A high-wear-resistant modified phenolic resin material for guide rings and its preparation process

Abstract

This invention relates to a high-wear-resistant modified phenolic resin material for guide rings and its preparation process. The high-wear-resistant modified phenolic resin material for guide rings is prepared from the following raw materials in parts by weight: 100 parts linear phenolic resin, 20-35 parts polyimide prepolymer, 20-45 parts reinforcement, 10-25 parts wear-resistant filler, 1-3 parts silane coupling agent, and 8-12 parts curing agent; the polyimide prepolymer is prepared by reacting pyromellitic dianhydride with 4,4'-diaminodiphenyl ether; the high-wear-resistant modified phenolic resin material for guide rings prepared by this invention exhibits excellent high-temperature wear resistance.

Description

Technical Field

[0001] This invention belongs to the field of polymer resin technology, specifically relating to a high wear-resistant modified phenolic resin material for guide rings and its preparation process. Background Technology

[0002] Phenolic resins, with their excellent mechanical strength, good dimensional stability, heat resistance, and cost advantages, have long been used to manufacture various wear-resistant sealing and guiding components, such as guide rings, bearings, and sealing rings. However, the inherent defects of traditional phenolic resins, such as high brittleness, high coefficient of friction, and insufficient high-temperature wear resistance, limit their service life and reliability under harsh working conditions such as high speed, high pressure, and heavy load.

[0003] To improve the wear resistance of phenolic resins, existing technologies mainly focus on two aspects: one is to add rigid or lubricating fillers, such as carbon fibers and inorganic nanoparticles, through physical blending; the other is to chemically modify the resin matrix or to compound it with other polymers.

[0004] For example, Chinese patent application CN108752861A discloses a phenolic resin composite friction material. This method prepares a polystyrene microsphere, which is coated with sheet graphene oxide linked by silk fibroin on the outside. This is introduced into the phenolic resin system to improve the friction performance. However, the preparation process of this additive is extremely complicated, and the heat resistance of the polystyrene microsphere is relatively poor, which restricts its high-temperature performance and industrial application.

[0005] For example, Chinese patent application CN105061980A discloses a method for preparing a modified phenolic resin with ultra-wear-resistant nanomaterials. This method uses organic surfactants to modify the surface of nanoparticles and focuses on using a variety of surfactants and dispersion processes to disperse the nanoparticles in the phenolic resin. Although it has a certain effect, the mass ratio of phenolic resin to surfactant in this method is 100:(10-100). The amount of surfactant used is relatively wide, and the maximum amount is the same as the amount of phenolic resin. Excessive small molecule surfactants will plasticize the resin matrix and may also remain in the subsequent curing process, leading to an increase in the internal porosity of the material, which affects the mechanical strength, thermal stability and wear resistance.

[0006] Therefore, there is a need to develop a high-wear-resistant modified phenolic resin material for guide rings with excellent overall performance. Summary of the Invention

[0007] Existing phenolic resin materials suffer from poor wear resistance and heat resistance. To address this issue, this invention provides a highly wear-resistant modified phenolic resin material for guide rings and its preparation process.

[0008] To achieve the objectives of this invention, the following technical solution is adopted:

[0009] In a first aspect, the present invention provides a high-wear-resistant modified phenolic resin material for guide rings, which is prepared from the following raw materials in parts by weight:

[0010] 100 parts linear phenolic resin, 20-35 parts polyimide prepolymer, 20-45 parts reinforcement, 10-25 parts wear-resistant filler, 1-3 parts silane coupling agent, and 8-12 parts curing agent;

[0011] The polyimide prepolymer was prepared by reacting pyromellitic dianhydride with 4,4'-diaminodiphenyl ether.

[0012] By adopting the above technical solution, polyimide prepolymer is introduced into the phenolic resin matrix as a rigid organic skeleton. During the subsequent curing process, the prepolymer undergoes a co-crosslinking reaction with the phenolic resin to form a polymer network. The excellent heat resistance and mechanical strength of polyimide are used to improve the overall rigidity and high-temperature dimensional stability of the material. Furthermore, the synergistic effect of the interface between phenolic resin and polyimide can effectively inhibit crack propagation, thereby improving the wear resistance and mechanical properties of the material.

