Modified glass powder for composite material, preparation method of modified glass powder and composite resin material

Abstract

The invention relates to modified glass powder for a composite material, a preparation method of the modified glass powder and a composite resin material, preparation raw materials of the modified glass powder for the composite material comprise an inorganic component and an organic component, the inorganic component is glass powder, and the organic component comprises a modifier and a modification auxiliary agent; the modification degree of the modified glass powder for the composite material is 0.5%-10%, the weight loss difference before and after soaking in water is smaller than or equal to 0.8%, and the water contact angle is larger than 130 degrees. The composite resin material prepared from the composite material has excellent mechanical properties, the mechanical strength preferably reaches up to 200 MPa or above, and the preparation method is short in technological process and easy for industrial production.

Description

Technical Field

[0001] This invention relates to the field of composite resin materials and their preparation technology, specifically to a modified glass powder for composite materials, its preparation method, and composite resin materials, and more particularly to a modified glass powder for dental composite materials, its preparation method, and dental composite resin materials. Background Technology

[0002] Composite resins, with their superior aesthetics and excellent handling flexibility, have been widely used in various fields. In the industrial sector, they are used to manufacture lightweight structural components for aerospace parts and insulating encapsulation materials for electronic devices, ensuring product reliability through their good mechanical properties and corrosion resistance. In the construction sector, they are commonly used as high-performance coatings, adhesives, and repair materials for surface decoration, structural reinforcement, and damage repair of buildings, improving their durability and aesthetics. In the consumer goods sector, they are also used to manufacture various wear-resistant and easily colored plastic products, such as furniture parts and appliance casings. In recent years, composite resins have become one of the most widely used restorative materials in dental clinics due to their aesthetics, handling flexibility, and high tooth preservation rate.

[0003] Inorganic fillers such as glass powder play an irreplaceable and crucial role as an important component of composite resins, such as enhancing mechanical properties like high strength that flexible resins cannot provide. However, untreated glass powder cannot effectively bond with the resin matrix, not only failing to improve material properties but also potentially reducing repair effectiveness due to problems like agglomeration or interface separation. Therefore, surface treatment is often performed on glass powder before filling the resin to improve its oleophilicity, thereby improving the bonding effect between the glass powder and the resin matrix.

[0004] Common surface treatment methods for improving the bonding between glass powder and resin include silane coupling agent treatment, surface coating with organic compounds, and plasma treatment. Among these, γ-methacryloyloxypropyltrimethoxysilane (γ-MPS), also known as KH570, is a common silane coupling agent frequently used in dental restorative composite resins. However, as a traditional silane coupling agent, KH570 relies solely on a single covalent bond (Si-O-Si) to connect glass powder and resin, resulting in significantly limited bonding effectiveness.

[0005] For example, although the Si-O-Si bond is a covalent bond, it is a monodentate connection with limited bond energy and is easily hydrolyzed and broken under humid and hot conditions. Furthermore, the excess silanol groups generated during the hydrolysis of KH570 readily self-polymerize instead of binding with the glass powder, remaining at the interface to form a defect layer and preventing multi-site bonding. In addition, when KH570 is bonded to resins, it participates in free radical copolymerization only through the double bond of the methacryloyloxy group, resulting in a narrow range of compatible resins (only acrylates or unsaturated polyesters, etc.). Moreover, due to steric hindrance, the copolymerization rate is low, showing almost no effective reaction with epoxy and polyurethane resins, relying solely on weak van der Waals forces for bonding. This weak bonding hinders stress transfer in the composite material, resulting in limited improvement in tensile and flexural strength, making it difficult to meet the requirements of high-strength applications.

[0006] For example, CN120573955A discloses a glass powder and its preparation method and uses. In this scheme, the modification method uses a 1:1 alcohol-water solution with a mass concentration of 2wt%~10wt% silane coupling agent. That is, it uses a single silane coupling agent. The modification effect still has a lot of room for improvement and still faces problems such as insufficient bonding force and unstable structure.

[0007] Therefore, there is an urgent need in the field to provide a modified glass powder for composite materials that can significantly improve the bonding force with resin and its preparation method, so as to solve the problems of low strength, poor wear resistance and limited fatigue resistance of existing composite resins after the combination of modified glass powder and resin. Summary of the Invention

[0008] To address the aforementioned technical problems, this invention provides a modified glass powder for composite materials, its preparation method, and a composite resin material. This improves the hydrolysis resistance of the modified glass powder, thereby increasing the tightness of the bond between the modified glass powder and the resin material, ultimately enhancing the mechanical properties of the resulting composite resin material and broadening the range of resin material selection.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides a modified glass powder for composite materials, wherein the raw materials for preparing the modified glass powder for composite materials include inorganic components and organic components, wherein the inorganic components are glass powder, and the organic components include modifiers and modifying additives;

[0011] The modified glass powder used in the composite material has a modification degree of 0.5%~10%, a weight loss difference before and after soaking in water ≤0.8%, and a water contact angle >130°.

[0012] The weight loss difference before and after soaking in water refers to the difference in weight loss rate of the composite material before and after soaking in water with modified glass powder.

[0013] This invention modifies the glass powder by using a modifier and a modifying additive. The two work synergistically to improve the modification effect and hydrolysis resistance of the modified glass powder for the resulting composite material, which in turn helps to improve its bonding strength with the resin material, thereby obtaining a composite resin material with excellent properties.

[0014] Specifically, the particle size D50 of the glass powder is 0.1~10μm, for example, it can be 0.1μm, 0.5μm, 1μm, 3μm, 5μm, 8μm or 10μm, etc.; the degree of modification of the modified glass powder for the composite material is 0.5%~10%, for example, it can be 0.5%, 1%, 3%, 5%, 8% or 10%, etc.

[0015] The weight loss before and after soaking in water is ≤0.8%, for example, it can be 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2% or 0.1%, etc., and the water contact angle is >130°, for example, it can be 135°, 138°, 140°, 141° or 142°, etc.

[0016] Preferably, the modifier comprises any two or at least three combinations of γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or γ-mercaptopropyltrimethoxysilane. Typical but non-limiting combinations include combinations of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, combinations of γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, or combinations of γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane, etc., preferably a combination of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane.

