High-wear-resistance phenolic resin plate and preparation method thereof

Abstract

The invention relates to a high-wear-resistance phenolic resin plate and a preparation method thereof, and belongs to the technical field of modified phenolic resin. The high-wear-resistance phenolic resin plate comprises the following components in parts by weight: 100 parts of phenolic resin, 20-30 parts of high-wear-resistance modified graphene oxide, 0.5-0.8 part of an antioxidant and 1-1.5 parts of a flame retardant. Wherein the high-wear-resistance modifier can be coupled with the graphene oxide, so that the agglomeration phenomenon of the graphene oxide in the phenolic resin is reduced, and a macromolecular branched-chain-containing structure in the high-wear-resistance modifier can be embedded into a phenolic resin molecular chain in the blending process; a fluorine-containing benzene ring structure is introduced while the compatibility of the graphene oxide and a phenolic resin matrix is improved, the antifriction and wear-resistant properties of the phenolic resin are further improved, and the multi-benzene ring structure of the high-wear-resistant modifier can improve the thermal stability of the phenolic resin at high friction temperature and reinforce the antifriction and wear-resistant properties of the phenolic resin at high temperature.

Description

Technical Field

[0001] The present invention belongs to the technical field of modified phenolic resins, and specifically relates to a highly wear-resistant phenolic resin plate and a preparation method thereof. Background Art

[0002] Phenolic resin, also known as bakelite, also called bakelite powder, as one of the three major synthetic thermosetting resins, has good mechanical properties, water resistance and certain heat resistance, and is widely used in industries such as transportation, aviation, military equipment, electronics and electrical appliances. However, with the development of industry, especially the technological innovation of the automotive industry and high-speed trains, new requirements are put forward for high-performance phenolic resins.

[0003] Friction materials based on phenolic resins (such as vehicle brake pads, clutches) require good wear resistance and sufficient friction coefficient, while traditional phenolic resins are increasingly unable to meet the development requirements of friction materials, greatly restricting the development of China's materials industry.

[0004] Graphene oxide has good anti-friction effect as an anti-friction agent. During the friction process, the ultra-thin sheet structure of graphene oxide makes it extremely easy to embed into the unevenness of the counter friction surface, making it easy to form a flat transfer film on the counter friction surface, reducing the direct contact between the two rough surfaces, reducing the abrasion and consumption of the matrix, and improving its mechanical properties and wear resistance. However, there is a strong intermolecular force between the graphene oxide sheets, resulting in a weak force between the graphene and the phenolic resin matrix, easy agglomeration, and under the action of high friction temperature, due to the generation of friction debris, graphene oxide will also migrate out of the phenolic resin matrix, resulting in a decrease in the wear resistance of the phenolic resin matrix. Further restricting the application of phenolic resins in the field of high wear resistance. Summary of the Invention

[0005] In order to solve the technical problems mentioned in the background art, the purpose of the present invention is to provide a highly wear-resistant phenolic resin plate and a preparation method thereof.

[0006] The purpose of the present invention can be achieved by the following technical solutions: A highly wear-resistant phenolic resin plate, comprising the following materials by weight: 100 parts of phenolic resin, 20 - 30 parts of highly wear-resistant modified graphene oxide, 0.5 - 0.8 parts of antioxidant, 1 - 1.5 parts of flame retardant; Preparation of highly wear-resistant modified graphene oxide: Step A1: Take 4-nitrophthalic acid, γ-glycidyletheroxypropyltrimethoxysilane, hydrochloric acid and benzene and mix them into a reaction kettle, control the reaction rate at 150 - 250 r / min, heat up to 65 - 75 °C, stir for 1 - 2 h and then carry out rotary evaporation under reduced pressure to obtain a phthalate intermediate; Further, the dosage ratio of 4-nitrophthalic acid, glycidyletheroxypropyltrimethoxysilane, hydrochloric acid, and benzene is 1 mol: 2 mol: 3 - 5 mL: 400 mL; In the above reaction, 4-nitrophthalic acid and γ-glycidyletheroxypropyltrimethoxysilane undergo a ring-opening esterification reaction to graft the silane coupling agent onto the 4-nitrophthalic acid molecule. The specific reaction process is as follows:

