Wear-resistant low-shrinkage dental resin composite material and preparation method thereof

Abstract

The application relates to the technical field of dental biomaterials, in particular to a wear-resistant low-shrinkage dental resin composite material and a preparation method thereof, which comprises the following raw materials: bisphenol A-glycidyl methacrylate, modified black phosphorus nanosheet, modified Zr-MOF, benzoyl peroxide, silane coupling agent, camphorquinone, hydroquinone, chlorhexidine and triethylene glycol dimethacrylate. In the application, the bisphenol A-glycidyl methacrylate, the modified black phosphorus nanosheet and the modified Zr-MOF play a role through a synergistic effect. The bisphenol A-glycidyl methacrylate provides a stable carrier support for the modified black phosphorus nanosheet and the modified Zr-MOF. The modified black phosphorus nanosheet effectively reduces the friction coefficient, helps the resin matrix to maintain a better curing network structure, the modified Zr-MOF increases the rigidity and strength of the resin matrix, adsorbs free monomers in the resin matrix, delays the curing rate, reduces stress concentration, fills the shrinkage voids of the resin matrix, and ensures the long-term usability of the dental resin composite material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of dental biomaterials, and particularly relates to a wear-resistant low-shrinkage dental resin composite material and a preparation method thereof. BACKGROUND

[0002] With the progress of dental repair technology, dental resin composites have become the mainstream material for tooth repair. Resin composites are widely used in tooth repair, inlay repair, tooth whitening, etc. due to their excellent aesthetic performance, good adhesion and low invasiveness. However, the existing dental resin composites still have some shortcomings. If the wear resistance is not good and the shrinkage rate is high, the service life and repair effect of the composite material will be directly affected. In the oral environment, due to the masticatory force and friction force of the teeth, long-term use can easily cause wear of the surface of the composite material, and even cause material peeling or cracking. Therefore, how to maintain good aesthetic effect while improving the wear resistance of the resin composite material has become the key to improving its clinical application performance. Low shrinkage is another important factor affecting the long-term performance of dental resin composites. During the curing process of the dental resin composite material, a large volume shrinkage often occurs due to the double bond polymerization reaction, which not only causes gaps between the repaired part and the tooth, leading to secondary caries or repair body falling off, but also affects the mechanical properties of the composite material, such as bending strength and compressive strength. Therefore, reducing the curing shrinkage of the dental resin composite material has also become the key to improving the stability and long-term use performance of the composite material. In summary, improving the wear resistance and low shrinkage of the dental resin composite material is the key to improving its clinical application effect. Therefore, it is very meaningful to develop a wear-resistant low-shrinkage dental resin composite material. SUMMARY

[0003] (1) Technical problem to be solved

[0004] The present application aims to provide a wear-resistant low-shrinkage dental resin composite material and a preparation method thereof. By optimizing the material formula of the dental resin composite material and combining modern nanotechnology to optimize the interface bonding and dispersibility of the material, the wear resistance of the material is improved, and the curing shrinkage of the material is controlled. A wear-resistant low-shrinkage dental resin composite material is prepared, which meets the performance requirements of high wear resistance and low shrinkage.

[0005] (2) Technical scheme

[0006] To achieve the above object, in one aspect, the present application provides a wear-resistant low-shrinkage dental resin composite material, comprising the following raw materials by weight: bisphenol A-glycidyl methacrylate 45-55 parts, modified Zr-MOF 1-2 parts, benzoyl peroxide 1-3 parts, silane coupling agent 1-3 parts, camphorquinone 0.1-0.5 parts, hydroquinone 0.1-0.2 parts, chlorhexidine 0.1-0.5 parts, triethylene glycol dimethacrylate 15-25 parts;

[0007] The wear-resistant low-shrinkage dental resin composite material further comprises:

[0008] Modified black phosphorus nanosheets;

[0009] The modified black phosphorus nanosheets and bisphenol A-glycidyl methacrylate are in a weight ratio of 1:(45-55);

[0010] The modified black phosphorus nanosheets are prepared by introducing a methacryloyl group on the surface of black phosphorus nanosheets, and have a lateral size of 90-120 nm, a thickness of 5-8 nm, and a specific surface area of 160-200 m 2 / g;

[0011] The preparation method of the modified black phosphorus nanosheets comprises:

[0012] S11. Disperse bulk black phosphorus crystals in N-methylpyrrolidone and perform ultrasonic treatment at an ultrasonic frequency of 40-50 kHz at room temperature for 0.5-1 h to obtain a black phosphorus nanosheet dispersion;

[0013] S12. Perform high-speed centrifugal separation of the black phosphorus nanosheet dispersion at a speed of 6000-8000 rpm, collect the upper layer containing the black phosphorus nanosheet dispersion after centrifugation for 5-10 min, and perform vacuum drying at a drying temperature of 50-60°C for 12-14 h to obtain black phosphorus nanosheets and grind them into a powder for standby use;

[0014] S13. Dissolve the black phosphorus nanosheet powder in purified water under nitrogen protection and stirring, and heat to 75-85°C, then slowly add hydrogen peroxide solution after stirring for 0.5-1 h, and continue stirring for 5-6 h to obtain a first mixed solution;

[0015] S14. Perform high-speed centrifugal separation of the first mixed solution at a speed of 10000-12000 rpm for 15-20 min, wash the obtained solid with purified water for 5 times, and perform vacuum drying at a drying temperature of 55-65°C for 18-24 h to obtain a black phosphorus nanosheet intermediate and grind it into a powder for standby use;

[0016] S15. The black phosphorus nanosheet intermediate powder is dissolved in dimethyl sulfoxide under stirring, triethylamine is slowly added after stirring for 0.5-1 h, methacryloyl chloride is slowly added after stirring for 0.5-1 h, the mass ratio of methacryloyl chloride to black phosphorus nanosheet is (0.05-0.1):1, and a second mixed solution is obtained after continuing to stir for 1-2 h;

[0017] S16. The second mixed solution is transferred to a reaction kettle for reaction, the reaction temperature is set to 65-75°C, the reaction liquid is collected after reaction for 6-8 h, high-speed centrifugal separation is performed at a speed of 10000-12000 rpm for 15-20 min, the obtained solid is washed with purified water for 5 times, vacuum drying is performed at a drying temperature of 55-65°C for 18-24 h, and then modified black phosphorus nanosheets are obtained and ground into powder for standby use.

