阅读说明：本技术 一种纳米纤维增强树脂基修复材料及其制备方法 (Nanofiber reinforced resin-based repair material and preparation method thereof ) 是由 张良俊 李燕燕 叶示威 于 2021-09-04 设计创作，主要内容包括：本发明的目的旨在提供一种纳米纤维增强树脂基光固化修复材料及其制备方法。纤维作为复合材料重要的增强体,在齿科修复材料的应用上,具有提高光固化树脂的强度、模量,降低材料的固化收缩等优点。本发明采用熔融纺丝技术制备成纳米纤维,作为聚合物修复材料的组分,制备光固化修复材料。纳米纤维的添加提高了复合材料的拉伸强度、断裂强度,大大降低了固化后产品的变形和开裂。采用光固化方式,复合光引发体系的使用,提高了固化速率和固化完成率,同时提高了产品的储存稳定性。纳米纤维增强树脂基修复材料固化后的吸水率小于30μg/mm～(3),挠曲强度大于185Mpa,弹性模量介于1.7～3.6Gpa,表面的耐摩擦性达到8万次无变化。(The invention aims to provide a nanofiber reinforced resin-based photocuring repair material and a preparation method thereof. The fiber is used as an important reinforcement of the composite material, and has the advantages of improving the strength and modulus of the light-cured resin, reducing the curing shrinkage of the material and the like in the application of dental repair materials. The invention adopts the melt spinning technology to prepare the nano-fiber,the light-cured repair material is prepared as a component of a polymer repair material. The addition of the nano-fiber improves the tensile strength and the breaking strength of the composite material, and greatly reduces the deformation and cracking of the cured product. By adopting a photocuring mode and using a composite photo-initiation system, the curing speed and the curing completion rate are improved, and the storage stability of the product is improved. The water absorption rate of the cured nanofiber reinforced resin-based repair material is less than 30 mu g/mm 3 The flexural strength is more than 185Mpa, the elastic modulus is between 1.7 and 3.6Gpa, and the surface friction resistance is unchanged for 8 ten thousand times.)

1. A nanofiber reinforced resin-based repair material is characterized by mainly comprising the following components: the nano-fiber, acrylic resin, inorganic nano-particles, porcelain powder materials, a photoinitiator, an initiation aid and an acrylic hydroxyl compound;

the dosage of the components is as follows according to the mass parts: 0.5-5 parts of nano fiber, 8-41 parts of acrylic resin, 6-28 parts of inorganic nano particles, 3-22 parts of porcelain powder material, 1-8 parts of photoinitiator, 0-2 parts of initiation assistant and 0.5-5 parts of acrylic hydroxyl compound.

2. The nanofiber reinforced resin-based repair material as claimed in claim 1, wherein the nanofibers are prepared from glass powder and polymethyl methacrylate (PMMA) by melt spinning and hot drawing; the glass powder is prepared from the following components in parts by mass of polymethyl methacrylate (PMMA) 100: 3-9 parts; the polymethyl methacrylate (PMMA) has the hardness of 2H and the tensile strength of more than or equal to 77 Mpa; the glass powder has the mesh number of 3500-4000 meshes.

3. The nanofiber reinforced resin-based repair material according to claim 1, wherein the acrylic resin 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 dimethylaminoethyl methacrylate.

4. The nanofiber reinforced resin-based repair material according to claim 1, wherein the inorganic nanoparticles are a composite of alumina powder, silica powder, hydroxyapatite and glass powder; the inorganic nano-particles comprise 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; the inorganic nano-particles are subjected to surface treatment by adopting a silane coupling agent, and the using amount of the silane coupling agent is 12-36% of that of the inorganic nano-particles by mass ratio; the surface treatment steps are as follows:

1) weighing each component of the inorganic nano particles respectively, adding the components into a reaction kettle, and uniformly mixing;

2) slowly adding a silane coupling agent in a stirring state; after the addition, continuously stirring for 45-90 min;

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.

