High-performance polyurethane composite material and preparation method thereof

Abstract

The invention discloses a high-performance polyurethane composite material and a preparation method thereof, and belongs to the technical field of composite materials, the mass ratio of a component A to a component B is 100: 45-55; the component A is prepared from the following raw materials in parts by weight: 70 to 120 parts of polyether polyol, 8 to 15 parts of chain extender, 0.5 to 1.5 parts of catalyst, 0.5 to 1 part of foam stabilizer, 10 to 20 parts of foaming agent and 2 to 5 parts of modified filler; the component B is prepared from the following raw materials in parts by weight: 10 to 20 parts of polyether polyol, 60 to 80 parts of diphenylmethane diisocyanate and 2 to 6 parts of polymethylene polyphenyl polyisocyanate; the modified filler is a phenolic alkoxy silane modified MoS2 / Ti 3C2Tx hybrid material, and the polyurethane composite material has the advantages that through the accurate formula design, the rebound resilience and the aging resistance of the obtained polyurethane composite material are obviously improved, and the internal heat generation problem is obviously improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite materials, and particularly relates to a high-performance polyurethane composite material and a preparation method thereof. Background Art

[0002] Based on the characteristics of high elasticity, excellent wear resistance (2-10 times that of NR), good ozone resistance and low-temperature performance of polyurethane (PU), the technology of casting PU elastomers to manufacture automobile tires has been widely spread. One reason is that the preparation process is simple and does not involve the use of large and complex equipment; the other reason is that compared with traditional rubber tires, polyurethane tires have the advantages of high hardness, large load-bearing capacity and high strength.

[0003] With the development of the modern logistics industry, there are higher requirements for the usage speed of polyurethane tires. The increase in tire speed causes a large amount of heat to be generated when polyurethane tires are subjected to alternating stress and friction with the ground, increasing the internal energy of the tires and raising the tire temperature. The increase in temperature will cause the strength of the polyurethane material to decrease, and moreover, the temperature will affect the phase separation degree of the polyurethane material. When the temperature rises, the phase separation degree decreases, and the elasticity of the polyurethane will deteriorate. These factors will lead to a reduction in the service life of polyurethane tires. Therefore, to meet higher usage requirements, it is necessary to reduce the internal heat generated during the use of polyurethane materials. Currently, heat-conducting fillers are usually added to the polyurethane casting material to improve the heat dissipation performance and solve the problem of large internal heat generated during the use of polyurethane materials. However, there are problems such as poor dispersion of the heat-conducting fillers and insignificant improvement effects. Summary of the Invention

[0004] The purpose of the present invention is to provide a high-performance polyurethane composite material and a preparation method thereof to solve the problem of large internal heat generated during the use of existing polyurethane materials.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A high-performance polyurethane composite material includes component A and component B, and the mass ratio of component A to component B is 100:45 - 55.

[0007] Component A includes the following raw materials in parts by weight: 70 - 120 parts of polyether polyol, 8 - 15 parts of chain extender, 0.5 - 1.5 parts of catalyst, 0.5 - 1 part of foam stabilizer, 10 - 20 parts of foaming agent, 2 - 5 parts of modified filler;

[0008] Component B includes the following raw materials in parts by weight: 10 - 20 parts of polyether polyol, 60 - 80 parts of diphenylmethane diisocyanate, 2 - 6 parts of polymethylene polyphenyl polyisocyanate.

[0009] The modified filler is phenoxyalkoxysilane-modified MoS2 / Ti3C2Tx Hybrid material.

[0010] Furthermore, the preparation method of the modified filler includes the following steps:

[0011] Add the MoS2 / Ti3C2T x hybrid material into an ethanol solution, ultrasonically disperse for 120 min, add phenolic alkoxysilane, continue to ultrasonically disperse for 1 h, then place it at 70 - 80 °C and stir for reaction for 6 - 8 h. After the reaction ends, filter by suction, wash and dry the filter cake to obtain the modified filler.

