High-strength wear-resistant composite resin material and preparation method thereof
By preparing nanohybrids of modified nanocellulose and polyaniline/potassium silicate nanomaterials, the interface bonding force of the composite resin material is enhanced and crack propagation is hindered, the problem of insufficient wear resistance of existing resin materials is solved, and high strength and wear resistance are improved.
Patent Information
- Application Number
- CN202510780635.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-12
- Publication Date
- 2025-09-05
AI Technical Summary
Existing composite resin materials have shortcomings in wear resistance and strength, especially after long-term use, which limits their use in certain application fields.
By preparing modified nanocellulose and polyaniline/potassium silicate nanomaterials, combined with modifications of distearoyloxyisopropyl aluminate and silane coupling agent, nanohybrids are formed and mixed with epoxy resin to enhance interfacial adhesion and hinder crack propagation.
The strength and wear resistance of composite resin materials are improved, and especially after coating the surface of metal and wood substrates, they show good wear resistance and hardness.
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Figure CN120590833A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of polymer materials, and in particular to a high-strength wear-resistant composite resin material and a preparation method thereof. Background Art
[0002] Composite resin materials are made by combining two or more materials with different properties through physical or chemical methods. They are usually composed of a resin matrix such as epoxy resin or phenolic resin and reinforcing materials such as glass fiber and carbon fiber. Through the composite effect, the overall performance of the material is better than that of a single component material. Among them, epoxy resin as the resin matrix is a high-performance polymer material that is widely used in functional coating materials, such as surface coatings for metal materials and wood substrates. However, it has the disadvantages of high brittleness and poor wear resistance. After long-term use, it is prone to severe wear, which reduces its service life and limits its application in wear-resistant fields. Therefore, nanomaterials are often added to improve and enhance the performance of the resin. The reinforcing materials of composite resins include glass fiber, carbon fiber, aramid fiber, ultra-high molecular weight polyethylene fiber and nanomaterials. Glass fiber is suitable for cost-sensitive applications with high requirements for insulation and corrosion resistance, but is not suitable for scenarios with extremely high requirements for weight and impact resistance. Carbon fiber is suitable for fields with extremely high requirements for lightweight, high strength and high temperature resistance, but it is expensive, brittle and has insufficient wear resistance. Aramid fiber and ultra-high molecular weight polyethylene fiber are expensive and have complex preparation processes. Nanomaterials are more suitable for improving and strengthening the physical strength and wear resistance of resin materials.
[0003] Nanomaterials conventionally added to composite resin materials include nano-silicon dioxide, nano-titanium dioxide and nano-cellulose. Among them, nano-cellulose is a green and environmentally friendly reinforcing material that can improve the physical properties of composite resin materials. However, nano-cellulose easily agglomerates in the resin, affecting its uniform dispersion, thereby reducing the performance of the composite material and making it difficult to mix and polymerize with other materials to achieve better wear resistance. Therefore, the present invention provides a high-strength, wear-resistant composite resin material and a preparation method thereof to solve the problems existing in the above-mentioned prior art. Summary of the Invention
[0004] In view of the shortcomings of the prior art, the present invention aims to provide a high-strength wear-resistant composite resin material and a preparation method thereof.
[0005] A method for preparing a high-strength wear-resistant composite resin material comprises the following steps: S1: Preparation of modified nanocellulose Weighing nanocellulose and adding it to a mixed solution of anhydrous ethanol and deionized water, then mixing distearoyloxyisopropylaluminate with the anhydrous ethanol and deionized water, and then mixing and stirring the two solutions to react to obtain modified nanocellulose; S2: Preparation of polyaniline / potassium silicate nanomaterials A potassium nitrate solution and an ethanol solution are mixed and sodium silicate and NaOH are added, and the mixture is sealed for reaction. After the reaction is completed, the mixture is added to a toluene solution, ultrasonically dispersed, and then a silane coupling agent is added to react to obtain surface-modified nano-potassium silicate. The surface-modified nano-potassium silicate is weighed and added to deionized water, and then a ferric chloride solution is added. After mixing, the mixture is added to an aniline solution to react to obtain a polyaniline / potassium silicate nanomaterial. S3: Preparation of Nanohybrids The polyaniline / potassium silicate nanomaterials were weighed and dispersed in N-N-dimethylformamide to form a uniform suspension, and then the modified nanocellulose was added to the suspension to react and obtain a nanohybrid; S4: Preparation of high-strength and wear-resistant composite resin materials The nano-hybrid is dispersed in benzyl alcohol and epoxy resin suspension, subjected to ultrasonic treatment, and then a defoaming agent is added and stirred to obtain a high-strength and wear-resistant composite resin material.