[0007] Step A2: Take the phthalate intermediate, sodium disulfide, and ethanol, mix them and feed them into a reaction kettle. Control the reaction rate at 200 - 300 r / min, heat up to 40 - 50 °C, stir and react for 2 - 3 h, then add castor oil acid and DCC, heat up to 60 - 70 °C, continue to react for 3 - 5 h, and then filter and dry to obtain an unsaturated amide-ester intermediate; Further, the dosage ratio of the phthalate intermediate, sodium disulfide, ethanol, castor oil acid, and DCC is 1 mol: 30 - 40 g: 500 mL: 1 mol: 1.2 mol; In the above reaction, the nitro group of the phthalate intermediate is reduced to an amino group by sodium sulfide reduction, and then it reacts with castor oil acid to graft the castor oil acid onto the nitrobenzene ester intermediate. The specific reaction process is as follows:

[0008] Step A3: Take the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, concentrated sulfuric acid-modified silica gel, and DMF, mix them and feed them into a reaction kettle. Control the stirring reaction rate at 300 - 400 r / min, heat up to 50 - 60 °C, stir and react for 1 - 2 h to obtain a high wear-resistant modifier; Further, the dosage ratio of the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, concentrated sulfuric acid-modified silica gel, and DMF is 1 mol: 3 mol: 1.5 - 2 g: 600 mL; In the above reaction, the unsaturated amide-ester intermediate and 2,3,4-trifluorobenzoic acid undergo an esterification reaction to introduce a fluorine-containing benzene ring structure and form a macromolecular branched-chain organic compound. The specific reaction process is as follows:

[0009] Step A4: Mix graphene oxide and ethanol and feed them into an ultrasonic disperser. After dispersing for 0.5 h, add glacial acetic acid to adjust the pH of the solution to 5. Then add the high wear-resistant modifier, continue to stir for 3 h, and then dry to obtain high wear-resistant modified graphene oxide; Further, the dosage ratio of graphene oxide, ethanol, and the high wear-resistant modifier is 1 mol: 800 mL: 2 - 2.5 mol; In the above reaction, the silane coupling agent structure in the high wear-resistant modifier undergoes a grafting reaction with graphene oxide, grafting the high wear-resistant modifier onto the surface of graphene oxide to modify the graphene oxide; The high wear-resistant phenolic resin plate is prepared by the following method: Phenolic resin, high wear-resistant modified graphene oxide, antioxidant and flame retardant are mixed and fed into a stirrer. After stirring for 0.5 h, it is placed in a mold at 170 °C and kept under pressure at 30 Mpa for 1 h, and then taken out to obtain the high wear-resistant phenolic resin plate.

[0010] Advantages of the present invention: The present invention discloses a high wear-resistant phenolic resin plate, which uses phenolic resin as the matrix, modifies graphene oxide by compounding and self-making a high wear-resistant modifier to form high wear-resistant modified graphene oxide and participates in the blending to improve the dispersibility of graphene oxide in the phenolic resin matrix and enhance the wear resistance of phenolic resin at high temperatures; The high wear-resistant modifier is prepared by reacting 4-nitrophthalic acid with γ-glycidoxypropyltrimethoxysilane, then reducing the nitro group to an amino group under the action of sodium sulfide and condensing it with ricinoleic acid, and finally esterifying it with 2,3,4-trifluorobenzoic acid to form a macromolecular organic compound with a fluorobenzene structure; among them, the high wear-resistant modifier can be coupled with graphene oxide through the silane coupling agent structure to anchor the high wear-resistant modifier onto the surface of graphene oxide, reducing the agglomeration phenomenon of graphene oxide in phenolic resin and effectively improving the wear resistance of the phenolic resin matrix; and the macromolecular branched structure in the high wear-resistant modifier can "embed" into the phenolic resin molecular chain during the blending process, while improving the compatibility between graphene oxide and the phenolic resin matrix, introducing a fluorobenzene ring structure, and the synergistic effect of the fluorine structure and graphene oxide further enhances the friction reduction and wear resistance of phenolic resin, and the multi-benzene ring structure of the high wear-resistant modifier can improve the thermal stability of phenolic resin at high friction temperatures, effectively inhibiting the migration phenomenon of graphene oxide in the phenolic resin matrix due to high friction temperatures and strengthening the friction reduction and wear resistance of phenolic resin at high temperatures. Specific embodiments

