A high-toughness wear-resistant laminate and its preparation method

Abstract

The present invention discloses a high-toughness wear-resistant laminate and a preparation method thereof, characterized in that: the high-toughness wear-resistant laminate is obtained by hot pressing after proportionally matching multiple layers of high-toughness wear-resistant resin fiber fabric prepregs; the high-toughness wear-resistant resin fiber fabric prepreg is obtained by coating a high-toughness wear-resistant resin adhesive on a fiber fabric and then baking; the weight percentage of the high-toughness wear-resistant resin adhesive in the high-toughness wear-resistant resin fiber fabric prepreg is 30% ～ 60%, and the weight percentage of the fiber fabric is 40% ～ 70%; the high-toughness wear-resistant resin adhesive is composed of a mixture of epoxy resin, phenolic resin, curing agent, nano modifier, carbon nanotube, nano tungsten nitride, modification treatment agent and solvent. By adopting the present invention, the high-toughness wear-resistant laminate has the characteristics of high mechanical toughness, relatively high mechanical strength and good wear resistance, and is suitable for use in the fields of mining ore mining, cement mortar mining, construction machinery, etc.

Description

Technical Field

[0001] The present invention belongs to laminates and their preparation, and relates to a high-toughness wear-resistant laminate and a preparation method thereof. The high-toughness wear-resistant laminate prepared by the present invention is applicable to fields such as mining of ores in mines, mining of cement mortar, and construction machinery. Background Art

[0002] With the rapid development of modern industry, the performance requirements for mechanical products in production are becoming increasingly strict. To enable equipment to operate stably for a long time under harsh working conditions such as high temperature, high pressure, and high speed, higher requirements must be put forward for its surface strength, wear resistance, etc. The application of wear-resistant materials can effectively reduce this consumption, thereby improving production efficiency and saving costs.

[0003] Since the wear problem is actually inevitable and objectively exists in industry, the wear-resistant material industry is also called an "immortal industry". According to preliminary statistics by relevant institutions, in 2009, the annual consumption of wear-resistant materials for abrasive wear working conditions in China has increased from about 2 million tons in 2004 to more than 3.5 million tons in 2009, with an annual compound growth rate of 11.8%; it is expected that the annual growth rate from 2011 to 2020 will reach 5% - 10%. Wear-resistant composite materials are emerging technologies and products developed on the basis of traditional wear-resistant materials. With the continuous progress of industry and the continuous upgrading of market demand, it has become an inevitable trend for wear-resistant composite materials to replace traditional wear-resistant materials in some application fields, and the prospect is very broad.

[0004] In the prior art, the research on wear-resistant composite materials at home and abroad has been increasing year by year. Wear-resistant composite materials such as composite hammers, liners, jaw plates, and bucket teeth have been well applied, and research has also been carried out on composite pipe and roller mechanical parts, etc., and good practical production applications have been achieved. With the improvement of the process and the optimization of materials, the application of wear-resistant composite materials will be more extensive, and the application demands in fields such as mining of ores in mines, mining of cement mortar, and construction machinery are particularly urgent.

[0005] However, modern industrial development has put forward higher requirements for the performance of wear-resistant materials. Most wear-resistant materials need to have both good toughness and high-strength characteristics. However, it is very difficult to achieve high toughness and high strength in one material in practice. Therefore, developing new wear-resistant laminates has become one of the urgent problems to be solved in industrial production. Summary of the Invention

[0006] The objective of the present invention is to overcome the deficiencies in the above-mentioned prior art and provide a high-toughness wear-resistant laminate and its preparation method. Thus, a high-toughness wear-resistant laminate with high mechanical strength (usually referring to a flexural strength of 620 MPa - 758 MPa at room temperature and 328 MPa - 403 MPa at 180 °C), high mechanical toughness (usually referring to a notch impact strength of 185 KJ / m 2 ~345 KJ / m 2 ), and wear resistance reaching (usually referring to being able to withstand a wear resistance test > 120 h at room temperature) and its preparation method are provided.

[0007] The content of the present invention is: A high-toughness wear-resistant laminate, characterized in that: the high-toughness wear-resistant laminate is obtained by hot pressing multi-layer high-toughness wear-resistant resin fiber fabric prepregs under the conditions of a temperature of 140 °C - 185 °C and a pressure of 1 MPa - 25 MPa.

[0008] The high-toughness wear-resistant resin fiber fabric prepreg is prepared by coating a high-toughness wear-resistant resin adhesive on a fiber fabric and then baking (semi-curing).

[0009] In the high-toughness wear-resistant resin fiber fabric prepreg: the weight percentage of the high-toughness wear-resistant resin adhesive is 30% - 60%, and the weight percentage of the fiber fabric is 40% - 70%.

[0010] The high-toughness wear-resistant resin adhesive is composed of 20 - 40 parts by weight of epoxy resin, 10 - 32 parts by weight of phenolic resin, 3 - 24 parts by weight of curing agent, 5 - 20 parts by weight of nano modifier, 2 - 15 parts by weight of carbon nanotubes, 3 - 45 parts by weight of nano tungsten nitride, 4 - 15 parts by weight of modification treatment agent, and 5 - 15 parts by weight of solvent mixed together.

[0011] The preparation method of the high-toughness wear-resistant resin adhesive is: at room temperature, mix the carbon nanotubes, modification treatment agent, and solvent and stir at a rotation speed of 600 r / min - 1300 r / min. After stirring for 0.5 h - 2.5 h, a gel is obtained and reserved; mix and stir the remaining all materials, namely epoxy resin, phenolic resin, curing agent, nano modifier, and nano tungsten nitride, at a temperature of 50 °C - 85 °C for 0.75 h - 3 h, then cool down to room temperature, add the prepared gel, and stir at a rotation speed of 600 r / min - 1300 r / min at room temperature for 0.5 h - 1.5 h to obtain the high-toughness wear-resistant resin adhesive.

[0012] In the high-toughness wear-resistant laminate described in the content of the present invention:

[0013] The epoxy resin is any one of glycidyl ester epoxy resin, amino epoxy resin, biphenyl epoxy resin, and phenolic epoxy resin, or a mixture of two or more thereof;

[0014] The phenolic resin is any one of boron-modified phenolic resin, xylene-modified phenolic resin, and benzoxazine resin, or a mixture of two or more thereof;

[0015] The curing agent is any one of diaminodiphenyl sulfone, cardanol curing agent, active ester curing agent, or a mixture of two or more thereof;

[0016] The nano modifier is any one of nano montmorillonite, nano vermiculite, nano talc, and nano kaolin, or a mixture of two or more thereof;

[0017] The carbon nanotubes are single-walled carbon nanotubes and / or multi-walled carbon nanotubes;

[0018] The modifying agent is any one of 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and high molecular weight polymer alkyl ammonium salt, or a mixture of two or more thereof;

[0019] The solvent is any one of methyl ethyl ketone, butanone, acetone, propylene glycol, and alcohol (ie, ethanol), or a mixture of two or more thereof.

[0020] In the content of the present invention: the fiber fabric is glass fiber fabric and nylon fiber cloth, and the number ratio of the fabrics is (1 to 10): (1 to 10); wherein the glass fiber fabric is at least one of E-type glass fiber cloth, E-type glass fiber woven cloth, E-type glass fiber mat, E-type high-strength glass fiber cloth, S-type glass fiber cloth, and S-type high-strength glass fiber cloth.

[0021] In the content of the present invention: the multi-layer high-toughness wear-resistant resin fiber fabric prepreg is: 2 to 300 layers of high-toughness wear-resistant resin fiber fabric prepreg.

[0022] Another aspect of the present invention is a method for preparing a high-toughness wear-resistant laminate, which is characterized by comprising the following steps:

[0023] a. Ingredients: Prepare the raw materials according to the following ratios: 20-40 parts by weight of epoxy resin, 10-32 parts by weight of phenolic resin, 3-24 parts by weight of curing agent, 5-20 parts by weight of nano-modifier, 2-15 parts by weight of carbon nanotubes, 3-45 parts by weight of nano-tungsten nitride, 4-15 parts by weight of modifying agent and 5-15 parts by weight of solvent;

[0024] b. Preparation of high-toughness wear-resistant resin adhesive: At room temperature, mix the carbon nanotubes, modification agent, and solvent, and stir at a rotation speed of 600 r / min to 1300 r / min for 0.5 h to 2.5 h to obtain a gel for standby; mix the remaining materials, namely epoxy resin, phenolic resin, curing agent, nano-modification agent, and nano-tungsten nitride, at a temperature of 50 °C to 85 °C, stir for 0.75 h to 3 h, then cool down to room temperature, add the prepared gel, and stir at a rotation speed of 600 r / min to 1300 r / min for 0.5 h to 1.5 h at room temperature to obtain the high-toughness wear-resistant resin adhesive;

[0025] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: Coating the high-toughness wear-resistant resin adhesive obtained in step b on the fiber fabric, and then baking to obtain the high-toughness wear-resistant resin fiber fabric prepreg;

[0026] d. Preparation of laminate: Preheat the mold at a temperature of 125 °C to 155 °C, stack the high-toughness wear-resistant resin fiber fabric prepregs obtained in step c in proportion by the number of sheets in the mold, and after closing the mold, hot press and form under the conditions of a temperature of 140 °C to 185 °C and a pressure of 1 MPa to 25 MPa for a hot pressing time of 0.5 h to 50 h to obtain the high-toughness wear-resistant laminate.