[0017] The present invention further preferably uses a combination of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane as the modifier. On the one hand, the Si-O-Si covalent bonds generated by the hydrolysis of γ-methacryloxypropyltrimethoxysilane serve as the basic framework. On the other hand, the amino groups introduced by γ-aminopropyltriethoxysilane form strong hydrogen bonds with the -SiOH groups on the surface of the glass powder, achieving multi-site bonding composed of "covalent bonds + hydrogen bonds". This reduces the exposed sites on the surface and inhibits the hydrolysis of Si-O-Si bonds. In other words, the two work synergistically to improve the hydrolysis resistance of the obtained modified glass powder.

[0018] Preferably, when the modifier is a combination of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, the mass content of γ-methacryloxypropyltrimethoxysilane is ≤75% based on the total mass of the modifier being 100wt%, for example, it can be 75%, 70%, 65%, 60% or 50%, etc.

[0019] In a further preferred embodiment of this invention, when the modifier is a combination of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, the mass content of γ-methacryloxypropyltrimethoxysilane is ≤75% based on a total mass of 100wt% of the modifier. Within this content range, the formation of Si-O-Si bonds is optimal, and γ-aminopropyltriethoxysilane will not form excessive self-polymers that coat the glass powder, affecting the modification effect. The copolymerization of the two components not only inhibits the self-polymerization of a single component and strengthens the hydrogen bonding with the glass powder surface, but also increases the Si-O-Si bond content, further enhancing the modification effect and thus strengthening the bonding effect between the modified glass powder and the resin. If the amount of γ-methacryloxypropyltrimethoxysilane added to the modifier is too high, its molecular weight... The steric hindrance of the methacryloyloxy group on the chain can cause steric repulsion, resulting in excessive free γ-methacryloyloxypropyltrimethoxysilane. This reduces the Si-O-Si bonds that bind to the glass powder. Simultaneously, if the amount of γ-aminopropyltriethoxysilane added is too low, the hydrogen bonding with the glass powder surface weakens, affecting the modification effect on the glass powder. If the amount of γ-methacryloyloxypropyltrimethoxysilane added in the modifier is too low or too high, the -SiOH group of γ-aminopropyltriethoxysilane preferentially self-polymerizes. This self-polymerized γ-aminopropyltriethoxysilane coats the surface of the glass powder. Since the self-polymerized γ-aminopropyltriethoxysilane lacks double bonds that can react with the resin, it affects the bonding effect between the glass powder and the resin.

[0020] Preferably, the modifying agent includes polyol-based additives.

[0021] Preferably, the polyol adjuvant includes any one or a combination of at least two of glycerol, 1,2-propanediol or xylitol, wherein typical but non-limiting combinations include combinations of glycerol and 1,2-propanediol, combinations of glycerol and xylitol, and combinations of 1,2-propanediol and xylitol, etc., with glycerol being preferred.

[0022] This invention utilizes the modified additive in combination with the modified agent, preferably glycerol. The hydroxyl and methyl groups in the glycerol molecule balance the polarity difference between the oily modifier and the polar glass powder, reducing the interfacial tension difference between the modifier and the glass powder. This lowers the contact angle between the modifier and the glass powder, improving the spreadability of the modifier on the glass powder surface. This avoids the problem of uneven coating of the glass powder due to high surface tension caused by the silane-based oily components in the modifier. The modified agent can be evenly spread on the glass powder surface, preventing localized or excessive coating, which would otherwise degrade the modification effect.

[0023] Preferably, the glass powder raw materials in the glass powder, by mass percentage, include 55-70 wt% SiO2, 0-5 wt% ZrO2, 8-15 wt% Al2O3, 8-15 wt% B2O3, 0-5 wt% CaO, 0-8 wt% MgO and 0-25 wt% SrO.

[0024] Among them, 55~70wt% SiO2, for example, can be 55wt%, 58wt%, 60wt%, 62wt%, 65wt%, 68wt%, or 70wt%, etc.; 0~5wt% ZrO2, for example, can be 0wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, or 5wt%, etc.; 8~15wt% Al2O3, for example, can be 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, or 15wt%, etc.; 0~5wt% CaO, for example, can be 0wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, or 5wt%, etc.; 0~8wt% MgO, for example, can be 0wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, or 8wt%; SrO, for example, can be 0wt%, 5wt%, 10wt%, 15wt%, 20wt%, or 25wt%.

[0025] Preferably, the glass powder raw material comprises, by mass percentage, 55-70 wt% SiO2, 2-5 wt% ZrO2, 8-15 wt% Al2O3, 8-15 wt% B2O3, 0.5-5 wt% CaO, 1-8 wt% MgO and 1-25 wt% SrO.

[0026] The glass powder raw material described in this invention has a relatively high SiO2 content of 55-70 wt%, which is beneficial for increasing the proportion of Si-O-Si in the network, enhancing the stability of the product network, and improving its hydrolysis resistance. While B2O3 can lower the melting temperature, the melt product it forms has a triangular structure and poor stability. Therefore, controlling the B2O3 content within the range of 8-15 wt% can reduce easily hydrolyzed sites. ZrO2 contains Zr... 4+ The resulting stable octahedral structure can enhance the overall hydrolysis resistance of the glass network.

[0027] Preferably, the particle size D50 of the glass powder is 0.01~50μm, for example, it can be 0.01μm, 0.05μm, 1μm, 5μm, 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm or 50μm, etc., and is preferably 0.1~10μm.

[0028] Preferably, the raw materials for preparing the modified glass powder for the composite material also include a dispersant.

[0029] Preferably, the dispersant comprises an alcohol-water mixture.

[0030] Preferably, the mass ratio of alcohol to water in the alcohol-water mixture is (1~4):(6~9), for example, it can be 1:9, 2:8, 3:7 or 4:6, etc.

[0031] Preferably, the alcohol in the alcohol-water mixture includes ethanol.

[0032] Preferably, the mass ratio of the glass powder to the dispersant is 1:(3~10), for example, it can be 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc.

[0033] Preferably, based on the dispersant, the amount of the modifier added is 10-15 wt%, for example, it can be 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, or 15 wt%.

[0034] Preferably, based on the glass powder, the amount of the modified additive added is 2 to 4 wt%, for example, it can be 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.2 wt%, 3.5 wt%, 3.8 wt%, or 4 wt%.

[0035] In a further preferred embodiment of the present invention, the amount of the modifying agent added is 2-4 wt%, based on the glass powder, which is beneficial to ensure that the modifying agent is uniformly coated on the surface of the glass powder. If the amount of the modifying agent added is too low, it cannot effectively reduce the surface tension difference between the glass powder and the oil-based modifier, and the modifier will appear as "droplets" on the surface of the glass powder matrix, failing to achieve effective bonding between the modifier and the glass powder. If the amount of the modifying agent added is too high, the hydroxyl groups contained in the modifying agent will form hydrogen bonds with the amino groups in the modifier, reducing the effective bonding between the modifier and the glass powder, and thus failing to improve the modification effect.

