阅读说明：本技术 一种可自修复的光固化修复材料及其制备方法 (Self-repairable photocuring repair material and preparation method thereof ) 是由 张良俊 李燕燕 叶世威 于 2021-09-08 设计创作，主要内容包括：在口腔临床修复上,复合树脂材料发挥着重要的作用；复合树脂材料制成的修复体长期处于口腔环境中,每天需要承担数千次的、最高达数百兆帕的咀嚼力,难免会出现微裂纹,降低修复体的使用寿命。本发明的目的旨在提供一种可自修复的光固化树脂修复材料,通过制备能够与复合树脂基体共融的微胶囊,加入到复合树脂修复材料中。由于无极纳米颗粒和微胶囊的添加,体积收缩率小,固化后体积收率≤0.03%,同时提高了修复树脂材料的拉伸强度、断裂韧性、耐磨性。通过表面微裂纹自修复测试显示具有自修复功能的树脂材料能够实现68%的微裂纹修复成功率,能有效的延长临床使用寿命。(In the clinical restoration of the oral cavity, the composite resin material plays an important role; the restoration made of the composite resin material is in an oral cavity environment for a long time, needs to bear the chewing force which is thousands of times and up to hundreds of megapascals every day, and has inevitable microcracks, so that the service life of the restoration is shortened. The invention aims to provide a self-repairable photo-cured resin repair material, which is prepared by preparing microcapsules capable of being co-melted with a composite resin matrix and adding the microcapsules into the composite resin repair material. Due to the addition of the electrodeless nano-particles and the microcapsules, the volume shrinkage rate is small, the volume yield after curing is less than or equal to 0.03%, and meanwhile, the tensile strength, fracture toughness and wear resistance of the repair resin material are improved. The surface microcrack self-repairing test shows that the resin material with the self-repairing function can realize 68% of microcrack repairing success rate and effectively prolong the clinical service life.)

1. A self-repairable photo-curing resin repair material is characterized by mainly comprising the following components: microcapsules, a resin matrix, an active diluent, a photoinitiator, a photosensitive auxiliary agent, electrodeless nanoparticles and other auxiliary agents; according to the mass portion, relative to 100 portions of resin matrix, 9-22 portions of reactive diluent, 2-12 portions of microcapsule, 1.8-3.2 portions of photoinitiator, 0.2-3 portions of photosensitive auxiliary agent, 35-70 portions of electrodeless nano-particles and 0-2 portions of other auxiliary agents.

2. The self-repairable photo-curable resin repair material according to claim 1, wherein the resin matrix is a composition of acrylic resin, epoxy resin, a reinforcing cross-linking agent and an acrylic prepolymer; according to the mass portion, calculated by 100 portions of the total amount, 36-61 portions of acrylic resin, 3-8 portions of epoxy resin, 1-4 portions of reinforcing cross-linking agent and 27-60 portions of acrylic prepolymer;

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 reinforcing crosslinking agent is a monomer with two double bonds, and is one or a composition of more than one of ethylene glycol dimethacrylate, polyethylene glycol diacrylate and methylene bisacrylamide;

the acrylic prepolymer is one or more of bisphenol A-Bis (glycidyl methacrylate) resin (Bis-GMA), Urethane Dimethacrylate (UDMA), ethoxylated bisphenol A dimethacrylate (Bis-EMA) and N, N-dimethylamino ethyl methacrylate.

3. The self-repairable photo-curable resin repair material according to claim 1, wherein the reactive diluent is a monomer containing a carbon-carbon double bond, including a monomer containing an acryloxy group, methacryloxy group and a vinyl group, including but 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.

4. The self-repairable photo-curable resin repair material according to claim 1, wherein the photo-initiator is a radical photo-initiator and a cationic photo-initiator;

the cationic photoinitiator is one or more of xanthone-based phenyliodonium salt, fluorenone-based phenyliodonium salt, cumen (II) hexafluorophosphate, dialkyl benzoyl sulfide salt, triaryl (1-pyrene) bismuth salt, dialkyl benzoyl sulfide salt, bis (5-fluorothien-2-yl) iodonium formate, S-dialkyl-S- (dimethylphenyl) sulfide salt and thiophenyl phenyl diphenyl sulfonium salt;

the free radical photoinitiator is one or more of (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-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.