[0027] In another aspect of the present invention: The baking in step c is as follows: Put the fiber fabric coated with the high-toughness wear-resistant resin adhesive by a vertical sizing machine into a baking tunnel. The baking tunnel is 50 m long, divided into 4 sections, each section is 12.5 m long, and the baking temperature range is 80 °C to 175 °C, where: the first section is 80 °C to 105 °C, the second section is 115 °C to 135 °C, the third section is 145 °C to 175 °C, and the fourth section is 100 °C to 110 °C. The speed of the sizing machine is 3 m / min to 24 m / min, and the baking tunnel is pre-baked before baking.

[0028] In another aspect of the preparation method of the high-toughness wear-resistant laminate of the present invention:

[0029] The epoxy resin is any one or a mixture of two or more of glycidyl epoxy resin, amino epoxy resin, biphenyl-type epoxy resin, and phenolic-type epoxy resin;

[0030] The phenolic resin is any one or a mixture of two or more of boron-modified phenolic resin, xylene-modified phenolic resin, and benzoxazine resin;

[0031] The curing agent is any one or a mixture of two or more of diaminodiphenyl sulfone, cashew phenol curing agent, and active ester curing agent;

[0032] The nano modifier is any one or a mixture of two or more of nano-montmorillonite, nano-vermiculite, nano-talc powder, and nano-kaolin;

[0033] The carbon nanotubes are single-walled carbon nanotubes or / and multi-walled carbon nanotubes;

[0034] The modification treatment agent is any one or a mixture of two or more of 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and high molecular weight polymer alkyl ammonium salt;

[0035] The solvent is any one or a mixture of two or more of methyl ethyl ketone, butanone, acetone, propylene glycol, and alcohol (i.e., ethanol).

[0036] In another aspect of the present invention: The fiber fabric is a glass fiber fabric or a nylon fiber cloth, and the number of sheets used is in a ratio of (1 to 10):(1 to 10); among them, the glass fiber fabric is at least one of E-type glass fiber cloth, E-type glass fiber square cloth, E-type glass fiber mat, E-type high-strength glass fiber cloth, S-type glass fiber cloth, and S-type high-strength glass fiber cloth.

[0037] In another aspect of the present invention: In step d, the multi-layer overlapping placement of the high-toughness wear-resistant resin fiber fabric prepreg in the mold means that the high-toughness wear-resistant resin fiber fabric prepreg is multi-layer overlapped and placed in the mold in 2 to 300 layers.

[0038] In another aspect of the present invention: In the high-toughness wear-resistant resin fiber fabric prepreg prepared in step c, the weight percentage of the high-toughness wear-resistant resin adhesive is 30% to 60%, and the weight percentage of the fiber fabric is 40% to 70%.

[0039] Compared with the prior art, the present invention has the following characteristics and beneficial effects:

[0040] (1) The high-toughness wear-resistant laminate of the present invention uses a variety of resins such as high-performance special epoxy and phenolic resins as the matrix, supplemented with modifiers, treatment agents, etc. to improve the overall microscopic topological structure of the system. Combined with a high-performance curing agent, on the basis of simple mechanical dispersion and mixing, the laminate has excellent toughness, normal and high-temperature mechanical strength, and achieves excellent wear resistance; it avoids the defects in the prior art that the addition of rubber-like substances (such as nitrile rubber, etc.) and modification additives directly lead to poor high-temperature resistance of the laminate (usually referring to the bending strength being less than 50 MPa under the condition of 180 °C), and at the same time seriously affects the wear resistance and cannot meet the use conditions in the field of toughness and wear resistance;

[0041] (2) The present invention adopts a tungsten nitride-carbon nanotube composite system, enabling the prepared high-toughness wear-resistant laminate to have excellent mechanical strength and toughness while having high wear resistance (wear resistance time > 120 h), achieving a flexural strength of 620 MPa to 758 MPa under normal conditions and a notch impact strength of 185 KJ / m 2 ~345 KJ / m 2 ); It solves the technical problems in the prior art that the addition amount of a single modification additive (such as molybdenum disulfide, etc.) is large and the mechanical strength, especially the toughness performance, is poor, making it fully meet the usage requirements of high-toughness wear-resistant materials in the wear-resistant field;

[0042] (3) In the preparation process of the high-toughness wear-resistant resin adhesive involved in the high-toughness wear-resistant laminate of the present invention, a simple mechanical dispersion method is adopted. The raw materials are gradually added and stirred and mixed at medium and low temperatures to obtain a uniform resin solution that meets the prepreg preparation process; the preparation process is simple, the process quality is easy to control, the production cost is low, the requirements for production equipment are low, it can meet the requirements of "green, environmental protection, and high efficiency" for enterprise production in China, and greatly reduces the production cost, simplifies the process, and has excellent quality, with good practical use value and application prospects;

[0043] (4) The matrix resin and each raw material adopted in the present invention are all materials that can withstand high temperatures for a long time, meeting the strict requirements that the prepared high-toughness wear-resistant laminate can reach high mechanical strength at 180°C for a long time; the flexural strength of the high-toughness wear-resistant laminate of the present invention is 620 MPa to 758 MPa at room temperature and 328 MPa to 403 MPa at a temperature of 180°C. Especially under high toughness (the notch impact strength reaches 185 KJ / m 2 ~345 KJ / m 2 ), the high-temperature (180°C) strength retention rate is relatively high (the flexural strength retention rate at 180°C is greater than or equal to 53%); it solves the technical problems in the prior art that after using a toughening modifier (such as nitrile rubber, etc.), the strength of the laminate is poor and cannot meet the requirement that the flexural strength retention rate at 180°C is greater than or equal to 50%;

[0044] (5) The present invention uses a hybrid fiber to replace the use of a single fiber, effectively improving the wettability of the single fiber of the material to the resin adhesive and the bonding force between prepregs, and solving the technical problems that the mechanical strength and toughness of the laminate are low due to poor interlayer adhesion of the material and it is difficult to ensure wear resistance;

[0045] (6) The preparation process of the product of the present invention is simple, the process is convenient, it is easy to operate, and it has strong practicability. Detailed implementation mode

[0046] The following embodiments are intended to further illustrate the present invention, but should not be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made to the present invention by those skilled in the art based on the above-mentioned contents of the present invention still fall within the scope of protection of the present invention.

[0047] Example 1:

[0048] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0049] a. Ingredients: Prepare 25 parts of biphenyl epoxy resin ("parts" in Examples 1-16 are all "parts by weight"), 13 parts of benzoxazine resin, 6 parts of diaminodiphenyl sulfone, 3 parts of single-walled carbon nanotubes, 11 parts of nano-talc powder, 9 parts of nano-tungsten nitride, 6 parts of high molecular weight polymer alkyl ammonium salt, and 8 parts of acetone;

[0050] b. Preparation of high-toughness wear-resistant resin adhesive: At room temperature, first stir the single-walled carbon nanotubes, high molecular weight polymer alkyl ammonium salt and acetone at a speed of 810r / min, and stir for 0.75h to form a gel for standby use. Mix all the remaining materials (i.e., biphenyl epoxy resin, benzoxazine resin, diaminodiphenyl sulfone, nano talc powder, nano tungsten nitride) (the "remaining all materials" in the following Examples 2-16 are the other raw materials in the "ingredients" of step a except carbon nanotubes, modifying agents and solvents) at 65°C, stir for 2.5h, cool to room temperature, add the prepared gel, and stir at room temperature at a speed of 1200r / min for 1h to obtain a high-toughness wear-resistant resin adhesive;

[0051] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., E-type glass fiber cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m long. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 6m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0052] d. Preparation of high-toughness wear-resistant laminate: preheat the template at 125°C to 155°C, overlap the high-toughness wear-resistant resin fiber fabric prepreg (i.e., E-type glass fiber cloth prepreg: nylon fiber cloth prepreg in a ratio of 1:8) and place them in the template. After closing the mold, hot press molding is carried out at 140°C to 185°C and 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0053] Example 2:

[0054] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0055] a. Ingredients: prepare 22 parts of glycidyl ester epoxy resin, 10 parts of boron-modified phenolic resin, 8 parts of cardanol curing agent, 7 parts of multi-walled carbon nanotubes, 7 parts of nano-montmorillonite, 13 parts of nano-tungsten nitride, 5 parts of 3-aminopropyltriethoxysilane, and 9 parts of alcohol;

[0056] b. Preparation of a high-toughness, wear-resistant resin adhesive: First, at room temperature, stir the multi-walled carbon nanotubes, 3-aminopropyltriethoxysilane, and alcohol at 1050 rpm for 1.1 hours to form a gel. The remaining materials were mixed and stirred at 55°C for 1.25 hours, then cooled to room temperature, and the prepared gel was added. The mixture was stirred at 700 rpm at room temperature for 1.25 hours to obtain a high-toughness, wear-resistant resin adhesive.