5. The nanofiber reinforced resin-based repair material as claimed in claim 1, wherein the ceramic powder material is one or more of glass ceramic and all-ceramic; the glass ceramic is one or more of apatite glass ceramic, mica glass ceramic, leucite glass ceramic and lithium disilicate glass ceramic; the above full-ceramic is one or more of feldspar ceramic full-ceramic, leucite full-ceramic, alumina full-ceramic, zirconia full-ceramic and spinel full-ceramic.

6. The nanofiber reinforced resin-based repair material according to claim 1, characterized in that the photoinitiator is a 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 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.

7. The nanofiber reinforced resin-based repair material as claimed in claim 1, wherein the initiation assistant is 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.

8. The nanofiber reinforced resin-based repair material according to claim 1, wherein the hydroxyl acrylate compound is one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.

9. The nanofiber reinforced resin-based repair material as claimed in claim 1, wherein the preparation method of the nanofiber reinforced resin-based repair material comprises the following steps:

(1) firstly, preparing nano fibers and inorganic nano particles for later use;

(2) weighing the nano-fiber, the acrylic resin, the inorganic nano-particles and the porcelain powder material, and stirring and mixing the materials in a shear dispersion machine to be uniform; the shearing dispersion machine is of an 8-rotor structure, the torque is 3.5-26 Nm, and the rotating speed is 2000-3000 rpm during working;

(3) weighing a photoinitiator, an initiation aid and an acrylic hydroxyl compound, adding the photoinitiator, the initiation aid and the acrylic hydroxyl compound into the mixture, and uniformly stirring the mixture at the rotating speed of 2000-3000 rpm for 90-360 min; and degassing for 4-15 min in vacuum to obtain the nanofiber reinforced resin matrix repairing material.

10. The nanofiber according to claim 2, wherein the nanofiber is prepared by the following method:

(1) weighing corresponding polymethyl methacrylate (PMMA) and glass powder according to the specified mass parts, uniformly mixing, and adding into a hopper of a melt-blowing injection molding machine; controlling the melt-blowing temperature at 210-270 ℃, and heating to melt the mixture; (2) pressurizing to extrude the molten mixture from a nozzle, wherein the pore size of the nozzle is 1-5 um, so as to obtain initial fiber yarns; (3) stretching the initial fiber yarns by unidirectional hot stretching at the stretching temperature of 110-170 ℃ for 5-10 min, wherein the stretching rate is 30% -80%; and cutting the stretched fiber filaments for 3 times, controlling the cutting precision to be 2-10 um and the cutting speed to be 1000-1900 mm/s, and obtaining the nano fibers through cutting.

Technical Field

The invention belongs to the field of high-molecular light-cured composite materials, and relates to a nanofiber reinforced resin-based light-cured repair material and a preparation method thereof.

Background

The research and practice of human dental restoration has been in the past millennium history, and the adopted dental restoration materials have undergone several serious changes from the initial precious metals such as gold, silver, copper and the like to the silver-mercury alloy which is used in the world in large area in recent times, and then to the resin-based dental restoration materials which are raised in the last 60 th century. The innovation and development of the repair material are the basis of the dental repair revolution, and the dental clinical repair technology is not developed without the improvement and development of material science. Today, clinical restoration is focused on not only the function of teeth, but also aesthetics and minimally invasive technology.

In clinical application, functionalized metal materials and novel resin-based composite materials are two important types of repair materials. The composite material based on the polymer resin is more and more popular with doctors in clinical application, and occupies more and more market space. With the progress and the performance improvement of the resin-based composite material, the resin-based composite material can be clinically used for cavity filling, defect repair, false tooth manufacturing, orthodontics, temporary oral cavity repair and the like. The types of resin-based composite materials are more and more diversified along with the increase of clinical application, and the resin-based composite materials comprise simple resin, inorganic filler reinforced composite materials, fiber reinforced composite materials and the like. The fiber reinforced composite material is added with the fiber as the reinforcing component of the resin material, thereby improving the mechanical property and long-term fatigue resistance of the composite material and greatly improving the effect of clinical application.