[0036] Preferably, the preparation method of the glass powder in the modified glass powder for the composite material includes the following steps: mixing the glass powder raw materials according to the formula, and sequentially performing melting treatment, water quenching treatment and ball milling treatment to obtain the glass powder.

[0037] Preferably, the glass powder raw material is further subjected to a first drying process before the melting treatment.

[0038] Preferably, the melting process includes a first heating and holding, a second heating and holding, and a third heating and holding.

[0039] Preferably, the final temperature of the first heating and heat preservation is 600~800℃, for example, it can be 600℃, 620℃, 650℃, 680℃, 700℃, 720℃, 750℃ or 800℃, etc.

[0040] Preferably, the heat preservation time for the first heating and heat preservation is 1 to 2 hours, for example, it can be 1 hour, 1.2 hours, 1.5 hours, 1.8 hours or 2 hours.

[0041] Preferably, the final temperature of the second heating and heat preservation is 1200~1400℃, for example, it can be 1200℃, 1250℃, 1300℃, 1350℃ or 1400℃, etc.

[0042] Preferably, the heat preservation time for the second heating and heat preservation is 2 to 4 hours, for example, it can be 2 hours, 2.5 hours, 3 hours, 3.5 hours or 4 hours.

[0043] Preferably, the final temperature of the third heating and heat preservation is 1500~1600℃, for example, it can be 1500℃, 1520℃, 1550℃, 1580℃ or 1600℃, etc.

[0044] Preferably, the heat preservation time for the third heating and heat preservation is 2 to 4 hours, for example, it can be 2 hours, 2.5 hours, 3 hours, 3.5 hours or 4 hours.

[0045] Preferably, the heating rates of the first heating and holding, the second heating and holding, and the third heating and holding are each independently 5~10℃ / min, for example, 5℃ / min, 6℃ / min, 7℃ / min, 8℃ / min, 9℃ / min, or 10℃ / min.

[0046] The present invention further preferably includes a three-stage heating and holding process: a first heating and holding stage, a second heating and holding stage, and a third heating and holding stage. This involves melting the glass powder raw material in three stages. Firstly, in the initial heating stage, the temperature is raised slowly to remove some of the CO2 and water vapor generated by the decomposition of the glass powder raw material at high temperatures. The heating rate should not be too fast, and the melting temperature should not be too high to prevent the gases generated by decomposition from being trapped in the melt and unable to escape. The intermediate transition temperature stage not only allows for the slow and complete release of gases but also allows the low-melting-point glass powder raw material to melt slowly, preventing the low-melting-point raw material from rapidly melting at excessively high temperatures and encasing the unmelted high-melting-point raw material, thus affecting the uniformity of the glass powder. Furthermore, the uniformity of the glass powder is also a key factor affecting its hydrolysis resistance. The three-stage heating process, through process optimization, eliminates the "defect" that easily leads to hydrolysis, further improving the uniformity and hydrolysis resistance of the glass powder.

[0047] Preferably, the water temperature for the water quenching treatment is 0~20℃, for example, it can be 0℃, 3℃, 5℃, 8℃, 10℃, 12℃, 15℃, 18℃ or 20℃, etc.

[0048] Preferably, the water quenching process further includes a second drying of the water-quenched glass powder raw material.

[0049] Preferably, the endpoint of the ball milling process is that the particle size D50 of the glass powder is 0.01~50μm, for example, it can be 0.01μm, 0.05μm, 1μm, 5μm, 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm or 50μm, etc.

[0050] Preferably, the ball milling process further includes a third drying of the ball-milled glass powder.

[0051] Preferably, the temperatures of the first drying, the second drying, and the third drying are each independently 105~120℃, for example, 105℃, 110℃, 115℃, or 120℃.

[0052] Preferably, the drying times for the first drying, the second drying, and the third drying are each 2 to 4 hours, for example, 2 hours, 2.5 hours, 3 hours, 3.5 hours, or 4 hours.

[0053] In a second aspect, the present invention provides a method for preparing the modified glass powder for composite materials described in the first aspect, the method comprising the following steps:

[0054] Glass powder, modifier, and modifying additives are mixed and heated to react and obtain modified glass powder slurry. The modified glass powder slurry is then dried to obtain the modified glass powder for the composite material.

[0055] The modified glass powder used in the composite material has a modification degree of 0.5%~10%, a weight loss difference before and after soaking in water ≤0.8%, and a water contact angle >130°.

[0056] The preparation method of the present invention modifies the glass powder by using a modifier and a modifying additive to obtain a modified glass powder for composite materials with strong modification degree and strong hydrolysis resistance. The preparation method has a short process, wide availability of raw materials, no need for complex equipment, low cost, and is easy to industrialize.

[0057] Preferably, the mixing further includes the addition of a dispersant.

[0058] Preferably, the mixing includes first mixing the glass powder and the dispersant according to the formula to obtain a glass powder slurry, and then mixing the glass powder slurry, the modifier and the modifying additive according to the formula.

[0059] Preferably, the preparation method further includes pH adjustment of the glass powder slurry before the second mixing.

[0060] Preferably, the pH adjustment agent used includes ammonia and / or triethanolamine.

[0061] The pH adjustment agent used in the preparation method of the present invention is not limited, as long as it can adjust the pH of the glass powder slurry to 8-9, is non-biotoxic and does not affect the test process, such as ammonia and / or triethanolamine.

[0062] Preferably, the endpoint of the pH adjustment is that the pH of the glass powder slurry is 8 to 9, for example, it can be 8, 8.2, 8.5, 8.8 or 9, etc.

[0063] The present invention further preferably sets the pH adjustment endpoint to a pH of 8-9 for the glass powder slurry. This not only promotes the condensation of silanol groups in the modifier after hydrolysis of γ-methacryloyloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane to form Si-O-Si bonds, generating a copolymer containing complete amino groups and double bonds, but also maintains the free state of amino groups to enhance hydrogen bonding with -SiOH groups on the surface of the glass powder. The covalent bonds and hydrogen bonds work together to form a dual anchoring, reducing side reactions, improving the modification effect of the modifier on the glass powder, increasing the bonding strength between the two, and thus improving the hydrolysis resistance of the resulting modified glass powder.

[0064] Preferably, the second mixing includes first mixing the glass powder slurry and the modifying agent according to the formula, and then adding the modifying agent according to the formula.