[0057] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., E-type glass fiber woven cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m long. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 11m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0058] d. Preparation of high-toughness wear-resistant laminate: preheat the mold at 125°C to 155°C, overlap the high-toughness wear-resistant resin fiber fabric prepreg (i.e., E-type glass fiber woven cloth prepreg: nylon fiber cloth prepreg in a ratio of 2:5) and place them in the mold. After closing the mold, hot press molding is performed at 140°C to 185°C and 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0059] Example 3:

[0060] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0061] a. Ingredients: prepare 24 parts of amino epoxy resin, 16 parts of xylene-modified phenolic resin, 11 parts of active ester curing agent, 4 parts of single-walled carbon nanotubes, 5 parts of nano-vermiculite, 5 parts of nano-tungsten nitride, 4 parts of 3-glycidyloxypropyltrimethoxysilane, and 5 parts of butanone;

[0062] b. Preparation of a high-toughness wear-resistant resin adhesive: First, at room temperature, the single-walled carbon nanotubes, 3-glycidyloxypropyltrimethoxysilane, and butanone were stirred at a speed of 790 r / min for 2 hours to form a gel for later use; all the remaining materials (i.e., amino epoxy resin, xylene-modified phenolic resin, active ester curing agent, nano-vermiculite, and nano-tungsten nitride) were mixed and stirred at 70° C. for 3 hours, then cooled to room temperature, and the prepared gel was added. The mixture was stirred at a speed of 1050 r / min for 0.75 hours at room temperature to obtain a high-toughness wear-resistant resin adhesive;

[0063] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., E-type glass fiber felt, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 13m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0064] d. Preparation of high-toughness wear-resistant laminate: preheat the mold at 125°C to 155°C, overlap the high-toughness wear-resistant resin fiber fabric prepreg (i.e., E-type glass fiber felt prepreg: nylon fiber cloth prepreg in a ratio of 7:3) and place them in the mold. After closing the mold, hot press molding is performed at 140°C to 185°C and 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0065] Example 4:

[0066] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0067] a. Ingredients: prepare 20 parts of phenolic epoxy resin, 12 parts of xylene-modified phenolic resin, 3 parts of active ester curing agent, 3.5 parts of multi-walled carbon nanotubes, 16 parts of nano-kaolin, 11 parts of nano-tungsten nitride, 7 parts of 3-glycidyloxypropyltrimethoxysilane, and 11 parts of methyl ethyl ketone;

[0068] b. Preparation of a high-toughness, wear-resistant resin adhesive: First, at room temperature, stir the multi-walled carbon nanotubes, 3-glycidyloxypropyltrimethoxysilane, and methyl ethyl ketone at 600 r / min for 2.25 hours to form a gel. The remaining materials are mixed and stirred at 85°C for 2 hours, then cooled to room temperature, and the prepared gel is added. The mixture is stirred at 900 r / min at room temperature for 0.5 hours to obtain a high-toughness, wear-resistant resin adhesive.

[0069] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., S-type high-strength glass fiber cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 10m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0070] d. Preparation of high-toughness wear-resistant laminate: preheat the mold at 125°C to 155°C, overlap the high-toughness wear-resistant resin fiber fabric prepreg (i.e., S-type high-strength glass fiber cloth prepreg: nylon fiber cloth prepreg in a ratio of 4:9) and place them in the mold. After closing the mold, hot press molding is performed at 140°C to 185°C and 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0071] Example 5:

[0072] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0073] a. Ingredients: prepare 14 parts of glycidyl ester epoxy resin, 13 parts of biphenyl diepoxy resin, 16 parts of boron-modified phenolic resin, 5 parts of benzoxazine resin, 14 parts of diaminodiphenyl sulfone, 4.5 parts of multi-walled carbon nanotubes, 5 parts of nano talc, 4 parts of nano vermiculite, 40 parts of nano tungsten nitride, 11 parts of high molecular weight polymer alkyl ammonium salt, and 5.5 parts of propylene glycol;

[0074] b. Preparation of high-toughness wear-resistant resin adhesive: At room temperature, first stir the multi-walled carbon nanotubes, high-molecular-weight polymer alkyl ammonium salt, and propylene glycol at a speed of 940 r / min. After stirring for 2.05 h, a gel is prepared for standby. Mix and stir all the remaining materials at 80 °C for 1.75 h, then cool down to room temperature, add the prepared gel, and stir at a speed of 1100 r / min at room temperature for 0.75 h to obtain the high-toughness wear-resistant resin adhesive;

[0075] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: Put the fiber fabrics (i.e., S-type fiberglass cloth, S-type high-strength fiberglass cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical sizing machine into a drying oven. The drying oven is 50 m long and divided into 4 sections, each section being 12.5 m. The baking temperature ranges from 80 °C to 175 °C, where the first section is 80 °C to 105 °C, the second section is 115 °C to 135 °C, the third section is 145 °C to 175 °C, and the fourth section is 100 °C to 110 °C. The speed of the sizing machine is 3 m / min to obtain the high-toughness wear-resistant resin fiber fabric prepreg. The drying oven is pre-dried before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0076] d. Preparation of high-toughness wear-resistant laminate: Preheat the mold at 125 °C to 155 °C, and overlap and place the high-toughness wear-resistant resin fiber fabric prepreg (i.e., the ratio of S-type fiberglass cloth prepreg:S-type high-strength fiberglass cloth:nylon fiber cloth prepreg is 0.3:0.7:3) in the mold. After closing the mold, hot press and form it under the conditions of 140 °C to 185 °C and 1 MPa to 25 MPa, and the hot pressing time is 0.5 h to 50 h to obtain the high-toughness wear-resistant laminate.

[0077] Example 6:

[0078] A preparation method of a high-toughness wear-resistant laminate, comprising the following steps:

[0079] a. Ingredients: Prepare 16 parts of biphenyl-type epoxy resin, 12 parts of phenolic-type epoxy resin, 13 parts of benzoxazine resin, 10 parts of xylene-modified phenolic resin, 16 parts of cashew phenol curing agent, 3 parts of single-walled carbon nanotubes, 8 parts of nano-montmorillonite, 5 parts of nano-kaolin, 23 parts of nano-tungsten nitride, 9 parts of high-molecular-weight polymer alkyl ammonium salt, 2 parts of alcohol, and 5 parts of methyl ethyl ketone;

[0080] b. Preparation of a high-toughness, wear-resistant resin adhesive: First, at room temperature, stir the single-walled carbon nanotubes, high molecular weight polymer alkyl ammonium salt, alcohol, and butanone at 1160 r / min for 0.5 h to form a gel. The remaining materials are mixed and stirred at 65°C for 2.05 h, then cooled to room temperature, and the prepared gel is added. The mixture is stirred at 750 r / min at room temperature for 1.05 h to obtain a high-toughness, wear-resistant resin adhesive.

[0081] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., S-type high-strength glass fiber cloth, E-type high-strength glass fiber cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 17m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0082] d. Preparation of high-toughness wear-resistant laminate: preheat the mold at 125°C to 155°C, overlap the high-toughness wear-resistant resin fiber fabric prepreg (i.e., S-type high-strength glass fiber cloth prepreg: E-type high-strength glass fiber cloth: nylon fiber cloth prepreg: 1.2:3.8:6) and place them in the mold. After closing the mold, hot press molding is carried out at 140°C to 185°C and 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0083] Example 7:

[0084] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0085] a. Ingredients: prepare 13 parts of amino epoxy resin, 19 parts of phenolic epoxy resin, 12 parts of boron-modified phenolic resin, 16 parts of benzoxazine resin, 8 parts of diaminodiphenyl sulfone, 11 parts of cardanol curing agent, 10 parts of single-walled carbon nanotubes, 4 parts of nano-talc powder, 2 parts of nano-kaolin, 34 parts of nano-tungsten nitride, 13 parts of 3-aminopropyltriethoxysilane, 4.5 parts of methyl ethyl ketone, and 4 parts of alcohol;

[0086] b. Preparation of a high-toughness, wear-resistant resin adhesive: First, at room temperature, stir the single-walled carbon nanotubes, 3-aminopropyltriethoxysilane, methyl ethyl ketone, and alcohol at 980 rpm for 1.75 hours to form a gel. The remaining materials were mixed and stirred at 50°C for 1.5 hours, then cooled to room temperature, and the prepared gel was added. The mixture was stirred at 600 rpm for 0.65 hours at room temperature to obtain a high-toughness, wear-resistant resin adhesive.