[0013] Preferably, the method for preparing the polyimide prepolymer includes the following steps:

[0014] Under anaerobic conditions, 4,4'-diaminodiphenyl ether, pyromellitic dianhydride and N,N-dimethylacetamide are mixed evenly and reacted at 15-20℃ for 4-6 hours. After filtration, a polyimide prepolymer with a solid content of 15%-18% is obtained.

[0015] By adopting the above technical solution, 4,4'-diaminodiphenyl ether reacts with pyromellitic dianhydride to generate an anhydride-terminated polyamic acid prepolymer. The anhydride groups at the chain ends can react chemically with the phenolic hydroxyl or hydroxymethyl groups of the phenolic resin during subsequent blending and curing, forming stronger chemical crosslinking points. This can promote the compatibility between the polyimide network and the phenolic network, forming a denser and more stable interpenetrating polymer network structure, and enhancing the interfacial strength, anti-delamination ability, and overall wear resistance of the material.

[0016] Preferably, the molar ratio of 4,4'-diaminodiphenyl ether to pyromellitic dianhydride is 1:(1-1.05).

[0017] By adopting the above technical solution, this ratio can ensure that the diamine monomer in the reaction system is completely consumed, and the molecular chain ends of the generated polyimide prepolymer (polyamic acid) are mainly capped with acid anhydrides with low reactivity, thus ensuring the activity and stability of the prepolymer.

[0018] Preferably, the reinforcement is prepared by mixing rare earth modified carbon fiber and aramid pulp at a mass ratio of (3-5):1.

[0019] By adopting the above technical solution, the reinforcement system of rare earth modified carbon fiber and aramid pulp can play a synergistic reinforcement role at multiple scales and through multiple mechanisms. As the main load-bearing skeleton, the rare earth oxides loaded on the surface of the rare earth modified carbon fiber can improve the interfacial bonding between the fiber and the resin matrix and effectively transfer the load. The aramid pulp can fill the gaps between the fibers and play a bridging and crack-arresting role when the material is subjected to impact or friction, which significantly improves the toughness, anti-delamination and wear resistance uniformity of the material.

[0020] Preferably, the method for preparing the rare earth modified carbon fiber includes the following steps:

[0021] Carbon fibers were impregnated in a 0.5 mol / L cerium nitrate solution, ultrasonically treated, dried, and heat-treated to obtain rare earth modified carbon fibers.

[0022] By employing the above technical solution, a process combining liquid-phase impregnation and subsequent heat treatment is used to modify the surface of carbon fibers. After cerium ions coordinate with active groups such as hydroxyl groups on the carbon fiber surface, they decompose and transform into a cerium oxide coating during heat treatment, which can enhance the chemical bonding between carbon fibers and resins.

[0023] Cerium nitrate solution is an aqueous solution of cerium nitrate.

[0024] Preferably, the ratio of the carbon fiber to the cerium nitrate solution is 1 g:(20-35) mL.

[0025] By adopting the above technical solution, sufficient solution volume is ensured to fully wet the carbon fiber, preventing fiber accumulation and ensuring that all fiber surfaces can be uniformly contacted with rare earth ions, thus achieving uniform modification.

[0026] Preferably, the heat treatment temperature is 700-800℃ and the heat treatment time is 1-3h.

[0027] By employing the above technical solution, if the temperature is too low, decomposition will be incomplete, resulting in insufficient coating activity; if the temperature is too high, the coating may be over-sintered or damage the carbon fiber matrix. Optimal coating crystallinity and bonding strength are ensured within a time frame of 1-3 hours.

[0028] Preferably, the wear-resistant filler is selected from one or more combinations of molybdenum disulfide, graphite, and polytetrafluoroethylene micro powder.