[0065] Preferably, the preparation method further includes a first heating and a first stirring sequentially after mixing the glass powder slurry and the modified additive.

[0066] Preferably, the endpoint temperature of the first heating is 45~50°C, for example, it can be 45°C, 46°C, 47°C, 48°C, 49°C or 50°C.

[0067] Preferably, the first stirring time is 15 to 30 minutes, for example, it can be 15 minutes, 18 minutes, 20 minutes, 22 minutes, 25 minutes, 28 minutes or 30 minutes.

[0068] Preferably, the preparation method further includes a second heating and heat preservation process after the addition of the modified additive.

[0069] Preferably, the endpoint temperature of the second heating is 60~70°C, for example, it can be 60°C, 62°C, 64°C, 65°C, 68°C or 70°C, etc.

[0070] Preferably, the heat preservation time is 1.5 to 4 hours, for example, it can be 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours or 4 hours.

[0071] Preferably, the second heating process is accompanied by a second stirring.

[0072] Preferably, the rotation speed of the first stirring and the second stirring is independently 300~700 r / min, for example, it can be 300 r / min, 350 r / min, 400 r / min, 450 r / min, 500 r / min, 550 r / min, 600 r / min or 700 r / min, etc.

[0073] Preferably, the first heating and the second heating methods each independently include water bath heating.

[0074] Preferably, the preparation method involves sequentially cooling, separating, and washing the modified glass powder slurry before drying.

[0075] Preferably, the final temperature of the cooling is 35~40℃, for example, it can be 35℃, 36℃, 37℃, 38℃, 39℃ or 40℃, etc.

[0076] Preferably, the separation method includes centrifugation.

[0077] Preferably, the washing endpoint is when the pH of the modified glass powder slurry is 6.5 to 7.5, for example, it can be 6.5, 6.8, 7.0, 7.2 or 7.5, etc.

[0078] Preferably, the drying method includes baking.

[0079] Preferably, the drying temperature is 40~60℃, for example, it can be 40℃, 42℃, 45℃, 48℃, 50℃, 52℃, 55℃, 58℃ or 60℃, etc.

[0080] Thirdly, the present invention provides a composite resin material, wherein the composite resin material is composed of resin and modified glass powder used for the composite material described in the first aspect.

[0081] The composite resin material of the present invention is made by combining resin with modified glass powder of the composite material described in the first aspect, and has excellent mechanical properties.

[0082] Preferably, the monomers in the raw materials of the resin include any two or at least three of the following: urethane dimethacrylate, bisphenol A dimethacrylate oxyacetate, or 1,6-hexanediol dimethacrylate. Typical but non-limiting combinations include combinations of urethane dimethacrylate, bisphenol A dimethacrylate oxyacetate, and 1,6-hexanediol dimethacrylate.

[0083] In this invention, there are no special restrictions on the initiator in the raw materials of the resin. As long as it can be used as an ultraviolet photoinitiator and is not biotoxic and can be compatible with the monomer, it is acceptable. For example, it can be methyl benzoate, etc.

[0084] The composite resin material described in this invention has a wider range of resin selectivity. This is because when the modified glass powder of the composite material described in the first aspect is combined with the resin material, it can adapt to free radical polymerized resins such as acrylates by relying on the double bond of γ-methacryloyloxypropyltrimethoxysilane in the modifier, and it can also react with the amino group of γ-aminopropyltriethoxysilane in the modifier to the epoxy group of epoxy resin and the isocyanate group of polyurethane, thereby adapting to more resin types and forming a continuous covalent network.

[0085] Preferably, the preparation method of the composite resin material includes the following steps: mixing the modified glass powder for the composite material and the resin material to obtain a mixed slurry, then ball milling the mixed slurry, finally printing the ball-milled mixed slurry using a 3D printer, and then curing it to obtain the composite resin material.

[0086] Preferably, the mass ratio of the modified glass powder to the resin material is (0.8~1.3):1, for example, it can be 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1 or 1.3:1, etc.

[0087] Preferably, the mixing process is accompanied by stirring.

[0088] Preferably, the stirring speed is 1000~1400 r / min, for example, it can be 1000 r / min, 1100 r / min, 1200 r / min, 1300 r / min or 1400 r / min, etc.

[0089] Preferably, the stirring time is 1 to 3 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours.

[0090] Preferably, the ball milling treatment time is 2 to 5 hours, for example, it can be 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours.

[0091] Preferably, the curing temperature is 65~100℃, for example, it can be 65℃, 68℃, 70℃, 80℃, 90℃ or 100℃.

[0092] Preferably, the flexural strength of the composite resin material is ≥200MPa, for example, it can be 200MPa, 205MPa, 210MPa, 215MPa or 220MPa.

[0093] Compared with the prior art, the present invention has at least the following beneficial effects:

[0094] (1) The modified glass powder for composite materials provided by the present invention modifies the glass powder by using a modifier and a modifying additive. The modifier is preferably a combination of γ-methacryloyloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, and is compounded with a specific modifying additive. This achieves high bonding strength and uniform coating modification of the glass powder, thereby significantly improving its hydrolysis resistance. The degree of modification of the modified glass powder for composite materials is in the range of 0.5 to 10%, and its weight loss before and after soaking in water is preferably as low as 0.80% or less. The water contact angle is >130°, which is more conducive to subsequent bonding with resin materials, so that the resulting composite resin material has excellent mechanical properties.

[0095] (2) The preparation method of the modified glass powder for composite materials provided by the present invention uses the above-mentioned raw materials for preparing the modified glass powder for composite materials in combination with specific process parameters to prepare the modified glass powder for composite materials with excellent hydrolysis resistance. The preparation method has a short process flow, does not require complex equipment, and is easy to scale up for production.

[0096] (3) The composite resin material provided by the present invention is made by combining the above-mentioned composite material with modified glass powder and resin material. The bonding force between the two is significantly improved, and it has excellent mechanical properties. The flexural strength is preferably as high as 200MPa or more. Moreover, the resin material has a wider range of compatibility. This improves the problems of low strength, poor wear resistance and limited fatigue resistance of existing composite resins after combining modified glass powder and resin. It has great application potential, especially in the field of dental restoration. Detailed Implementation

[0097] The technical solution of the present invention will be further illustrated below through specific embodiments. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims.