5. The self-repairable photo-curable resin repair material according to claim 1, wherein the photo-sensitive auxiliary is one or a combination of more than one 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.

6. The self-repairable photo-curable resin repair material according to claim 1, wherein the inorganic nanoparticles are a composite of alumina powder, silica powder, hydroxyapatite and glass powder which are uniformly mixed by stirring; the inorganic nano material comprises the following components in parts by weight: 3-23 parts of alumina powder, 6-21 parts of silica powder, 1-5 parts of hydroxyapatite and 8-38 parts of glass powder.

7. The self-repairable photo-curable resin repair material according to claim 1, wherein the microcapsule is prepared from a urea formaldehyde resin prepolymer, a mixture of methacrylic acid and butyl acrylate, an emulsifier and an initiator;

calculated by mass parts, 100 parts of deionized water, and the dosage of each component is as follows: 5-12 parts of urea-formaldehyde resin prepolymer, 15-36 parts of a mixture of methacrylic acid and butyl acrylate, 0.9-4.2 parts of an emulsifier, 1-2.3 parts of an initiator and the balance of deionized water;

the emulsifier is as follows: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, ethylene maleic anhydride copolymer, span 80, tween 60 and tween 80;

the initiator is one or more of benzoyl peroxide, ammonium persulfate, potassium persulfate and azobisisobutyronitrile.

8. The microcapsule according to claim 7, wherein the urea resin prepolymer is prepared by the following steps: adding 37% of formaldehyde and urea into a reaction container, stirring and mixing to fully dissolve the urea in the formaldehyde; adding sodium hydroxide to adjust the pH value to 8-10, and reacting at the temperature of 60-85 ℃ for 1-3 h to obtain a urea-formaldehyde resin prepolymer; the mass ratio of the 37 percent of formaldehyde to the urea is 6: (1.5-3);

the preparation method of the mixture of methacrylic acid and butyl acrylate comprises the following steps: adding a reaction promoter into methacrylic acid and butyl acrylate, and uniformly stirring and mixing; the mass ratio of the methacrylic acid to the butyl acrylate is as follows: 10: (3.5-4.5);

the reaction accelerator comprises: one or more of N, N-Dimethylaniline (DMA), N-dimethyl-p-toluidine, N-di-2-hydroxyethylaniline, N-di (2-hydroxyethyl) p-toluidine and N, N-di (2-hydroxypropyl) p-toluidine (DHPT), and the using amount of the composition is 0.9% -2.2% of the total amount of methacrylic acid and butyl acrylate.

9. A microcapsule according to claim 7, characterized in that the preparation process comprises the following steps: (1) adding deionized water and an emulsifier into a reaction container, and uniformly stirring and dispersing; adding a mixture of methacrylic acid and butyl acrylate, dropwise adding 1/2 initiator under a stirring state, and stirring for reacting for 1-3 h; the reaction temperature is 55-85 ℃, and the stirring speed is 200-750 r/min; (2) adding the urea-formaldehyde resin prepolymer, stirring and dispersing, dropwise adding 1/2 initiator, stirring and reacting for 2-4 h to form stable emulsion; the reaction temperature is 55-85 ℃, and the stirring speed is 200-750 r/min;

(3) and (3) adding hydrochloric acid to adjust the pH value to 3-4 to form a suspension, repeatedly filtering and washing for 3-5 times by using deionized water, and drying in a drying oven at 50-60 ℃ for 24 hours to obtain the microcapsule.

10. The self-repairable photo-cured resin repair material according to claim 1, wherein the preparation method of the self-repairable photo-cured resin repair material comprises the following steps:

(1) preparing microcapsules, inorganic nano particles and a resin matrix according to the preparation method of the invention respectively for later use;

(2) weighing electrodeless nano particles and half of the required amount of reactive diluent, and adding the reactive diluent into the electrodeless nano particles; fully stirring and mixing the materials by a star-shaped stirring dispersion machine at the stirring speed of 500-1500 r/min for 1-2 h;

(3) weighing matrix resin, microcapsules and other additives, adding the matrix resin, the microcapsules and the other additives into the other half of the reactive diluent, and shearing and stirring the mixture uniformly; stirring at a speed of 500-1500 r/min for 2-4 h;

(4) weighing a photoinitiator and a photosensitive auxiliary agent, adding the photoinitiator and the photosensitive auxiliary agent into the mixture, uniformly stirring, and performing vacuum degassing to obtain the self-repairable photocuring resin repair material; and (3) stirring at the speed of 50-100 r/min while degassing, and keeping the vacuum degree of-0.1 MPa for 5-10 min.