[0018] Further, the preparation method of the modified Zr-MOF comprises:

[0019] S21. Zr-MOF is dispersed in anhydrous ethanol for ultrasonic treatment, the ultrasonic frequency is 40-50 kHz, and the Zr-MOF dispersion liquid is obtained after ultrasonic treatment at room temperature for 0.5-1 h;

[0020] S22. 3-Aminopropyltriethoxysilane is added to the Zr-MOF dispersion liquid under stirring, and the temperature is increased to 75-85°C, and a third mixed solution is obtained after stirring for 12-15 h;

[0021] S23. The third mixed solution is subjected to high-speed centrifugal separation at a speed of 10000-12000 rpm for 10-15 min, the obtained solid is washed with anhydrous ethanol for 3 times, vacuum drying is performed at a drying temperature of 55-65°C for 18-24 h, and then a Zr-MOF intermediate is obtained and ground into powder for standby use;

[0022] S24. Aniline is dissolved in a 0.1 mol / L hydrochloric acid solution under stirring, the ice bath temperature is set to 0-5°C, Zr-MOF intermediate powder is slowly added after stirring for 0.5-1 h, ammonium persulfate is slowly added dropwise after continuing to stir for 0.5-1 h, and then the fourth mixed solution is obtained after continuing to stir for 12-15 h;

[0023] S25. The fourth mixed solution is subjected to high-speed centrifugal separation at a speed of 10000-12000 rpm for 10-15 min, the obtained solid is washed with a 0.1 mol / L hydrochloric acid solution, anhydrous ethanol and purified water alternately for 3 times, vacuum drying is performed at a drying temperature of 45-55°C for 18-24 h, and then a modified Zr-MOF is obtained and ground into powder for standby use.

[0024] Further, the modified Zr-MOF is prepared by growing polyaniline nanorods in situ on the surface of the Zr-MOF, and the particle size of the modified Zr-MOF is 90-120 nm, and the specific surface area is 800-900 m 2 / g.

[0025] Further, the silane coupling agent is a complex of 3-aminopropyl triethoxysilane, 3-vinylpropyl triethoxysilane and 3-epoxypropyl trimethoxysilane, and the weight ratio of 3-aminopropyl triethoxysilane, 3-vinylpropyl triethoxysilane and 3-epoxypropyl trimethoxysilane is (1-2):(1-1.5):(0.5-1).

[0026] On the other hand, based on the same inventive concept, the application further provides a preparation method of the wear-resistant low-shrinkage dental resin composite material, which is applied to the wear-resistant low-shrinkage dental resin composite material and comprises the following steps:

[0027] S31. The modified black phosphorus nanosheet and the modified Zr-MOF are dispersed in anhydrous ethanol respectively and subjected to ultrasonic treatment, the ultrasonic frequency is 40-50 kHz, and the modified black phosphorus nanosheet dispersion and the modified Zr-MOF dispersion are obtained after ultrasonic treatment for 1-2 h;

[0028] S32. The bisphenol A-glycidyl methacrylate and the triethylene glycol dimethacrylate are mixed under stirring, the silane coupling agent, the modified black phosphorus nanosheet dispersion and the modified Zr-MOF dispersion are sequentially added after stirring for 1-2 h and subjected to ultrasonic treatment, and the fifth mixed solution is obtained after ultrasonic treatment for 1-2 h;

[0029] S33. The benzoyl peroxide, the camphorquinone, the hydroquinone and the chlorhexidine are sequentially added to the fifth mixed solution under stirring, and the mixture is placed in a vacuum drying box for degassing after continuing to stir for 2-3 h, the degassing temperature is 35-45 DEG C, and the degassing is performed for 0.5-1 h, and then the solidification is performed;

[0030] S34. The solidification is performed in a blast drying oven, the solidification temperature is set to 65-80 DEG C, and the solidification time is 0.5-1 h, and then the wear-resistant low-shrinkage dental resin composite material is obtained.

[0031] The mechanism of the above raw material components is as follows:

[0032] In the wear-resistant low-shrinkage dental resin composite, bisphenol A-glycidyl methacrylate, modified black phosphorus nanosheet and modified Zr-MOF synergistically improve the wear resistance of the dental resin composite and reduce its shrinkage. Bisphenol A-glycidyl methacrylate is a commonly used dental resin matrix material, which has high mechanical strength, good chemical stability and low hydrolysis. The rigid bisphenol A backbone in its molecular structure can be cross-linked through polymerization to form a strong three-dimensional cross-linked network, which provides the resin with hardness and strength to some extent and improves the wear resistance of the composite. However, due to its inherent weakness, its wear resistance is poor and its shrinkage is high when used alone, which affects the overall stability of the material. In addition, bisphenol A-glycidyl methacrylate as a matrix material can provide stable carrier support for modified black phosphorus nanosheet and modified Zr-MOF, so that the two can be uniformly dispersed in the matrix material. Black phosphorus nanosheet is a new type of two-dimensional material with high specific surface area, excellent mechanical properties and good electrical conductivity. Its nanosheet structure can significantly enhance the mechanical properties of the dental resin composite. However, due to its layered structure, it is prone to agglomeration, which affects its dispersion in the resin matrix. By introducing methacryl groups onto the surface of black phosphorus nanosheet, modified black phosphorus nanosheet can further copolymerize with bisphenol A-glycidyl methacrylate matrix to enhance the chemical bonding between the two, making the modified black phosphorus nanosheet more uniformly dispersed in the bisphenol A-glycidyl methacrylate matrix. The layered structure of modified black phosphorus nanosheet can effectively reduce the friction coefficient and the wear rate. Its three-dimensional cross-linked network structure with the bisphenol A-glycidyl methacrylate matrix is distributed in a staggered manner, which can further improve the shear resistance and prevent the material from peeling off during friction, thereby improving the wear resistance and helping the resin matrix to maintain a better curing network structure. The layered structure of the modified black phosphorus nanosheet can hinder the free movement of molecular chains in the resin matrix, thereby reducing the volume shrinkage during curing. In addition, the flexible nature of the modified black phosphorus nanosheet can further absorb part of the internal stress generated during the curing and shrinking process, slow down the shrinkage effect of the material and improve the dimensional stability of the material.The modified Zr-MOF has a high-rigidity nano-frame structure, and the porous and ordered arrangement of the structure can form a solid support skeleton in the resin matrix, providing additional mechanical support, so that the overall rigidity of the material is enhanced, and the -NH and -N= groups on the surface of the modified Zr-MOF form hydrogen bonds and π-π interactions with the bisphenol A-glycidyl methacrylate matrix, further improving the interfacial bonding force of the two, so that a more stable nano-network structure is formed in the resin matrix, thereby increasing the rigidity and strength of the resin matrix, and the polyaniline nanorods on the surface of the modified Zr-MOF have good lubricity, and the flexible structure of the polymer chain can form a protective film during friction, and the polyaniline nanorods are filled in the pores and surface of the modified Zr-MOF, further forming a micro-lubricating layer, so that the composite material exhibits better wear resistance and fatigue resistance during use. At the same time, the Zr-MOF and the polyaniline nanorods form a rigid-flexible combined structure, the Zr-MOF provides rigid support, and the polyaniline nanorods buffer the polymer shrinkage stress, thereby reducing the overall volume shrinkage. In addition, the modified Zr-MOF has a high specific surface area and a nano-porous structure, which can adsorb free monomers in the resin matrix during curing, so that the shrinkage stress during resin curing is dispersed, the curing rate is delayed, stress concentration is reduced, and the porous network of the modified Zr-MOF can further fill the shrinkage voids of the resin matrix, reducing the volume change, so that the composite material is more stable. In summary, the bisphenol A-glycidyl methacrylate, the modified black phosphorus nanosheet and the modified Zr-MOF work together to synergistically improve the wear resistance of the dental resin composite material, reduce the shrinkage rate of the dental resin composite material, and ultimately improve the stability of the dental resin composite material, ensuring its long-term use.

[0033] Benzoyl peroxide is a commonly used free radical initiator that decomposes to produce free radicals under light or heat conditions, initiating the polymerization reaction of the resin matrix. The decomposition rate and initiation efficiency of benzoyl peroxide directly affect the curing process and final performance of the resin. At the same time, benzoyl peroxide ensures the full curing of the resin matrix, forming a dense cross-linked network structure, thereby improving the mechanical properties and wear resistance of the material.

[0034] Silane coupling agents are commonly used to improve the interfacial bonding between inorganic fillers and organic resin matrices by forming an organic silane layer on the surface of the fillers through chemical reactions, thereby enhancing the compatibility and interfacial bonding between the fillers and the resin matrix, and further improving the mechanical properties and wear resistance of the material. The silane coupling agent of the present invention is a complex of 3-aminopropyl triethoxysilane, 3-vinylpropyl triethoxysilane and 3-epoxypropyl trimethoxysilane. The 3-aminopropyl triethoxysilane molecule contains amino and silane groups, the 3-vinylpropyl triethoxysilane contains vinyl and silane groups, and the 3-epoxypropyl trimethoxysilane has epoxy groups and silane groups. These groups can form covalent bonds with the surface of inorganic fillers, enhance the chemical bonding and crosslinking reaction between inorganic fillers and resin, and thus improve the mechanical properties of the composite material.

[0035] Camphorquinone is a photoinitiator commonly used with amine compounds to play a photosensitive curing role in dental composites. When the composite is exposed to ultraviolet or blue light, camphorquinone can absorb light energy and convert it into free radicals, initiating the polymerization of acrylate monomers in the resin matrix, thus achieving curing. Camphorquinone ensures rapid curing of the resin matrix, forming a dense crosslinked network structure, thereby improving the mechanical properties and wear resistance of the material.

[0036] Hydroquinone is a commonly used antioxidant to control the polymerization rate of the resin matrix and prevent premature curing. During the production of resin materials, hydroquinone prevents the resin matrix from polymerizing before use by inhibiting the generation of free radicals, thus maintaining its good flowability and processability.

[0037] Chlorhexidine is a broad-spectrum antibacterial agent that can inhibit the growth and reproduction of bacteria in the oral environment, increasing the antibacterial properties of dental composites and reducing bacterial erosion and deterioration of the material, thereby extending the service life of the material. At the same time, the addition of chlorhexidine also helps to enhance the biocompatibility of the material, reducing the irritation of bacteria in the oral cavity to the teeth and gums.

[0038] Triethylene glycol dimethacrylate is a low-viscosity monomer commonly used as a diluent for bisphenol A-glycidyl methacrylate. The introduction of triethylene glycol dimethacrylate can reduce the viscosity of the resin matrix, improve the flowability and processability of the material, and at the same time participate in the polymerization reaction of the resin matrix to form a crosslinked network structure, improving the mechanical properties and wear resistance of the material.