[0029] By adopting the above technical solution, solid lubricants with layered structures or low surface energy can be used as wear-resistant fillers to form a continuous and stable transfer lubrication film during friction, effectively reducing adhesive wear and abrasive wear.

[0030] Preferably, the silane coupling agent is γ-aminopropyltriethoxysilane; and the curing agent is hexamethylenetetramine.

[0031] By adopting the above technical solution, γ-aminopropyltriethoxysilane (silane coupling agent KH550) has a hydrolyzable ethoxy group at one end, which can bind with the reinforcement; and an amino group at the other end, which can react with the functional groups in phenolic resin and polyimide prepolymer to enhance the interfacial chemical bonding between the inorganic / organic reinforcement and the organic resin matrix, thereby improving the durability and mechanical properties of the material.

[0032] By adopting the above technical solution, hexamethylenetetramine decomposes to produce formaldehyde and ammonia when heated, which undergo a cross-linking reaction with the phenolic hydroxyl groups of phenolic resin to form a dense three-dimensional network structure, ensuring the curing degree, thermal stability and mechanical strength of the phenolic resin matrix.

[0033] Secondly, the present invention also provides a preparation process for the above-mentioned high wear-resistant modified phenolic resin material for guide rings, comprising the following steps:

[0034] S1: Mix linear phenolic resin, reinforcement and wear-resistant filler evenly to obtain mixture 1;

[0035] S2: Mix the silane coupling agent, ethanol and mixture 1 evenly to obtain mixture 2;

[0036] S3: Mix the polyimide prepolymer with mixture 2 until homogeneous to obtain mixture 3;

[0037] S4: Mix the curing agent with mixture 3 evenly, knead, mold and cure, cool to obtain a high wear-resistant modified phenolic resin material for guide rings.

[0038] By adopting the above technical solution, the preparation process is simple and the flow is clear. Steps S1-S3 first involve dry mixing the resin, filler, and reinforcement, then uniformly impregnating and surface-treating the mixture with an ethanol solution of silane coupling agent, and finally introducing a polyimide prepolymer solution for overall plasticization. This maximizes the bridging effect of the silane coupling agent and facilitates the uniform distribution of the prepolymer. Step S4, mixing and compression molding, transforms the uniformly mixed materials into a high-performance phenolic resin material.

[0039] Preferably, in step S4, the molding and curing process is as follows: maintaining the temperature and pressure at 5-15 MPa and 160-180℃ for 30-60 minutes; then raising the temperature to 200-220℃ and maintaining the temperature and pressure for 1-2 hours.

[0040] By employing the above technical solution, gradient heating ensures the full curing and deep fusion of polyimide resin and phenolic resin. The first stage primarily achieves initial cross-linking and curing of the phenolic resin and hexamethylenetetramine, forming a basic framework. Simultaneously, the polyimide prepolymer (polyamic acid) begins to undergo dehydration, cyclization, and imidization reactions. The moderate temperature at this stage facilitates the removal of small-molecule volatiles, preventing the formation of bubbles and defects within the material. The second stage promotes the complete imidization reaction of the polyimide and further co-crosslinks it with the phenolic resin network, forming a more complete and stable interpenetrating network structure, thereby enabling the material to achieve optimal heat resistance, mechanical strength, and wear resistance.

[0041] In summary, the beneficial effects of this invention are:

[0042] (1) This invention introduces a polyimide prepolymer with active end groups, which reacts with the phenolic hydroxyl / hydroxymethyl groups of linear phenolic resin during the curing process to form an interpenetrating polymer network with chemical bonding points; through strong interfacial bonding and synergistic effect between the two phases, crack propagation can be effectively hindered, and the balance between hardness and toughness of the material can be taken into account.

[0043] (2) The present invention consists of rare earth modified carbon fiber and aramid pulp microfiber network as reinforcement to jointly resist load and impact; solid lubricants such as molybdenum disulfide / graphite / polytetrafluoroethylene are used as fillers to form a continuous and stable transfer film at the friction interface, reducing the friction coefficient and adhesive wear. The three work together to improve the overall wear resistance and service life of the material. Detailed Implementation

[0044] The technical solution of the present invention will be explained in detail below with reference to several representative embodiments.