Technical Field

The invention belongs to the field of functional polymer materials, and particularly relates to a light-cured composite resin repair material with a self-repair function and a preparation method thereof.

Background

With the improvement of scientific technology and living standard, the health of teeth is more and more emphasized by people. As one of many successful paradigms of biomaterial research, composite resin materials are increasingly used in dental restorations. The oral cavity is a relatively complex environment and has relatively high requirements for repair materials. Firstly, the material has good biocompatibility, no irritation to gum and soft tissue, no cytotoxicity and the like; can not be corroded by saliva or food, has higher chemical stability, and is simple to operate. Dental filling materials, restorative materials, are used to restore, achieve, or improve the function of a patient's teeth. At present, the dental repair material commonly used in oral clinic is light-cured composite resin. In China, the research on dental light-cured composite resin materials is still in the primary stage, and the dental light-cured composite resin materials are weak in technology, poor in product and far behind imported products in performance.

In clinical oral cavity repair and beauty treatment, the light-cured composite resin material consists of matrix resin, a light initiation system, inorganic filler, an auxiliary agent and the like. Different components and organic-inorganic interface properties in the composite resin material have different influences on the material performance. The resin matrix mainly determines the photocuring rate, polymerization shrinkage, water absorption, color stability, storage stability and the like. The inorganic filler mainly affects the mechanical properties, the glossiness and the like of the material. While flexural strength, elastic modulus, consistency, transparency, water solubility and biocompatibility are determined by the filler and matrix together. In addition, the interfacial bonding strength of the matrix and the filler is a key factor for maintaining the stability and prolonging the service life of the material.

When the composite resin material is in an oral environment for a long time, water molecules gradually permeate into the material to cause polymer depolymerization, and simultaneously, the water molecules can weaken the intermolecular force of the polymer to generate microcracks. The composite repairing material needs to bear the chewing force which is thousands of times and up to hundreds of megapascals every day, and the repairing resin material inevitably generates microcracks, so that the repairing body is fractured, and the service life is shortened. The self-repairing technology is a hotspot of research in recent years, and can improve the physical and chemical properties of the material and prolong the service life of the repairing material. The self-repairing material realizes self healing of the material by designing a high molecular structure or introducing a self-repairing starting medium. The design of the macromolecular structure relates to the introduction of the interaction such as ring-opening addition reaction, exchange reaction, hydrogen bond, ionic bond, coordination bond, pi-pi bond stacking and the like. These interactions are dynamically reversible, and when damage occurs, the interaction is destroyed, macroscopically by breaking or scratching of the material, microscopically by breaking of the molecular chains and disappearance of the inter-chain forces. In healing, the damaged sections need to be closely contacted together, certain conditions are provided, reverse reaction is triggered, and the molecular chain can move highly. Thus, the lost inter-chain forces recombine, the molecular chains reform, and macroscopically appear as self-healing of the material.

Aiming at the condition that the service life of the composite resin repairing material is influenced by the damage caused by the influence of a humid environment, chewing pressure and the like when the composite resin repairing material is clinically applied, the invention prepares the microcapsule which can be co-melted with the composite resin matrix through an in-situ polymerization method and adds the microcapsule into the composite resin repairing material. Due to the addition of the microcapsule, the biocompatibility of the repair resin material is not influenced, and the tensile strength, the fracture toughness and the wear resistance of the repair resin material are improved. The surface microcrack self-repairing test shows that the resin material with the self-repairing function can realize 68% of microcrack repairing success rate and effectively prolong the clinical service life.

Disclosure of Invention

The invention aims to provide a composite resin repairing material, in particular to a light-cured composite resin repairing material with a self-repairing function and a preparation method thereof. The invention improves the mechanical property of the composite resin repairing material and prolongs the clinical service life by introducing the microcapsule into the composite resin.