[0006] Furthermore, step S1 of preparing modified nanocellulose comprises the following steps: 0.2-0.3 parts by mass of nanocellulose are weighed and added to a mixed solution of 80-85 parts by mass of anhydrous ethanol and 15-20 parts by mass of deionized water, and ultrasonically dispersed for 1-1.5 hours. Then, 2-3 parts by mass of distearoyloxyisopropylaluminate are mixed with 80-85 parts by mass of anhydrous ethanol and 15-20 parts by mass of deionized water, and heated and stirred at 50-55°C for 1-1.5 hours. Subsequently, the two solutions are mixed and stirred at 70-75°C for 12-13 hours. After the reaction, the solution is washed and dried at 60-65°C for 4.5-5 hours to obtain modified nanocellulose.
[0007] Furthermore, step S2 of preparing polyaniline / potassium silicate nanomaterials comprises the following steps: S2.1: Mix 2-3 parts by volume of potassium nitrate solution and 8-10 parts by volume of ethanol solution and stir at a speed of 100-120 r / min. Add 2-3 parts by volume of sodium silicate and 1-2 parts by volume of NaOH while stirring. Then transfer the mixture to an autoclave, seal it, and heat it to 210-220°C for hydrothermal reaction for 24-25 hours. After the reaction, wash the product and vacuum dry it. Then add it to a toluene solution and ultrasonically disperse it for 30-35 minutes. Then add 0.2-0.5 parts by volume of silane coupling agent. Then, react in an oil bath at 95-100°C for 24-25 hours. Then, wash and dry it to obtain surface-modified nano-potassium silicate. S2.2: Weigh 0.2-0.4 parts by mass of surface-modified nano-potassium silicate and add it to 5-10 parts by mass of deionized water, then add 3-4 parts by mass of ferric chloride solution. After mixing, add it to the upper layer of 15-20 parts by mass of aniline solution, maintain at 0°C for 8-9 hours, wash and dry to obtain polyaniline / potassium silicate nanomaterial.
[0008] Furthermore, step S3 of preparing the nanohybrid comprises the following steps: 0.1-0.3 parts by mass of polyaniline / potassium silicate nanomaterials were dispersed in 100 parts by mass of NN dimethylformamide, and ultrasonicated for 30-35 minutes to form a uniform suspension. Then, 0.1-0.4 parts by mass of modified nanocellulose were added to the suspension and ultrasonicated for 30-35 minutes. The suspension was then heated to 100-105°C and stirred for 5-6 hours. After the reaction was completed, the mixture was filtered, washed and dried to obtain a nanohybrid.
[0009] Furthermore, step S4 of preparing a high-strength wear-resistant composite resin material comprises the following steps: 1-2 parts by mass of the nanohybrid is dispersed in 100 parts by mass of benzyl alcohol and epoxy resin suspension, and ultrasonically treated for 30-35 minutes. Then, 2-3 parts by mass of a defoaming agent is added, and the mixture is stirred at a speed of 500-550 r / min for 50-60 minutes to obtain a high-strength and wear-resistant composite resin material.
[0010] Furthermore, the concentration of the aniline solution is 0.1-0.5 mg / mL.
[0011] Furthermore, the benzyl alcohol and epoxy resin suspension is prepared by mixing benzyl alcohol and epoxy resin in a mass ratio of 1:(1-2).
[0012] Furthermore, the defoaming agent is specifically polydimethylsiloxane.
[0013] Furthermore, the concentration of the ferric chloride solution is 10%.
[0014] Furthermore, it is prepared by the above-mentioned method for preparing the high-strength wear-resistant composite resin material.