[0011] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention. Embodiment

[0012] The specific implementation process of preparing a high wear-resistant phenolic resin plate in this embodiment is as follows: 1) Preparation of highly wear-resistant modified graphene oxide a1: Take 4-nitrophthalic acid, γ-glycidyletheroxypropyltrimethoxysilane, hydrochloric acid and benzene and mix them into a reaction kettle. Control the reaction rate at 150 r / min, heat up to 65 °C, stir for 1 h, and then perform rotary evaporation under reduced pressure to obtain a phthalate intermediate; in the above reaction, the dosage ratio of 4-nitrophthalic acid, γ-glycidyletheroxypropyltrimethoxysilane, hydrochloric acid and benzene is 1 mol: 2 mol: 3 mL: 400 mL; a2: Take the phthalate intermediate, sodium disulfide and ethanol and mix them into a reaction kettle. Control the reaction rate at 200 r / min, heat up to 40 °C, stir and react for 2 h, then add ricinoleic acid and DCC, heat up to 60 °C, continue to react for 3 h, and then filter and dry to obtain an unsaturated amide-ester intermediate; in the above reaction, the dosage ratio of the phthalate intermediate, sodium disulfide, ethanol, ricinoleic acid and DCC is 1 mol: 30 g: 500 mL: 1 mol: 1.2 mol; a3: Take the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, concentrated sulfuric acid modified silica gel and DMF and mix them into a reaction kettle. Control the stirring reaction rate at 300 r / min, heat up to 50 °C, stir and react for 1 h to obtain a highly wear-resistant modifier; in the above reaction, the dosage ratio of the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, concentrated sulfuric acid modified silica gel and DMF is 1 mol: 3 mol: 1.5 g: 600 mL; a4: Mix graphene oxide and ethanol and put them into an ultrasonic disperser. After dispersing for 0.5 h, add glacial acetic acid to adjust the pH of the solution to 5, then add the highly wear-resistant modifier, continue to stir for 3 h, and then dry to obtain highly wear-resistant modified graphene oxide; in the above reaction, the dosage ratio of graphene oxide, ethanol and the highly wear-resistant modifier is 1 mol: 800 mL: 2 mol; 2) Preparation of highly wear-resistant phenolic resin plate s1: Mix 100 kg of phenolic resin (both this example and the comparative example select phenolic resin from Shanghai Aladdin Biochemical Technology Co., Ltd., model P195710), 20 kg of highly wear-resistant modified graphene oxide, 0.5 kg of antioxidant (both this example and the comparative example select antioxidant 1010) and 1 kg of flame retardant (both this example and the comparative example select flame retardant LD-302 from Dongguan Lianding New Materials Technology Co., Ltd.) into a stirrer. After stirring for 0.5 h, place it in a mold at 170 °C and keep the pressure at 30 Mpa for 1 h, and then take it out to obtain a highly wear-resistant phenolic resin plate. Example