[0098] The following examples use the following 3D printer (EZPRINT-P1, model: Aidite (Qinhuangdao) Technology Co., Ltd.), γ-methacryloyloxypropyltrimethoxysilane (Shanghai Yuanye Biotechnology Co., Ltd., CAS: 2530-85-0), γ-aminopropyltriethoxysilane (Shanghai McLean Biochemical Technology Co., Ltd., CAS: 919-30-2), and glycerol (Shanghai McLean Biochemical Technology Co., Ltd., CAS: 56-81-5).

[0099] The composition and content of the glass powder raw materials in Examples 1 to 3 are shown in Table 1.

[0100] Table 1

[0101]

[0102] The resin described in the following application examples or comparative application examples is composed of urethane dimethacrylate (UDMA), bisphenol A dimethacrylate (BPA2EODMA), and 1,6-hexanediol dimethacrylate (HDDMA), with methyl benzoylformate (MBF) as the initiator. The resin system composition is UDMA:BPA2EODMA:HDDMA = 5:3:2, and the initiator accounts for 3% of the total mass of the composite resin.

[0103] I. Implementation Examples

[0104] Example 1

[0105] This embodiment provides a modified glass powder for composite materials. The raw materials for preparing the modified glass powder for composite materials include glass powder, dispersant, modifier and modifying additives.

[0106] The dispersant is an alcohol-water mixture of ethanol and water in a mass ratio of 3:7; the glass powder is in a mass ratio of 1:5 to the dispersant.

[0107] Based on a total mass of 100 wt% for the modifier, the modifier is a combination of 75 wt% γ-methacryloyloxypropyltrimethoxysilane and 25 wt% γ-aminopropyltriethoxysilane; the modifying agent is glycerol;

[0108] Based on the alcohol-water mixed solution dispersant, the amount of the modifier added is 15 wt%.

[0109] Based on the glass powder, the amount of the modifying agent added is 3 wt%;

[0110] The preparation method of the glass powder includes the following steps: the glass powder raw materials are mixed according to the formula of Example 1 in Table 1 and dried at 110°C for 3 hours, and then melt-treated. The melt-treatment includes first heating to 700°C at a heating rate of 8°C / min for 1.5 hours, then heating to 1300°C at a heating rate of 5°C / min for 3 hours, and then heating to 1550°C at a heating rate of 10°C / min for 2.5 hours; then water quenching in water at 10°C, and then drying at 108°C for 2.5 hours; then ball milling until the particle size D50 of the obtained glass powder is 5 μm, and finally drying at 110°C for 3 hours to obtain the glass powder.

[0111] This embodiment also provides a method for preparing modified glass powder for composite materials, using the raw materials and proportions described in this embodiment. The preparation method includes the following steps:

[0112] First, the glass powder and the dispersant are mixed according to the formula to obtain a glass powder slurry. Then, the pH of the glass powder slurry is adjusted to 8.5 using ammonia. Next, the glass powder slurry is mixed with the modifier according to the formula and heated to 48°C. Then, it is stirred at 600 r / min for 20 min. Then, the modifier is added according to the formula and heated to 65°C under a second stirring condition of 500 r / min. The mixture is then kept at this temperature for 2.5 h to obtain a modified glass powder slurry. The modified glass powder slurry is then cooled to 40°C, centrifuged to remove the liquid, and washed with ethanol until the pH reaches 7. Finally, it is dried at 50°C to obtain the modified glass powder for the composite material.

[0113] Example 2

[0114] This embodiment provides a modified glass powder for composite materials. The raw materials for preparing the modified glass powder for composite materials include glass powder, dispersant, modifier and modifying additives.

[0115] The dispersant is an alcohol-water mixture of ethanol and water in a mass ratio of 3:7; the glass powder is in a mass ratio of 1:5 to the dispersant.

[0116] Based on a total mass of 100 wt% for the modifier, the modifier is a combination of 71.4 wt% γ-methacryloyloxypropyltrimethoxysilane and 28.6 wt% γ-aminopropyltriethoxysilane; the modifying agent is glycerol.

[0117] Based on the alcohol-water mixed solution dispersant, the amount of the modifier added is 10 wt%;

[0118] Based on the glass powder, the amount of the modifying agent added is 3.5 wt%.

[0119] The preparation method of the glass powder includes the following steps: the glass powder raw materials are mixed according to the formula of Example 2 in Table 1 and dried at 105°C for 4 hours, and then melt-treated. The melt-treatment includes first heating to 600°C at a heating rate of 7°C / min for 2 hours, then heating to 1200°C at a heating rate of 9°C / min for 4 hours, and then heating to 1500°C at a heating rate of 8°C / min for 4 hours; then water quenching in water at 15°C, and then drying at 112°C for 3 hours; then ball milling until the particle size D50 of the obtained glass powder is 3μm, and finally drying at 120°C for 2 hours to obtain the glass powder.

[0120] This embodiment also provides a method for preparing modified glass powder for composite materials, using the raw materials and proportions described in this embodiment. The preparation method includes the following steps:

[0121] First, the glass powder and the dispersant are mixed according to the formula to obtain a glass powder slurry. Then, the pH of the glass powder slurry is adjusted to pH 8 using ammonia. Next, the glass powder slurry and the modifier are mixed according to the formula and heated to 45°C. Then, the mixture is stirred at 650 r / min for 15 min. Then, the modifier is added according to the formula and the mixture is heated to 60°C under a second stirring condition of 500 r / min and kept at that temperature for 4 h to obtain a modified glass powder slurry. The modified glass powder slurry is then cooled to 35°C, centrifuged to remove the liquid, and washed with ethanol until the pH reaches 6.5. Finally, it is dried at 40°C to obtain the modified glass powder for the composite material.

[0122] Example 3

[0123] This embodiment provides a modified glass powder for composite materials. The raw materials for preparing the modified glass powder for composite materials include glass powder, dispersant, modifier and modifying additives.

[0124] The dispersant is an alcohol-water mixture of ethanol and water in a mass ratio of 3:7; the glass powder is in a mass ratio of 1:5 to the dispersant.

[0125] Based on a total mass of 100 wt% for the modifier, the modifier is a combination of 66.7 wt% γ-methacryloyloxypropyltrimethoxysilane and 33.3 wt% γ-aminopropyltriethoxysilane; the modifying agent is glycerol;

[0126] Based on the alcohol-water mixed solution dispersant, the amount of the modifier added is 15 wt%.