[0015] Compared with the prior art, the present invention has at least the following beneficial effects: 1. The present invention modifies nanocellulose with distearoyloxyisopropylaluminate, and heating and stirring help the aluminate coupling agent to be fully dissolved and activated, so that the polar groups in its molecules are oriented with the non-polar long chains, laying the foundation for the subsequent reaction with nanocellulose. Subsequently, the polar end of the aluminate forms a chemical bond with the hydroxyl groups on the surface of the nanocellulose, and the long-chain alkyl groups are introduced into the surface of the nanocellulose, giving it hydrophobicity and improving its compatibility with the organic system. The polarity difference between the long alkyl chains on the surface of the modified nanocellulose and the epoxy resin is reduced, the compatibility is improved, and the phase separation is reduced. At the same time, the residual polar groups of the aluminate may further react with the epoxy groups or hydroxyl groups of the epoxy resin to form chemical bonds, thereby enhancing the interfacial bonding force, thereby improving the subsequent bonding force between the nanocellulose and the polyaniline / potassium silicate nanomaterial, improving the binding performance of the two, and improving the rigidity and strength of the epoxy resin after the addition of the epoxy resin, hindering the expansion of cracks, thereby improving the strength and wear resistance of the composite resin material when coated on the surface of metal materials and wooden substrates.
[0016] 2. The present invention prepares a polyaniline / potassium silicate nanomaterial by adding potassium silicate to an aniline solution. Ferric chloride serves as an oxidant to promote aniline polymerization, and nano-potassium silicate serves as an inorganic filler to provide a support structure for the polymerized aniline. In addition, the surface of the potassium silicate modified with a silane coupling agent contains organic functional groups that can form interactive chemical bonds with the benzene rings or imine groups of the polyaniline, thereby enhancing interfacial bonding and reducing phase separation between the inorganic filler and the organic matrix. At the same time, the potassium silicate nanoparticles serve as physical crosslinking points to hinder the growth of microcracks in the polyaniline matrix. When added to an epoxy resin to prepare a composite resin material, the crack propagation can be hindered, the brittle fracture of the epoxy resin can be reduced, and the toughness can be improved, thereby forming a high-strength composite resin material. Furthermore, the composite resin material has good strength and wear resistance after being coated on the surface of a metal material or a wooden substrate. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] The accompanying drawings, which are incorporated herein and constitute a part of the specification, illustrate embodiments of the present disclosure and, together with the description, further serve to explain the principles of the present disclosure and to enable one skilled in the relevant art to make and use the present disclosure.
[0018] Figure 1 This is a flow chart of a method for preparing a high-strength, wear-resistant composite resin material used in an embodiment of the present invention. DETAILED DESCRIPTION
[0019] The following describes in detail a high-strength, wear-resistant composite resin material and its preparation method provided by the present invention, with reference to the accompanying drawings and specific embodiments. It is also noted that, for the sake of completeness, the following embodiments are best and preferred embodiments, and those skilled in the art may employ alternative implementations for known techniques. Furthermore, the accompanying drawings are intended solely for the purpose of describing the embodiments in greater detail and are not intended to limit the present invention.
[0020] Example 1: A method for preparing a high-strength wear-resistant composite resin material, such as Figure 1 As shown, the following steps are included: S1: Preparation of modified nanocellulose 0.2 parts by mass of nanocellulose was weighed and added to a mixed solution of 80 parts by mass of anhydrous ethanol and 15 parts by mass of deionized water, and ultrasonically dispersed for 1 hour. Then, 2 parts by mass of distearoyloxyisopropylaluminate was mixed with 80 parts by mass of anhydrous ethanol and 15 parts by mass of deionized water, heated and stirred at 50°C for 1 hour, and then the two solutions were mixed and stirred at 70°C for 12 hours. After the reaction, the modified nanocellulose was washed and dried at 60°C for 4.5 hours to obtain.
[0021] S2: Preparation of polyaniline / potassium silicate nanomaterials S2.1: 2 parts by volume of potassium nitrate solution and 8 parts by volume of ethanol solution were mixed and stirred at 100 r / min. 2 parts by volume of sodium silicate and 1 part by volume of NaOH were added under stirring. The mixture was then transferred to an autoclave, sealed, and heated to 210°C for hydrothermal reaction for 24 hours. After the reaction, the product was cleaned and vacuum-dried, then added to a toluene solution and ultrasonically dispersed for 30 minutes. 0.2 parts by volume of a silane coupling agent was then added, and the mixture was reacted in an oil bath at 95°C for 24 hours. The mixture was then cleaned and dried to obtain surface-modified nano-potassium silicate. S2.2: Weigh 0.2 parts by mass of surface-modified nano-potassium silicate and add it to 5 parts by mass of deionized water. Then add 3 parts by mass of 10% ferric chloride solution. After mixing, add it to the upper layer of 15 parts by mass of 0.5 mg / mL aniline solution. Keep it at 0°C for 8 hours, wash and dry it to obtain polyaniline / potassium silicate nanomaterial.