[0087] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., E-type glass fiber woven cloth, E-type high-strength glass fiber cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m long. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 20m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0088] d. Preparation of high-toughness wear-resistant laminate: preheat the mold at 125°C to 155°C, overlap the high-toughness wear-resistant resin fiber fabric prepreg (i.e., E-type glass fiber woven cloth prepreg: E-type high-strength glass fiber cloth prepreg: nylon fiber cloth prepreg in a ratio of 0.4:0.6:10) and place them in the mold. After closing the mold, hot press molding is carried out at 140°C to 185°C and 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0089] Example 8:

[0090] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0091] a. Ingredients: prepare 17 parts of glycidyl ester epoxy resin, 12 parts of phenolic epoxy resin, 20 parts of boron-modified phenolic resin, 12 parts of xylene-modified phenolic resin, 9 parts of diaminodiphenyl sulfone, 14 parts of active ester curing agent, 2 parts of single-walled carbon nanotubes, 12 parts of nano-montmorillonite, 6 parts of nano-vermiculite, 26 parts of nano-tungsten nitride, 12 parts of 3-glycidyloxypropyltrimethoxysilane, 7 parts of acetone, and 4.5 parts of methyl ethyl ketone;

[0092] b. Preparation of a high-toughness, wear-resistant resin adhesive: First, at room temperature, stir the single-walled carbon nanotubes, 3-glycidyloxypropyltrimethoxysilane, acetone, and methyl ethyl ketone at 1200 r / min for 1.35 hours to form a gel for later use. Mix all remaining materials at 55°C for 0.75 hours, then cool to room temperature, add the prepared gel, and continue stirring at 1150 r / min at room temperature for 1.25 hours to obtain a high-toughness, wear-resistant resin adhesive.

[0093] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., E-type glass fiber cloth, E-type glass fiber felt, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 22m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0094] d. Preparation of high-toughness wear-resistant laminate: preheat the mold at 125°C to 155°C, overlap the high-toughness wear-resistant resin fiber fabric prepreg (i.e., E-type glass fiber cloth prepreg: E-type glass fiber felt prepreg: nylon fiber cloth prepreg in the ratio of 2:3:10) and place them in the mold. After closing the mold, hot press molding is carried out at 140°C to 185°C and 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0095] Example 9:

[0096] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0097] a. Ingredients: prepare 28 parts of glycidyl ester epoxy resin, 9 parts of biphenyl epoxy resin, 9 parts of boron-modified phenolic resin, 6 parts of xylene-modified phenolic resin, 9 parts of cardanol curing agent, 6 parts of active ester curing agent, 15 parts of multi-walled carbon nanotubes, 5 parts of nano vermiculite, 9 parts of nano kaolin, 17 parts of nano tungsten nitride, 6 parts of 3-aminopropyltriethoxysilane, 4 parts of 3-glycidyloxypropyltrimethoxysilane, 8 parts of methyl ethyl ketone, and 6 parts of alcohol;

[0098] b. Preparation of a high-toughness, wear-resistant resin adhesive: First, at room temperature, stir the multi-walled carbon nanotubes, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyl ethyl ketone, and alcohol at 1060 r / min for 1.35 hours to form a gel for later use. Mix all remaining materials at 70°C for 1.45 hours, then cool to room temperature, add the prepared gel, and stir at 1200 r / min at room temperature for 1.35 hours to obtain a high-toughness, wear-resistant resin adhesive.

[0099] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., E-type glass fiber felt, S-type high-strength glass fiber cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 12m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0100] d. Preparation of high-toughness wear-resistant laminate: preheat the mold at 125°C to 155°C, overlap the high-toughness wear-resistant resin fiber fabric prepreg (i.e., E-type glass fiber felt prepreg: S-type high-strength glass fiber cloth prepreg: nylon fiber cloth prepreg in a ratio of 1:2:4) and place them in the mold. After closing the mold, hot press molding is carried out at 140°C to 185°C and 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0101] Example 10:

[0102] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0103] a. Ingredients: prepare 13 parts of amino epoxy resin, 17 parts of glycidyl ester epoxy resin, 3 parts of xylene modified phenolic resin, 18 parts of benzoxazine resin, 12 parts of diaminodiphenyl sulfone, 8 parts of cardanol curing agent, 6 parts of multi-walled carbon nanotubes, 10 parts of nano talc, 7 parts of nano montmorillonite, 38 parts of nano tungsten nitride, 4 parts of high molecular weight polymer alkyl ammonium salt, 5 parts of 3-glycidyloxypropyltrimethoxysilane, 2 parts of methyl ethyl ketone, 7 parts of butanone, and 3 parts of propylene glycol;

[0104] b. Preparation of a high-toughness, wear-resistant resin adhesive: First, at room temperature, stir the multi-walled carbon nanotubes, high molecular weight polymer alkyl ammonium salt, 3-glycidyloxypropyltrimethoxysilane, methyl ethyl ketone, butanone, and propylene glycol at 1300 r / min for 0.75 h to form a gel for later use. Mix all remaining materials at 80°C for 1 h, then cool to room temperature, add the prepared gel, and stir at 650 r / min at room temperature for 1.5 h to obtain a high-toughness, wear-resistant resin adhesive.

[0105] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., E-type glass fiber cloth, E-type glass fiber high-strength cloth, S-type glass fiber cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 16m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0106] d. Preparation of high-toughness wear-resistant laminate: preheat the mold at 125°C to 155°C, overlap the high-toughness wear-resistant resin fiber fabric prepreg (i.e., E-type glass fiber cloth prepreg: S-type glass fiber cloth prepreg: E-type glass fiber high-strength cloth prepreg: nylon fiber cloth prepreg in a ratio of 4:3:2:2) and place them in the mold. After closing the mold, hot press molding is carried out at 140°C to 185°C and 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0107] Example 11:

[0108] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0109] a. Ingredients: prepare 21 parts of biphenyl epoxy resin, 13 parts of amino epoxy resin, 8 parts of diphenyl ether formaldehyde resin, 6 parts of xylene-modified phenolic resin, 11 parts of benzoxazine resin, 5 parts of diaminodiphenyl sulfone, 8 parts of active ester curing agent, 11 parts of single-walled carbon nanotubes, 5 parts of nano talc, 2 parts of nano montmorillonite, 3 parts of nano vermiculite, 15 parts of nano tungsten nitride, 2 parts of 3-glycidoxypropyltrimethoxysilane, 5 parts of 3-aminopropyltriethoxysilane, 4 parts of acetone, 7 parts of alcohol, and 2.5 parts of propylene glycol;

[0110] b. Preparation of a high-toughness, wear-resistant resin adhesive: First, at room temperature, stir the single-walled carbon nanotubes, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, acetone, alcohol, and propylene glycol at 870 r / min for 1.65 hours to form a gel for later use. Mix all remaining materials at 85°C for 1.75 hours, then cool to room temperature, add the prepared gel, and stir at 1000 r / min at room temperature for 1.15 hours to obtain a high-toughness, wear-resistant resin adhesive.

[0111] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., E-type glass fiber woven cloth, E-type glass fiber felt, E-type glass fiber high-strength cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m long. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 19m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0112] d. Preparation of high-toughness wear-resistant laminate: preheat the mold at 125°C to 155°C, overlap the high-toughness wear-resistant resin fiber fabric prepreg (i.e., E-type glass fiber woven cloth prepreg: E-type glass fiber felt prepreg: E-type glass fiber high-strength cloth prepreg: nylon fiber cloth prepreg in a ratio of 1:1:1:7) and place them in the mold. After closing the mold, hot press molding is performed at 140°C to 185°C and 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0113] Example 12:

[0114] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0115] a. Ingredients: prepare 12 parts of biphenyl epoxy resin, 9 parts of glycidyl ester epoxy resin, 14 parts of amino epoxy resin, 9 parts of benzoxazine resin, 8 parts of boron-modified phenolic resin, 6 parts of cardanol curing agent, 6 parts of active ester curing agent, 2 parts of single-walled carbon nanotubes, 6 parts of multi-walled carbon nanotubes, 5 parts of nano talc, 6 parts of nano montmorillonite, 4 parts of nano kaolin, 31 parts of nano tungsten nitride, 4 parts of high molecular weight polymer alkyl ammonium salt, 4 parts of 3-glycidyloxypropyltrimethoxysilane, 7 parts of 3-aminopropyltriethoxysilane, 5 parts of butanone, 6 parts of propylene glycol, and 4 parts of methyl ethyl ketone;

[0116] b. Preparation of a high-toughness, wear-resistant resin adhesive: First, at room temperature, stir the single-walled carbon nanotubes, multi-walled carbon nanotubes, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, butanone, propylene glycol, and methyl ethyl ketone at 1100 r / min for 1 hour to form a gel for later use. Mix all remaining materials at 55°C for 1.15 hours, then cool to room temperature, add the prepared gel, and stir at 800 r / min at room temperature for 1.25 hours to obtain a high-toughness, wear-resistant resin adhesive.