[0013] The specific implementation process of preparing a highly wear-resistant phenolic resin plate in this example is as follows: 1) Preparation of highly wear-resistant modified graphene oxide a1: Take 4-nitrophthalic acid, γ-glycidyletheroxypropyltrimethoxysilane, hydrochloric acid and benzene and mix them into a reaction kettle. Control the reaction rate at 200 r / min, heat up to 70 °C, stir for 1.5 h, and then carry out rotary evaporation under reduced pressure to obtain a phthalate intermediate; in the above reaction, the dosage ratio of 4-nitrophthalic acid, γ-glycidyletheroxypropyltrimethoxysilane, hydrochloric acid and benzene is 1 mol: 2 mol: 4 mL: 400 mL; a2: Take the phthalate intermediate, sodium disulfide and ethanol and mix them into a reaction kettle. Control the reaction rate at 250 r / min, heat up to 45 °C, stir and react for 3 h, then add ricinoleic acid and DCC, heat up to 65 °C, continue to react for 4 h, and then filter and dry to obtain an unsaturated amide-ester intermediate; in the above reaction, the dosage ratio of the phthalate intermediate, sodium disulfide, ethanol, ricinoleic acid and DCC is 1 mol: 34 g: 500 mL: 1 mol: 1.2 mol; a3: Take the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, sulfuric acid-modified silica gel and DMF and mix them into a reaction kettle. Control the stirring reaction rate at 350 r / min, heat up to 55 °C, stir and react for 1.5 h to obtain a highly wear-resistant modifier; in the above reaction, the dosage ratio of the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, sulfuric acid-modified silica gel and DMF is 1 mol: 3 mol: 1.6 g: 600 mL; a4: Mix graphene oxide and ethanol and put them into an ultrasonic disperser. After dispersing for 0.5 h, add glacial acetic acid to adjust the pH of the solution to 5, then add the highly wear-resistant modifier, continue to stir for 3 h, and then dry to obtain highly wear-resistant modified graphene oxide; in the above reaction, the dosage ratio of graphene oxide, ethanol and the highly wear-resistant modifier is 1 mol: 800 mL: 2.2 mol; 2) Preparation of highly wear-resistant phenolic resin board s1: Mix 100 kg of phenolic resin, 24 kg of highly wear-resistant modified graphene oxide, 0.6 kg of antioxidant and 1.2 kg of flame retardant and put them into a stirrer. After stirring for 0.5 h, place them in a mold at 170 °C, keep the pressure at 30 Mpa for 1 h, and then take them out to obtain a highly wear-resistant phenolic resin board. Example

[0014] The specific implementation process of preparing a highly wear-resistant phenolic resin board in this example is as follows: 1) Preparation of highly wear-resistant modified graphene oxide a1: Charge 4-nitrophthalic acid, γ-glycidyletheroxypropyltrimethoxysilane, hydrochloric acid and benzene into a reaction kettle, control the reaction rate at 250 r / min, heat up to 75 °C, stir for 2 h, and then carry out rotary evaporation under reduced pressure to obtain a phthalate intermediate; in the above reaction, the dosage ratio of 4-nitrophthalic acid, γ-glycidyletheroxypropyltrimethoxysilane, hydrochloric acid and benzene is 1 mol: 2 mol: 5 mL: 400 mL; a2: Charge the phthalate intermediate, sodium disulfide and ethanol into a reaction kettle, control the reaction rate at 300 r / min, heat up to 50 °C, stir and react for 3 h, then add ricinoleic acid and DCC, heat up to 70 °C, continue to react for 5 h, and then filter and dry to obtain an unsaturated amide-ester intermediate; in the above reaction, the dosage ratio of the phthalate intermediate, sodium disulfide, ethanol, ricinoleic acid and DCC is 1 mol: 36 g: 500 mL: 1 mol: 1.2 mol; a3: Charge the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, sulfuric acid modified silica gel and DMF into a reaction kettle, control the stirring reaction rate at 400 r / min, heat up to 60 °C, stir and react for 2 h to obtain a high wear-resistant modifier; in the above reaction, the dosage ratio of the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, sulfuric acid modified silica gel and DMF is 1 mol: 3 mol: 1.6 g: 600 mL; a4: Mix graphene oxide and ethanol and charge them into an ultrasonic disperser, disperse for 0.5 h, then add glacial acetic acid to adjust the pH of the solution to 5, then add the high wear-resistant modifier, continue to stir for 3 h, and then dry to obtain high wear-resistant modified graphene oxide; in the above reaction, the dosage ratio of graphene oxide, ethanol and the high wear-resistant modifier is 1 mol: 800 mL: 2.3 mol; 2) Preparation of high wear-resistant phenolic resin plate s1: Mix 100 kg of phenolic resin, 26 kg of high wear-resistant modified graphene oxide, 0.7 kg of antioxidant and 1.3 kg of flame retardant and charge them into a stirrer, stir for 0.5 h, then place them in a mold at 170 °C, keep the pressure at 30 Mpa for 1 h, and then take out to obtain a high wear-resistant phenolic resin plate. Example