[0127] Based on the glass powder, the amount of the modifying agent added is 4 wt%;

[0128] The preparation method of the glass powder includes the following steps: the glass powder raw materials are mixed according to the formula of Example 3 in Table 1 and dried at 120°C for 2 hours, and then melt-treated. The melt-treatment includes first heating to 800°C at a heating rate of 9°C / min and holding for 1 hour, then heating to 1400°C at a heating rate of 5°C / min and holding for 2 hours, and then heating to 1600°C at a heating rate of 6°C / min and holding for 2 hours; then water quenching in water at 0°C, and then drying at 105°C for 4 hours; then ball milling until the particle size D50 of the obtained glass powder is 10 μm, and finally drying at 110°C for 3.5 hours to obtain the glass powder.

[0129] This embodiment also provides a method for preparing modified glass powder for composite materials, using the raw materials and proportions described in this embodiment. The preparation method includes the following steps:

[0130] First, the glass powder and the dispersant are mixed according to the formula to obtain a glass powder slurry. Then, the pH of the glass powder slurry is adjusted to pH 9 using ammonia. Next, the glass powder slurry is mixed with the modifier according to the formula and heated to 50°C. Then, it is stirred at 700 r / min for 30 min. Then, the modifier is added according to the formula and heated to 70°C under a second stirring condition at 500 r / min. The mixture is then kept at this temperature for 2 h to obtain a modified glass powder slurry. The modified glass powder slurry is then cooled to 35°C, centrifuged to remove the liquid, and washed with ethanol until the pH reaches 7.5. Finally, it is dried at 55°C to obtain the modified glass powder for the composite material.

[0131] Example 4

[0132] This embodiment provides a modified glass powder for composite materials. The raw materials for preparing the modified glass powder for composite materials are based on an alcohol-water mixed solution dispersant. Except for the amount of the modifier added being 8 wt%, the rest are the same as in Example 1.

[0133] This embodiment also provides a method for preparing modified glass powder for composite materials. Except for using the raw materials described in this embodiment, the preparation method is the same as that in Example 1.

[0134] Example 5

[0135] This embodiment provides a modified glass powder for composite materials. The raw materials for preparing the modified glass powder for composite materials are based on an alcohol-water mixed solution dispersant. Except for the amount of the modifier added being 20wt%, the rest are the same as in Example 1.

[0136] This embodiment also provides a method for preparing modified glass powder for composite materials. Except for using the raw materials described in this embodiment, the preparation method is the same as that in Example 1.

[0137] Example 6

[0138] This embodiment provides a modified glass powder for composite materials. The modified glass powder for composite materials is prepared using 60wt% γ-methacryloxypropyltrimethoxysilane and 40wt% γ-aminopropyltriethoxysilane as the modifiers, and the rest are the same as in Example 1.

[0139] This embodiment also provides a method for preparing modified glass powder for composite materials. Except for using the raw materials described in this embodiment, the preparation method is the same as that in Example 1.

[0140] Example 7

[0141] This embodiment provides a modified glass powder for composite materials. The modified glass powder for composite materials is prepared using 77.8 wt% γ-methacryloyloxypropyltrimethoxysilane and 22.2 wt% γ-aminopropyltriethoxysilane as the modifiers, and the rest are the same as in Example 1.

[0142] This embodiment also provides a method for preparing modified glass powder for composite materials. Except for using the raw materials described in this embodiment, the preparation method is the same as that in Example 1.

[0143] Example 8

[0144] This embodiment provides a modified glass powder for composite materials. Except for the addition of 1.5 wt% of the modifying agent glycerol in the raw materials for preparing the modified glass powder for composite materials, the rest are the same as in Example 1.

[0145] This embodiment also provides a method for preparing modified glass powder for composite materials. Except for using the raw materials described in this embodiment, the preparation method is the same as that in Example 1.

[0146] Example 9

[0147] This embodiment provides a modified glass powder for composite materials. Except for the addition of 4.3 wt% of the modifying agent glycerol in the raw materials for preparing the modified glass powder for composite materials, the rest are the same as in Example 1.

[0148] This embodiment also provides a method for preparing modified glass powder for composite materials. Except for using the raw materials described in this embodiment, the preparation method is the same as that in Example 1.

[0149] Example 10

[0150] This embodiment provides a method for preparing modified glass powder for composite materials. Except for the pH of the glass powder slurry after pH adjustment being 7.5, the rest of the preparation method is the same as in Example 1.

[0151] Example 11

[0152] This embodiment provides a method for preparing modified glass powder for composite materials. Except for the pH of the glass powder slurry after pH adjustment being 9.5, the rest of the preparation method is the same as in Example 1.

[0153] Example 12

[0154] This embodiment provides a modified glass powder for composite materials. The modifier in the raw materials for preparing the modified glass powder for composite materials is only γ-methacryloyloxypropyltrimethoxysilane, and the total amount of the modifier remains unchanged. All other aspects are the same as in Example 1.

[0155] This embodiment also provides a method for preparing modified glass powder for composite materials. Except for the raw materials used in this embodiment, the preparation method is the same as that in Example 1.

[0156] Example 13

[0157] This embodiment provides a modified glass powder for composite materials. The modifier in the raw materials for preparing the modified glass powder for composite materials is only γ-aminopropyltriethoxysilane, and the total amount of the modifier remains unchanged. All other aspects are the same as in Example 1.

[0158] This embodiment also provides a method for preparing modified glass powder for composite materials. Except for the raw materials used in this embodiment, the preparation method is the same as that in Example 1.

[0159] II. Comparative Example

[0160] Comparative Example 1

[0161] This comparative example provides a modified glass powder for composite materials. Except for the absence of modifying additives, i.e., glycerol, in the raw materials for preparing the modified glass powder for composite materials, all other aspects are the same as in Example 1.

[0162] This comparative example also provides a method for preparing modified glass powder for composite materials. Except for using the raw materials described in this comparative example, the preparation method is the same as that in Example 1.

[0163] III. Application Examples

[0164] Application Example 1

[0165] This application example provides a composite resin material, which is made by combining resin with modified glass powder used for the composite material described in Example 1.

[0166] This application example also provides a method for preparing a composite resin material, the method comprising the following steps:

[0167] The modified glass powder and resin of the composite material described in Example 1 were mixed in a mass ratio of 1:1 and stirred at 1200 r / min for 2 hours to obtain a mixed slurry. The mixed slurry was then ball-milled for 3 hours. Finally, the ball-milled mixed slurry was printed using a 3D printer and then cured at 70°C to obtain the composite resin material.

[0168] Application Example 2

[0169] This application example provides a composite resin material, which is made by combining resin with modified glass powder used for the composite material described in Example 2.