[0117] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., E-type glass fiber cloth, E-type glass fiber felt, S-type glass fiber high-strength cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 24m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0118] d. Preparation of high-toughness wear-resistant laminate: preheat the mold at 125°C to 155°C, overlap the high-toughness wear-resistant resin fiber fabric prepreg (i.e., E-type glass fiber cloth prepreg: E-type glass fiber felt prepreg: S-type glass fiber high-strength cloth: nylon fiber cloth prepreg in a ratio of 2:1:3:5) and place them in the mold. After closing the mold, hot press molding is carried out at 140°C to 185°C and 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0119] Example 13:

[0120] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0121] a. Ingredients: prepare 15 parts of glycidyl ester epoxy resin, 9 parts of amino epoxy resin, 9 parts of phenolic epoxy resin, 15 parts of boron-modified phenolic resin, 11 parts of xylene-modified phenolic resin, 6 parts of diaminodiphenyl sulfone, 12 parts of cardanol curing agent, 3 parts of single-walled carbon nanotubes, 3 parts of multi-walled carbon nanotubes, 4 parts of nano-montmorillonite, 5 parts of nano-vermiculite, 3 parts of nano-kaolin, 32 parts of nano-tungsten nitride, 5 parts of high molecular weight polymer alkyl ammonium salt, 3 parts of 3-glycidyloxypropyltrimethoxysilane, 2 parts of methyl ethyl ketone, 4 parts of butanone, and 3.5 parts of acetone;

[0122] b. Preparation of a high-toughness, wear-resistant resin adhesive: First, at room temperature, stir the single-walled carbon nanotubes, multi-walled carbon nanotubes, high molecular weight polymer alkyl ammonium salt, 3-glycidyloxypropyltrimethoxysilane, methyl ethyl ketone, butanone, and acetone at 630 r / min for 2.5 hours to form a gel for later use. Mix all remaining materials at 65°C for 2.75 hours, then cool to room temperature, add the prepared gel, and stir at 950 r / min at room temperature for 1.05 hours to obtain a high-toughness, wear-resistant resin adhesive.

[0123] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., E-type glass fiber felt, E-type glass fiber high-strength cloth, S-type glass fiber cloth, S-type glass fiber high-strength cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 23m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0124] d. Preparation of high-toughness wear-resistant laminate: preheat the mold at 125°C to 155°C, overlap the high-toughness wear-resistant resin fiber fabric prepreg (i.e., E-type glass fiber felt prepreg: E-type glass fiber high-strength cloth prepreg: S-type glass fiber cloth prepreg: S-type glass fiber high-strength cloth prepreg: nylon fiber cloth prepreg in a ratio of 2:1:1:1:5) and place them in the mold. After closing the mold, hot press molding is carried out at 140°C to 185°C and 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0125] Example 14:

[0126] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0127] a. Ingredients: prepare 7 parts of amino epoxy resin, 18 parts of biphenyl epoxy resin, 13 parts of phenolic epoxy resin, 8 parts of benzoxazine resin, 3 parts of boron-modified phenolic resin, 10 parts of diaminodiphenyl sulfone, 6 parts of cardanol curing agent, 8 parts of active ester curing agent, 5.5 parts of single-walled carbon nanotubes, 2 parts of multi-walled carbon nanotubes, 6 parts of nano talc, 5 parts of nano vermiculite, 2 parts of nano kaolin, 42 parts of nano tungsten nitride, 3 parts of 3-aminopropyltriethoxysilane, 10 parts of high molecular weight polymer alkyl ammonium salt, 1 part of propylene glycol, 1 part of acetone, 2 parts of alcohol, and 2 parts of acetone;

[0128] b. Preparation of a high-toughness wear-resistant resin adhesive: At room temperature, first stir the single-walled carbon nanotubes, multi-walled carbon nanotubes, 3-aminopropyltriethoxysilane, high-molecular-weight polymer alkyl ammonium salt, propylene glycol, acetone, alcohol, and acetone at a rotation speed of 1250 r / min. After stirring for 0.65 h, a gel is prepared for standby. Mix and stir the remaining all materials at 70 °C for 2.35 h, then cool down to room temperature, add the prepared gel, and stir at a rotation speed of 1300 r / min for 0.75 h at room temperature to obtain a high-toughness wear-resistant resin adhesive;

[0129] c. Preparation of a high-toughness wear-resistant resin fiber fabric prepreg: Put the fiber fabrics (i.e., E-type fiberglass cloth, E-type high-strength fiberglass cloth, E-type fiberglass square cloth, S-type fiberglass cloth, nylon fiber cloth) coated with the high-toughness wear-resistant resin adhesive by a vertical sizing machine into a drying oven. The drying oven is 50 m long and divided into 4 sections, each section being 12.5 m. The baking temperature range is 80 °C to 175 °C, where the first section is 80 °C to 105 °C, the second section is 115 °C to 135 °C, the third section is 145 °C to 175 °C, and the fourth section is 100 °C to 110 °C. The speed of the sizing machine is 21 m / min to obtain a high-toughness wear-resistant resin fiber fabric prepreg. Pre-dry the drying oven before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0130] d. Preparation of a high-toughness wear-resistant laminate: Preheat the mold at 125 °C to 155 °C, and overlap and place the high-toughness wear-resistant resin fiber fabric prepregs (i.e., E-type fiberglass cloth prepreg, E-type fiberglass square cloth prepreg, E-type high-strength fiberglass cloth prepreg, S-type fiberglass cloth prepreg, nylon fiber cloth prepreg in a ratio of 3:1:2:2:4) in the mold. After closing the mold, hot press and form at 140 °C to 185 °C and 1 MPa to 25 MPa for 0.5 h to 50 h to obtain a high-toughness wear-resistant laminate.

[0131] Example 15:

[0132] A method for preparing a high-toughness wear-resistant laminate, comprising the following steps:

[0133] a. Ingredients: Prepare 15 parts of glycidyl epoxy resin, 6 parts of biphenyl epoxy resin, 18 parts of phenolic epoxy resin, 4 parts of benzoxazine resin, 7 parts of xylene-modified phenolic resin, 3 parts of boron-modified phenolic resin, 9 parts of diaminodiphenyl sulfone, 7 parts of cashew phenol curing agent, 5 parts of active ester curing agent, 7 parts of single-walled carbon nanotubes, 5 parts of multi-walled carbon nanotubes, 8 parts of nano-talc powder, 8 parts of nano-montmorillonite, 4 parts of nano-kaolin, 3 parts of nano-tungsten nitride, 5 parts of 3-aminopropyltriethoxysilane, 3 parts of high molecular weight polymer alkyl ammonium salt, 3 parts of methyl ethyl ketone, 5 parts of alcohol, 4 parts of methyl butyl ketone, and 2.5 parts of acetone;

[0134] b. Preparation of high-toughness wear-resistant resin adhesive: At room temperature, first stir the single-walled carbon nanotubes, multi-walled carbon nanotubes, 3-aminopropyltriethoxysilane, high molecular weight polymer alkyl ammonium salt, methyl ethyl ketone, alcohol, methyl butyl ketone, and acetone at a speed of 1000 r / min for 1.25 h to form a gel for standby. Mix and stir the remaining all materials at 60 °C for 1.15 h, then cool down to room temperature, add the prepared gel, and stir at a speed of 900 r / min for 0.65 h at room temperature to obtain a high-toughness wear-resistant resin adhesive;

[0135] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: Put the fiber fabrics (i.e., E-glass fiber cloth, E-glass fiber mat, E-glass fiber square cloth, S-glass fiber cloth, S-high-strength glass fiber cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive through a vertical sizing machine into a drying oven. The drying oven is 50 m long and divided into 4 sections, each section being 12.5 m. The baking temperature ranges from 80 °C to 175 °C, where the first section is 80 °C to 105 °C, the second section is 115 °C to 135 °C, the third section is 145 °C to 175 °C, and the fourth section is 100 °C to 110 °C. The speed of the sizing machine is 14 m / min to obtain a high-toughness wear-resistant resin fiber fabric prepreg. Pre-dry the drying oven before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0136] d. Preparation of high-toughness wear-resistant laminate: Preheat the mold at 125 °C to 155 °C, and stack the high-toughness wear-resistant resin fiber fabric prepregs (i.e., E-glass fiber cloth prepreg: E-glass fiber mat prepreg: E-glass fiber square cloth prepreg: S-glass fiber cloth prepreg: S-high-strength glass fiber cloth prepreg: nylon fiber cloth prepreg is 2:2:2:1:1:12) in the mold. After closing the mold, hot press and form at 140 °C to 185 °C and 1 MPa to 25 MPa for 0.5 h to 50 h to obtain a high-toughness wear-resistant laminate.