[0015] The specific implementation process of preparing a high wear-resistant phenolic resin plate in this example is as follows: 1) Preparation of high wear-resistant modified graphene oxide a1: Charge 4-nitrophthalic acid, γ-glycidyletheroxypropyltrimethoxysilane, hydrochloric acid and benzene into a reaction kettle, control the reaction rate at 250 r / min, heat up to 75 °C, stir for 2 h, and then perform rotary evaporation under reduced pressure to obtain a phthalate intermediate; in the above reaction, the dosage ratio of 4-nitrophthalic acid, γ-glycidyletheroxypropyltrimethoxysilane, hydrochloric acid and benzene is 1 mol: 2 mol: 5 mL: 400 mL; a2: Charge the phthalate intermediate, sodium disulfide and ethanol into a reaction kettle, control the reaction rate at 200 r / min, heat up to 50 °C, stir and react for 3 h, then add castor oil acid and DCC, heat up to 70 °C, continue to react for 5 h, and then filter and dry to obtain an unsaturated amide-ester intermediate; in the above reaction, the dosage ratio of the phthalate intermediate, sodium disulfide, ethanol, castor oil acid and DCC is 1 mol: 38 g: 500 mL: 1 mol: 1.2 mol; a3: Charge the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, sulfuric acid-modified silica gel and DMF into a reaction kettle, control the stirring reaction rate at 400 r / min, heat up to 60 °C, stir and react for 2 h to obtain a high wear-resistant modifier; in the above reaction, the dosage ratio of the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, sulfuric acid-modified silica gel and DMF is 1 mol: 3 mol: 1.6 g: 600 mL; a4: Mix graphene oxide and ethanol and charge them into an ultrasonic disperser. After dispersing for 0.5 h, add glacial acetic acid to adjust the pH of the solution to 5. Then add the high wear-resistant modifier and continue to stir for 3 h, and then dry to obtain high wear-resistant modified graphene oxide; in the above reaction, the dosage ratio of graphene oxide, ethanol and the high wear-resistant modifier is 1 mol: 800 mL: 2.4 mol; 2) Preparation of high wear-resistant phenolic resin board s1: Mix 100 kg of phenolic resin, 28 kg of high wear-resistant modified graphene oxide, 0.8 kg of antioxidant and 1.4 kg of flame retardant and charge them into a stirrer. After stirring for 0.5 h, place them in a mold at 170 °C and keep the pressure at 30 Mpa for 1 h, and then take them out to obtain a high wear-resistant phenolic resin board. Example