[0039] (3) Beneficial effects

[0040] Compared with the prior art, the beneficial effects of the present invention are:

[0041] 1. Bisphenol A-glycidyl methacrylate, modified black phosphorus nanosheet and modified Zr-MOF play a role through synergistic effect, and the bisphenol A-glycidyl methacrylate provides stable carrier support for the modified black phosphorus nanosheet and the modified Zr-MOF, so that the two can be uniformly dispersed in the matrix material;

[0042] 2. The modified black phosphorus nanosheet and the bisphenol A-glycidyl methacrylate matrix undergo copolymerization, enhancing the chemical bonding force of the two, and the layered structure effectively reduces the friction coefficient, reduces the wear speed, improves the wear resistance of the material, and helps the resin matrix maintain a better curing network structure and slow down the material shrinkage effect;

[0043] 3. The modified Zr-MOF forms a more stable nano network structure in the resin matrix, increases the rigidity and strength of the resin matrix, and forms a micro lubricating layer, so that the composite material exhibits better wear resistance and fatigue resistance during use;

[0044] 4. The rigid-flexible combined structure of the modified Zr-MOF further buffers the polymer shrinkage stress, and the high specific surface area and nano-porous structure can adsorb free monomers in the resin matrix, delay the curing rate, reduce stress concentration, and further fill the shrinkage voids of the resin matrix, making the composite material more stable. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 SEM image of the modified black phosphorus nanosheet of the present application embodiment 1;

[0046] Figure 2 SEM image of the modified Zr-MOF of the present application embodiment 1. DETAILED DESCRIPTION

[0047] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0048] The test equipment and preparations of the following described examples are as follows: electronic balance (Germany Sartorius), electric heating constant temperature water bath (Jiangsu Keduo), magnetic stirrer (Shanghai Meiyinqiu), ultrasonic instrument (Shanghai Yixin), high-speed centrifuge (Guangzhou Jidi), vacuum drying oven (Shanghai Jeteng), pH meter (Shanghai Yidian), scanning electron microscope (Germany Zeiss), specific surface area analyzer (Beijing Bessier Instrument Technology), universal material testing machine (Suzhou Jianzhuo), bending tester (Jinan Xinghuo), sliding wear tester (Lanzhou Huahui), optical microscope (Keen), chemical medicines and reagents were purchased from Sigma-Aldrich Company.

[0049] Example 1: The present example discloses a wear-resistant low-shrinkage dental resin composite material, comprising the following raw materials by weight: bisphenol A-glycidyl methacrylate 50 parts, modified Zr-MOF 1.5 parts, benzoyl peroxide 2 parts, silane coupling agent 2 parts, camphorquinone 0.3 parts, hydroquinone 0.15 parts, chlorhexidine 0.3 parts, triethylene glycol dimethacrylate 20 parts, the wear-resistant low-shrinkage dental resin composite material further comprises modified black phosphorus nanosheets, the modified black phosphorus nanosheets and bisphenol A-glycidyl methacrylate are in a weight ratio of 1:50, the modified black phosphorus nanosheets are prepared by introducing methacryl groups on the surface of black phosphorus nanosheets, and the modified black phosphorus nanosheets have a lateral size of 90 nm-120 nm, a thickness of 5 nm-8 nm, and a specific surface area of 160-200 m 2 / g.

[0050] In the wear-resistant low-shrinkage dental resin composite, bisphenol A-glycidyl methacrylate, modified black phosphorus nanosheet and modified Zr-MOF synergistically improve the wear resistance of the dental resin composite and reduce its shrinkage. Bisphenol A-glycidyl methacrylate is a commonly used dental resin matrix material, which has high mechanical strength, good chemical stability and low hydrolysis. The acrylate group (-C=CH2) in its molecular structure can be crosslinked by polymerization under ultraviolet irradiation to form a strong three-dimensional crosslinked network, which provides the resin with hardness and strength to some extent and improves the wear resistance of the composite. However, due to its inherent weakness, it is prone to breakage or cracking when subjected to impact or pressure when used alone, and has poor wear resistance and high shrinkage. Especially under long-term wear and masticatory stress, the resin material will show problems such as wear and cracking, affecting the overall stability of the material. In addition, as a matrix material, bisphenol A-glycidyl methacrylate can provide stable carrier support for modified black phosphorus nanosheet and modified Zr-MOF, allowing them to be uniformly dispersed in the matrix material to exert their reinforcing effect. Black phosphorus nanosheet is a new type of two-dimensional material with high specific surface area, excellent mechanical properties and good electrical conductivity. Its nanosheet structure can significantly enhance the mechanical properties of the dental resin composite. However, due to its layered structure, it is prone to agglomeration, which affects its dispersion in the resin matrix. By introducing methacryloyl groups onto the surface of black phosphorus nanosheet, Figure 1 The SEM image of the modified black phosphorus nanosheet shows that the modified black phosphorus nanosheet has a very obvious layered structure, and its large specific surface area can effectively increase the contact area with the resin matrix. The surface of the modified black phosphorus nanosheet contains methacryloyl groups, which can further undergo free radical copolymerization with the bisphenol A-glycidyl methacrylate matrix to firmly embed the modified black phosphorus nanosheet into the crosslinked network of the matrix material, enhancing the chemical interfacial bonding between the two. The modified black phosphorus nanosheet can be more uniformly dispersed in the bisphenol A-glycidyl methacrylate matrix. The layered structure of the modified black phosphorus nanosheet can effectively reduce the friction coefficient and the wear rate. The three-dimensional crosslinked network structure of the bisphenol A-glycidyl methacrylate matrix and the modified black phosphorus nanosheet is distributed in a staggered manner, which can further enhance the shear resistance and prevent the material from peeling off during friction, thereby improving the wear resistance. At the same time, it also helps the resin matrix to maintain a better curing network structure. The layered structure of the modified black phosphorus nanosheet in the resin matrix can hinder the free movement of molecular chains, thereby reducing the volume shrinkage during curing. In addition, the flexibility of the modified black phosphorus nanosheet can further absorb part of the internal stress generated during the curing and shrinking process, thereby slowing down the shrinkage effect of the material and improving the dimensional stability of the material. The modified Zr-MOF has a high-rigidity nanoframe structure, Figure 2For the SEM image of the modified Zr-MOF, it can be seen that the modified Zr-MOF has a high specific surface area and a rich pore structure, and its porous and ordered arrangement structure can form a strong support skeleton in the resin matrix, providing additional mechanical support, so that the overall rigidity of the material is enhanced. At the same time, the -NH and -N= groups on the surface of the modified Zr-MOF form hydrogen bonds and π-π interactions with the bisphenol A-glycidyl methacrylate matrix, further enhancing the chemical interfacial bonding force between the two, so that a more stable nanometer network structure is formed in the resin matrix, thereby increasing the rigidity and strength of the resin matrix. The polyaniline nanorods on the surface of the modified Zr-MOF have good lubricity, and their flexible polymer chain structure can form a protective film during the friction process. The polyaniline nanorods are filled in the pores and surface of the modified Zr-MOF, further forming a micro-lubricating layer, so that the composite material exhibits better wear resistance and fatigue resistance during use. At the same time, the Zr-MOF and the polyaniline nanorods form a rigid-flexible combined structure, the Zr-MOF provides rigid support, and the polyaniline nanorods buffer the polymer shrinkage stress, thereby reducing the overall volume shrinkage. In addition, the modified Zr-MOF has a high specific surface area and a nano-porous structure, which can adsorb free monomers in the resin matrix during the curing process, so that the shrinkage stress during resin curing can be dispersed, the curing rate is delayed, the stress concentration is reduced, and the porous network of the modified Zr-MOF can further fill the shrinkage voids of the resin matrix, reducing the volume change, so that the composite material is more stable. In summary, the bisphenol A-glycidyl methacrylate, the modified black phosphorus nanosheet and the modified Zr-MOF work together to synergistically improve the wear resistance of the dental resin composite material, reduce the shrinkage rate of the dental resin composite material, and ultimately improve the stability of the dental resin composite material, ensuring its long-term usability.