The dental restoration material mainly comprises the following components: polymer resins, fillers, catalysts, and the like. Dental fillers are mainly inorganic fillers. The inorganic filler is used as a dispersion phase and a reinforcement in the composite material, so that the mechanical properties of the composite material, such as strength, modulus and the like, can be improved, and meanwhile, the wear resistance of the material can be improved, so that the service life of the material is prolonged. Because the modulus of the inorganic filler is different from that of the resin, the inorganic filler can play a role in reducing the volume shrinkage rate in the curing process of the composite material. During the development of inorganic fillers, particles have gone from micron to nanometer in size; the variety of products also ranges from the earliest quartz powders to silica to barium, silver, glass powders and ceramic powders, to name a few. The nano particles have huge specific surface area, and the characteristics of the nano particles such as surface effect, quantum size effect, macroscopic quantum tunneling effect and the like enable the nano particles to greatly improve the performance of the material under the condition of small addition amount. As a result, nanofillers are becoming more and more of a concern to researchers and users. Fibers have played an irreplaceable role as an important reinforcement in composites in many products. In the application of dental repair materials, the fiber has the advantages of improving the strength and modulus of the light-cured resin, reducing the curing shrinkage of the material, prolonging the service life of the material and the like. Due to the existence of the fiber, the composite material is limited in crack growth when being stressed to generate cracks, so that the toughness and the breaking strength of the material are improved.

The invention adopts the melt spinning technology to blend the inorganic nano-filler into the high polymer material to prepare the nano-fiber. The surface of the nanofiber is modified through infiltration, and then the nanofiber is used as a component of a polymer repair material to prepare the photocuring repair material. Because the inorganic nano-filler and the fiber are adopted to reinforce and modify the polymer material, the resin-based repair material prepared by the invention has the advantages of low shrinkage, high mechanical strength, good fracture toughness, durable wear resistance and the like. Can be used for preparing restorations such as crowns, bridges, inlays and the like in clinical application.

Disclosure of Invention

The invention aims to provide a fiber reinforced light curing repair material, and particularly provides a resin-based repair material reinforced by nano fibers and a preparation method thereof. The nano-fiber is prepared by a melt spinning technology. When the resin-based repair material is applied to dental repair, the curing method is photocuring.

The nanofiber reinforced resin-based repair material mainly comprises the following components: nano-fiber, acrylic resin, inorganic nano-particles, porcelain powder material, photoinitiator, initiation assistant and acrylic hydroxyl compound.

The dosage of the components is as follows according to the mass parts:

0.5-5 parts of nano fiber, 8-41 parts of acrylic resin, 6-28 parts of inorganic nano particles, 3-22 parts of porcelain powder material, 1-8 parts of photoinitiator, 0-2 parts of initiation assistant and 0.5-5 parts of acrylic hydroxyl compound.

The nano-fiber is prepared from glass powder and polymethyl methacrylate (PMMA) through melt spinning and hot stretching. The glass powder is prepared from the following components in parts by mass of polymethyl methacrylate (PMMA) 100: 3-9 parts; the polymethyl methacrylate (PMMA) has the hardness of 2H and the tensile strength of more than or equal to 77 Mpa; the glass powder has the mesh number of 3500-4000 meshes.

The preparation method of the nanofiber comprises the following steps:

(1) weighing corresponding polymethyl methacrylate (PMMA) and glass powder according to the specified parts by weight, uniformly mixing, and adding into a hopper of a melt-blowing injection molding machine. Controlling the melt-blowing temperature at 210-270 ℃, and heating to melt the mixture.

(2) And (3) extruding the molten mixture from a nozzle under pressurization, wherein the aperture of the nozzle is 1-5 um, so as to obtain the initial fiber yarn.

(3) The initial fiber yarns are elongated through unidirectional hot drawing, the drawing temperature is 110-170 ℃, the drawing time is 5-10 min, and the drawing rate is 30% -80%. And cutting the stretched fiber filaments for 3 times, wherein the cutting precision is controlled to be 2-10 um, and the cutting speed is 1000-1900 mm/s. Cutting to obtain the nano-fiber.

The acrylic resin is one or a composition of more than one of bisphenol A-Bis glycidyl methacrylate resin (Bis-GMA), carbamate dimethacrylate (UDMA), ethoxylated bisphenol A dimethacrylate (Bis-EMA) and N, N dimethylamino ethyl methacrylate.