[0045] Unless otherwise specified, the experimental methods used in the following examples and comparative examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples and comparative examples are commercially available.

[0046] Preparation Example 1

[0047] The preparation method of rare earth modified carbon fiber in this example includes the following specific steps:

[0048] 50g of short-cut carbon fibers with a length of 0.5-3mm were impregnated in 1.5L of 0.5 mol / L cerium nitrate solution and ultrasonically treated for 12h. After being removed, they were placed in a vacuum drying oven and dried at 80℃ for 12h. They were then transferred to a muffle furnace and heat-treated at 750℃ for 2h under a nitrogen atmosphere at a heating rate of 5℃ / min to obtain rare earth modified carbon fibers.

[0049] Preparation Example 2

[0050] The preparation method of rare earth modified carbon fiber in this example includes the following specific steps:

[0051] 50g of short-cut carbon fibers with a length of 0.5-3mm were impregnated in 1.2L of 0.5 mol / L cerium nitrate solution and ultrasonically treated for 12h. After being removed, they were placed in a vacuum drying oven and dried at 80℃ for 12h. They were then transferred to a muffle furnace and heat-treated at 780℃ for 1h under a nitrogen atmosphere at a heating rate of 5℃ / min to obtain rare earth modified carbon fibers.

[0052] Preparation Example 3

[0053] The preparation method of rare earth modified carbon fiber in this example includes the following specific steps:

[0054] 50g of short-cut carbon fibers with a length of 0.5-3mm were impregnated in 1.75L of 0.5 mol / L cerium nitrate solution and ultrasonically treated for 12h. After being removed, they were placed in a vacuum drying oven and dried at 80℃ for 12h. They were then transferred to a muffle furnace and heat-treated at 800℃ for 3h under a nitrogen atmosphere at a heating rate of 5℃ / min to obtain rare earth modified carbon fibers.

[0055] Preparation Example 4

[0056] The specific steps of the preparation method of the polyimide prepolymer in this example are as follows:

[0057] Add 20.024 g of 4,4'-diaminodiphenyl ether and N,N-dimethylacetamide to a dry three-necked flask, and stir for 30 min under nitrogen protection. Under ice-water protection, control the temperature at 20 °C, and slowly add 22.256 g of pyromellitic dianhydride in three portions. React for 6 h, filter, and obtain a polyimide prepolymer with a solid content of 18%.

[0058] Preparation Example 5

[0059] The specific steps of the preparation method of the polyimide prepolymer in this example are as follows:

[0060] Add 20.024 g of 4,4'-diaminodiphenyl ether and N,N-dimethylacetamide to a dry three-necked flask, and stir for 30 min under nitrogen protection. Under ice-water protection, control the temperature at 16 °C, and slowly add 22.872 g of pyromellitic dianhydride in three portions. React for 4 h, filter, and obtain a polyimide prepolymer with a solid content of 18%.

[0061] Preparation Example 6

[0062] The specific steps of the preparation method of the polyimide prepolymer in this example are as follows:

[0063] Add 20.024 g of 4,4'-diaminodiphenyl ether and N,N-dimethylacetamide to a dry three-necked flask, and stir for 30 min under nitrogen protection. Under ice-water protection, control the temperature at 18 °C, and slowly add 22.128 g of pyromellitic dianhydride in three portions. React for 4 h, filter, and obtain a polyimide prepolymer with a solid content of 18%.

[0064] Preparation Example 7

[0065] The specific steps of the preparation method of the polyimide prepolymer in this example are as follows:

[0066] Add 20.024 g of 4,4'-diaminodiphenyl ether and N,N-dimethylacetamide to a dry three-necked flask, and stir for 30 min under nitrogen protection. Under ice-water protection, control the temperature at 15 °C, and slowly add 21.815 g of pyromellitic dianhydride in three portions. React for 5 h, filter, and obtain a polyimide prepolymer with a solid content of 15%.