[0022] S3: Preparation of Nanohybrids 0.1 parts by mass of polyaniline / potassium silicate nanomaterials were dispersed in 100 parts by mass of NN dimethylformamide and ultrasonicated for 30 minutes to form a uniform suspension. Then 0.1 parts by mass of modified nanocellulose was added to the suspension and ultrasonicated for 30 minutes. The suspension was then heated to 100°C and stirred for 5 hours. After the reaction was completed, the mixture was filtered, washed and dried to obtain a nanohybrid.
[0023] S4: Preparation of high-strength and wear-resistant composite resin materials 1 part by mass of the nanohybrid is dispersed in 100 parts by mass of a benzyl alcohol and epoxy resin suspension, and ultrasonically treated for 30 minutes. 2 parts by mass of a defoaming agent, polydimethylsiloxane, is then added, and the mixture is stirred at a speed of 500 r / min for 50 minutes to obtain a high-strength, wear-resistant composite resin material. The benzyl alcohol and epoxy resin suspension is specifically prepared by mixing benzyl alcohol and epoxy resin in a mass ratio of 1:1.
[0024] Example 2: A method for preparing a high-strength wear-resistant composite resin material, such as Figure 1 As shown, the following steps are included: S1: Preparation of modified nanocellulose 0.3 parts by mass of nanocellulose was weighed and added to a mixed solution of 85 parts by mass of anhydrous ethanol and 20 parts by mass of deionized water, and ultrasonically dispersed for 1 hour. Then, 3 parts by mass of distearoyloxyisopropylaluminate was mixed with 85 parts by mass of anhydrous ethanol and 20 parts by mass of deionized water, heated and stirred at 50°C for 1 hour, and then the two solutions were mixed and stirred at 70°C for 12 hours. After the reaction, the modified nanocellulose was washed and dried at 60°C for 4.5 hours to obtain.
[0025] S2: Preparation of polyaniline / potassium silicate nanomaterials S2.1: 3 parts by volume of potassium nitrate solution and 8 parts by volume of ethanol solution were mixed and stirred at 100 r / min. 3 parts by volume of sodium silicate and 2 parts by volume of NaOH were added under stirring. The mixture was then transferred to an autoclave, sealed, and heated to 210°C for hydrothermal reaction for 24 hours. After the reaction, the product was cleaned and vacuum-dried, then added to a toluene solution and ultrasonically dispersed for 30 minutes. 0.5 parts by volume of a silane coupling agent was then added, and the mixture was reacted in an oil bath at 95°C for 24 hours. The mixture was then cleaned and dried to obtain surface-modified nano-potassium silicate. S2.2: Weigh 0.4 parts by mass of surface-modified nano-potassium silicate and add it to 10 parts by mass of deionized water. Then add 4 parts by mass of a 10% ferric chloride solution. After mixing, add the mixture to the upper layer of 20 parts by mass of a 0.5 mg / mL aniline solution. Keep the mixture at 0°C for 8 hours, wash it, and dry it to obtain a polyaniline / potassium silicate nanomaterial.
[0026] S3: Preparation of Nanohybrids 0.3 parts by mass of polyaniline / potassium silicate nanomaterials were dispersed in 100 parts by mass of NN dimethylformamide and ultrasonicated for 30 minutes to form a uniform suspension. Then 0.4 parts by mass of modified nanocellulose was added to the suspension and ultrasonicated for 30 minutes. The suspension was then heated to 100°C and stirred for 5 hours. After the reaction was completed, the mixture was filtered, washed and dried to obtain a nanohybrid.
[0027] S4: Preparation of high-strength and wear-resistant composite resin materials 2 parts by mass of the nanohybrid are dispersed in 100 parts by mass of a benzyl alcohol and epoxy resin suspension, and ultrasonically treated for 30 minutes. 3 parts by mass of a defoaming agent, polydimethylsiloxane, are then added, and the mixture is stirred at a speed of 500 r / min for 50 minutes to obtain a high-strength, wear-resistant composite resin material. The benzyl alcohol and epoxy resin suspension is specifically prepared by mixing benzyl alcohol and epoxy resin in a mass ratio of 1:2.