[0051] The preparation method of the modified black phosphorus nanosheet comprises:

[0052] S11. Disperse the bulk black phosphorus crystal in N-methylpyrrolidone and perform ultrasonic treatment, the ultrasonic frequency is 40-50 kHz, and after ultrasonic treatment at room temperature for 0.5-1 h, a black phosphorus nanosheet dispersion liquid is obtained;

[0053] S12. Perform high-speed centrifugal separation on the black phosphorus nanosheet dispersion liquid, the rotation speed is 6000-8000 rpm, and after centrifugation for 5-10 min, the upper layer containing the black phosphorus nanosheet is collected and vacuum dried, the drying temperature is 50-60°C, and after drying for 12-14 h, the black phosphorus nanosheet is obtained and ground into a powder for standby use;

[0054] S13. Dissolve the black phosphorus nanosheet powder in purified water under the conditions of nitrogen protection and stirring, and at the same time, heat to 75-85°C, slowly add hydrogen peroxide solution after stirring for 0.5-1 h, and continue to stir for 5-6 h to obtain a first mixed solution;

[0055] S14. The first mixed solution is subjected to high-speed centrifugal separation at a speed of 10000-12000 rpm for 15-20 min, and the separated solid is washed with purified water for 5 times and then vacuum dried at a temperature of 55-65°C for 18-24 h to obtain black phosphorus nanosheet intermediates which are ground into powder for standby use;

[0056] S15. The black phosphorus nanosheet intermediate powder is dissolved in dimethyl sulfoxide under stirring for 0.5-1 h, then triethylamine is slowly added, and the mixture is stirred for 0.5-1 h, followed by slowly adding methacryloyl chloride, with the mass ratio of methacryloyl chloride to black phosphorus nanosheet being (0.05-0.1):1, and the mixture is continuously stirred for 1-2 h to obtain a second mixed solution;

[0057] S16. The second mixed solution is transferred to a reaction kettle for reaction at a temperature of 65-75°C for 6-8 h, and the reaction liquid is collected and subjected to high-speed centrifugal separation at a speed of 10000-12000 rpm for 15-20 min, and the separated solid is washed with purified water for 5 times and then vacuum dried at a temperature of 55-65°C for 18-24 h to obtain modified black phosphorus nanosheets which are ground into powder for standby use.

[0058] The preparation method of the modified Zr-MOF includes:

[0059] S21. Zr-MOF is dispersed in anhydrous ethanol and subjected to ultrasonic treatment at a frequency of 40-50 kHz at room temperature for 0.5-1 h to obtain a Zr-MOF dispersion liquid;

[0060] S22. 3-Aminopropyltriethoxysilane is added to the Zr-MOF dispersion liquid under stirring, and the temperature is raised to 75-85°C, and the mixture is stirred for 12-15 h to obtain a third mixed solution;

[0061] S23. The third mixed solution is subjected to high-speed centrifugal separation at a speed of 10000-12000 rpm for 10-15 min, and the separated solid is washed with anhydrous ethanol for 3 times and then vacuum dried at a temperature of 55-65°C for 18-24 h to obtain Zr-MOF intermediates which are ground into powder for standby use;

[0062] S24. Aniline is dissolved in a 0.1 mol / L hydrochloric acid solution under stirring, and the temperature is set to 0-5°C by ice bath, and the mixture is stirred for 0.5-1 h, then the Zr-MOF intermediate powder is slowly added, and the mixture is continuously stirred for 0.5-1 h, followed by slowly adding ammonium persulfate dropwise, and the mixture is continuously stirred for 12-15 h to obtain a fourth mixed solution;

[0063] S25. The fourth mixed solution is subjected to high-speed centrifugal separation at a speed of 10,000-12,000 rpm for 10-15 min, and the separated solid is washed with 0.1 mol / L hydrochloric acid solution, anhydrous ethanol and purified water alternately for 3 times and then vacuum dried at a temperature of 45-55°C for 18-24 h to obtain modified Zr-MOF, which is ground into powder and reserved for use.

[0064] The modified Zr-MOF is prepared by in-situ growth of polyaniline nanorods on the surface of Zr-MOF, and the particle size of the modified Zr-MOF is 90-120 nm, and the specific surface area is 800-900 m 2 / g.