[0170] This application example also provides a method for preparing a composite resin material, the method comprising the following steps:

[0171] The modified glass powder and resin material of the composite material described in Example 2 were mixed at a mass ratio of 0.9:1 and stirred at 1300 r / min for 1 hour to obtain a mixed slurry. The mixed slurry was then ball-milled for 2 hours. Finally, the ball-milled mixed slurry was printed using a 3D printer and then cured at 75°C to obtain the composite resin material.

[0172] Application Example 3

[0173] This application example provides a composite resin material, which is made by combining resin with modified glass powder used for the composite material described in Example 3.

[0174] This application example also provides a method for preparing a composite resin material, the method comprising the following steps:

[0175] The modified glass powder and resin of the composite material described in Example 3 were mixed at a mass ratio of 1.1:1 and stirred at 1350 r / min for 3 h to obtain a mixed slurry. The mixed slurry was then ball-milled for 5 h. Finally, the ball-milled mixed slurry was printed using a 3D printer and then cured at 80°C to obtain the composite resin material.

[0176] Application Examples 4 to 13

[0177] The preparation methods of the composite resin materials provided in Application Examples 4 to 13 are the same as those in Application Example 1, except that they use the modified glass powder for the composite materials described in Examples 4 to 13 respectively.

[0178] IV. Comparative Application Examples

[0179] Comparative Application Example 1

[0180] This comparative application example provides a method for preparing a composite resin material. The preparation method is the same as that in application example 1, except that it uses the modified glass powder for the composite material described in comparative example 1.

[0181] V. Tests and Results

[0182] (I) The weight loss rate (i.e., degree of modification) of the modified glass powder for composite materials before soaking in water and the weight loss rate of the modified glass powder for composite materials after soaking in water were tested in the above examples or comparative examples, and the difference in weight loss rate of the modified glass powder for composite materials before and after soaking in water was calculated. The results are shown in Table 2.

[0183] Test method:

[0184] ① The weight loss rate of the modified glass powder for composite materials obtained in the above embodiments or comparative examples was tested using a synchronous thermal device, that is, the weight loss rate of the modified glass powder for composite materials before soaking in water;

[0185] ② The modified glass powder for the composite material obtained in the above examples or comparative examples was placed in pure water at 80°C and soaked for 24 hours. After soaking, the liquid was removed by centrifugation and then placed in an oven at 105°C for drying for 12 hours. Finally, the weight loss rate of the modified glass powder for the composite material after drying was tested using a synchronous thermal device, which is the weight loss rate of the modified glass powder for the composite material before soaking in water.

[0186] Test conditions: The test was conducted using a simultaneous thermogravimetric analyzer. 15 mg of glass powder was placed in a crucible, and the furnace door was closed. Test parameters were set, and the test was started. The test curve was as follows: the temperature was increased from room temperature to 105°C at a rate of 10°C / min, held at 105°C for 30 min, and then increased to 700°C at a rate of 10°C / min. The thermogravimetric analysis was conducted in an air atmosphere with an equilibrium flow rate of 100 mL / min.

[0187] (II) Water Contact Angle Test: Take 0.5g of the modified glass powder obtained from the above examples or comparative examples and place it on the groove of the stage. Use a glass plate to press the surface evenly and smoothly. Place the stage under the needle of the water contact angle tester and start the test. In the water contact angle test, the water added to the needle is pure water. The water droplets squeezed out from the needle will exhibit different residence states when they fall on the smooth glass powder surface. The water contact angle test results can be obtained by software fitting, and the results are shown in Table 2.

[0188] Table 2

[0189]

[0190] (III) Flexural strength test: According to standard YY0710-2009 "Polymer-based crown bridge materials", the composite resin material obtained in the above application example or comparative application example was printed into a sample of 2±0.1mm×2±0.1mm×25±2mm. The surface was polished by wet grinding with 2000-grit sandpaper. The sample was loaded with a loading rate of (50±16) N / min using a testing machine until it broke. Five samples were measured and the average value was taken. The flexural strength of the composite resin material was recorded. The results are shown in Table 3.

[0191] (IV) Thermal Cycling Test: The composite resin material obtained in the above application example or comparative application example was printed into a sample of 2±0.1mm×2±0.1mm×25±2mm, and the surface was polished by wet grinding with 2000-grit sandpaper. The sample was immersed in water at (5±1)℃ for 30s~35s and water at (55±1)℃ for 30s~35s, and this cycle was repeated 10,000 times. According to standard YY0710-2009 "Polymer-based Crown Bridge Materials", the sample of the above application example or comparative application example after 10,000 thermal cycles was loaded into a testing machine at a loading rate of (50±16) N / min until the sample broke. Five samples were measured and the average value was taken. The flexural strength of the composite resin material after 10,000 thermal cycles was recorded. The results are shown in Table 3.

[0192] Table 3

[0193]

[0194] The data in Tables 2 and 3 show that:

[0195] (1) Based on Examples 1 to 3 and Application Examples 1 to 3, it can be seen that the weight loss difference of the modified glass powder used in the composite material provided by the present invention before and after soaking in water is as low as 0.80%, and the water contact angle is as high as 140° or more. It has excellent hydrolysis resistance. Furthermore, the composite resin material made by combining it with resin has excellent mechanical properties and stability, with a flexural strength as high as 200 MPa or more. After 10,000 cycles of hot and cold, the flexural strength is still as high as 180 MPa or more.

[0196] (2) Based on Examples 1 and 4 to 7, and Application Examples 1 and 4 to 7, it can be seen that the present invention further preferably uses the alcohol-water mixed solution dispersant as a basis, and the amount of the modifier added is 10 to 15 wt%. Furthermore, when the modifier is a combination of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, the mass content of γ-methacryloxypropyltrimethoxysilane is 65 to 75% based on the total mass of the modifier being 100 wt%. Together, they further improve the hydrolysis resistance of the modified glass powder used in the obtained composite material, and further improve the mechanical properties and stability of the composite resin material formed by combining it with the resin.

[0197] (3) Based on the combined examples 1, 8 and 9, and application examples 1, 8 and 9, it can be seen that the present invention further preferably uses the glass powder as a base, and the amount of the modifier added is 2 to 4 wt%. The modifier with the specific component composition and the specific amount of added modifier works synergistically to further improve the modification effect on the glass powder, further improve its hydrolysis resistance, and further improve the bonding strength with the resin, so that the mechanical properties and stability of the resulting composite resin material are significantly improved.

