Wet-skid-resistant composite thermoplastic elastomer as well as preparation method and application thereof

Abstract

The invention relates to a wet-skid-resistant composite thermoplastic elastomer as well as a preparation method and application thereof, and belongs to the technical field of thermoplastic elastomers. The wet-skid-resistant composite thermoplastic elastomer is prepared from the following components in parts by weight: 5 to 25 parts of butyl rubber, 1 to 10 parts of liquid nitrile rubber, 1 to 10 parts of surface modified needle-shaped wollastonite, 0.2 to 1.5 parts of vulcanizing agent, 0.1 to 0.5 part of vulcanizing aid, 70 to 95 parts of thermoplastic polyurethane elastomer particles and 1 to 5 parts of compatilizer. The preparation method is simple, VOCs emission is avoided, leftover materials can be recycled, the prepared sports shoe outsole has the advantages of being excellent in wear resistance, rebound resilience, slip resistance and particularly wet-slip resistance, slipping of athletes in the sports process is effectively prevented, particularly in a humid or rainy environment, more reliable safety guarantee is provided for the athletes, and the sports shoe outsole is suitable for being used in sports. The market application value is high.

Description

Technical Field

[0001] The invention relates to an anti-slip composite thermoplastic elastomer and a preparation method and application thereof, belonging to the technical field of thermoplastic elastomers. Background Art

[0002] As the part that directly contacts the ground, the material properties of sports shoe outsoles play a decisive role in the wear resistance, skid resistance, shock absorption and service life of the shoes. At present, there are many limitations in the materials of sports shoe outsoles.

[0003] Vulcanized rubber materials are highly favored in the sports shoe market due to their excellent anti-slip, wear-resistant and rebound properties, and have shown unique advantages in the application of sports shoe outsoles. The anti-slip performance of vulcanized rubber ensures that athletes can maintain stability under various ground conditions, the wear resistance ensures the durability of the sole, and the rebound performance helps to improve the comfort of wearing and sports performance. However, there are some urgent problems to be solved in the production process of vulcanized rubber. On the one hand, the efficiency of the vulcanization process is relatively low, which to a certain extent restricts the large-scale production and wide application of vulcanized rubber materials. On the other hand, the production process is prone to produce volatile organic compounds (VOCs). This will not only pollute the production environment, but also pose a potential threat to the health of operators. Moreover, even if VOCs emissions are strictly controlled during the production process, finished shoes will still release VOCs during packaging, warehousing, and use, especially when consumers open the box, affecting the quality inspection pass rate, sales and purchasing experience of finished shoes.

[0004] When materials such as polyvinyl chloride, ethylene-vinyl acetate resin and thermoplastic polyurethane are used in the outsoles of sports shoes, their anti-skid performance, especially anti-wet skid performance, is relatively poor. This means that on wet and slippery surfaces, the anti-skid effect of these materials is difficult to achieve the ideal state, which in turn increases the risk of injury to athletes. Although polyvinyl chloride has good hardness and wear resistance, its anti-wet skid performance is unsatisfactory; ethylene-vinyl acetate resin has excellent flexibility and processing properties, but its anti-skid performance in wet and slippery environments is not ideal; thermoplastic polyurethane has attracted attention due to its excellent elasticity and wear resistance, but its anti-wet skid performance still needs to be further improved.

[0005] Therefore, a sports shoe outsole material with better mechanical strength and elasticity, better anti-slip and especially anti-wet-slip performance, and greater safety and comfort has better market application value. Summary of the invention

[0006] The object of the present invention is to provide a wet-slip resistant composite thermoplastic elastomer and its preparation method and application. It aims to prepare a composite thermoplastic elastomer by blending surface-modified acicular wollastonite, butyl rubber and liquid nitrile rubber through a dynamic vulcanization reaction, and directly injection mold the obtained elastomer into the outsole of sports shoes, so as to solve the problems of poor wear resistance, poor resilience and poor anti-slip performance of the outsole of sports shoes, as well as solve the problems of complex production process, VOC emissions and recycling of leftover materials.

[0007] The technical solution provided by the present invention is as follows: One of the objects of the present invention is to provide a wet-slip resistant composite thermoplastic elastomer, which comprises the following components in parts by weight: 5-25 parts of butyl rubber, 1-10 parts of liquid nitrile rubber, 1-10 parts of surface-modified acicular wollastonite, 0.2-1.5 parts of vulcanizing agent, 0.1-0.5 parts of vulcanization aid, 70-95 parts of thermoplastic polyurethane elastomer particles, and 1-5 parts of compatibilizer.