[0012] Furthermore, during the preparation of the modified filler, the dosage ratio of the MoS2 / Ti3C2T x hybrid material, ethanol solution and phenolic alkoxysilane is 10 g : 100 - 200 mL : 0.1 - 0.3 g, the mass fraction of the ethanol solution is 95%. In order to improve the dispersion of the MoS2 / Ti3C2T x hybrid material in the polyurethane matrix, phenolic alkoxysilane is used to perform surface functionalization treatment on the MoS2 / Ti3C2T x hybrid material to improve its hydrophobic and lipophilic properties. In addition, since phenolic alkoxysilane carries a catechol structure and has antioxidant properties, introducing the modified filler into the polyurethane matrix helps to improve the aging resistance of the polyurethane material.

[0013] Furthermore, the MoS2 / Ti3C2T x hybrid material is prepared through the following steps:

[0014] Mix hydrochloric acid solution and deionized water, add sodium fluoride, stir at 60 °C until sodium fluoride is completely dissolved, then add Ti3AlC2 powder, ultrasonically disperse for 30 min, keep warm and stir magnetically for reaction for 48 h, centrifuge, wash the precipitate with deionized water and then dry it under vacuum to obtain the Ti3C2T x material;

[0015] Ultrasonically disperse the Ti3C2T x material in deionized water to obtain a dispersion. Add sodium molybdate tetrahydrate, thiourea and deionized water to the dispersion, stir evenly, adjust the pH value to 3 with hydrochloric acid solution, then transfer it to a reaction kettle lined with polytetrafluoroethylene, keep the temperature at 210 °C for 24 h, then cool to room temperature, wash the solid product obtained from the reaction, and dry it to obtain the MoS2 / Ti3C2T x hybrid material.

[0016] Furthermore, the Ti3C2T xDuring the material preparation process, the dosage ratio of hydrochloric acid solution, deionized water, sodium fluoride, and Ti3AlC2 powder is 20 - 30 mL: 20 - 30 mL: 2 g: 1.5 - 2 g, and the mass fraction of the hydrochloric acid solution is 36 - 38%.

[0017] Further, in the preparation process of the MoS2 / Ti3C2T x hybrid material, the mass ratio of Ti3C2T x material, sodium molybdate tetrahydrate, and thiourea is 10 - 50 mg: 0.12 g: 0.135 g.

[0018] Ti3C2T x material has good thermal conductivity, electrical conductivity, and thermal stability. MoS2 has good lubrication performance. Based on this, the present invention synthesizes MoS2 / Ti3C2T x hybrid material by hydrothermal method to improve the problem of high endothermic heat of polyurethane materials. Compared with physical mixing, the hydrothermal reaction makes Ti3C2T x and MoS2 form a tight combination, enhancing the interfacial interaction, which is beneficial to improving the thermal conductivity and mechanical stability of the composite material. Physical mixing is difficult to achieve tight combination between materials, and the interfacial thermal resistance is high.

[0019] Further, the phenolic alkoxysilane is prepared by the following steps:

[0020] Mix hydrochloric acid dopamine and anhydrous DMF, then add triethylamine, ultrasonically treat for 5 min, filter to remove the generated triethylamine hydrochloride precipitate, transfer the filtrate to a flask, under nitrogen protection, stir at a temperature of 45 - 50 °C, and dropwise add 3 - isocyanatopropyltrimethoxysilane to the filtrate. After the addition is complete, keep stirring and reacting for 4 - 6 h. After the reaction is completed, rotary evaporate to remove DMF to obtain phenolic alkoxysilane.

[0021] Further, the dosage ratio of hydrochloric acid dopamine, anhydrous DMF, triethylamine, and 3 - isocyanatopropyltrimethoxysilane is 0.1 mol: 180 - 250 mL: 0.2 - 0.3 mol: 0.11 mol. Phenolic alkoxysilane is prepared from hydrochloric acid dopamine and 3 - isocyanatopropyltrimethoxysilane through the coupling reaction of isocyanate group and amino group.

[0022] Further, the polyether polyol is a polytetrahydrofuran ether polyol with a functionality of 2 - 3, a number average molecular weight of 10000 - 20000 g / mol, and is selected from at least one of PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000, and PTMG3000 of Mitsubishi Chemical Corporation, Japan.

[0023] Further, the chain extender is at least one of ethylene glycol, glycerol, 1,4-butanediol, diethylene glycol, and cyclohexanediol.