The inorganic nano particles are a compound of alumina powder, silica powder, hydroxyapatite and glass powder.

The inorganic nano-particles comprise 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.

The inorganic nano-particles are subjected to surface treatment by adopting a silane coupling agent, and the using amount of the silane coupling agent is 12-36% of that of the inorganic nano-particles by mass ratio. The surface treatment steps are as follows:

1) weighing each component of the inorganic nano-particles respectively, adding the components into a reaction kettle, and uniformly mixing.

2) Slowly adding a silane coupling agent in a stirring state; after the addition, stirring is continued for 45-90 min.

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 ceramic powder material is one or a composition of more than one of glass ceramics and all ceramics; the glass ceramic is one or more of apatite glass ceramic, mica glass ceramic, leucite glass ceramic and lithium disilicate glass ceramic; the above full-ceramic is one or more of feldspar ceramic full-ceramic, leucite full-ceramic, alumina full-ceramic, zirconia full-ceramic and spinel full-ceramic.

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 initiation 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 acrylic hydroxyl compound is one or a composition of more than one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.

The preparation method of the nanofiber reinforced resin-based repair material comprises the following steps:

(1) firstly, preparing the nano-fiber and the inorganic nano-particles for standby.

(2) Weighing the nano-fiber, the acrylic resin, the inorganic nano-particles and the porcelain powder material, and stirring and mixing the materials in a shear dispersion machine until the materials are uniform. The shearing dispersion machine is of an 8-rotor structure, the torque is 3.5-26 Nm, and the rotating speed is 2000-3000 rpm during working.

(3) Weighing a photoinitiator, an initiation aid and an acrylic hydroxyl compound, adding the photoinitiator, the initiation aid and the acrylic hydroxyl compound into the mixture, and uniformly stirring the mixture at the rotating speed of 2000-3000 rpm for 90-360 min; and degassing for 4-15 min in vacuum to obtain the nanofiber reinforced resin matrix repairing material.

The preparation method of the nanofiber reinforced resin-based repair material does not represent the only form in which the present 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 volume shrinkage rate of the nanofiber reinforced resin-based repair material prepared by the invention is small, the tensile strength and the breaking strength of the composite material are improved by adding the nanofibers, and the deformation and the cracking of a cured product are greatly reduced. By adopting a photocuring mode and using a composite photo-initiation system, the curing speed and the curing completion rate are improved, and the storage stability of the product is improved. The water absorption rate of the cured nanofiber reinforced resin-based repair material is less than 30 mu g/mm³The flexural strength is more than 185Mpa, the elastic modulus is between 1.7 and 3.6Gpa, and the surface friction resistance is unchanged for 8 ten thousand times.

Detailed Description

The present invention is further illustrated by the following examples.

Example 1

Firstly, preparing nano fibers: weighing 10kg of polymethyl methacrylate (PMMA) and 500g of 3500-mesh glass powder, uniformly mixing, adding into a hopper of a melt-blowing injection molding machine, and heating to 250 ℃ to melt the mixture. And (3) extruding the molten mixture from a nozzle under the action of pressurization, wherein the aperture of the nozzle is 3um, and thus obtaining the initial fiber yarn. And then, stretching the initial fiber yarns by unidirectional hot stretching at the stretching temperature of 110 ℃ for 10min, wherein the stretching rate is 50%. And cutting the drawn fiber filaments for 3 times to obtain the nano fibers. The cutting precision is controlled to be 2-10 um, and the cutting speed is 1000-1900 mm/s.

Secondly, preparing inorganic nano particles: weighing 300g of alumina powder, 1600g of silica powder, 40g of hydroxyapatite and 2800g of glass powder, adding into a reaction kettle, and uniformly mixing. The stirring blade of the reactor was started and 948g of gamma-methacryloxypropyltrimethoxysilane and 5-hexenyltrimethoxysilane were added with stirring and stirring was continued for 60 minutes.