[0137] Example 16:

[0138] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0139] a. Ingredients: prepare 16 parts of glycidyl ester epoxy resin, 7 parts of amino epoxy resin, 9 parts of phenolic epoxy resin, 8 parts of biphenyl epoxy resin, 7 parts of boron-modified phenolic resin, 5 parts of xylene-modified phenolic resin, 8 parts of benzoxazine resin, 3 parts of xylene-modified phenolic resin, 5 parts of diaminodiphenyl sulfone, 8 parts of cardanol curing agent, 9 parts of active ester curing agent, 1 part of single-walled carbon nanotubes, 3.5 parts of multi-walled carbon nanotubes, 2 parts of nano-talc powder, 1 part of nano-montmorillonite, 1 part of nano-vermiculite, 1 part of nano-kaolin, 45 parts of nano-tungsten nitride, 1 part of high molecular weight polymer alkyl ammonium salt, 2 parts of 3-aminopropyltriethoxysilane, 2 parts of 3-glycidyloxypropyltrimethoxysilane, 2 parts of methyl ethyl ketone, 1 part of butanone, 2 parts of alcohol, 1 part of acetone, and 2.5 parts of propylene glycol;

[0140] b. Preparation of a high-toughness, wear-resistant resin adhesive: First, at room temperature, stir the single-walled carbon nanotubes, multi-walled carbon nanotubes, high molecular weight polymer alkyl ammonium salt, 3-aminopropyl triethoxysilane, 3-glycidyloxypropyl trimethoxysilane, methyl ethyl ketone, butanone, alcohol, acetone, and propylene glycol at 910 r / min for 1.45 hours to form a gel for later use. Mix all the remaining materials at 55°C for 1.75 hours, then cool to room temperature, add the prepared gel, and stir at 850 r / min at room temperature for 0.85 hours to obtain a high-toughness, wear-resistant resin adhesive.

[0141] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: The fiber fabric (i.e., E-type glass fiber cloth, E-type glass fiber woven cloth, E-type glass fiber felt, E-type high-strength glass fiber cloth, S-type glass fiber cloth, S-type high-strength glass fiber cloth, nylon fiber cloth) coated with high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel. The drying tunnel is 50m long and divided into 4 sections, each 12.5m long. The baking temperature range is 80℃~175℃, of which the first section is 80℃~105℃, the second section is 115℃~135℃, the third section is 145℃~175℃, and the fourth section is 100℃~110℃. The speed of the gluing machine is 18m / min to obtain high-toughness wear-resistant resin fiber fabric prepreg. The drying tunnel is pre-baked before baking. The soluble resin content of the fiber fabric prepreg is greater than or equal to 95%, and the volatile matter is less than or equal to 2%;

[0142] d. Preparation of high-toughness wear-resistant laminate: preheat the mold at 125°C to 155°C, overlap and place the high-toughness wear-resistant resin fiber fabric prepreg (i.e., E-type glass fiber cloth prepreg: E-type glass fiber woven cloth prepreg: E-type glass fiber felt prepreg: E-type high-strength glass fiber cloth prepreg: S-type glass fiber cloth prepreg: S-type high-strength glass fiber cloth prepreg: nylon fiber cloth prepreg in a ratio of 1:1:3:1:2:2:1) in the mold, and after closing the mold, hot press molding is carried out at 140°C to 185°C and 1MPa to 25MPa for a time of 0.5h to 50h to obtain a high-toughness wear-resistant laminate.

[0143] The specific process parameters of Examples 1 to 16 and the technical performance test results of the high-toughness wear-resistant laminate are shown in Tables 1, 2, and 3 below respectively:

[0144] Table 1: Preparation process parameters and central control technical indicators of high-toughness wear-resistant resin fiber fabric prepreg in Example

[0145]

[0146] Table 2: Pressing process parameters of high toughness wear-resistant laminate

[0147]

[0148]

[0149] Table 3: Technical performance test data of high toughness wear-resistant laminate

[0150]

[0151] As shown in Table 1 and Table 2, the high toughness wear-resistant laminated plate of the present invention has a bending strength greater than or equal to 620 MPa at room temperature, a bending strength greater than or equal to 320 MPa at 180°C, and a notched impact strength greater than or equal to 180 KJ / m 2 , wear resistance is greater than or equal to 120 hours, and it is particularly suitable for use in the field of toughness and wear resistance.

[0152] Example 17:

[0153] A high-toughness wear-resistant laminated board, which is made by hot-pressing multiple layers of high-toughness wear-resistant resin fiber fabric prepreg at a temperature of 140° C. and a pressure of 1 MPa.

[0154] The high-toughness wear-resistant resin fiber fabric prepreg is prepared by coating a high-toughness wear-resistant resin adhesive on a fiber fabric and then baking (semi-curing);

[0155] In the high-toughness wear-resistant resin fiber fabric prepreg: the weight percentage of the high-toughness wear-resistant resin adhesive is 30%, and the weight percentage of the fiber fabric is 70%;

[0156] The high-toughness wear-resistant resin adhesive is composed of 20 parts by weight of epoxy resin, 10 parts by weight of phenolic resin, 3 parts by weight of curing agent, 5 parts by weight of nano modifier, 2 parts by weight of carbon nanotubes, 3 parts by weight of nano tungsten nitride, 4 parts by weight of modification treatment agent and 5 parts by weight of solvent;

[0157] The preparation method of the high-toughness wear-resistant resin adhesive is as follows: at room temperature, mix the carbon nanotubes, modification treatment agent and solvent and stir at a rotation speed of 600 r / min. After stirring for 0.5 h, a gel is obtained and reserved; mix the remaining all materials, namely epoxy resin, phenolic resin, curing agent, nano modifier and nano tungsten nitride, at a temperature of 50 °C and stir. After stirring for 3 h, cool down to room temperature, add the prepared gel, and stir at a rotation speed of 600 r / min at room temperature for 0.5 h to obtain the high-toughness wear-resistant resin adhesive.

[0158] Example 18:

[0159] A high-toughness wear-resistant laminate, which is prepared by hot pressing multiple layers of high-toughness wear-resistant resin fiber fabric prepregs under the conditions of a temperature of 185 °C and a pressure of 25 MPa;

[0160] The high-toughness wear-resistant resin fiber fabric prepreg is obtained by coating a high-toughness wear-resistant resin adhesive on a fiber fabric and then baking (semi-curing);

[0161] In the high-toughness wear-resistant resin fiber fabric prepreg: the weight percentage of the high-toughness wear-resistant resin adhesive is 60%, and the weight percentage of the fiber fabric is 40%;

[0162] The high-toughness wear-resistant resin adhesive is composed of 40 parts by weight of epoxy resin, 32 parts by weight of phenolic resin, 24 parts by weight of curing agent, 20 parts by weight of nano modifier, 15 parts by weight of carbon nanotubes, 45 parts by weight of nano tungsten nitride, 15 parts by weight of modification treatment agent and 15 parts by weight of solvent;

[0163] The preparation method of the high-toughness wear-resistant resin adhesive is as follows: at room temperature, mix the carbon nanotubes, the modification agent and the solvent, and stir at a rotation speed of 1300 r / min. After stirring for 2.5 h, a gel is obtained and reserved. Mix the remaining all materials, namely epoxy resin, phenolic resin, curing agent, nano-modifying agent and nano-tungsten nitride, at a temperature of 85 °C and stir. After stirring for 3 h, cool down to room temperature, add the prepared gel, and stir at a rotation speed of 1300 r / min at room temperature for 1.5 h to obtain the high-toughness wear-resistant resin adhesive.

[0164] Example 19:

[0165] A high-toughness wear-resistant laminate, which is obtained by hot pressing and forming multiple layers of high-toughness wear-resistant resin fiber fabric prepregs under the conditions of a temperature of 165 °C and a pressure of 13 MPa.

[0166] The high-toughness wear-resistant resin fiber fabric prepreg is obtained by coating a high-toughness wear-resistant resin adhesive on a fiber fabric and then baking (semi-curing).