[0024] Further, the catalyst is at least one of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, dibutyltin bis(dodecyl mercaptide), dibutyltin dimercaptoacetate, and dioctyltin dimercaptoacetate.

[0025] Further, the foam stabilizer is one or a mixture of several of B8900 (commercially available, Evonik Specialty Chemicals Co., Ltd.), B8946 (commercially available, Evonik Specialty Chemicals Co., Ltd.), and B8707LF2 (commercially available, Evonik Specialty Chemicals Co., Ltd.).

[0026] Further, the foaming agent is HCFC-141b or dichloromethane.

[0027] Further, the polymethylene polyphenyl polyisocyanate is at least one of Huntsman 5005, Wanhua PM130, Wanhua PM200, and BASF M20S.

[0028] The preparation method of the above high-performance polyurethane composite material includes the following steps:

[0029] S1. Prepare component A: Add polyether polyol into a reaction kettle, stir and heat up to 90-100 °C, dehydrate and degas under vacuum conditions for 2-3 h, cool down to room temperature, add a chain extender, a catalyst, a foam stabilizer, a foaming agent, and a modified filler under stirring, stir for 1-2 h and then seal and store.

[0030] S2. Prepare component B: Add polyether polyol into a reaction kettle, stir and heat up to 90-100 °C, dehydrate and degas under vacuum conditions for 2-3 h, cool down to 40 °C, add diphenylmethane diisocyanate, heat up to 80-85 °C and stir and react for 2-3 h, add polymethylene polyphenyl polyisocyanate, stir and react until the mass content of -NCO reaches 20-30%, cool down to 40-50 °C, and seal and store.

[0031] S3. Heat the tire mold to 50-55 °C. Under the condition that the tire mold rotates, mix component A and component B according to the mass ratio and pour them into the tire mold. After 5 min, stop the rotation of the mold, let it stand for 30-60 min, and then open the mold to obtain the high-performance polyurethane composite material.

[0032] The beneficial effects of the present invention:

[0033] The present invention provides a high-performance polyurethane composite material. Through precise formulation design, the resilience and aging resistance of the obtained polyurethane composite material are significantly improved, and the problem of internal heat generation is significantly improved. The main reason is that a modified filler is added to component A, and the modified filler is MoS2 / Ti3C2T x hybrid material modified by phenoxyalkoxysilane. After being modified by phenoxyalkoxysilane, the dispersion of MoS2 / Ti3C2T x hybrid material in the polyurethane system is significantly improved, which helps to form a heat conduction network and improve the heat dissipation performance of the polyurethane composite material; and the catechol structure carried by phenoxyalkoxysilane has good antioxidant properties, which can improve the aging resistance of the polyurethane composite material; the lamellar structure of MoS2 / Ti3C2T x hybrid material can block the damage of heat and oxygen to the molecular structure of polyurethane, and improve the aging resistance of the polyurethane composite material; in addition, the lubricating property of MoS2 helps to reduce frictional heat generation and further reduce the internal heat generation of the polyurethane composite material;

[0034] Compared with physical mixing, in the present invention, hydrothermal reaction is used to form a tight bond between Ti3C2T x and MoS2 to obtain MoS2 / Ti3C2T x hybrid material, enhancing the interfacial interaction, which is beneficial to improving the thermal conductivity and mechanical stability of the composite material. Physical mixing is difficult to achieve tight bonding between materials, and the interfacial thermal resistance is high, resulting in an insignificant improvement in the problem of internal heat generation of the polyurethane composite material. Specific Embodiments

[0035] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application clearer, the present application will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0036] The technical solutions of the present application will be described below through specific examples and comparative examples.

[0037] Preparation Example 1

[0038] A modified filler, the preparation method steps are as follows:

[0039] Add 10 g of MoS2 / Ti3C2T x hybrid material to 100 mL of 95 wt% ethanol solution, ultrasonically disperse for 120 min, add 0.1 g of phenoxyalkoxysilane, continue ultrasonically disperse for 1 h, then place it under stirring reaction at 70 °C for 6 h. After the reaction is completed, filter by suction, wash the filter cake three times with anhydrous ethanol and deionized water respectively, and finally dry it to constant weight at 80 °C to obtain the modified filler.