Preparing a nanofiber reinforced resin-based repair material: weighing 5g and 350g of nano-fiber bisphenol A-bis (formazan)Glycidyl acrylate resin (Bis-GMA), 280g of inorganic nanoparticles, 25g of apatite glass ceramic and 35g of feldspar porcelain all-ceramic powder are added into a shear dispersion machine with an 8-rotor structure and uniformly dispersed. Then 20g of fluorenone phenyl iodonium salt, 2.0g of camphorquinone and 30g of hydroxyethyl methacrylate are added, stirred for 260min, and then vacuum degassing is carried out for 8min, thus obtaining the nano-fiber reinforced resin matrix repair material. The water absorption of the repair material after curing is 18 mu g/mm³The flexural strength is 215MPa, the elastic modulus is 2.7Gpa, and the surface friction resistance reaches 8 ten thousand times without change.

Example 2

Firstly, preparing nano fibers: weighing 10kg of polymethyl methacrylate (PMMA) and 300g of 4000-mesh glass powder, uniformly mixing, adding into a hopper of a melt-blowing injection molding machine, and heating to 210 ℃ to melt the mixture. And (3) extruding the molten mixture from a nozzle under the action of pressurization, wherein the aperture of the nozzle is 1um, so as to obtain the initial fiber yarn. And then, stretching the initial fiber yarns by unidirectional hot stretching at the stretching temperature of 170 ℃ for 5min at the stretching rate of 30%. And cutting the drawn fiber filaments for 3 times to obtain the nano fibers. The cutting precision is controlled to be 2-10 um, and the cutting speed is 1000-1900 mm/s.

Secondly, preparing inorganic nano particles: weighing 2300g of alumina powder, 600g of silica powder, 50g of hydroxyapatite and 800g of glass powder, adding into a reaction kettle, and uniformly mixing. The stirring blade of the reactor was started and 350g of gamma-methacryloxypropyltrimethoxysilane and 1000g of 5-hexenyltrimethoxysilane were added with stirring and stirring was continued for 90 minutes.

Preparing a nanofiber reinforced resin-based repair material: 50g of nanofiber, 80g of ethoxylated bisphenol A dimethacrylate, 20g of bisphenol A-Bis glycidyl methacrylate resin (Bis-GMA), 120g of inorganic nanoparticles, 15g of apatite glass ceramic and 40g of feldspar ceramic all-ceramic powder are weighed and added into a shear dispersion machine with an 8-rotor structure, and the dispersion is uniform. Then 20g of fluorenone phenyl iodonium salt, 60g of cumen (II) hexafluorophosphate, 30g of hydroxyethyl methacrylate and 20g of hydroxypropyl acrylate are added, stirred for 360min and then vacuum degassed for 15min to obtain the nano-fiber reinforced resin matrix repair material. After the repair material is curedWater absorption of 13. mu.g/mm³The flexural strength is 233Mpa, the elastic modulus is 2.83GPa, and the surface friction resistance reaches 8 ten thousand times without change.

Example 3

Firstly, preparing nano fibers: weighing 10kg of polymethyl methacrylate (PMMA) and 900g of 3500-mesh glass powder, uniformly mixing, adding into a hopper of a melt-blowing injection molding machine, and heating to 270 ℃ to melt the mixture. And (3) extruding the molten mixture from a nozzle under the action of pressurization, wherein the aperture of the nozzle is 5um, and thus obtaining the initial fiber filament. And then, stretching the initial fiber yarns by unidirectional hot stretching at the stretching temperature of 130 ℃, for 10min and at the stretching rate of 80%. And cutting the drawn fiber filaments for 3 times to obtain the nano fibers. The cutting precision is controlled to be 2-10 um, and the cutting speed is 1000-1900 mm/s.

Secondly, preparing inorganic nano particles: weighing 800g of alumina powder, 2100g of silica powder, 10g of hydroxyapatite and 3800g of glass powder, adding into a reaction kettle, and mixing uniformly. The stirring blade of the reactor was started and 200g of allyltriethoxysilane and 165.2g of gamma-methacryloxypropyltrimethoxysilane were added with stirring and stirring was continued for 45 minutes.