[0167] In the high-toughness wear-resistant resin fiber fabric prepreg: the weight percentage of the high-toughness wear-resistant resin adhesive is 45%, and the weight percentage of the fiber fabric is 55%.

[0168] The high-toughness wear-resistant resin adhesive is composed of a mixture of 30 parts by weight of epoxy resin, 21 parts by weight of phenolic resin, 13 parts by weight of curing agent, 12 parts by weight of nano-modifying agent, 13 parts by weight of carbon nanotubes, 24 parts by weight of nano-tungsten nitride, 9 parts by weight of modification agent and 10 parts by weight of solvent.

[0169] The preparation method of the high-toughness wear-resistant resin adhesive is as follows: at room temperature, mix the carbon nanotubes, the modification agent and the solvent, and stir at a rotation speed of 900 r / min. After stirring for 1.5 h, a gel is obtained and reserved. Mix the remaining all materials, namely epoxy resin, phenolic resin, curing agent, nano-modifying agent and nano-tungsten nitride, at a temperature of 65 °C and stir. After stirring for 2 h, cool down to room temperature, add the prepared gel, and stir at a rotation speed of 900 r / min at room temperature for 1 h to obtain the high-toughness wear-resistant resin adhesive.

[0170] Example 20:

[0171] A preparation method of a high-toughness wear-resistant laminate includes the following steps:

[0172] a. Ingredients: Take each component raw material according to the ratio of 20 parts by weight of epoxy resin, 10 parts by weight of phenolic resin, 3 parts by weight of curing agent, 5 parts by weight of nano modifier, 2 parts by weight of carbon nanotubes, 3 parts by weight of nano tungsten nitride, 4 parts by weight of modification treatment agent and 5 parts by weight of solvent;

[0173] b. Preparation of high-toughness wear-resistant resin adhesive: At room temperature, mix the carbon nanotubes, modification treatment agent and solvent and stir at a speed of 600 r / min. After stirring for 0.5 h, a gel is prepared and reserved; Mix the remaining all materials, namely epoxy resin, phenolic resin, curing agent, nano modifier and nano tungsten nitride, at a temperature of 50 °C and stir. After stirring for 0.75 h, cool down to room temperature, add the prepared gel, and stir at a speed of 600 r / min at room temperature for 0.5 h to prepare a high-toughness wear-resistant resin adhesive;

[0174] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: Coat the high-toughness wear-resistant resin adhesive prepared in step b on the fiber fabric, and then bake to obtain a high-toughness wear-resistant resin fiber fabric prepreg;

[0175] The baking is as follows: Put the fiber fabric coated with high-toughness wear-resistant resin adhesive by a vertical sizing machine into a baking tunnel. The baking tunnel is 50 m long, divided into 4 sections, each section is 12.5 m, and the baking temperature range is 80 °C to 145 °C. Among them: the first section is 80 °C, the second section is 115 °C, the third section is 145 °C, the fourth section is 100 °C, the speed of the sizing machine is 3 m / min, and the baking tunnel is pre-baked before baking;

[0176] d. Preparation of laminate: Preheat the mold at a temperature of 125 °C, place the high-toughness wear-resistant resin fiber fabric prepreg prepared in step c in the mold according to the ratio of the number of sheets, close the mold, and hot press and form under the conditions of a temperature of 140 °C and a pressure of 1 MPa. The hot press time is 0.5 h, and a high-toughness wear-resistant laminate is obtained.

[0177] Example 21:

[0178] A preparation method of a high-toughness wear-resistant laminate, comprising the following steps:

[0179] a. Ingredients: Take each component raw material according to the ratio of 40 parts by weight of epoxy resin, 32 parts by weight of phenolic resin, 24 parts by weight of curing agent, 20 parts by weight of nano modifier, 15 parts by weight of carbon nanotubes, 45 parts by weight of nano tungsten nitride, 15 parts by weight of modification treatment agent and 15 parts by weight of solvent;

[0180] b. Preparation of a high-toughness wear-resistant resin adhesive: At room temperature, the carbon nanotubes, the modifying agent, and the solvent were mixed and stirred at a speed of 1300 r / min for 2.5 hours to obtain a gel for later use; all the remaining materials, namely the epoxy resin, phenolic resin, curing agent, nano-modifier, and nano-tungsten nitride, were mixed and stirred at a temperature of 85° C., stirred for 3 hours, and then cooled to room temperature. The prepared gel was added and stirred at a speed of 1300 r / min for 1.5 hours at room temperature to obtain a high-toughness wear-resistant resin adhesive;

[0181] c. Preparing a high-toughness wear-resistant resin fiber fabric prepreg: coating the high-toughness wear-resistant resin adhesive prepared in step b on the fiber fabric, and then baking to obtain a high-toughness wear-resistant resin fiber fabric prepreg;

[0182] The baking process comprises: placing the fiber fabric coated with a high-toughness wear-resistant resin adhesive by a vertical gluing machine into a drying tunnel, wherein the drying tunnel is 50 meters long and divided into four sections, each section being 12.5 meters long, wherein the first section is 105° C., the second section is 135° C., the third section is 175° C., and the fourth section is 110° C. The speed of the gluing machine is between 3 m / min and 24 m / min, and the drying tunnel is pre-baked before baking;

[0183] d. Preparation of laminated boards: preheating the mold at a temperature of 125°C to 155°C, placing the high-toughness wear-resistant resin fiber fabric prepregs prepared in step c in the mold in an overlapping manner according to the number of sheets, and after closing the mold, hot pressing is performed at a temperature of 140°C to 185°C and a pressure of 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminated board.

[0184] Example 22:

[0185] A method for preparing a high-toughness wear-resistant laminate comprises the following steps:

[0186] a. Ingredients: Prepare the following ingredients: 30 parts by weight of epoxy resin, 21 parts by weight of phenolic resin, 14 parts by weight of curing agent, 13 parts by weight of nano-modifier, 9 parts by weight of carbon nanotubes, 24 parts by weight of nano-tungsten nitride, 10 parts by weight of modifying agent, and 10 parts by weight of solvent;

[0187] b. Preparation of a high-toughness wear-resistant resin adhesive: at room temperature, the carbon nanotubes, the modifying agent, and the solvent were mixed and stirred at a speed of 950 r / min for 1.5 hours to obtain a gel for later use; all the remaining materials, namely the epoxy resin, phenolic resin, curing agent, nano-modifier, and nano-tungsten nitride, were mixed and stirred at a temperature of 65° C., stirred for 2 hours, cooled to room temperature, and the prepared gel was added. The mixture was stirred at a speed of 950 r / min at room temperature for 1 hour to obtain a high-toughness wear-resistant resin adhesive;

[0188] c. Preparation of high-toughness wear-resistant resin fiber fabric prepreg: Coat the high-toughness wear-resistant resin adhesive obtained in step b on the fiber fabric, and then bake it to obtain the high-toughness wear-resistant resin fiber fabric prepreg;

[0189] The baking is as follows: Put the fiber fabric coated with the high-toughness wear-resistant resin adhesive by a vertical sizing machine into a baking tunnel. The baking tunnel is 50 m long, divided into 4 sections, each section being 12.5 m. The baking temperature range is 92°C to 160°C, where: the first section is 92°C, the second section is 125°C, the third section is 160°C, and the fourth section is 105°C. The speed of the sizing machine is 3 m / min to 24 m / min. Pre-bake the baking tunnel before baking;

[0190] d. Preparation of laminate: Preheat the mold at 140°C, place the high-toughness wear-resistant resin fiber fabric prepreg obtained in step c in the mold in an overlapping manner according to the number of sheets, and after closing the mold, perform hot pressing and molding under the conditions of a temperature of 165°C and a pressure of 13 MPa. The hot pressing time is 26 h, thus obtaining the high-toughness wear-resistant laminate.

[0191] In the above Examples 17 - 22:

[0192] The epoxy resin is any one or a mixture of two or more of glycidyl epoxy resin, amino epoxy resin, biphenyl-type epoxy resin, and phenolic-type epoxy resin;

[0193] The phenolic resin is any one or a mixture of two or more of boron-modified phenolic resin, xylene-modified phenolic resin, and benzoxazine resin;

[0194] The curing agent is any one or a mixture of two or more of diaminodiphenyl sulfone, cashew phenol curing agent, and active ester curing agent;

[0195] The nano modifier is any one or a mixture of two or more of nano-montmorillonite, nano-vermiculite, nano-talc powder, and nano-kaolin;

[0196] The carbon nanotubes are single-walled carbon nanotubes or / and multi-walled carbon nanotubes;

[0197] The modification treatment agent is any one or a mixture of two or more of 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and high molecular weight polymer alkyl ammonium salt;

[0198] The solvent is any one or a mixture of two or more of methyl ethyl ketone, butanone, acetone, propylene glycol, and alcohol (i.e., ethanol).