[0008] Further, the preparation method of the surface-modified acicular wollastonite comprises the following steps: putting acicular wollastonite into a high-speed stirrer at 90-110 °C, spraying a surface modifier into the high-speed stirrer, and stirring at high speed for 10-30 minutes, and obtaining the surface-modified acicular wollastonite after cooling.

[0009] Further, the surface modifier is one or more of silane coupling agent Si-69 (bis-[γ-(triethoxysilyl)propyl]tetrasulfide), KH550 (γ-aminopropyltriethoxysilane), KH560 (γ-methacryloxypropyltrimethoxysilane), KH570 (3-(2,3-epoxypropoxy)propyltrimethoxysilane).

[0010] Further, the mass of the surface modifier is 2-5% of the mass of the acicular wollastonite.

[0011] Further, the viscosity of the liquid nitrile rubber is 100-3000 Pa·s.

[0012] Further, the vulcanizing agent is phenolic resin or brominated phenolic resin, the vulcanization aid is stannous chloride or zinc oxide, and the compatibilizer is one or more of polypropylene grafted maleic anhydride, POE grafted maleic anhydride, SEBS grafted maleic anhydride.

[0013] Further, the thermoplastic polyurethane elastomer particles are injection molding grade or polyether type.

[0014] Another object of the present invention is to provide a preparation method of the above-mentioned wet-slip resistant composite thermoplastic elastomer, which comprises the following steps: (1)Mix the surface-modified acicular wollastonite, butyl rubber, liquid nitrile rubber, vulcanizing agent and vulcanization accelerator to obtain a kneaded material; (2)Put the kneaded material into a rubber granulator, and while cutting into particles, mix in surface-modified acicular wollastonite accounting for 0.8 - 1.2% of the weight of the kneaded material to obtain kneaded material particles; (3)Put the kneaded material particles, thermoplastic polyurethane elastomer particles and compatibilizer into a twin-screw extruder for dynamic vulcanization and granulation, and the anti-slip composite thermoplastic elastomer can be obtained after cooling.

[0015] Further, the blending in step (1) is carried out in a rubber open mill or an internal mixer.

[0016] Further, the screw speed of the twin-screw extruder in step (3) is 250 - 450 rpm, and the temperature of each section of the twin-screw extruder is 160 - 200 °C.

[0017] The third object of the present invention is to provide an application of the above anti-slip composite thermoplastic elastomer in the outsole of sports shoes.

[0018] The technical solution provided by the present invention has the following beneficial effects compared with the prior art: 1. In the present invention, the prepared surface-modified acicular wollastonite is filled into a two-component rubber of butyl rubber and liquid nitrile rubber, and dynamically vulcanized to prepare a composite thermoplastic elastomer, which can be directly injection-molded into the outsole of sports shoes. The production process is simple, there is no VOC emission, and the leftover materials can be recycled. The outsole of sports shoes made of this composite thermoplastic elastomer has excellent wear resistance, resilience, anti-slip property, especially excellent anti-wet-slip property, and is suitable for application in the outsole of sports shoes, having broad market application value.

[0019] 2. The present invention innovatively uses the prepared anti-slip composite thermoplastic elastomer in the outsole of sports shoes. By using a composite rubber material of butyl rubber and liquid nitrile rubber, the anti-slip performance of the material on the surfaces of polar and non-polar media can be improved. The composite rubber material is filled with surface-modified acicular wollastonite, and the synergistic effect of surface-modified acicular wollastonite, butyl rubber and liquid nitrile rubber shows excellent anti-slip performance, improves the grip and stability of sports shoes, and thus effectively prevents athletes from slipping during exercise, especially in humid or rainy environments, providing more reliable safety protection and comfortable wearing experience for athletes.