Preparing a nanofiber reinforced resin-based repair material: 40g of nanofibers, 110g of Urethane Dimethacrylate (UDMA), 300g of bisphenol A-Bis glycidyl methacrylate resin (Bis-GMA), 60g of inorganic nanoparticles, 150g of mica glass ceramic and 70g of alumina all-ceramic powder are weighed and added into a shear dispersion machine with an 8-rotor structure, and the materials are uniformly dispersed. Then 10g of fluorenone phenyl iodonium salt, 20g of camphorquinone and 5g of hydroxypropyl methacrylate are added, stirred for 200min, and then vacuum degassing is carried out for 4min, thus obtaining the nano-fiber reinforced resin matrix repair material. The water absorption of the repair material after curing is 15 mu g/mm³The flexural strength is 213MPa, the elastic modulus is 3.6Gpa, and the surface friction resistance reaches 8 ten thousand times without change.

Example 4

Preparing a nanofiber reinforced resin-based repair material: the nanofibers prepared in example 1 and the inorganic nanoparticles prepared in example 2 were used. 16g and 80g of bisphenol A-bis glycidyl methacrylate resin of the nanofiber prepared in example 1 were weighed(Bis-GMA), 60g of inorganic nano particles and 30g of zirconia all-ceramic powder are added into a shear dispersion machine with an 8-rotor structure and uniformly dispersed. Then 15g of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 3g of fluorenone phenyl iodonium salt, 5g of camphorquinone, 8g of hydroxypropyl methacrylate and 5g of hydroxyethyl acrylate are added, the mixture is stirred for 90min, and then vacuum degassing is carried out for 11min, so as to obtain the nano-fiber reinforced resin matrix repair material. The water absorption of the repair material after curing is 16 mu g/mm³The flexural strength is 203MPa, the elastic modulus is 2.5Gpa, and the surface friction resistance reaches 8 ten thousand times without change.

Example 5

Firstly, preparing nano fibers: weighing 10kg of polymethyl methacrylate (PMMA) and 600g of 3800-mesh glass powder, uniformly mixing, adding into a hopper of a melt-blowing injection molding machine, and heating to 240 ℃ to melt the mixture. And (3) extruding the molten mixture from a nozzle under the action of pressurization, wherein the aperture of the nozzle is 3um, and thus obtaining the initial fiber yarn. And then, stretching the initial fiber yarns by unidirectional hot stretching at the stretching temperature of 140 ℃ for 6min, wherein the stretching rate is 60%. And cutting the drawn fiber filaments for 3 times to obtain the nano fibers. The cutting precision is controlled to be 2-10 um, and the cutting speed is 1000-1900 mm/s.

Secondly, preparing inorganic nano particles: weighing 1500g of alumina powder, 1100g of silica powder, 20g of hydroxyapatite and 1800g of glass powder, adding into a reaction kettle, and uniformly mixing. The stirring blades of the reactor were started and 1000g of allyltriethoxysilane and 326g of gamma-methacryloxypropyltrimethoxysilane were added with stirring and stirring was continued for 65 minutes.

Preparing a nanofiber reinforced resin-based repair material: weighing 26g of prepared nanofiber, 100g of N, N dimethylamino ethyl methacrylate, 80g of bisphenol A-Bis glycidyl methacrylate resin (Bis-GMA), 170g of inorganic nanoparticles, 35g of zirconia full ceramic powder and 30g of leucite glass ceramic, adding the materials into a shear dispersion machine with an 8-rotor structure, and uniformly dispersing. Then 12g of (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide, 3g of fluorenone-phenyliodonium salt, 2g of 1-hydroxycyclohexylphenylketone, 5g of camphorquinone, 5g of hydroxypropyl methacrylate and 5g of hydroxyethyl acrylate were added, stirred for 190min, and then degassed under vacuumAnd 8min to obtain the nanofiber reinforced resin matrix repair material. The water absorption of the repair material after curing is 16 mu g/mm³The flexural strength is 218Mpa, the elastic modulus is 2.26Gpa, and the surface friction resistance reaches 8 ten thousand times without change.