[0199] In the above-mentioned Examples 17-22: The fiber fabric is a glass fiber fabric or a nylon fiber cloth, and any ratio of the number of sheets used is (1-10):(1-10); among them, the glass fiber fabric is at least one of E-type glass fiber cloth, E-type glass fiber square cloth, E-type glass fiber felt, E-type high-strength glass fiber cloth, S-type glass fiber cloth, and S-type high-strength glass fiber cloth.

[0200] In the above-mentioned Examples 17-22: The multi-layer is 2-300 layers.

[0201] In the above-mentioned Examples 20-22: In the high-toughness wear-resistant resin fiber fabric prepreg prepared in step c, the weight percentage of the high-toughness wear-resistant resin adhesive is one of 30%-60%, and the fiber fabric is one of 40%-70%, and the sum of the weight percentages of the two is 100%.

[0202] The above is only the preferred embodiment of the present invention. It should be understood that the present invention is not limited to the form disclosed herein, should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be changed within the scope of the concept described herein through the above teachings or the technology or knowledge in the relevant field. And the changes and modifications made by those skilled in the art that do not depart from the spirit and scope of the present invention should all be within the protection scope of the appended claims of the present invention.

[0203] In the above-mentioned examples: In the percentage ratios used, unless otherwise specified, they are all mass (weight) percentage ratios or percentage ratios well-known to those skilled in the art; in the ratios used, unless otherwise specified, they are all mass (weight) ratios; the weight parts can all be grams or kilograms.

[0204] In the above-mentioned examples: For the process parameters (temperature, time, concentration, etc.) and the numerical values of the amounts of each component in each step that are in a range, any point can be applied.

[0205] The technical content not specifically described in the content of the present invention and the above-mentioned examples is the same as the prior art, and the raw materials are all commercially available products.

[0206] The present invention is not limited to the above-mentioned examples, and all the content described in the present invention can be implemented and has the above-mentioned good effects.

Claims

1. A high-toughness wear-resistant laminate, characterized by: The high toughness wear-resistant laminate is a multi-layer high toughness wear-resistant resin fiber fabric prepreg at a temperature of 140 ℃ ～ High-toughness wear-resistant laminated board made by hot pressing at 185℃ and pressure of 1MPa~25MPa; The high-toughness wear-resistant resin fiber fabric prepreg is prepared by coating a high-toughness wear-resistant resin adhesive on a fiber fabric and then baking the fabric. In the high-toughness wear-resistant resin fiber fabric prepreg: the weight percentage of the high-toughness wear-resistant resin adhesive is 30% ～ 60%, the weight percentage of the fiber fabric is 40% ～ 70%; The high-toughness wear-resistant resin adhesive is composed of 20 to 40 parts by weight of epoxy resin, 10 to 32 parts by weight of phenolic resin, 3 to 24 parts by weight of curing agent, 5 to 20 parts by weight of nano-modifier, 2 to 15 parts by weight of carbon nanotubes, 3 to 45 parts by weight of nano-tungsten nitride, 4 to 15 parts by weight of modifying agent and 5 to 15 parts by weight of solvent; The epoxy resin is any one of glycidyl ester epoxy resin, amino epoxy resin, biphenyl epoxy resin, and phenolic epoxy resin, or a mixture of two or more thereof; The phenolic resin is any one of boron-modified phenolic resin, xylene-modified phenolic resin, and benzoxazine resin, or a mixture of two or more thereof; The curing agent is any one of diaminodiphenyl sulfone, cardanol curing agent, active ester curing agent, or a mixture of two or more thereof; The nano modifier is any one of nano montmorillonite, nano vermiculite, nano talc, and nano kaolin, or a mixture of two or more thereof; The carbon nanotubes are single-walled carbon nanotubes and / or multi-walled carbon nanotubes; The modifying agent is any one of 3-aminopropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane or a mixture of the two; The solvent is any one of butanone, acetone, propylene glycol, and alcohol, or a mixture of two or more thereof.

2. The high-toughness wear-resistant laminate according to claim 1, characterized in that: The fiber fabrics are glass fiber fabrics and nylon fiber cloth, and the ratio of the number of fabrics used is 1-10:1-10.

3. The high-toughness wear-resistant laminate according to claim 1, characterized in that: The multi-layer high-toughness wear-resistant resin fiber fabric prepreg comprises 2 to 300 layers of high-toughness wear-resistant resin fiber fabric prepreg.

4. A method for preparing a high-toughness wear-resistant laminate, characterized in that: The following steps are involved: a. Ingredients: Prepare the raw materials according to the following ratios: 20-40 parts by weight of epoxy resin, 10-32 parts by weight of phenolic resin, 3-24 parts by weight of curing agent, 5-20 parts by weight of nano-modifier, 2-15 parts by weight of carbon nanotubes, 3-45 parts by weight of nano-tungsten nitride, 4-15 parts by weight of modifying agent and 5-15 parts by weight of solvent; The epoxy resin is any one of glycidyl ester epoxy resin, amino epoxy resin, biphenyl epoxy resin, and phenolic epoxy resin, or a mixture of two or more thereof; The phenolic resin is any one of boron-modified phenolic resin, xylene-modified phenolic resin, and benzoxazine resin, or a mixture of two or more thereof; The curing agent is any one of diaminodiphenyl sulfone, cardanol curing agent, active ester curing agent, or a mixture of two or more thereof; The nano modifier is any one of nano montmorillonite, nano vermiculite, nano talc, and nano kaolin, or a mixture of two or more thereof; The carbon nanotubes are single-walled carbon nanotubes and / or multi-walled carbon nanotubes; The modifying agent is any one of 3-aminopropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane or a mixture of the two; The solvent is any one of butanone, acetone, propylene glycol, and alcohol, or a mixture of two or more thereof; b. Preparation of a high-toughness wear-resistant resin adhesive: at room temperature, the carbon nanotubes, the modifying agent and the solvent are mixed and stirred at a speed of 600 r / min to 1300 r / min, and the gel is obtained after stirring for 0.5 h to 2.5 h, and the gel is set aside; all the remaining materials, namely the epoxy resin, phenolic resin, curing agent, nano-modifier and nano-tungsten nitride, are mixed and stirred at a temperature of 50° C. to 85° C., stirred for 0.75 h to 3 h, and then cooled to room temperature, and the prepared gel is added, and the mixture is stirred at a speed of 600 r / min to 1300 r / min for 0.5 h to 1.5 h at room temperature to obtain a high-toughness wear-resistant resin adhesive; c. Preparing a high-toughness wear-resistant resin fiber fabric prepreg: coating the high-toughness wear-resistant resin adhesive prepared in step b on the fiber fabric, and then baking to obtain a high-toughness wear-resistant resin fiber fabric prepreg; d. Preparation of laminated boards: preheating the mold at a temperature of 125°C to 155°C, placing the high-toughness wear-resistant resin fiber fabric prepregs prepared in step c in the mold in an overlapping manner according to the number of sheets, and after closing the mold, hot pressing is performed at a temperature of 140°C to 185°C and a pressure of 1MPa to 25MPa for 0.5h to 50h to obtain a high-toughness wear-resistant laminated board.

5. The method for preparing the high-toughness wear-resistant laminate according to claim 4, characterized in that: The baking in step c is as follows: the fiber fabric coated with a high-toughness wear-resistant resin adhesive by a vertical gluing machine is placed in a drying tunnel, wherein the drying tunnel is 50m long and divided into 4 sections, each section is 12.5m, and the baking temperature range is 80°C to 175°C, wherein: the first section is 80°C to 105°C, the second section is 115°C to 135°C, the third section is 145°C to 175°C, and the fourth section is 100°C to 110°C. The speed of the gluing machine is 3m / min to 24m / min, and the drying tunnel is pre-baked before baking.

6. The method for preparing the high-toughness wear-resistant laminate according to claim 4 or 5, characterized in that: The fiber fabrics are glass fiber fabrics and nylon fiber cloth, and the ratio of the number of fabrics used is 1-10:1-10.

7. The method for preparing the high-toughness wear-resistant laminate according to claim 4 or 5, characterized in that: In step d, 2 to 300 layers of high-toughness wear-resistant resin fiber fabric prepregs are overlapped and placed in the mold according to the ratio of the number of sheets.

8. The method for preparing the high-toughness wear-resistant laminate according to claim 4 or 5, characterized in that: In the high-toughness wear-resistant resin fiber fabric prepreg prepared in step c, the weight percentage of the high-toughness wear-resistant resin adhesive is 30% ～ 60%, the weight percentage of fiber fabric is 40% ～ 70%.

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