[0016] The specific implementation process of preparing a high wear-resistant phenolic resin board in this example is as follows: 1) Preparation of high wear-resistant modified graphene oxide a1: Charge 4-nitrophthalic acid, γ-glycidyletheroxypropyltrimethoxysilane, hydrochloric acid and benzene into a reaction kettle, control the reaction rate at 250 r / min, heat up to 75 °C, stir for 2 h, and then perform rotary evaporation under reduced pressure to obtain a phthalate intermediate; in the above reaction, the dosage ratio of 4-nitrophthalic acid, γ-glycidyletheroxypropyltrimethoxysilane, hydrochloric acid and benzene is 1 mol: 2 mol: 5 mL: 400 mL; a2: Charge the phthalate intermediate, sodium disulfide and ethanol into a reaction kettle, control the reaction rate at 200 r / min, heat up to 50 °C, stir and react for 3 h, then add ricinoleic acid and DCC, heat up to 70 °C, continue to react for 5 h, and then filter and dry to obtain an unsaturated amide-ester intermediate; in the above reaction, the dosage ratio of the phthalate intermediate, sodium disulfide, ethanol, ricinoleic acid and DCC is 1 mol: 38 g: 500 mL: 1 mol: 1.2 mol; a3: Charge the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, sulfuric acid modified silica gel and DMF into a reaction kettle, control the stirring reaction rate at 400 r / min, heat up to 60 °C, stir and react for 2 h to obtain a high wear-resistant modifier; in the above reaction, the dosage ratio of the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, sulfuric acid modified silica gel and DMF is 1 mol: 3 mol: 1.6 g: 600 mL; a4: Mix graphene oxide and ethanol and charge them into an ultrasonic disperser, disperse for 0.5 h, then add glacial acetic acid to adjust the pH of the solution to 5, then add the high wear-resistant modifier, continue to stir for 3 h, and then dry to obtain high wear-resistant modified graphene oxide; in the above reaction, the dosage ratio of graphene oxide, ethanol and the high wear-resistant modifier is 1 mol: 800 mL: 2.4 mol; 2) Preparation of high wear-resistant phenolic resin board s1: Mix 100 kg of phenolic resin, 30 kg of high wear-resistant modified graphene oxide, 0.8 kg of antioxidant and 1.5 kg of flame retardant and charge them into a stirrer, stir for 0.5 h, then place them in a mold at 170 °C, and keep the pressure at 30 Mpa for 1 h, and then take out to obtain a high wear-resistant phenolic resin board.

[0017] Comparative Example 1 The specific implementation process of preparing a wear-resistant phenolic resin board in this comparative example is as follows: S1: Mix 100 kg of phenolic resin (the wear-resistant phenolic resin powder from Dongguan Jiamai Plastic Co., Ltd. with model JM-150 is selected in this comparative example), 30 kg of highly wear-resistant modified graphene oxide, 0.8 kg of antioxidant, and 1.5 kg of flame retardant and feed them into a stirrer. After stirring for 0.5 h, place them in a mold at 170 °C and keep the pressure at 30 Mpa for 1 h, then take them out to obtain a highly wear-resistant phenolic resin plate.

[0018] Comparative Example 2 The specific implementation process for preparing the wear-resistant phenolic resin plate in this comparative example is as follows: S1: Mix graphene oxide and ethanol and feed them into an ultrasonic disperser. After dispersing for 0.5 h, add glacial acetic acid to adjust the pH of the solution to 5, then add KH-560 and continue stirring for 3 h, and then dry to obtain modified graphene oxide; in the above reaction, the dosage ratio of graphene oxide, ethanol, and KH-560 is 1 mol: 600 mL: 0.2 mol; S2: Mix 100 kg of phenolic resin, 12 kg of modified graphene oxide, 18 kg of polyvinylidene fluoride, 0.8 kg of antioxidant, and 1.5 kg of flame retardant and feed them into a stirrer. After stirring for 0.5 h, place them in a mold at 170 °C and keep the pressure at 30 Mpa for 1 h, then take them out to obtain a wear-resistant phenolic resin plate.

[0019] Inject the highly wear-resistant phenolic resin plates prepared in Examples 1-5 and the wear-resistant phenolic resin plates of Comparative Examples 1-2 into test specimens with dimensions of 30 mm X 7 mm and a thickness of 6 mm in an injection molding machine at 170 °C. And according to GB / T3960-2016 for friction coefficient testing; Inject the highly wear-resistant phenolic resin plates prepared in Examples 1-5 and the wear-resistant phenolic resin plates of Comparative Examples 1-2 into test specimens with dimensions of 25 mm X 25 mm and a thickness of 5 mm in an injection molding machine at 170 °C, and conduct friction loss performance testing according to GB5763-2008 under a pressing force of 0.98 Mpa; After placing the test specimens in an oven at 350 °C for 3 h, conduct friction coefficient and friction loss performance testing respectively according to GB / T3960-2016 and GB5763-2008. The specific test data are shown in Table 1: Table 1