[0067] Example 1

[0068] The guide ring in this embodiment is made of a high-wear-resistant modified phenolic resin material, which is prepared from the following raw materials by weight:

[0069] 100g of linear phenolic resin, 22g of polyimide prepolymer prepared in Preparation Example 4, 35g of reinforcement, 20g of wear-resistant filler, 2g of silane coupling agent KH550 (γ-aminopropyltriethoxysilane), and 8g of hexamethylenetetramine;

[0070] The reinforcement was prepared by mixing the rare earth modified carbon fiber prepared in Preparation Example 2 with aramid pulp at a mass ratio of 4:1;

[0071] The wear-resistant filler is prepared by mixing graphite and polytetrafluoroethylene micro powder in a mass ratio of 1:1.

[0072] The preparation process of the high wear-resistant modified phenolic resin material for the guide ring in this embodiment is as follows:

[0073] S1: Linear phenolic resin, reinforcement and wear-resistant filler are added to a high-speed mixer and mixed at 60°C for 20 min to obtain mixture 1;

[0074] S2: Dilute the silane coupling agent KH550 with ethanol and spray it into the mixture 1 in step S1 in the form of atomization. Continue mixing for 8 minutes to fully wet the surface of the material to obtain mixture 2.

[0075] S3: Knead the polyimide prepolymer and mixture 2 in a kneader at 50°C to make the polyimide prepolymer uniformly coat mixture 2. Remove 80% of the solvent under vacuum at 80°C to obtain mixture 3.

[0076] S4: Mix hexamethylenetetramine with mixture 3, control the roller temperature at 100℃, mix for 10 min, transfer to mold, and keep warm and pressurized at 10 MPa and 180℃ for 40 min; then raise the temperature to 220℃, keep warm and pressurized for 2 h, and cool to obtain high wear-resistant modified phenolic resin material for guide rings.

[0077] Example 2

[0078] The guide ring in this embodiment is made of a high-wear-resistant modified phenolic resin material, which is prepared from the following raw materials by weight:

[0079] 100g of linear phenolic resin, 30g of polyimide prepolymer prepared in Preparation Example 4, 25g of reinforcement, 12g of wear-resistant filler, 3g of silane coupling agent KH550, and 10g of hexamethylenetetramine;

[0080] The reinforcement was prepared by mixing the rare earth modified carbon fiber prepared in Preparation Example 2 with aramid pulp at a mass ratio of 4:1;

[0081] The wear-resistant filler is polytetrafluoroethylene micro powder.

[0082] The preparation process of the high wear-resistant modified phenolic resin material for the guide ring in this embodiment is as follows:

[0083] S1: Linear phenolic resin, reinforcement and wear-resistant filler are added to a high-speed mixer and mixed at 60°C for 20 min to obtain mixture 1;

[0084] S2: Dilute the silane coupling agent KH550 with ethanol and spray it into the mixture 1 in step S1 in the form of atomization. Continue mixing for 8 minutes to fully wet the surface of the material to obtain mixture 2.

[0085] S3: Knead the polyimide prepolymer and mixture 2 in a kneader at 50°C to make the polyimide prepolymer uniformly coat mixture 2. Remove 80% of the solvent under vacuum at 80°C to obtain mixture 3.

[0086] S4: Mix hexamethylenetetramine with mixture 3, control the roller temperature at 100℃, mix for 10 min, transfer to mold, and keep warm and pressurized at 5 MPa and 160℃ for 60 min; then raise the temperature to 200℃, keep warm and pressurized for 2 h, and cool to obtain high wear-resistant modified phenolic resin material for guide rings.

[0087] Example 3

[0088] The guide ring in this embodiment is made of a high-wear-resistant modified phenolic resin material, which is prepared from the following raw materials by weight:

[0089] 100g of linear phenolic resin, 35g of polyimide prepolymer prepared in Preparation Example 6, 20g of reinforcement, 10g of wear-resistant filler, 2g of silane coupling agent KH550, and 10g of hexamethylenetetramine;

[0090] The reinforcement was prepared by mixing the rare earth modified carbon fiber prepared in Preparation Example 3 with aramid pulp at a mass ratio of 3:1;

[0091] The wear-resistant filler is molybdenum disulfide.