[0028] Example 3: A method for preparing a high-strength wear-resistant composite resin material, such as Figure 1 As shown, the following steps are included: S1: Preparation of modified nanocellulose 0.2 parts by mass of nanocellulose was weighed and added to a mixed solution of 80 parts by mass of anhydrous ethanol and 15 parts by mass of deionized water, and ultrasonically dispersed for 1.5 hours. Then, 2 parts by mass of distearoyloxyisopropylaluminate was mixed with 80 parts by mass of anhydrous ethanol and 15 parts by mass of deionized water, and heated and stirred at 55°C for 1.5 hours. Subsequently, the two solutions were mixed and stirred at 75°C for 13 hours. After the reaction, the modified nanocellulose was washed and dried at 65°C for 5 hours to obtain.
[0029] S2: Preparation of polyaniline / potassium silicate nanomaterials S2.1: 2 parts by volume of potassium nitrate solution and 8 parts by volume of ethanol solution were mixed and stirred at 100 r / min. 2 parts by volume of sodium silicate and 1 part by volume of NaOH were added under stirring. The mixture was then transferred to an autoclave, sealed, and heated to 220°C for a hydrothermal reaction for 25 hours. After the reaction, the product was cleaned and dried under vacuum, then added to a toluene solution and ultrasonically dispersed for 35 minutes. 0.2 parts by volume of a silane coupling agent was then added, and the mixture was reacted in an oil bath at 100°C for 25 hours. The mixture was then cleaned and dried to obtain surface-modified nano-potassium silicate. S2.2: Weigh 0.2 parts by mass of surface-modified nano-potassium silicate and add it to 5 parts by mass of deionized water. Then add 3 parts by mass of a 10% ferric chloride solution. After mixing, add the mixture to the upper layer of 15 parts by mass of a 0.5 mg / mL aniline solution. Keep at 0°C for 9 hours, wash and dry to obtain a polyaniline / potassium silicate nanomaterial.
[0030] S3: Preparation of Nanohybrids 0.1 parts by mass of polyaniline / potassium silicate nanomaterials were dispersed in 100 parts by mass of NN dimethylformamide and ultrasonicated for 35 minutes to form a uniform suspension. Then 0.1 parts by mass of modified nanocellulose was added to the suspension and ultrasonicated for 35 minutes. The suspension was then heated to 105°C and stirred for 6 hours. After the reaction was completed, the mixture was filtered, washed and dried to obtain a nanohybrid.
[0031] S4: Preparation of high-strength and wear-resistant composite resin materials 1 part by mass of the nanohybrid was dispersed in 100 parts by mass of a benzyl alcohol and epoxy resin suspension, and ultrasonically treated for 35 minutes. 2 parts by mass of a defoaming agent, polydimethylsiloxane, was then added, and the mixture was stirred at a speed of 550 r / min for 60 minutes to obtain a high-strength, wear-resistant composite resin material. The benzyl alcohol and epoxy resin suspension was specifically prepared by mixing benzyl alcohol and epoxy resin in a mass ratio of 1:1.
[0032] Example 4: S1: Preparation of modified nanocellulose 0.2 parts by mass of nanocellulose was weighed and added to a mixed solution of 80 parts by mass of anhydrous ethanol and 15 parts by mass of deionized water, and ultrasonically dispersed for 1 hour. Then, 2 parts by mass of distearoyloxyisopropylaluminate was mixed with 80 parts by mass of anhydrous ethanol and 15 parts by mass of deionized water, heated and stirred at 50°C for 1 hour, and then the two solutions were mixed and stirred at 70°C for 12 hours. After the reaction, the modified nanocellulose was washed and dried at 60°C for 4.5 hours to obtain.