[0020] 3. In the dispersed phase of the butyl rubber vulcanizate of the present invention, the isobutene segment in the molecular chain has a high-density structure, which endows the dispersed phase with low surface polarity and dense characteristics, effectively reducing the adsorption of moisture on the material surface, thereby reducing the decrease in the friction coefficient caused by the formation of a water film under wet and slippery conditions. This helps to maintain the stability of the microscopic surface deformation of the material during dynamic contact and further improve the grip in a wet and slippery environment. The dispersed phase of nitrile butadiene rubber vulcanizate contains acrylonitrile polar groups, and these groups can play a role in reducing sliding with polar media through intermolecular forces. The surface-modified acicular wollastonite, as an inorganic filler with high modulus, is filled into the composite rubber material. The filler forms a physical cross-linking network with the rubber matrix, increasing the hardness of the material, inhibiting dynamic deformation, and reducing friction loss caused by elastic hysteresis. At the same time, the microscopic convex structure of the surface-modified acicular wollastonite can disrupt the continuity of the water film, increase the actual friction area of the contact surface, and enhance the frictional force under wet and slippery conditions, enabling the outsole of sports shoes made of this composite rubber material to still maintain good anti-slip performance on wet or oily floors. In addition, the surface-modified acicular wollastonite also has excellent dispersibility and processing performance, can be evenly dispersed in rubber or thermoplastic elastomer substrates to form a stable composite material system, and during the processing process, this filler will not have an adverse impact on the fluidity and formability of the composite material, thus ensuring production efficiency and product quality. Detailed Embodiments

[0021] The principles and features of the present invention are described below in conjunction with examples. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0022] In the following examples and comparative examples, unless otherwise specified, the raw materials used are commercially available products.

[0023] Butyl rubber: Purchased from Sinopec Yanshan Petrochemical Co., Ltd., product model: IIR - 1751.

[0024] Liquid nitrile butadiene rubber: Purchased from Hengshui Ruien Rubber and Plastic Technology Co., Ltd., product model: LNBR - 29 - 1E. The viscosity range of LNBR - 29 - 1E is usually 800 - 1000 Pa·s (23°C).

[0025] Phenolic resin: Purchased from SI Group, product model: SP - 1045.

[0026] TPU particles, that is, thermoplastic polyurethane elastomer particles, purchased from BASF, product model: 1180A.

[0027] SEBS grafted maleic anhydride purchased from KRATON, product model: SEBS FG1901.

[0028] Polypropylene grafted maleic anhydride was purchased from DuPont, product model: 353D.

[0029] POE grafted maleic anhydride was purchased from Coase Chemical Co., Ltd., product model: W1A.

[0030] Preparation Example 1 A preparation method of surface-modified needle-shaped wollastonite comprises the following steps: heating a 10L high-speed stirrer to 100°C, adding 5000g of needle-shaped wollastonite, spraying 150g of surface modifier silane coupling agent Si-69 with a spray pot, starting a high-speed stirring mode, mixing for 25 minutes, and obtaining surface-modified needle-shaped wollastonite.

[0031] Preparation Example 2 A preparation method of surface-modified needle-shaped wollastonite comprises the following steps: heating a 10L high-speed stirrer to 100°C, adding 5000g of needle-shaped wollastonite, spraying 150g of surface modifier silane coupling agent KH560 with a spray pot, starting a high-speed stirring mode, mixing for 20 minutes, and obtaining surface-modified needle-shaped wollastonite.

[0032] Preparation Example 3 A preparation method of surface-modified needle-shaped wollastonite comprises the following steps: heating a 10L high-speed stirrer to 100°C, adding 5000g of needle-shaped wollastonite, spraying 150g of surface modifier silane coupling agent KH570 and 60g of surface modifier silane coupling agent Si-69 with a spray pot, starting a high-speed stirring mode, mixing for 30 minutes, and obtaining surface-modified needle-shaped wollastonite. Example 1

[0033] A wet and slip-resistant composite thermoplastic elastomer comprises the following components in parts by weight: 15 parts of butyl rubber, 5 parts of liquid nitrile rubber, 5 parts of surface-modified needle-shaped wollastonite obtained in Preparation Example 1, 1 part of a vulcanizing agent phenolic resin, 0.3 parts of a vulcanizing aid stannous chloride, 85 parts of thermoplastic polyurethane elastomer particles, and 3 parts of a compatibilizing agent POE grafted maleic anhydride.