[0065] The silane coupling agent is a complex of 3-aminopropyl triethoxysilane, 3-vinylpropyl triethoxysilane and 3-epoxypropyl trimethoxysilane, and the weight ratio of 3-aminopropyl triethoxysilane, 3-vinylpropyl triethoxysilane and 3-epoxypropyl trimethoxysilane is (1-2):(1-1.5):(0.5-1).

[0066] A preparation method of a wear-resistant low-shrinkage dental resin composite material, applied to the wear-resistant low-shrinkage dental resin composite material, comprising the following steps:

[0067] S31. The modified black phosphorus nanosheet and the modified Zr-MOF are dispersed in anhydrous ethanol respectively and subjected to ultrasonic treatment at a frequency of 40-50 kHz for 1-2 h to obtain a modified black phosphorus nanosheet dispersion and a modified Zr-MOF dispersion;

[0068] S32. The bisphenol A-glycidyl methacrylate and triethylene glycol dimethacrylate are mixed under stirring, and after stirring for 1-2 h, the silane coupling agent, the modified black phosphorus nanosheet dispersion and the modified Zr-MOF dispersion are sequentially added and subjected to ultrasonic treatment for 1-2 h to obtain a fifth mixed solution;

[0069] S33. The benzoyl peroxide, camphorquinone, hydroquinone and chlorhexidine are sequentially added to the fifth mixed solution under stirring, and after continuing to stir for 2-3 h, the mixture is subjected to degassing in a vacuum drying box at a temperature of 35-45°C for 0.5-1 h and then cured;

[0070] S34. The curing is performed in a forced air drying oven, and the cured product is poured into a corresponding mold as needed, and the curing temperature is set to 65-80°C, and the curing time is 0.5-1 h to obtain the wear-resistant low-shrinkage dental resin composite material.

[0071] Example 2: This example discloses a wear-resistant, low-shrinkage dental resin composite material, comprising the following raw materials in parts by weight: 45 parts of bisphenol A-glycidyl methacrylate, 1 part of modified Zr-MOF, 1 part of benzoyl peroxide, 1 part of silane coupling agent, 0.1 part of camphorquinone, 0.1 part of hydroquinone, 0.1 part of chlorhexidine, and 15 parts of triethylene glycol dimethacrylate. The wear-resistant, low-shrinkage dental resin composite material also includes modified black phosphorus nanosheets, wherein the modified black phosphorus nanosheets and bisphenol A-glycidyl methacrylate are in a weight ratio of 1:45. The modified black phosphorus nanosheets are prepared by introducing methacryloyl groups on the surface of the black phosphorus nanosheets, and the modified black phosphorus nanosheets have a lateral size of 90 nm to 120 nm, a thickness of 5 nm to 8 nm, and a specific surface area of ​​160 to 200 m 2 The preparation methods of the modified black phosphorus nanosheets and modified Zr-MOF in this embodiment are the same as those in Example 1. The preparation method of the wear-resistant and low-shrinkage dental resin composite material in this embodiment is the same as that in Example 1.

[0072] Example 3: This example discloses a wear-resistant, low-shrinkage dental resin composite material, comprising the following raw materials in parts by weight: 55 parts of bisphenol A-glycidyl methacrylate, 2 parts of modified Zr-MOF, 3 parts of benzoyl peroxide, 3 parts of silane coupling agent, 0.5 parts of camphorquinone, 0.2 parts of hydroquinone, 0.5 parts of chlorhexidine, and 25 parts of triethylene glycol dimethacrylate. The wear-resistant, low-shrinkage dental resin composite material also includes modified black phosphorus nanosheets, wherein the modified black phosphorus nanosheets and bisphenol A-glycidyl methacrylate are in a weight ratio of 1:55. The modified black phosphorus nanosheets are prepared by introducing methacryloyl groups on the surface of the black phosphorus nanosheets, and the modified black phosphorus nanosheets have a lateral size of 90 nm to 120 nm, a thickness of 5 nm to 8 nm, and a specific surface area of ​​160 to 200 m 2 The preparation methods of the modified black phosphorus nanosheets and modified Zr-MOF in this embodiment are the same as those in Example 1. The preparation method of the wear-resistant and low-shrinkage dental resin composite material in this embodiment is the same as that in Example 1.

[0073] Control Group 1: This example differs from Example 1 in that it does not contain modified black phosphorus nanosheets. This example discloses a wear-resistant, low-shrinkage dental resin composite material, comprising the following raw materials in parts by weight: 50 parts of bisphenol A-glycidyl methacrylate, 1.5 parts of modified Zr-MOF, 2 parts of benzoyl peroxide, 2 parts of silane coupling agent, 0.3 parts of camphorquinone, 0.15 parts of hydroquinone, 0.3 parts of chlorhexidine, and 20 parts of triethylene glycol dimethacrylate. The preparation method of the modified Zr-MOF in this example is the same as that in Example 1. The preparation method of a wear-resistant, low-shrinkage dental resin composite material in this example is the same as that in Example 1.

[0074] Comparative group 2: The difference between this example and example 1 is that it does not contain modified Zr-MOF. This example discloses a wear-resistant low-shrinkage dental resin composite material, which comprises the following raw materials by weight: bisphenol A-glycidyl methacrylate 50 parts, benzoyl peroxide 2 parts, silane coupling agent 2 parts, camphorquinone 0.3 parts, hydroquinone 0.15 parts, chlorhexidine 0.3 parts, triethylene glycol dimethacrylate 20 parts, and the wear-resistant low-shrinkage dental resin composite material further comprises modified black phosphorus nanosheets, the modified black phosphorus nanosheets and bisphenol A-glycidyl methacrylate are in a weight ratio of 1:50, the modified black phosphorus nanosheets are prepared by introducing methacryloyl groups on the surface of black phosphorus nanosheets, and the modified black phosphorus nanosheets have a lateral size of 90 nm to 120 nm, a thickness of 5 nm to 8 nm, and a specific surface area of 160 m 2 / g to 200 m

[0075] Comparative group 3: The difference between this example and example 1 is that it does not contain modified black phosphorus nanosheets and modified Zr-MOF. This example discloses a wear-resistant low-shrinkage dental resin composite material, which comprises the following raw materials by weight: bisphenol A-glycidyl methacrylate 50 parts, benzoyl peroxide 2 parts, silane coupling agent 2 parts, camphorquinone 0.3 parts, hydroquinone 0.15 parts, chlorhexidine 0.3 parts, and triethylene glycol dimethacrylate 20 parts. The preparation method of the wear-resistant low-shrinkage dental resin composite material of this example is consistent with that of example 1.