[0033] S2: Preparation of polyaniline / potassium silicate nanomaterials S2.1: 2 parts by volume of potassium nitrate solution and 8 parts by volume of ethanol solution were mixed and stirred at 100 r / min. 2 parts by volume of sodium silicate and 1 part by volume of NaOH were added under stirring. The mixture was then transferred to an autoclave, sealed, and heated to 210°C for hydrothermal reaction for 24 hours. After the reaction, the product was cleaned and vacuum-dried, then added to a toluene solution and ultrasonically dispersed for 30 minutes. 0.2 parts by volume of a silane coupling agent was then added, and the mixture was reacted in an oil bath at 95°C for 24 hours. The mixture was then cleaned and dried to obtain surface-modified nano-potassium silicate. S2.2: Weigh 0.2 parts by mass of surface-modified nano-potassium silicate and add it to 5 parts by mass of deionized water. Then add 3 parts by mass of 10% ferric chloride solution. After mixing, add it to the upper layer of 15 parts by mass of 0.5 mg / mL aniline solution. Keep it at 0°C for 8 hours, wash and dry it to obtain polyaniline / potassium silicate nanomaterial.
[0034] S3: Preparation of Nanohybrids 0.1 parts by mass of polyaniline / potassium silicate nanomaterials were dispersed in 100 parts by mass of NN dimethylformamide and ultrasonicated for 30 minutes to form a uniform suspension. Then 0.1 parts by mass of modified nanocellulose was added to the suspension and ultrasonicated for 30 minutes. The suspension was then heated to 100°C and stirred for 5 hours. After the reaction was completed, the mixture was filtered, washed and dried to obtain a nanohybrid.
[0035] S4: Preparation of high-strength and wear-resistant composite resin materials 1 part by mass of the nanohybrid was dispersed in 100 parts by mass of a benzyl alcohol and epoxy resin suspension, and ultrasonically treated for 30 minutes. 3 parts by mass of a defoaming agent, polydimethylsiloxane, was then added, and the mixture was stirred at a speed of 500 r / min for 50 minutes to obtain a high-strength, wear-resistant composite resin material. The benzyl alcohol and epoxy resin suspension was specifically prepared by mixing benzyl alcohol and epoxy resin in a mass ratio of 1:2.
[0036] Comparative Example 1: Compared with Example 1, the difference of Comparative Example 1 is that step S1 is not performed, and the modified nanocellulose in step S3 is replaced by nanocellulose, specifically “0.1 parts by mass of polyaniline / potassium silicate nanomaterial is weighed and dispersed in 100 parts by mass of NN dimethylformamide, ultrasonicated for 30 minutes to form a uniform suspension, and then 0.1 parts by mass of nanocellulose is added to the suspension and ultrasonicated for 30 minutes, and then the temperature is raised to 100°C and stirred for reaction for 5 hours. After the reaction is completed, it is filtered, washed and dried to obtain a nanohybrid”. The remaining steps remain unchanged, and the prepared high-strength wear-resistant composite resin material is recorded as Comparative Example 1.
[0037] Comparative Example 2: Compared with Example 1, the difference of Comparative Example 2 is that step S2 is not performed, and the polyaniline / potassium silicate nanomaterial in step S3 is replaced with polyaniline, specifically “0.1 parts by mass of polyaniline is weighed and dispersed in 100 parts by mass of NN dimethylformamide, ultrasonicated for 30 minutes to form a uniform suspension, and then 0.1 parts by mass of modified nanocellulose is added to the suspension and ultrasonicated for 30 minutes, then heated to 100°C and stirred for 5 hours. After the reaction is completed, filtered, washed and dried to obtain a nanohybrid”, and the remaining steps remain unchanged. The prepared high-strength, wear-resistant composite resin material is recorded as Comparative Example 2.
[0038] Comparative Example 3: Compared with Example 1, the difference of Comparative Example 3 is that step S2 is not performed, and the polyaniline / potassium silicate nanomaterial in step S3 is replaced by nano potassium silicate, specifically “0.1 parts by mass of nano potassium silicate is weighed and dispersed in 100 parts by mass of NN dimethylformamide, ultrasonicated for 30 minutes to form a uniform suspension, and then 0.1 parts by mass of modified nano cellulose is added to the suspension and ultrasonicated for 30 minutes, then heated to 100 ° C and stirred for 5 hours. After the reaction is completed, filtered, washed and dried to obtain a nano hybrid”, and the remaining steps remain unchanged. The prepared high-strength wear-resistant composite resin material is recorded as Comparative Example 3.