[0092] The preparation process of the high wear-resistant modified phenolic resin material for the guide ring in this embodiment is as follows:

[0093] S1: Linear phenolic resin, reinforcement and wear-resistant filler are added to a high-speed mixer and mixed at 60°C for 20 min to obtain mixture 1;

[0094] S2: Dilute the silane coupling agent KH550 with ethanol and spray it into the mixture 1 in step S1 in the form of atomization. Continue mixing for 8 minutes to fully wet the surface of the material to obtain mixture 2.

[0095] S3: Knead the polyimide prepolymer and mixture 2 in a kneader at 50°C to make the polyimide prepolymer uniformly coat mixture 2. Remove 80% of the solvent under vacuum at 80°C to obtain mixture 3.

[0096] S4: Mix hexamethylenetetramine with mixture 3, control the roller temperature at 100℃, mix for 10 min, transfer to mold, and keep warm and pressurized at 5 MPa and 180℃ for 30 min; then raise the temperature to 210℃, keep warm and pressurized for 1 h, and cool to obtain high wear-resistant modified phenolic resin material for guide rings.

[0097] Example 4

[0098] The guide ring in this embodiment is made of a high-wear-resistant modified phenolic resin material, which is prepared from the following raw materials by weight:

[0099] 100g of linear phenolic resin, 20g of polyimide prepolymer prepared in Preparation Example 6, 20g of reinforcement, 22g of wear-resistant filler, 1g of silane coupling agent KH550, and 11g of hexamethylenetetramine;

[0100] The reinforcement was prepared by mixing the rare earth modified carbon fiber prepared in Preparation Example 3 with aramid pulp at a mass ratio of 5:1.

[0101] The wear-resistant filler is prepared by mixing molybdenum disulfide and polytetrafluoroethylene micro powder in a mass ratio of 1:1.

[0102] The preparation process of the high wear-resistant modified phenolic resin material for the guide ring in this embodiment is as follows:

[0103] S1: Linear phenolic resin, reinforcement and wear-resistant filler are added to a high-speed mixer and mixed at 60°C for 20 min to obtain mixture 1;

[0104] S2: Dilute the silane coupling agent KH550 with ethanol and spray it into the mixture 1 in step S1 in the form of atomization. Continue mixing for 8 minutes to fully wet the surface of the material to obtain mixture 2.

[0105] S3: Knead the polyimide prepolymer and mixture 2 in a kneader at 50°C to make the polyimide prepolymer uniformly coat mixture 2. Remove 80% of the solvent under vacuum at 80°C to obtain mixture 3.

[0106] S4: Mix hexamethylenetetramine with mixture 3, control the roller temperature at 100℃, mix for 10 min, transfer to mold, and keep warm and pressurize at 12 MPa and 160℃ for 30 min; then raise the temperature to 200℃, keep warm and pressurize for 2 h, and cool to obtain high wear-resistant modified phenolic resin material for guide rings.

[0107] Example 5

[0108] The difference from Example 1 is that the amount of the reinforcing agent used is 25g.

[0109] Example 6

[0110] The difference from Example 1 is that the amount of polyimide prepolymer used is 30g and the amount of wear-resistant filler used is 10g.

[0111] Comparative Example 1

[0112] The difference from Example 1 is that no polyimide prepolymer was added in this comparative example.

[0113] Comparative Example 2

[0114] The difference from Example 1 is that no aramid pulp was added in this comparative example.

[0115] Comparative Example 3

[0116] The difference from Example 1 is that the reinforcement in this comparative example is unmodified carbon fiber.

[0117] Related performance tests

[0118] The guide rings prepared in Examples 1-6 and Comparative Examples 1-3 were subjected to relevant performance tests using high wear-resistant modified phenolic resin materials. The test results are shown in Table 1.