[0040] The MoS2 / Ti3C2T x hybrid material is prepared through the following steps:

[0041] Mix 200 mL of 36 wt% hydrochloric acid solution and 200 mL of deionized water, then add 20 g of sodium fluoride. Stir at 60 °C until the sodium fluoride is completely dissolved. After that, add 15 g of Ti3AlC2 powder. After ultrasonic treatment for 30 min, keep the temperature and stir magnetically for 48 h, then centrifuge. Wash the precipitate with deionized water and then dry it under vacuum to obtain the Ti3C2T x material;

[0042] Disperse 10 g of the Ti3C2T x material ultrasonically in 1 L of deionized water to obtain a dispersion. Add 120 g of sodium molybdate tetrahydrate, 135 g of thiourea and 1 L of deionized water to the dispersion. After stirring evenly, adjust the pH value to 3 with 0.1 mol / L hydrochloric acid solution, then transfer it to a reaction kettle lined with polytetrafluoroethylene. Keep the temperature at 210 °C for 24 h, and then cool it to room temperature. Centrifuge and wash the solid product obtained from the reaction successively with deionized water and absolute ethanol. Finally, dry it at 50 °C to constant weight to obtain the MoS2 / Ti3C2T x hybrid material.

[0043] The phenolic alkoxysilane is prepared through the following steps:

[0044] Mix 0.1 mol of dopamine hydrochloride and 180 mL of anhydrous DMF, then add 0.2 mol of triethylamine. Perform ultrasonic treatment for 5 min, and filter to remove the precipitated triethylamine hydrochloride. Transfer the filtrate to a flask, protect it with nitrogen, and under stirring at 45 °C, dropwise add 0.11 mol of 3-isocyanatopropyltrimethoxysilane to the filtrate. After the addition is complete, keep the temperature and stir for 4 h. After the reaction ends, remove DMF by rotary evaporation to obtain the phenolic alkoxysilane.

[0045] Preparation Example 2

[0046] A modified filler, and the preparation method steps are as follows:

[0047] Add 10 g of the MoS2 / Ti3C2T x hybrid material to 150 mL of 95 wt% ethanol solution, ultrasonically disperse for 120 min, add 0.2 g of phenolic alkoxysilane, continue to ultrasonically disperse for 1 h, then place it at 75 °C and stir for 7 h. After the reaction ends, filter, wash the filter cake three times with absolute ethanol and deionized water respectively, and finally dry it at 80 °C to constant weight to obtain the modified filler.

[0048] The MoS2 / Ti3C2T x hybrid material is prepared through the following steps:

[0049] Mix 250 mL of 37 wt% hydrochloric acid solution and 250 mL of deionized water, add 20 g of sodium fluoride, stir at 60 °C until the sodium fluoride is completely dissolved, then add 18 g of Ti3AlC2 powder. After ultrasonic treatment for 30 min, keep the temperature and stir magnetically for 48 h, centrifuge, wash the precipitate, and then dry it under vacuum to obtain Ti3C2T x material;

[0050] Disperse 15 g of Ti3C2T x material ultrasonically in 1 L of deionized water to obtain a dispersion. Add 120 g of sodium molybdate tetrahydrate, 135 g of thiourea and 1 L of deionized water to the dispersion, stir evenly, adjust the pH value to 3 with 0.1 mol / L hydrochloric acid solution, and then transfer it to a reaction kettle lined with polytetrafluoroethylene. Keep the temperature at 210 °C for 24 h, then cool to room temperature. Centrifuge and wash the solid product obtained from the reaction with deionized water and absolute ethanol in turn, and finally dry it at 50 °C to constant weight to obtain MoS2 / Ti3C2T x hybrid material.

[0051] The preparation method of the phenolic alkoxysilane is the same as that of Preparation Example 1.

[0052] Preparation Example 3

[0053] A modified filler, the preparation method steps are as follows:

[0054] Add 10 g of MoS2 / Ti3C2T x hybrid material to 200 mL of 95 wt% ethanol solution, ultrasonically disperse for 120 min, add 0.3 g of phenolic alkoxysilane, continue to ultrasonically disperse for 1 h, then place it at 80 °C and stir for 8 h. After the reaction, filter by suction, wash the filter cake three times with absolute ethanol and deionized water respectively, and finally dry it at 80 °C to constant weight to obtain the modified filler.