The self-repairable photo-cured resin repair material mainly comprises the following components: microcapsules, a resin matrix, an active diluent, a photoinitiator, a photosensitive auxiliary agent, electrodeless nanoparticles and other auxiliary agents; according to the mass portion, relative to 100 portions of resin matrix, 9-22 portions of reactive diluent, 2-12 portions of microcapsule, 1.8-3.2 portions of photoinitiator, 0.2-3 portions of photosensitive auxiliary agent, 35-70 portions of electrodeless nano-particles and 0-2 portions of other auxiliary agents.

The resin matrix is a composition of acrylic resin, epoxy resin, a reinforcing cross-linking agent and an acrylic prepolymer; according to the mass portion, calculated by 100 portions of the total weight, 36-61 portions of acrylic resin, 3-8 portions of epoxy resin, 1-4 portions of reinforcing cross-linking agent and 27-60 portions of acrylic prepolymer.

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 reinforcing crosslinking agent is a monomer with two double bonds, and is one or a composition of more than one of ethylene glycol dimethacrylate, polyethylene glycol diacrylate and methylene bisacrylamide.

The acrylic prepolymer is one or more of bisphenol A-Bis (glycidyl methacrylate) resin (Bis-GMA), Urethane Dimethacrylate (UDMA), ethoxylated bisphenol A dimethacrylate (Bis-EMA) and N, N-dimethylamino ethyl methacrylate.

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 photoinitiator is a free radical photoinitiator and a cationic photoinitiator. 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, S-dialkyl-S- (dimethylphenyl) sulfide salt and thiophenyl-phenyl diphenyl sulfonium salt.

The free radical photoinitiator is one or more of (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-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.

The photosensitive auxiliary agent is one or a composition of more than one of camphorquinone, naphthalene, anthracene, pyrene, perylene, carbazole with N-unsaturated double bonds, benzophenone, dibenzoyl, 3, 5-diphenyl dithieno [3,2-b:2,3-a ] anthracene, coumarin and curcumin.

The inorganic nano particles are a compound of alumina powder, silica powder, hydroxyapatite and glass powder which are uniformly mixed by stirring.

The inorganic nano material comprises the following components in parts by weight: 3-23 parts of alumina powder, 6-21 parts of silica powder, 1-5 parts of hydroxyapatite and 8-38 parts of glass powder.

Such other adjuvants include, but are not limited to, odorants, coloring agents, bacteriostats, and the like.

The microcapsule is prepared from a urea-formaldehyde resin prepolymer, a mixture of methacrylic acid and butyl acrylate, an emulsifier and an initiator. Calculated by mass parts, 100 parts of deionized water, and the dosage of each component is as follows: 5-12 parts of urea-formaldehyde resin prepolymer, 15-36 parts of a mixture of methacrylic acid and butyl acrylate, 0.9-4.2 parts of an emulsifier, 1-2.3 parts of an initiator and the balance of deionized water.

The emulsifier is as follows: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, ethylene maleic anhydride copolymer, span 80, Tween 60 and Tween 80.

The initiator is one or more of benzoyl peroxide, ammonium persulfate, potassium persulfate and azobisisobutyronitrile.

The preparation method of the urea resin prepolymer comprises the following steps: adding 37% of formaldehyde and urea into a reaction vessel, stirring and mixing to fully dissolve the urea in the formaldehyde. Adding sodium hydroxide to adjust the pH value to 8-10, and reacting at the temperature of 60-85 ℃ for 1-3 h to obtain the urea-formaldehyde resin prepolymer. The mass ratio of the 37 percent of formaldehyde to the urea is 6: (1.5 to 3).

The preparation method of the mixture of methacrylic acid and butyl acrylate comprises the following steps: and (3) adding a reaction promoter into methacrylic acid and butyl acrylate, and stirring and mixing uniformly. The mass ratio of the methacrylic acid to the butyl acrylate is as follows: 10: (3.5-4.5). The reaction accelerator comprises: one or more of N, N-Dimethylaniline (DMA), N-dimethyl-p-toluidine, N-di-2-hydroxyethylaniline, N-di (2-hydroxyethyl) p-toluidine and N, N-di (2-hydroxypropyl) p-toluidine (DHPT), and the using amount of the composition is 0.9% -2.2% of the total amount of methacrylic acid and butyl acrylate.