[0198] (4) Based on the combined examples 1, 10 and 11, and application examples 1, 10 and 11, it can be seen that the pH adjustment endpoint in the preparation method of the present invention is preferably 8-9, which is more conducive to the formation of Si-O-Si bonds after hydrolysis of the modifier components and the maintenance of the free amino group to form -SiOH hydrogen bonds, thereby further improving the hydrolysis resistance of the modified glass powder for the obtained composite material and the mechanical properties of the obtained composite resin material.

[0199] (5) Based on the comprehensive comparison of Examples 1, 12, and 13, as well as Application Example 1, Comparative Application Example 12, and Comparative Application Example 13, it can be seen that the modifier described in Example 12 is only γ-methacryloxypropyltrimethoxysilane, and the modifier described in Example 13 is only γ-aminopropyltriethoxysilane, i.e., a single modifier, resulting in poor modification effect. This indicates that the present invention further preferably uses a combination of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane as the modifier, which further improves the hydrolysis resistance of the modified glass powder used in the obtained composite material, thereby improving the mechanical properties of the obtained composite resin material.

[0200] (6) As can be seen from the combined example 1 and comparative example 1, since no modifying agent was added in comparative example 1, the modifying agent could not uniformly coat the glass powder, resulting in a poor modification effect. This resulted in a low flexural strength of the obtained composite resin material, and a large decrease in strength after 10,000 cycles of hot and cold, as well as poor stability and anti-aging effect. This shows that the present invention uses the modifier and the modifying agent in combination, and the two work synergistically to improve the modification effect of the glass powder, thereby improving the hydrolysis resistance of the modified glass powder used in the obtained composite material, and further improving the mechanical properties and stability of the obtained composite resin material.

[0201] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A modified glass powder for composite materials, characterized in that, The raw materials for preparing the modified glass powder for the composite material include inorganic components and organic components. The inorganic components are glass powder, and the organic components include modifiers and modifying additives. The modified glass powder used in the composite material has a modification degree of 0.5%~10%, a weight loss difference before and after soaking in water ≤0.8%, and a water contact angle >130°.

2. The modified glass powder for composite materials according to claim 1, characterized in that, The modifier includes any two or at least three of γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or γ-mercaptopropyltrimethoxysilane, preferably a combination of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane. Preferably, when the modifier is a combination of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, the mass content of γ-methacryloxypropyltrimethoxysilane is ≤75%, preferably 65~75%, based on a total mass of 100wt% of the modifier; Preferably, the modifying agent includes polyol-based additives; Preferably, the polyol auxiliaries include any one or a combination of at least two of glycerol, 1,2-propanediol or xylitol, with glycerol being the most preferred.

3. The modified glass powder for composite materials according to claim 1 or 2, characterized in that, The glass powder raw materials, by weight percentage, include 55-70 wt% SiO2, 0-5 wt% ZrO2, 8-15 wt% Al2O3, 8-15 wt% B2O3, 0-5 wt% CaO, 0-8 wt% MgO and 0-25 wt% SrO; Preferably, the glass powder raw material comprises, by weight percentage, 55-70 wt% SiO2, 2-5 wt% ZrO2, 8-15 wt% Al2O3, 8-15 wt% B2O3, 0.5-5 wt% CaO, 1-8 wt% MgO and 1-25 wt% SrO; Preferably, the particle size D50 of the glass powder is 0.01~50μm, and more preferably 0.1~10μm.

4. The modified glass powder for composite materials according to any one of claims 1 to 3, characterized in that, The raw materials for preparing the modified glass powder for the composite material also include a dispersant; Preferably, the dispersant comprises an alcohol-water mixture; Preferably, the mass ratio of alcohol to water in the alcohol-water mixture is (1~4):(6~9); Preferably, the mass ratio of the glass powder to the dispersant is 1:(3~10); Preferably, the amount of the modifier added is 10-15 wt%, based on the dispersant; Preferably, based on the glass powder, the amount of the modified additive added is 2-4 wt%.

5. A method for preparing modified glass powder for composite materials according to any one of claims 1 to 4, characterized in that, The preparation method includes the following steps: Glass powder, modifier, and modifying additives are mixed and heated to react and obtain modified glass powder slurry. The modified glass powder slurry is then dried to obtain the modified glass powder for the composite material. The modified glass powder used in the composite material has a modification degree of 0.5%~10%, a weight loss difference before and after soaking in water ≤0.8%, and a water contact angle >130°.

6. The preparation method according to claim 5, characterized in that, The mixing also includes the addition of a dispersant; Preferably, the mixing includes first mixing the glass powder and the dispersant according to the formula to obtain a glass powder slurry, and then mixing the glass powder slurry, the modifier and the modifying additive according to the formula in a second mixing. Preferably, the preparation method further includes pH adjustment of the glass powder slurry before the second mixing; Preferably, the pH adjustment agent includes ammonia and / or triethanolamine; Preferably, the endpoint of the pH adjustment is when the pH of the glass powder slurry is 8-9.

7. The preparation method according to claim 6, characterized in that, The second mixing process includes first mixing the glass powder slurry and the modifying agent according to the formula, and then adding the modifying agent according to the formula. Preferably, the preparation method further includes a first heating and a first stirring sequentially after mixing the glass powder slurry and the modifying agent; Preferably, the endpoint temperature of the first heating is 45~50°C; Preferably, the first stirring time is 15-30 minutes; Preferably, the preparation method further includes a second heating and heat preservation process performed sequentially after adding the modified additive; Preferably, the endpoint temperature of the second heating is 60~70°C; Preferably, the heat preservation time is 1.5 to 4 hours; Preferably, the second heating process is accompanied by a second stirring; Preferably, the rotation speeds of the first stirring and the second stirring are each independently 300~700 r / min; Preferably, the first heating and the second heating methods each independently include water bath heating.

8. The preparation method according to any one of claims 5 to 7, characterized in that, The preparation method involves sequentially cooling, separating, and washing the modified glass powder slurry before drying. Preferably, the final temperature of the cooling is 35~40°C; Preferably, the washing endpoint is when the pH of the modified glass powder slurry is 6.5~7.5; Preferably, the drying method includes baking; Preferably, the drying temperature is 40~60℃.

9. A composite resin material, characterized in that, The composite resin material is made by combining resin and modified glass powder of the composite material according to any one of claims 1 to 4.

10. The composite resin material according to claim 9, characterized in that, The monomers in the raw materials of the resin include any two or at least three of the following: urethane dimethacrylate, bisphenol A dimethacrylate oxyacetate, or 1,6-hexanediol dimethacrylate. Preferably, the flexural strength of the composite resin material is ≥200MPa.

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