[0055] The preparation methods of the MoS2 / Ti3C2T x hybrid material and the phenolic alkoxysilane are the same as those of Preparation Example 1.

[0056] Control Example 1

[0057] A modified filler, the preparation method steps are as follows:

[0058] Add 10 g of MoS2 / Ti3C2T x hybrid material to 100 mL of 95 wt% ethanol solution, ultrasonically disperse for 120 min, add 0.1 g of 3-isocyanatopropyltrimethoxysilane, continue to ultrasonically disperse for 1 h, then place it at 70 °C and stir for 6 h. After the reaction, filter by suction, wash the filter cake three times with absolute ethanol and deionized water respectively, and finally dry it at 80 °C to constant weight to obtain the modified filler.

[0059] Comparative Example 2

[0060] A modified filler, compared with Preparation Example 1, is only different in that the MoS2 / Ti3C2T x hybrid material in Preparation Example 1 is replaced with an equal mass of Ti3C2T x material.

[0061] Comparative Example 3

[0062] A modified filler, compared with Preparation Example 1, is only different in that the MoS2 / Ti3C2T x hybrid material in Preparation Example 1 is replaced with an equal mass of MoS2 nanosheets.

[0063] Comparative Example 4

[0064] A modified filler, compared with Preparation Example 1, is only different in that the MoS2 / Ti3C2T x hybrid material in Preparation Example 1 is replaced with an equal mass of a mixture composed of MoS2 nanosheets and Ti3C2T x materials in a mass ratio of 1:3.46.

[0065] Example 1

[0066] A high-performance polyurethane composite material, including component A and component B, and the mass ratio of component A to component B is 100:45.

[0067] Component A includes the following raw materials in parts by weight: 70 parts of polyether polyol, 8 parts of ethylene glycol, 0.5 part of dibutyltin dilaurate, 0.5 part of foam stabilizer, 10 parts of foaming agent, and 2 parts of the modified filler of Preparation Example 1;

[0068] Component B includes the following raw materials in parts by weight: 10 parts of polyether polyol, 60 parts of diphenylmethane diisocyanate, and 2 parts of polymethylene polyphenyl polyisocyanate.

[0069] The preparation method of the above high-performance polyurethane composite material includes the following steps:

[0070] S1. Prepare component A: Add polyether polyol into a reaction kettle, stir and heat up to 90°C, dehydrate and degas under vacuum conditions for 2 h, cool down to room temperature, and add ethylene glycol, dibutyltin dilaurate, foam stabilizer, foaming agent and modified filler under stirring, and seal and store after stirring for 1 h;

[0071] S2. Prepare Component B: Add polyether polyol into a reaction kettle, stir and heat up to 90 °C, dehydrate and degas under vacuum conditions for 2 h, cool down to 40 °C, add diphenylmethane diisocyanate, heat up to 80 °C and stir for reaction for 2 h, add polymethylene polyphenyl polyisocyanate, stir and react until the mass content of -NCO reaches 20%, cool down to 40 °C, and store it sealed;

[0072] S3. Heat the tire mold to 50 °C. Under the condition that the tire mold rotates, mix Component A and Component B according to the mass ratio and pour them into the tire mold. After 5 min, stop the rotation of the mold, let it stand for 30 min, and then open the mold to obtain a high-performance polyurethane composite material.

[0073] The polyether polyol is PTMG1000 of Mitsubishi Chemical of Japan, the foam stabilizer is B8900, the blowing agent is HCFC-141b, and the polymethylene polyphenyl polyisocyanate is Huntsman 5005.

[0074] Example 2

[0075] A high-performance polyurethane composite material, including Component A and Component B, and the mass ratio of Component A to Component B is 100:50.

[0076] Component A includes the following raw materials in parts by weight: 90 parts of polyether polyol, 10 parts of glycerol, 1 part of dibutyltin dilaurate, 0.8 part of foam stabilizer, 15 parts of blowing agent, and 3.5 parts of the modified filler of Preparation Example 1;

[0077] Component B includes the following raw materials in parts by weight: 15 parts of polyether polyol, 70 parts of diphenylmethane diisocyanate, and 4 parts of polymethylene polyphenyl polyisocyanate.