The preparation method of the microcapsule comprises the following steps: (1) adding deionized water and an emulsifier into a reaction vessel, and stirring and dispersing uniformly. And adding a mixture of methacrylic acid and butyl acrylate, dropwise adding 1/2 initiator under a stirring state, and stirring for reacting for 1-3 h. The reaction temperature is 55-85 ℃, and the stirring speed is 200-750 r/min.

(2) Adding the urea-formaldehyde resin prepolymer, stirring and dispersing, dropwise adding 1/2 initiator, stirring and reacting for 2-4 h to form stable emulsion. The reaction temperature is 55-85 ℃, and the stirring speed is 200-750 r/min.

(3) And (3) adding hydrochloric acid to adjust the pH value to 3-4 to form a suspension, repeatedly filtering and washing for 3-5 times by using deionized water, and drying in a drying oven at 50-60 ℃ for 24 hours to obtain the microcapsule.

The preparation method of the self-repairable photocuring repair material comprises the following steps:

(1) the microcapsule, the inorganic nano-particles and the resin matrix are respectively prepared according to the preparation method of the invention for standby.

(2) Weighing electrodeless nano particles and half of the required amount of reactive diluent, and adding the reactive diluent into the electrodeless nano particles. Fully stirring and mixing the materials by a star-shaped stirring dispersion machine, wherein the stirring speed is 500-1500 r/min, and the dispersion time is 1-2 h.

(3) Weighing matrix resin, microcapsules and other additives, adding the matrix resin, the microcapsules and the other additives into the other half of the reactive diluent, and shearing and stirring the mixture uniformly; the stirring speed is 500-1500 r/min, and the time is 2-4 h.

(4) Weighing a photoinitiator and a photosensitive auxiliary agent, adding the photoinitiator and the photosensitive auxiliary agent into the mixture, uniformly stirring, and performing vacuum degassing to obtain the self-repairable photocuring resin repair material. And (3) stirring at the speed of 50-100 r/min while degassing, and keeping the vacuum degree of-0.1 MPa for 5-10 min.

The preparation method of the self-repairable photocuring repair material does not represent the only form in which the invention can be prepared 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 self-repairable photo-curing repair material prepared by the invention has small volume shrinkage due to the addition of the electrodeless nano-particles and the microcapsules, and the volume yield after curing is less than or equal to 0.03 percent. Under the coordination of the light curing agent and the photosensitizer, the curing rate and the curing completion rate are improved, and the storage stability of the product is improved. After the curing is finished, the resin matrix and the inorganic nano particles are completely integrated, and the mechanical property, the long-time stability, the wear resistance and the water absorption rate of the cured resin matrix are obviously improved. When the cured resin material is damaged by external force to generate microcracks, the microcracks can be repaired through the microcapsules, and the self-repairing rate reaches over 68 percent through observation of a scanning electron microscope.

Detailed Description

The present invention is further illustrated by the following examples.

Example 1

Preparing microcapsules: (1) 600g of 37% formaldehyde and 200g of urea are added to a reaction vessel, and the mixture is stirred and mixed until the urea is sufficiently dissolved in the formaldehyde. NaOH is added to adjust the pH value to 9, and the urea-formaldehyde resin prepolymer is obtained after the reaction for 3 hours at the temperature of 60 ℃. (2) 600g of methacrylic acid and 240g of butyl acrylate are weighed, 10g of N, N-Dimethylaniline (DMA) is added, and the mixture is stirred and mixed uniformly for later use. (3) 20g of sodium dodecyl benzene sulfonate and 10g of Tween 60 are weighed and added into 1KG ionized water, and stirred and dispersed until the sodium dodecyl benzene sulfonate and the Tween 60 are completely dissolved. 200g of a mixture of methacrylic acid and butyl acrylate was added thereto, and 8g of a benzoyl peroxide solution was added dropwise with stirring, followed by reaction with stirring for 1.5 hours. Adding 80g of urea-formaldehyde resin prepolymer, stirring and dispersing, dropwise adding 8g of benzoyl peroxide solution, stirring and reacting for 3 hours to form stable emulsion. The reaction temperature is 65 ℃, and the stirring speed is controlled between 200 and 750 r/min. And (3) adding hydrochloric acid to adjust the pH value to 3.5 to form a suspension, repeatedly filtering and washing the suspension for 3-5 times by using deionized water, and drying the suspension in a drying oven at the temperature of 50-60 ℃ for 24 hours to obtain the microcapsule.