[0076] Effect evaluation: Dental resin composite material performance determination: (1) Compression strength test: a universal material testing machine is used for testing, the sample is placed under the pressure head of the material testing machine, and the vertical alignment is ensured, the pressure is applied, and the compression strength of each experimental group material is recorded; (2) Bending strength test: a bending test machine is used to ensure that the center of the sample is located between the support points for bending test, and the bending strength is calculated according to the maximum load and the geometric size of the sample; (3) Friction and wear test: a sliding wear testing machine is used, the abrasive is set to 60# sandpaper to simulate the friction between food and teeth in the oral cavity, the sample is fixed on the support disc of the wear testing machine, and the mass change of the sample after wear is recorded during the test and the wear rate is calculated; (4) Curing shrinkage test: a digital vernier caliper and an optical microscope are used to measure the volume change of the sample before and after curing. Each experimental group has three parallel tests, and the experimental results are averaged.

[0077] Table 1 shows the performance determination results of the dental resin composite materials obtained in each experimental group

[0078]

[0079] Table 1 is the performance test results of the dental resin composite materials prepared in each experimental group. As can be seen from Table 1, the dental resin composite materials prepared in each experimental group have obvious differences in performance. Comparing the performance of the dental resin composite materials prepared in Examples 1-3 and Comparative Examples 1-3, it can be found that, overall, the dental resin composite materials prepared in Examples 1-3 have better performance. The dental resin composite material of Example 1 exhibits excellent performance, with a compressive strength of 242.5 MPa, a bending strength of 158 MPa, a surface that performs excellently during chewing, a wear rate of 0.11 mg / cycle, and a volume shrinkage rate of 2.5%, which exhibits excellent wear resistance and low shrinkage. Comparing Example 1 with Comparative Examples 1-3, it can be found that when the modified black phosphorus nanosheet and the modified Zr-MOF are added at the same time when preparing the dental resin composite material, the wear resistance of the material can be significantly improved, the shrinkage rate of the material can be reduced, and the overall performance of the dental resin composite material can be improved.

[0080] Through the above limited experiments, the application effect of the dental resin composite material with wear resistance and low shrinkage rate of Example 1 of the present application is remarkable. By optimizing the formula of the dental resin composite material and combining modern nanotechnology, the modified black phosphorus nanosheet and the modified Zr-MOF are added at the same time during the preparation process, the interface bonding and dispersibility of the material are optimized, the modified black phosphorus nanosheet effectively reduces the friction coefficient, helps the resin matrix to maintain a better curing network structure, the modified Zr-MOF increases the rigidity and strength of the resin matrix, adsorbs the free monomers in the resin matrix, delays the curing rate, reduces stress concentration, fills the shrinkage voids of the resin matrix, and ensures the long-term usability of the dental resin composite material.

[0081] Finally, it should be noted that although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or make equivalent replacements to part of the technical features, and any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A wear-resistant, low-shrinkage dental resin composite material, comprising 45-55 parts of bisphenol A-glycidyl methacrylate, 1-3 parts of benzoyl peroxide, 1-3 parts of a silane coupling agent, 0.1-0.5 parts of camphorquinone, 0.1-0.2 parts of hydroquinone, 0.1-0.5 parts of chlorhexidine, and 15-25 parts of triethylene glycol dimethacrylate, characterized in that: Further comprising the following raw materials by weight: 1-2 parts of modified Zr-MOF, modified black phosphorus nanosheet; The modified black phosphorus nanosheet and bisphenol A-glycidyl methacrylate are in a weight ratio of 1:(45-55); The bisphenol A-glycidyl methacrylate is a resin matrix material; The modified Zr-MOF is prepared by in-situ growth of polyaniline nanorods on the surface of Zr-MOF. The Zr-MOF and the polyaniline nanorods form a rigid-flexible combined structure and a nano-porous structure. The ordered porous structure forms a strong support skeleton in the resin matrix. At the same time, the -NH and -N= on the surface of the modified Zr-MOF form hydrogen bonds and π-π interactions with the bisphenol A-glycidyl methacrylate matrix, so that a nano-network structure is formed in the resin matrix. The polyaniline nanorods are filled in the pores and on the surface of the modified Zr-MOF, forming a micro-lubricating layer; The modified black phosphorus nanosheet is prepared by introducing a methacryl group on the surface of the black phosphorus nanosheet, and the modified black phosphorus nanosheet has a lateral size of 90 nm to 120 nm, a thickness of 5 nm to 8 nm, and a specific surface area of 160 m 2 / g; the surface of the modified black phosphorus nanosheet contains a methacryl group, and a free radical copolymerization reaction occurs between the methacryl group and a bisphenol A-glycidyl methacrylate matrix, so that the modified black phosphorus nanosheet is firmly embedded in the crosslinked network of the matrix material and is distributed in the three-dimensional crosslinked network structure of the bisphenol A-glycidyl methacrylate matrix; the modified black phosphorus nanosheet has a layered structure, and the layered structure hinders the free movement of molecular chain segments in the resin matrix; The preparation method of the modified black phosphorus nanosheet comprises: S11. Disperse the bulk black phosphorus crystal in N-methyl pyrrolidone and perform ultrasonic treatment. The ultrasonic frequency is 40-50 kHz. After ultrasonic treatment at room temperature for 0.5-1 h, a black phosphorus nanosheet dispersion liquid is obtained; S12. Perform high-speed centrifugal separation on the black phosphorus nanosheet dispersion liquid. The rotation speed is 6000-8000 rpm. After centrifugation for 5-10 min, the upper layer containing the black phosphorus nanosheet dispersion liquid is collected and vacuum dried. The drying temperature is 50-60°C. After drying for 12-14 h, the black phosphorus nanosheet is obtained and ground into powder for standby use; S13. Under the conditions of nitrogen protection and stirring, dissolve the black phosphorus nanosheet powder in purified water. At the same time, warm it to 75-85°C. After stirring for 0.5-1 h, slowly add hydrogen peroxide solution. Continue stirring for 5-6 h to obtain a first mixed solution; S14. Perform high-speed centrifugal separation on the first mixed solution. The rotation speed is 10000-12000 rpm. After centrifugation for 15-20 min, the separated solid is washed with purified water for 5 times and then vacuum dried. The drying temperature is 55-65°C. After drying for 18-24 h, the black phosphorus nanosheet intermediate is obtained and ground into powder for standby use; S15. Under the condition of stirring, dissolve the black phosphorus nanosheet intermediate powder in dimethyl sulfoxide. After stirring for 0.5-1 h, slowly add triethylamine. After stirring for 0.5-1 h, continue to slowly add methacryloyl chloride. The mass ratio of methacryloyl chloride to black phosphorus nanosheet is (0.05-0.1):