[0078] The preparation method of the above high-performance polyurethane composite material includes the following steps:

[0079] S1. Prepare Component A: Add polyether polyol into a reaction kettle, stir and heat up to 100 °C, dehydrate and degas under vacuum conditions for 3 h, cool down to room temperature, add glycerol, dibutyltin dilaurate, foam stabilizer, blowing agent and modified filler under stirring, and store it sealed after stirring for 2 h;

[0080] S2. Prepare Component B: Add polyether polyol into a reaction kettle, stir and heat up to 100 °C, dehydrate and degas under vacuum conditions for 3 h, cool down to 40 °C, add diphenylmethane diisocyanate, heat up to 85 °C and stir for reaction for 3 h, add polymethylene polyphenyl polyisocyanate, stir and react until the mass content of -NCO reaches 30%, cool down to 50 °C, and store it sealed;

[0081] S3. Heat the tire mold to 55°C. Under the condition that the tire mold is rotating, mix component A and component B according to the mass ratio and then pour them into the tire mold. After 5 minutes, stop the rotation of the mold. After standing for 60 minutes, open the mold to obtain a high-performance polyurethane composite material.

[0082] The polyether polyol is PTMG1300 of Mitsubishi Chemical Corporation of Japan, the foam stabilizer is B8900, the blowing agent is HCFC-141b, and the polymethylene polyphenyl polyisocyanate is Huntsman 5005.

[0083] Example 3

[0084] A high-performance polyurethane composite material includes component A and component B, and the mass ratio of component A to component B is 100:55.

[0085] Component A includes the following raw materials in parts by weight: 120 parts of polyether polyol, 15 parts of 1,4-butanediol, 1.5 parts of dibutyltin dilaurate, 1 part of foam stabilizer, 20 parts of blowing agent, and 5 parts of the modified filler of Preparation Example 1;

[0086] Component B includes the following raw materials in parts by weight: 20 parts of polyether polyol, 80 parts of diphenylmethane diisocyanate, and 6 parts of polymethylene polyphenyl polyisocyanate.

[0087] The preparation method of the above high-performance polyurethane composite material is the same as that of Example 1.

[0088] The polyether polyol is PTMG1500 of Mitsubishi Chemical Corporation of Japan, the foam stabilizer is B8900 (commercially available, Evonik Specialty Chemicals Co., Ltd.), the blowing agent is HCFC-141b or dichloromethane, and the polymethylene polyphenyl polyisocyanate is Wanhua PM130.

[0089] Example 4

[0090] A high-performance polyurethane composite material, compared with Example 1, is only different in that the modified filler in Example 1 is replaced with the product in Preparation Example 2 in equal parts by weight.

[0091] Example 5

[0092] A high-performance polyurethane composite material, compared with Example 1, is only different in that the modified filler in Example 1 is replaced with the product in Preparation Example 3 in equal parts by weight.

[0093] Example 6

[0094] A high-performance polyurethane composite material, compared with Example 1, is only different in that the weight part of the modified filler in Example 1 is adjusted from "2 parts" to "3.5 parts".

[0095] Example 7

[0096] A high-performance polyurethane composite material, compared with Example 1, the difference is only that the weight part of the foaming agent in Example 1 is adjusted from "10 parts" to "15 parts".

[0097] Example 8

[0098] A high-performance polyurethane composite material, compared with Example 3, the difference is only that the weight part of the modified filler in Example 3 is adjusted from "5 parts" to "2 parts".

[0099] Comparative Example 1

[0100] A high-performance polyurethane composite material, compared with Example 1, the difference is only that the modified filler in Example 1 is replaced with the product in Comparative Example 1 in an equal weight part.

[0101] Comparative Example 2

[0102] A high-performance polyurethane composite material, compared with Example 1, the difference is only that the modified filler in Example 1 is replaced with the product in Comparative Example 2 in an equal weight part.

[0103] Comparative Example 3

[0104] A high-performance polyurethane composite material, compared with Example 1, the difference is only that the modified filler in Example 1 is replaced with the product in Comparative Example 3 in an equal weight part.

[0105] Comparative Example 4

[0106] A high-performance polyurethane composite material, compared with Example 1, the difference is only that the modified filler in Example 1 is replaced with the product in Comparative Example 4 in an equal weight part.