[0039] The composite resin materials prepared in Examples 1-4 and Comparative Examples 1-3 were coated on the surface of a dry metal substrate after adding a curing agent. The amount of curing agent added was 2-3% of the total mass of the system. The curing agent was specifically polyetheramine D230. The coating thickness was 5 mm. After drying, the physical strength and wear resistance of the coatings formed by the composite resin materials of Examples 1-4 and Comparative Examples 1-3 were tested, as shown in Table 1.
[0040] The composite resin materials prepared in Examples 1-4 and Comparative Examples 1-3 were coated on the surface of a dried wood substrate after adding a curing agent. The amount of curing agent added was 2-3% of the total mass of the system. The curing agent was specifically polyetheramine D230. The coating thickness was 5 mm. After drying, the physical strength and wear resistance of the coatings formed by the composite resin materials of Examples 1-4 and Comparative Examples 1-3 were tested, as shown in Table 2.
[0041] The wear resistance was tested using the method in GB / T1768-2006 “Determination of abrasion resistance of paints and varnishes”; The hardness was tested using the method in GB / T6739-2022 “Paints and varnishes - Determination of film hardness by pencil method”.
[0042] Table 1
[0043] Table 2
[0044] As can be seen from Tables 1 and 2, when the composite resin material is coated on the metal surface as a coating, the wear resistance of Examples 1-4 is 9500 times and the hardness reaches 9H, while that of Comparative Example 1 is only 8700 times, and that of Comparative Examples 2 and 3 is only 8300 times. The hardness of Comparative Example 1 is 7H, and that of Comparative Examples 2 and 3 is 6H. When the composite resin material is coated on the wood surface as a coating, the wear resistance of Examples 1-4 is 8200 times and the hardness reaches 7H, while the wear resistance of Comparative Example 1 is only 7600 times, and Comparative Examples 2 and 3 are only 7200 times. The hardness of Comparative Example 1 is 6H, and the hardness of Comparative Examples 2 and 3 is 5H.
[0045] It can be seen that the present invention uses distearoyloxyisopropylaluminate to modify nanocellulose, so that the polarity difference between the long alkyl chains on the surface of the modified nanocellulose and the epoxy resin is reduced, the compatibility is improved, and the phase separation is reduced, thereby improving the subsequent bonding of the nanocellulose with the polyaniline / potassium silicate nanomaterial, and improving the rigidity and strength of the epoxy resin after the addition of the epoxy resin, thereby hindering crack propagation; and potassium silicate is added to the aniline solution to prepare the polyaniline / potassium silicate nanomaterial. Nano-potassium silicate serves as an inorganic filler and provides a support structure for the polymerized aniline. At the same time, the potassium silicate nanoparticles serve as physical cross-linking points and can hinder the growth of microcracks in the polyaniline matrix. When the composite resin material is prepared by adding the epoxy resin, the crack propagation can be hindered, the brittle fracture of the epoxy resin can be reduced, and the hardness and wear resistance of the composite resin material can be improved.
[0046] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical principles disclosed herein are intended to be covered by the claims of the present invention.
Claims
1. A method for preparing a high-strength wear-resistant composite resin material, characterized in that: The steps include: S1: Preparation of modified nanocellulose Weighing nanocellulose and adding it to a mixed solution of anhydrous ethanol and deionized water, then mixing distearoyloxyisopropylaluminate with the anhydrous ethanol and deionized water, and then mixing and stirring the two solutions to react to obtain modified nanocellulose; S2: Preparation of polyaniline / potassium silicate nanomaterials A potassium nitrate solution and an ethanol solution are mixed and sodium silicate and NaOH are added, and the mixture is sealed for reaction. After the reaction is completed, the mixture is added to a toluene solution, ultrasonically dispersed, and then a silane coupling agent is added to react to obtain surface-modified nano-potassium silicate. The surface-modified nano-potassium silicate is weighed and added to deionized water, and then a ferric chloride solution is added. After mixing, the mixture is added to an aniline solution to react to obtain a polyaniline / potassium silicate nanomaterial. S3: Preparation of Nanohybrids The polyaniline / potassium silicate nanomaterials were weighed and dispersed in N-N-dimethylformamide to form a uniform suspension, and then the modified nanocellulose was added to the suspension to react and obtain a nanohybrid; S4: Preparation of high-strength and wear-resistant composite resin materials The nano-hybrid is dispersed in benzyl alcohol and epoxy resin suspension, subjected to ultrasonic treatment, and then a defoaming agent is added and stirred to obtain a high-strength and wear-resistant composite resin material.