[0034] A method for preparing an anti-slip composite thermoplastic elastomer comprises the following steps: (1) At room temperature, 1000 g of the surface-modified needle-shaped wollastonite obtained in Preparation Example 1, 3000 g of butyl rubber, 1000 g of liquid nitrile rubber, 200 g of phenolic resin and 60 g of stannous chloride were put into a 6L internal mixer for blending to obtain a mixed material; during the mixing process, the material temperature was controlled to be below 70° C.; (2) placing the mixed material into a conical twin-screw forced-feed rubber pelletizer, and mixing the surface-modified needle-shaped wollastonite obtained in Preparation Example 1 accounting for 1% by weight of the mixed material into the pelletizer while cutting the pellets to prepare mixed material pellets; (3) Feed the compounding material particles, thermoplastic polyurethane elastomer particles, and POE-grafted maleic anhydride into a twin-screw extruder by a loss-in-weight feeder at a ratio of 15:85:3. Set the temperatures of each section of the twin-screw extruder to 160 - 190 °C, and the screw speed to 400 revolutions per minute. Conduct dynamic vulcanization and pelletizing. After cooling, the anti-slip composite thermoplastic elastomer is obtained. Example 2

[0035] An anti-slip composite thermoplastic elastomer, comprising the following components by weight: 25 parts of butyl rubber, 10 parts of liquid nitrile rubber, 10 parts of surface-modified acicular wollastonite obtained in Preparation Example 2, 1.5 parts of vulcanizing agent phenolic resin, 0.5 part of vulcanization aid stannous chloride, 70 parts of thermoplastic polyurethane elastomer particles, and 5 parts of compatibilizer polypropylene-grafted maleic anhydride.

[0036] A preparation method of an anti-slip composite thermoplastic elastomer, comprising the following steps: (1) At room temperature, put 1000 g of surface-modified acicular wollastonite obtained in Preparation Example 2, 2500 g of butyl rubber, 1000 g of liquid nitrile rubber, 150 g of phenolic resin, and 50 g of stannous chloride into a 6L internal mixer for blending to obtain a compounding material. During the blending process, control the material temperature below 70 °C; (2) Put the compounding material into a rubber granulator with a conical twin-screw forced feeding device, and isolate it by mixing 1% by weight of the surface-modified acicular wollastonite obtained in Preparation Example 2 while cutting the particles to prepare compounding material particles; (3) Feed the compounding material particles, thermoplastic polyurethane elastomer particles, and polypropylene-grafted maleic anhydride into a twin-screw extruder by a loss-in-weight feeder at a ratio of 20:70:5. Set the temperatures of each section of the twin-screw extruder to 160 - 200 °C, and the screw speed to 450 revolutions per minute. Conduct dynamic vulcanization and pelletizing. After cooling, the anti-slip composite thermoplastic elastomer is obtained. Example 3

[0037] An anti-slip composite thermoplastic elastomer, comprising the following components by weight: 5 parts of butyl rubber, 1 part of liquid nitrile rubber, 1 part of surface-modified acicular wollastonite obtained in Preparation Example 3, 0.2 part of vulcanizing agent phenolic resin, 0.1 part of vulcanization aid stannous chloride, 95 parts of thermoplastic polyurethane elastomer particles, and 1 part of compatibilizer SEBS-grafted maleic anhydride.

[0038] A preparation method of an anti-slip composite thermoplastic elastomer, comprising the following steps: (1) At room temperature, put 700 g of surface-modified acicular wollastonite obtained in Preparation Example 3, 3500 g of butyl rubber, 700 g of liquid nitrile rubber, 140 g of phenolic resin, and 70 g of stannous chloride into a 6L internal mixer for blending to obtain a compounding material. During the blending process, control the material temperature below 70 °C; (2) Put the kneaded material into a rubber granulator with a conical twin-screw forced feeding device, and while granulating, mix in 1% by weight of the surface-modified acicular wollastonite obtained in Preparation Example 3 to isolate it, and prepare kneaded material particles. (3) Put the kneaded material particles, thermoplastic polyurethane elastomer particles, and SEBS grafted maleic anhydride into a twin-screw extruder according to a ratio of 5:95:1 by loss-in-weight feeder. Set the temperature of each section of the twin-screw extruder to 160 - 190 °C, and the screw speed to 350 revolutions per minute, and conduct dynamic vulcanization and granulation. After cooling, the anti-slip composite thermoplastic elastomer is obtained.

[0039] Comparative Example 1 Use pure thermoplastic polyurethane elastomer particles.