[0107] Performance tests were carried out on the polyurethane composite materials obtained in Examples 1 - 8 and Comparative Examples 1 - 4, and the test process is as follows:

[0108] Tensile strength: Tested in accordance with GB / T 6344-2008 "Determination of Tensile Strength and Elongation at Break of Flexible Cellular Plastics".

[0109] Compression set: Tested in accordance with GB / T 10653-2001 "Testing of Compression Set of Cellular Elastomeric Materials".

[0110] Wet heat aging resistance: Treated at a temperature of 85 °C and a humidity of 85% for 500 h, and the tensile strength loss rate was calculated.

[0111] Endurance test temperature: The forklift wheel products prepared from the polyurethane composite materials of Examples 1-8 and Comparative Examples 1-4 were respectively installed on a tracked trolley. The trolley was loaded with 700 kg and the trolley was made to run at a speed of 4 km / h on a flat surface for the experiment. The temperature rise of the forklift wheel products was measured in real time, and their long-term operation and stable temperature were observed to determine the dynamic internal heat generation performance of the tires.

[0112] The results are shown in Table 1:

[0113] Table 1

[0114]

[0115] It can be seen from the records in Table 1 that the polyurethane composite materials for tires prepared in Examples 1-8 have both low heat generation, high mechanical properties, good resilience and aging resistance. Specifically, from the test results of Example 1 and Comparative Example 1, it can be seen that during the preparation of the modified filler, phenoxyalkoxysilane was replaced by 3-isocyanatopropyltrimethoxysilane. The isocyanate in 3-isocyanatopropyltrimethoxysilane participates in the cross-linking reaction of polyurethane, increasing the cross-linking density of the polyurethane system, resulting in a decrease in elasticity. And due to the lack of catechol groups, the aging resistance performance significantly decreases; from the test results of Example 1 and Comparative Example 2, it can be seen that when the MoS2 / Ti3C2T x hybrid material was replaced with an equal mass of Ti3C2T x material, due to the lack of MoS2, the frictional heat increases, resulting in a significant deterioration of the internal heat generation performance. From the test results of Example 1 and Comparative Example 3, it can be seen that when the MoS2 / Ti3C2T x hybrid material was replaced with an equal mass of MoS2 material, the lack of Ti3C2T x material prevents the formation of a heat conduction network, resulting in a significant deterioration of the internal heat generation performance. From the test results of Example 1 and Comparative Example 4, it can be seen that compared with physical mixing, through hydrothermal reaction, a tight combination is formed between Ti3C2T x and MoS2 to obtain the MoS2 / Ti3C2T x hybrid material, enhancing the interfacial interaction, which is beneficial to improving the thermal conductivity and mechanical stability of the composite material. Physical mixing is difficult to achieve tight combination between materials, with a high interfacial thermal resistance, and the internal heat generation performance of the composite material deteriorates slightly.

[0116] It should be noted that in this text, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, such that a process, method, article or device comprising a series of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article or device.

[0117] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A high-performance polyurethane composite material, comprising component A and component B, characterized in that, The mass ratio of component A to component B is 100:45 - 55; Component A includes the following raw materials in parts by weight: 70 - 120 parts of polyether polyol, 8 - 15 parts of chain extender, 0.5 - 1.5 parts of catalyst, 0.5 - 1 part of foam stabilizer, 10 - 20 parts of foaming agent, 2 - 5 parts of modified filler; Component B includes the following raw materials in parts by weight: 10 - 20 parts of polyether polyol, 60 - 80 parts of diphenylmethane diisocyanate, 2 - 6 parts of polymethylene polyphenyl polyisocyanate; The modified filler is a phenolic alkoxysilane-modified MoS2 / Ti3C2T x hybrid material.

2. A high-performance polyurethane composite material according to claim 1, characterized in that, The preparation method of the modified filler includes the following steps: Add the MoS2 / Ti3C2T x hybrid material into an ethanol solution, ultrasonically disperse it for 120 min, add phenolalkoxysilane, continue to ultrasonically disperse it for 1 h, then place it under stirring reaction at 70 - 80 °C for 6 - 8 h. After the reaction ends, perform suction filtration, wash and dry the filter cake to obtain the modified filler.