1. Continue to stir for 1-2 h to obtain a second mixed solution; S16. Transfer the second mixed solution to a reaction kettle for reaction. Set the reaction temperature to 65-75°C. After reaction for 6-8 h, collect the reaction liquid and perform high-speed centrifugal separation. The rotation speed is 10000-12000 rpm. After centrifugation for 15-20 min, the separated solid is washed with purified water for 5 times and then vacuum dried. The drying temperature is 55-65°C. After drying for 18-24 h, the modified black phosphorus nanosheet is obtained and ground into powder for standby use; The preparation method of the modified Zr-MOF comprises: S21. Ultrasonic treatment of Zr-MOF dispersion in anhydrous ethanol, ultrasonic frequency 40~50 kHz, ultrasonic treatment for 0.5~1h at room temperature to obtain Zr-MOF dispersion; S22. Under stirring, 3-aminopropyl triethoxysilane is added to the Zr-MOF dispersion, and the temperature is raised to 75~85°C, and after stirring for 12~15h, a third mixed solution is obtained; S23. High-speed centrifugal separation of the third mixed solution, speed 10000~12000 rpm, centrifugal separation for 10~15min, the separated solid is washed with anhydrous ethanol for 3 times, and then vacuum dried, drying temperature 55~65°C, drying for 18~24h to obtain Zr-MOF intermediate and grind into powder for standby; S24. Under stirring, aniline is dissolved in 0.1mol / L hydrochloric acid solution, the ice bath temperature is set to 0~5°C, stirring for 0.5~1h, then slowly add Zr-MOF intermediate powder, continue to stir for 0.5~1h, then slowly drop ammonium persulfate, and then continue to stir for 12~15h to obtain a fourth mixed solution; S25. High-speed centrifugal separation of the fourth mixed solution, speed 10000~12000 rpm, centrifugal separation for 10~15min, the separated solid is washed with 0.1mol / L hydrochloric acid solution, anhydrous ethanol and purified water alternately for 3 times, and then vacuum dried, drying temperature 45~55°C, drying for 18~24h to obtain modified Zr-MOF and grind into powder for standby.

2. The wear resistant low shrinkage dental resin composite material according to claim 1, characterized in that, The modified Zr-MOF is prepared by growing polyaniline nanorods in situ on the surface of the Zr-MOF, and the particle size of the modified Zr-MOF is 90-120 nm, and the specific surface area is 800-900 m 2 / g.

3. The wear resistant low shrinkage dental resin composite material according to claim 1, characterized in that, The silane coupling agent is a complex of 3-aminopropyl triethoxysilane, 3-vinylpropyl triethoxysilane and 3-epoxypropyl trimethoxysilane, and the weight ratio of 3-aminopropyl triethoxysilane, 3-vinylpropyl triethoxysilane and 3-epoxypropyl trimethoxysilane is (1~2):(1~1.5):(0.5~1).

4. The preparation method of the abrasion-resistant low-shrinkage dental resin composite material, which is applied to prepare the abrasion-resistant low-shrinkage dental resin composite material according to any one of claims 1-3, characterized in that, The method comprises the following steps: S31. Ultrasonic treatment of modified black phosphorus nanosheet and modified Zr-MOF dispersion in anhydrous ethanol, ultrasonic frequency 40~50 kHz, ultrasonic treatment for 1~2h to obtain modified black phosphorus nanosheet dispersion and modified Zr-MOF dispersion; S32. Under stirring, bisphenol A-glycidyl methacrylate and triethylene glycol dimethacrylate are mixed, stirring for 1~2h, then silane coupling agent, modified black phosphorus nanosheet dispersion and modified Zr-MOF dispersion are added in turn and ultrasonic treatment is carried out, ultrasonic treatment for 1~2h to obtain a fifth mixed solution; S33. Under stirring, benzoyl peroxide, camphorquinone, hydroquinone and chlorhexidine are added in turn to the fifth mixed solution, continue to stir for 2~3h, then degas in a vacuum drying oven, degassing temperature 35~45°C, degassing for 0.5~1h, and then solidify; S34. Solidification is carried out in a forced air drying oven, pour it into the corresponding mold as needed, set the solidification temperature to 65~80°C, and solidify for 0.5~1h to obtain the wear-resistant low-shrinkage dental resin composite material.

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