[0020] As can be seen from the data in Table 1, the friction coefficient of the high wear-resistant phenolic resin plates prepared in Examples 1-5 at room temperature is 0.23-0.27, and the friction loss is 0.52-0.58, slightly better than the wear-resistant phenolic resin plates of Comparative Examples 1-2. However, after baking at 350 °C, the friction coefficient of the high wear-resistant phenolic resin plates prepared in Examples 1-5 is 0.32-0.36, and the friction loss is 1.22-1.29; significantly better than the wear-resistant phenolic resin of Comparative Examples 1-2, indicating that the high wear-resistant phenolic resin plate disclosed in the present invention not only has good antifriction and wear resistance, but can still maintain good antifriction and wear resistance at high temperatures.

[0021] In the description of the specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0022] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined by the claims of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A highly wear-resistant phenolic resin board, characterized in that: The composition comprises 100 parts of phenolic resin, 20-30 parts of highly wear-resistant modified graphene oxide, 0.5-0.8 parts of antioxidant and 1-1.5 parts of flame retardant according to weight parts; Preparation of highly wear-resistant modified graphene oxide: Step A1: 4-nitrophthalic acid, γ-glycidyloxypropyltrimethoxysilane, hydrochloric acid and benzene are mixed and added, the temperature is raised to 65-75° C., and the mixture is stirred for 1-2 hours and then subjected to vacuum rotary evaporation to obtain a phthalate intermediate; Step A2: Take a phthalate intermediate, sodium disulfide and ethanol, mix them, heat them to 40-50°C, stir and react for 2-3h, then add ricinoleic acid and DCC, heat them to 60-70°C, continue to react for 3-5h, filter and dry to obtain an unsaturated amide-ester intermediate; Step A3: unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, concentrated sulfuric acid-modified silica gel and DMF were mixed and added, the temperature was raised to 50-60° C., and the mixture was stirred for reaction for 1-2 hours to obtain a highly wear-resistant modifier; Step A4: Graphene oxide and ethanol are mixed and added, and after dispersion for 0.5 hours, glacial acetic acid is added to adjust the solution to a pH of 5, and then a high wear-resistant modifier is added, and stirring is continued for 3 hours and then dried to obtain highly wear-resistant modified graphene oxide.

2. A highly wear-resistant phenolic resin board according to claim 1, characterized in that: In step A1, the usage ratio of 4-nitrophthalic acid, γ-glycidyloxypropyltrimethoxysilane, hydrochloric acid and benzene is 1 mol: 2 mol: 3-5 mL: 400 mL.

3. A highly wear-resistant phenolic resin board according to claim 2, characterized in that: In step A2, the usage ratio of the phthalate intermediate, sodium disulfide, ethanol, ricinoleic acid and DCC is 1 mol: 30-40 g: 500 mL: 1 mol: 1.2 mol.

4. A highly wear-resistant phenolic resin board according to claim 3, characterized in that: The usage ratio of the unsaturated amide-ester intermediate, 2,3,4-trifluorobenzoic acid, concentrated sulfuric acid-modified silica gel and DMF is 1 mol: 3 mol: 1.5-2 g: 600 mL.

5. A highly wear-resistant phenolic resin board according to claim 4, characterized in that: In step A4, the usage ratio of graphene oxide, ethanol and high wear-resistant modifier is 1 mol:800 mL:2-2.5 mol.

6. The method for preparing a highly wear-resistant phenolic resin board according to claim 5, characterized in that: Prepared by the following method: Phenolic resin, highly wear-resistant modified graphene oxide, antioxidant and flame retardant are mixed and stirred for 0.5 hours, and then placed in a mold at 170° C. and maintained at a pressure of 30 MPa for 1 hour before being taken out to obtain a highly wear-resistant phenolic resin board.

7. The method for preparing a highly wear-resistant phenolic resin board according to claim 6, characterized in that: The antioxidant was antioxidant 1010.

8. The method for preparing a highly wear-resistant phenolic resin board according to claim 7, characterized in that: The flame retardant is a phenolic resin flame retardant.

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