3. A high-performance polyurethane composite material according to claim 2, characterized in that, MoS2 / Ti3C2T x The dosage ratio of the MoS2 / Ti3C2T hybrid material, ethanol solution and phenol-based alkoxysilane is 10 g: 100 - 200 mL: 0.1 - 0.3 g.

4. A high-performance polyurethane composite material according to claim 2, characterized in that, The MoS2 / Ti3C2T x hybrid material is prepared through the following steps: Disperse the Ti3C2T x material by ultrasound in deionized water to obtain a dispersion. Add sodium molybdate tetrahydrate, thiourea and deionized water to the dispersion, stir evenly, adjust the pH value to 3 with hydrochloric acid solution, then transfer it to a reaction kettle lined with polytetrafluoroethylene, keep the temperature at 210 °C for 24 h, then cool it to room temperature, centrifuge and wash the solid product obtained from the reaction, and dry it to obtain MoS2 / Ti3C2T x hybrid material.

5. A high-performance polyurethane composite material according to claim 4, wherein, Ti3C2T x The mass ratio of the material, sodium molybdate tetrahydrate, and thiourea is 10 - 50 mg: 0.12 g: 0.135 g.

6. A high-performance polyurethane composite material according to claim 5, characterized in that, Ti3C2T x The material is made through the following steps: Mix the hydrochloric acid solution and deionized water, add sodium fluoride, stir at 60 °C until the sodium fluoride is completely dissolved, then add Ti3AlC2 powder. After ultrasonic treatment for 30 min, keep the temperature and stir magnetically for 48 h, centrifuge, wash the precipitate and dry it in vacuum to obtain Ti3C2T x material.

7. A high-performance polyurethane composite material according to claim 6, characterized in that, Ti3C2T x During the material preparation process, the dosage ratio of hydrochloric acid solution, deionized water, sodium fluoride, and Ti3AlC2 powder is 20 - 30 mL: 20 - 30 mL: 2 g: 1.5 - 2 g, and the mass fraction of the hydrochloric acid solution is 36 - 38%.

8. A high-performance polyurethane composite material according to claim 2, characterized in that, The phenolic alkoxysilane is prepared through the following steps: Mix dopamine hydrochloride and anhydrous DMF, then add triethylamine, ultrasonically treat for 5 min, filter by suction, transfer the filtrate to a flask, under nitrogen protection, stir at a temperature of 45 - 50 °C, dropwise add 3 - isocyanatopropyltrimethoxysilane to the filtrate, after the addition is complete, keep warm and stir for reaction for 4 - 6 h, after the reaction ends, rotary evaporate to remove DMF to obtain phenolic alkoxysilane.

9. The high-performance polyurethane composite material according to claim 8, characterized in that, The dosage ratio of dopamine hydrochloride, anhydrous DMF, triethylamine and 3 - isocyanatopropyltrimethoxysilane is 0.1 mol:180 - 250 mL:0.2 - 0.3 mol:0.11 mol.

10. A method for preparing a high-performance polyurethane composite material, characterized in that, For the preparation of the high - performance polyurethane composite material according to any one of claims 1 - 9, it includes the following steps: S1. Prepare component A: Add polyether polyol to a reaction kettle, stir and heat up to 90 - 100 °C, dehydrate and degas under vacuum conditions for 2 - 3 h, cool down to room temperature, add chain extender, catalyst, foam stabilizer, foaming agent and modified filler under stirring, stir for 1 - 2 h and then seal and store; S2. Prepare component B: Add polyether polyol to a reaction kettle, stir and heat up to 90 - 100 °C, dehydrate and degas under vacuum conditions for 2 - 3 h, cool down to 40 °C, add diphenylmethane diisocyanate, heat up to 80 - 85 °C and stir for reaction for 2 - 3 h, add polymethylene polyphenyl polyisocyanate, stir and react until the mass content of -NCO reaches 20 - 30%, cool down to 40 - 50 °C, seal and store; S3. Heat the tire mold to 50 - 55 °C, under the condition that the tire mold rotates, mix component A and component B according to the mass ratio and pour them into the tire mold, stop the mold rotation after 5 min, let it stand for 30 - 60 min and then open the mold to obtain the high - performance polyurethane composite material.

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