Preparing a resin matrix: 200g of methyl methacrylate, 200g of butyl acrylate, 40g of glycidyl ether epoxy resin, 30g of ethylene glycol dimethacrylate and 530g of bisphenol A-Bis glycidyl methacrylate resin (Bis-GMA) were stirred and mixed uniformly.

Preparing inorganic nano particles: weighing 30g of alumina powder, 100g of silica powder, 20g of hydroxyapatite and 350g of glass powder, and uniformly stirring and mixing for later use.

Preparing a self-repairable photocuring repair material: (1) 55g of tripropylene glycol diacrylate and 10g of triethylene glycol divinyl are weighed and added into 350g of inorganic nano particles, and the inorganic nano particles are fully stirred by a star-shaped stirring dispersion machine, wherein the dispersion time is 1.5h, and the stirring speed is controlled between 500r/min and 1500 r/min. (2) Weighing 1000g of resin matrix, 120g of microcapsule and 5g of mint odorant, adding the mixture into a mixture of 55g of tripropylene glycol diacrylate and 10g of triethylene glycol, and shearing and stirring for 2 hours, wherein the stirring speed is controlled between 500 and 1500 r/min. (3) Adding 20g fluorenone phenyl iodonium salt and 2.0g camphorquinone, stirring for 260min, vacuum degassing while stirring, and maintaining for 8min when the vacuum degree is-0.1 MPa. The water absorption of the repair material after curing is 28 mu g/mm³The flexural strength of a dumbbell type standard test piece is 215MPa, the breaking strength is 310MPa, and the self-repairing rate of microcracks is 78%.

Example 2

Preparing microcapsules: (1) 600g of 37% formaldehyde and 150g of urea are added into a reaction vessel, and stirred and mixed until the urea is fully dissolved in the formaldehyde. NaOH is added to adjust the pH value to 8, and the urea-formaldehyde resin prepolymer is obtained after the reaction for 1h at the temperature of 85 ℃. (2) 300g of methacrylic acid and 105g of butyl acrylate are weighed, 2g of N, N-Dimethylaniline (DMA) and 1.65g of N, N-dimethyl-p-toluidine are added, stirred and mixed uniformly for later use. (3) 5g of sodium dodecyl sulfate and 4g of Tween 80 are weighed and added into 1KG ionized water, and stirred and dispersed until the sodium dodecyl sulfate and the Tween 80 are completely dissolved. 150g of a mixture of methacrylic acid and butyl acrylate was added thereto, and 5g of potassium persulfate solution was added dropwise with stirring, followed by reaction with stirring for 2 hours. Adding 50g of urea-formaldehyde resin prepolymer, stirring and dispersing, dropwise adding 5g of potassium persulfate solution, stirring and reacting for 4 hours to form stable emulsion. The reaction temperature is 55 ℃, and the stirring speed is controlled between 200 and 750 r/min. And (3) adding hydrochloric acid to adjust the pH value to 3 to form a suspension, repeatedly filtering and washing the suspension for 3-5 times by using deionized water, and drying the suspension in a drying oven at the temperature of 50-60 ℃ for 24 hours to obtain the microcapsule.

Preparing a resin matrix: 200g of methacrylic acid, 160g of ethyl acrylate, 80g of glycidyl amine epoxy resin, 25g of ethylene glycol dimethacrylate and 535g of bisphenol A-Bis glycidyl methacrylate resin (Bis-GMA) were stirred and mixed uniformly.

Preparing inorganic nano particles: 230g of alumina powder, 60g of silica powder, 10g of hydroxyapatite and 150g of glass powder are weighed, stirred and mixed uniformly for later use.