2. The method for preparing a high-strength wear-resistant composite resin material according to claim 1, characterized in that: Step S1 prepares modified nanocellulose, comprising the following steps: 0.2-0.3 parts by mass of nanocellulose are weighed and added to a mixed solution of 80-85 parts by mass of anhydrous ethanol and 15-20 parts by mass of deionized water, and ultrasonically dispersed for 1-1.5 hours. Then, 2-3 parts by mass of distearoyloxyisopropylaluminate are mixed with 80-85 parts by mass of anhydrous ethanol and 15-20 parts by mass of deionized water, and heated and stirred at 50-55°C for 1-1.5 hours. Subsequently, the two solutions are mixed and stirred at 70-75°C for 12-13 hours. After the reaction, the solution is washed and dried at 60-65°C for 4.5-5 hours to obtain modified nanocellulose.
3. The method for preparing a high-strength wear-resistant composite resin material according to claim 2, characterized in that: Step S2 is to prepare polyaniline / potassium silicate nanomaterials, comprising the following steps: S2.1: Mix 2-3 parts by volume of potassium nitrate solution and 8-10 parts by volume of ethanol solution and stir at a speed of 100-120 r / min. Add 2-3 parts by volume of sodium silicate and 1-2 parts by volume of NaOH while stirring. Then transfer the mixture to an autoclave, seal it, and heat it to 210-220°C for hydrothermal reaction for 24-25 hours. After the reaction, wash the product and vacuum dry it. Then add it to a toluene solution and ultrasonically disperse it for 30-35 minutes. Then add 0.2-0.5 parts by volume of silane coupling agent. Then, react in an oil bath at 95-100°C for 24-25 hours. Then, wash and dry it to obtain surface-modified nano-potassium silicate. S2.2: Weigh 0.2-0.4 parts by mass of surface-modified nano-potassium silicate and add it to 5-10 parts by mass of deionized water, then add 3-4 parts by mass of ferric chloride solution. After mixing, add it to the upper layer of 15-20 parts by mass of aniline solution, maintain at 0°C for 8-9 hours, wash and dry to obtain polyaniline / potassium silicate nanomaterial.
4. The method for preparing a high-strength wear-resistant composite resin material according to claim 3, characterized in that: Step S3 is to prepare the nanohybrid, comprising the following steps: 0.1-0.3 parts by mass of polyaniline / potassium silicate nanomaterials were dispersed in 100 parts by mass of NN dimethylformamide, and ultrasonicated for 30-35 minutes to form a uniform suspension. Then, 0.1-0.4 parts by mass of modified nanocellulose were added to the suspension and ultrasonicated for 30-35 minutes. The suspension was then heated to 100-105°C and stirred for 5-6 hours. After the reaction was completed, the mixture was filtered, washed and dried to obtain a nanohybrid.
5. The method for preparing a high-strength wear-resistant composite resin material according to claim 4, characterized in that: Step S4 is to prepare a high-strength wear-resistant composite resin material, comprising the following steps: 1-2 parts by mass of the nanohybrid is dispersed in 100 parts by mass of benzyl alcohol and epoxy resin suspension, and ultrasonically treated for 30-35 minutes. Then, 2-3 parts by mass of a defoaming agent is added, and the mixture is stirred at a speed of 500-550 r / min for 50-60 minutes to obtain a high-strength and wear-resistant composite resin material.
6. The method for preparing a high-strength wear-resistant composite resin material according to claim 3, characterized in that: The concentration of the aniline solution is 0.1-0.5 mg / mL.
7. The method for preparing a high-strength wear-resistant composite resin material according to claim 5, characterized in that: The benzyl alcohol and epoxy resin suspension is prepared by mixing benzyl alcohol and epoxy resin in a mass ratio of 1:(1-2).
8. The method for preparing a high-strength wear-resistant composite resin material according to claim 5, characterized in that: The defoaming agent is specifically polydimethylsiloxane.
9. The method for preparing a high-strength wear-resistant composite resin material according to claim 5, characterized in that: The concentration of ferric chloride solution is 10%.
10. A high-strength wear-resistant composite resin material, characterized in that: The high-strength wear-resistant composite resin material is prepared by the preparation method of any one of claims 1 to 9.