-sensitive auxiliary agent includes, but is not limited to, one or more of camphorquinone, naphthalene, anthracene, pyrene, perylene, carbazole with an N-unsaturated double bond, benzophenone, dibenzoyl, 3, 5-diphenyldithieno [3,2-b:2,3-a ] anthracene, coumarin, and curcumin.

7. The expandable monomer-modified photocurable resin of claim 1, wherein the expandable monomer is prepared by heating a dihydroxy compound or a trihydroxy compound with a orthocarbonate in a corresponding solvent to perform a chemical reaction; the molar ratio of the hydroxy compound to the orthocarbonate is: 2: 1-3: 1, the dosage of the solvent is 15 to 30 times of the mass of the hydroxyl compound.

8. The swelling monomer of claim 7, wherein said dihydroxy compound and said trihydroxy compound are: one or more of ethylene glycol, trimethylolpropane monoallyl ether, propane allyl ether diol, allyl propane-1, 3-diol, phenyl-2-hydroxymethyl propanediol, 6, 8-dihydroxy-1-anylene and glycol-forming oxetane;

the orthocarbonates are tetraethyl orthocarbonate and tetrapropyl orthocarbonate;

the solvent is selected from toluene, xylene and diethyl ether;

the preparation method of the expansion monomer comprises the following steps: adding a dihydroxy compound or a trihydroxy compound and orthocarbonate into a solvent, stirring and heating to 100-120 ℃, and simultaneously carrying out reflux and water diversion; adding p-toluenesulfonic acid, reacting for 15-24h, and cooling to room temperature; the product is decompressed and compressed, and then the expanded monomer is separated and purified by column chromatography.

9. The expanded monomer-modified photocurable resin according to claim 1, wherein the nanoparticles are surface-modified nanoparticles using a silane coupling agent, and the ratio of the silane coupling agent to the modified nanoparticles is 1:3 to 1:10 in parts by mass.

10. The nano-particles according to claim 9, wherein the modified nano-particles are one or more of fumed silica, talc and mica powder, wherein the specific surface area of the fumed silica, the talc and the mica powder is more than 1000 meshes;

the silane coupling agent is siloxane containing unsaturated double bonds, and comprises but is not limited to one or more of gamma-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, allyltriethoxysilane, 5-hexenyltrimethoxysilane, 11-acetoxyundecyltriethoxysilane, 10-alkenylundecyltrimethoxysilane, unsaturated double-bond trimethoxysilane, unsaturated double-bond triethoxysilane, methyl unsaturated double-bond diethoxysilane, methyl unsaturated double-bond dimethoxysilane and tetramethyl di-unsaturated double-bond siloxane;

the preparation method of the nano-particles comprises the following steps:

⑴ respectively weighing silane coupling agent and nanoparticles;

⑵ adding the nanometer particles into the reaction kettle, adding the silane coupling agent while stirring, and stirring at constant speed for 1-2 hours for standby.