Preparing a self-repairable photocuring repair material: (1) weighing 110g of tripropylene glycol diacrylate, adding the tripropylene glycol diacrylate into 700g of inorganic nano-particles, and fully stirring the tripropylene glycol diacrylate by a star-shaped stirring dispersion machine for 2 hours at a stirring speed of 500-1500 r/min. (2) Weighing 1000g of resin matrix, 20g of microcapsule and 3g of nano silver particles, adding into 110g of tripropylene glycol diacrylate, shearing and stirring for 2 hours, wherein the stirring speed is controlled between 500r/min and 1500 r/min. (3) Adding 20g of fluorenone phenyl iodonium salt and 60g of cumen (II) hexafluorophosphate, stirring for 360min, vacuum degassing while stirring, and keeping the vacuum degree at-0.1 MPa for 8min to obtain the photocuring repair material. The water absorption of the repair material after curing is 32 mu g/mm³The flexural strength of the dumbbell type standard test piece is 315MPa, the breaking strength is 360MPa, and the self-repairing rate of microcracks is 70%.

Example 3

Preparing microcapsules: (1) 300g of 37% formaldehyde and 150g of urea are added into a reaction vessel, and stirred and mixed until the urea is fully dissolved in the formaldehyde. NaOH is added to adjust the pH value to 10, and the urea-formaldehyde resin prepolymer is obtained after the reaction for 3 hours at the temperature of 60 ℃. (2) 200g of methacrylic acid and 90g of butyl acrylate are weighed, 3g of N, N-bis (2-hydroxyethyl) p-toluidine and 3.38g of N, N-dimethyl p-toluidine are added, stirred and mixed uniformly for later use. (3) 20g of sodium dodecyl sulfate and 22g of Tween 80 are weighed and added into 1KG ionized water, and stirred and dispersed until the sodium dodecyl sulfate and the Tween 80 are completely dissolved. 350g of a mixture of methacrylic acid and butyl acrylate was added thereto, and 11.5g of an ammonium persulfate solution was added dropwise with stirring, followed by reaction with stirring for 3 hours. Adding 100g of urea-formaldehyde resin prepolymer, stirring and dispersing, dropwise adding 11.5g of potassium persulfate solution, stirring and reacting for 4 hours to form stable emulsion. The reaction temperature is 85 ℃, and the stirring speed is controlled to be 200-750 r/min. And (3) adding hydrochloric acid to adjust the pH value to 4 to form a suspension, repeatedly filtering and washing the suspension for 3-5 times by using deionized water, and drying the suspension in a drying oven at the temperature of 50-60 ℃ for 24 hours to obtain the microcapsule.

Preparing a resin matrix: 300g of butyl acrylate, 310g of ethyl methacrylate, 30g of glycidyl amine epoxy resin, 40g of ethylene glycol dimethacrylate, 150g of bisphenol A-Bis glycidyl methacrylate resin (Bis-GMA) and 170g of Urethane Dimethacrylate (UDMA) were stirred and mixed uniformly.

Preparing inorganic nano particles: weighing 130g of alumina powder, 210g of silica powder, 50g of hydroxyapatite and 80g of glass powder, and uniformly stirring and mixing for later use.

Preparing a self-repairable photocuring repair material: (1) 70g of tripropylene glycol diacrylate and 20g of triethylene glycol divinyl are weighed and added into 400g of inorganic nano particles, and the inorganic nano particles are fully stirred by a star-shaped stirring dispersion machine, wherein the dispersion time is 1h, and the stirring speed is controlled between 500r/min and 1500 r/min. (2) Weighing 1000g of resin matrix, 80g of microcapsule and 4g of nano silver particles, adding into 70g of tripropylene glycol diacrylate, shearing and stirring for 4 hours, wherein the stirring speed is controlled between 500r/min and 1500 r/min. (3) Adding 18g of fluorenone phenyl iodonium salt and 30g of camphorquinone, stirring for 280min, then vacuum degassing, stirring while vacuum degassing, and keeping for 5min when the vacuum degree is-0.1 Mpa, thereby obtaining the photocuring repair material for repair. The water absorption of the repair material after curing is 36 mu g/mm³The flexural strength of the dumbbell type standard test piece is 363MPa, the breaking strength is 378MPa, and the self-repairing rate of microcracks is 73%.

Example 4

Preparing microcapsules: the microcapsules prepared in example 1 were used.

Preparing a resin matrix: 240g of butyl acrylate, 110g of isobornyl ester, 60g of glycidyl amine epoxy resin, 10g of methylene bisacrylamide, 20g of ethylene glycol dimethacrylate, 160g of bisphenol A-Bis glycidyl methacrylate resin (Bis-GMA) and 400g of Urethane Dimethacrylate (UDMA) were uniformly mixed by stirring.