[0119] Table 1 Test Results

[0120]

[0121] As shown in Table 1, Examples 1-6 maintained low coefficients of friction and wear rates at 200℃, demonstrating the synergistic high-temperature strengthening effect of polyimide-modified, rare-earth-modified carbon fiber and aramid pulp compound.

[0122] The performance of Comparative Examples 1-3 decreased at 200℃, especially Comparative Example 1, which showed a more significant decrease. This demonstrates that the introduction of polyimide prepolymer, the use of rare earth modified carbon fiber, and the synergistic modification of carbon fiber and aramid pulp can improve the high-temperature wear resistance of the material.

[0123] The present invention has been described above by way of example. It should be noted that any simple modifications, alterations or other equivalent substitutions that can be made by those skilled in the art without creative effort without departing from the core of the present invention fall within the protection scope of the present invention.

Claims

1. A high-wear-resistant modified phenolic resin material for guide rings, characterized in that, It is prepared from the following parts by weight of raw materials: 100 parts linear phenolic resin, 20-35 parts polyimide prepolymer, 20-45 parts reinforcement, 10-25 parts wear-resistant filler, 1-3 parts silane coupling agent, and 8-12 parts curing agent; The polyimide prepolymer was prepared by reacting pyromellitic dianhydride with 4,4'-diaminodiphenyl ether. The preparation method of polyimide prepolymer is as follows: under anaerobic conditions, 4,4'-diaminodiphenyl ether, pyromellitic dianhydride and N,N-dimethylacetamide are mixed evenly and reacted at 15-20℃ for 4-6 hours. After filtration, a polyimide prepolymer with a solid content of 15%-18% is obtained.

2. The high wear-resistant modified phenolic resin material for guide rings according to claim 1, characterized in that, The molar ratio of the 4,4'-diaminodiphenyl ether to pyromellitic dianhydride is 1:(1-1.05).

3. The high wear-resistant modified phenolic resin material for guide rings according to claim 1, characterized in that, The reinforcement is prepared by mixing rare earth modified carbon fiber and aramid pulp at a mass ratio of (3-5):

1.

4. The high wear-resistant modified phenolic resin material for guide rings according to claim 3, characterized in that, The preparation method of the rare earth modified carbon fiber includes the following steps: Carbon fibers were impregnated in a 0.5 mol / L cerium nitrate solution, ultrasonically treated, dried, and heat-treated to obtain rare earth modified carbon fibers.

5. The high wear-resistant modified phenolic resin material for guide rings according to claim 4, characterized in that, The ratio of carbon fiber to cerium nitrate solution is 1 g:(20-35) mL; the heat treatment temperature is 700-800℃ and the heat treatment time is 1-3 h.

6. The high wear-resistant modified phenolic resin material for guide rings according to claim 1, characterized in that, The wear-resistant filler is selected from one or more combinations of molybdenum disulfide, graphite, and polytetrafluoroethylene micro powder.

7. The high wear-resistant modified phenolic resin material for guide rings according to claim 1, characterized in that, The silane coupling agent is γ-aminopropyltriethoxysilane; the curing agent is hexamethylenetetramine.

8. The preparation process of a high wear-resistant modified phenolic resin material for guide rings according to any one of claims 1-7, characterized in that, Includes the following steps: S1: Mix linear phenolic resin, reinforcement and wear-resistant filler evenly to obtain mixture 1; S2: Mix the silane coupling agent, ethanol and mixture 1 evenly to obtain mixture 2; S3: Mix the polyimide prepolymer with mixture 2 until homogeneous to obtain mixture 3; S4: Mix the curing agent with mixture 3 evenly, knead, mold and cure, cool to obtain a high wear-resistant modified phenolic resin material for guide rings.

9. The preparation process of a high wear-resistant modified phenolic resin material for guide rings according to claim 8, characterized in that, In step S4, the molding and curing process is as follows: maintain the temperature and pressure at 5-15 MPa and 160-180℃ for 30-60 minutes; then raise the temperature to 200-220℃ and maintain the temperature and pressure for 1-2 hours.

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