Preparing inorganic nano particles: weighing 60g of alumina powder, 110g of silica powder, 30g of hydroxyapatite and 380g of glass powder, and uniformly stirring and mixing for later use.

Preparing a self-repairable photocuring repair material: (1) balance60g of tripropylene glycol diacrylate, 35g of trimethylolpropane triacrylate and 10g of trimethylolpropane tetraacrylate are added into 450g of inorganic nano-particles, and the mixture is fully stirred by a star-shaped stirring dispersion machine for 1.5h, wherein the stirring speed is controlled between 500 and 1500 r/min. (2) Weighing 1000g of resin matrix, adding 85g of microcapsules into 105g of tripropylene glycol diacrylate, shearing and stirring for 2 hours, wherein the stirring speed is controlled between 500 and 1500 r/min. (3) Adding 15g (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 3g fluorenone phenyl iodonium salt and 5g camphorquinone, stirring for 280min, vacuum degassing while stirring, and maintaining for 10min when the vacuum degree is-0.1 MPa. The water absorption of the repair material after curing is 26 mu g/mm³The flexural strength 357Mpa, the breaking strength 396Mpa and the self-repairing rate of microcracks of the dumbbell type standard test piece are tested.

Example 5

Preparing microcapsules: (1) 300g of 37% formaldehyde and 100g of urea are added into a reaction vessel, and stirred and mixed until the urea is fully dissolved in the formaldehyde. NaOH is added to adjust the pH value to 9, and the urea-formaldehyde resin prepolymer is obtained after the reaction for 3 hours at the temperature of 65 ℃. (2) 200g of methacrylic acid and 80g of butyl acrylate are weighed, 3g of N, N-Dimethylaniline (DMA) and 3g of N, N-dimethyl-p-toluidine are added, stirred and mixed uniformly for later use. (3) 20g of sodium dodecyl benzene sulfonate, 5g of sodium dodecyl sulfate and 7g of Tween 60 are weighed and added into 1KG of ionized water, and the mixture is stirred and dispersed until the mixture is completely dissolved. Methacrylic acid and 220g butyl acrylate were added, and 12g of benzoyl peroxide solution was added dropwise with stirring, followed by reaction with stirring for 2 hours. Adding 80g of urea-formaldehyde resin prepolymer, stirring and dispersing, dropwise adding 12g of potassium persulfate solution, stirring and reacting for 3.5h to form stable emulsion. The reaction temperature is 70 ℃, and the stirring speed is controlled to be 200-750 r/min. And (3) adding hydrochloric acid to adjust the pH value to 3.5 to form a suspension, repeatedly filtering and washing the suspension for 3-5 times by using deionized water, and drying the suspension in a drying oven at the temperature of 50-60 ℃ for 24 hours to obtain the microcapsule.

Preparing a resin matrix: the resin matrix prepared in example 2 was used.

Preparing inorganic nano particles: weighing 90g of alumina powder, 120g of silica powder, 40g of hydroxyapatite and 350g of glass powder, and uniformly stirring and mixing for later use.

Preparing a self-repairable photocuring repair material: (1) 80g of trimethylolpropane triacrylate and 10g of ditrimethylolpropane tetraacrylate are weighed and added into 480g of inorganic nano particles, and the mixture is fully stirred for 2 hours by a star-shaped stirring dispersion machine, wherein the stirring speed is controlled between 500 and 1500 r/min. (2) Weighing 1000g of resin matrix, adding 90g of microcapsules into 60g of tripropylene glycol diacrylate and 30g of trimethylolpropane triacrylate, and shearing and stirring for 3 hours at a stirring speed of 500-1500 r/min. (3) Adding 12g (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 3g fluorenone phenyl iodonium salt, 2g 1-hydroxycyclohexyl phenyl ketone and 5g camphorquinone, stirring for 300min, vacuum degassing while stirring, and maintaining for 6min when the vacuum degree is-0.1 MPa to obtain the photocuring repair material. The water absorption of the repair material after curing is 33 mu g/mm³The flexural strength of the dumbbell type standard test piece is 369MPa, the breaking strength is 402MPa, and the self-repairing rate of microcracks is 75.6 percent.