[0040] Comparative Example 2 An anti-slip composite thermoplastic elastomer, comprising the following components by weight: 20 parts of butyl rubber, 5 parts of the surface-modified acicular wollastonite obtained in Preparation Example 1, 1 part of vulcanizing agent phenolic resin, 0.3 part of vulcanization aid stannous chloride, 85 parts of thermoplastic polyurethane elastomer particles, and 3 parts of compatibilizer POE grafted maleic anhydride.

[0041] A preparation method of an anti-slip composite thermoplastic elastomer, comprising the following steps: (1) At room temperature, put 1000 grams of the surface-modified acicular wollastonite obtained in Preparation Example 1, 4000 grams of butyl rubber, 200 grams of phenolic resin, and 60 grams of stannous chloride into a 6L internal mixer for blending to obtain a kneaded material, and control the material temperature below 70 °C during the kneading process; (2) Put the kneaded material into a rubber granulator with a conical twin-screw forced feeding device, and while granulating, mix in 1% by weight of the surface-modified acicular wollastonite to isolate it, and prepare kneaded material particles; (3) Put the kneaded material particles, thermoplastic polyurethane elastomer particles, and POE grafted maleic anhydride into a twin-screw extruder according to a ratio of 15:85:3 by loss-in-weight feeder. Set the temperature of each section of the twin-screw extruder to 160 - 190 °C, and the screw speed to 400 revolutions per minute, and conduct dynamic vulcanization and granulation. After cooling, the composite thermoplastic elastomer is obtained.

[0042] Comparative Example 3 An anti-slip composite thermoplastic elastomer, comprising the following components by weight: 20 parts of liquid nitrile rubber, 5 parts of the surface-modified acicular wollastonite obtained in Preparation Example 1, 1 part of vulcanizing agent phenolic resin, 0.3 part of vulcanization aid stannous chloride, 85 parts of thermoplastic polyurethane elastomer particles, and 3 parts of compatibilizer POE grafted maleic anhydride.

[0043] A preparation method of an anti-slip composite thermoplastic elastomer, comprising the following steps: (1) At room temperature, 1000 g of surface-modified acicular wollastonite obtained in Preparation Example 1, 4000 g of liquid nitrile rubber, 200 g of phenolic resin, and 60 g of stannous chloride were put into a 6 L internal mixer for blending to obtain a blended material, and the temperature of the material was controlled below 70 °C during the blending process; (2) The blended material was put into a rubber granulator with a conical twin-screw forced feeding device, and surface-modified acicular wollastonite accounting for 1% of the weight of the blended material was mixed in during granulation for isolation to prepare blended material particles; (3) The blended material particles, thermoplastic polyurethane elastomer particles, and POE grafted maleic anhydride were fed into a twin-screw extruder by a loss-in-weight feeder in a ratio of 15:85:3. The temperature of each section of the twin-screw extruder was set at 160 - 190 °C, and the screw speed was 400 revolutions per minute for dynamic vulcanization and granulation. After cooling, a composite thermoplastic elastomer was obtained.

[0044] Comparative Example 4 A wet-slip resistant composite thermoplastic elastomer, comprising the following components by weight: 15 parts of butyl rubber, 5 parts of liquid nitrile rubber, 1 part of phenolic resin as vulcanizing agent, 0.3 part of stannous chloride as vulcanization aid, 85 parts of thermoplastic polyurethane elastomer particles, and 3 parts of POE grafted maleic anhydride as compatibilizer.

[0045] A preparation method of a wet-slip resistant composite thermoplastic elastomer, comprising the following steps: (1) At room temperature, 3000 g of butyl rubber, 1000 g of liquid nitrile rubber, 200 g of phenolic resin, and 60 g of stannous chloride were put into a 6 L internal mixer for blending to obtain a blended material, and the temperature of the material was controlled below 70 °C during the blending process; (2) The blended material was put into a rubber granulator with a conical twin-screw forced feeding device to prepare blended material particles; (3) The blended material particles, thermoplastic polyurethane elastomer particles, and POE grafted maleic anhydride were fed into a twin-screw extruder by a loss-in-weight feeder in a ratio of 15:85:3. The temperature of each section of the twin-screw extruder was set at 160 - 190 °C, and the screw speed was 400 revolutions per minute for dynamic vulcanization and granulation. After cooling, a wet-slip resistant composite thermoplastic elastomer was obtained.

[0046] Comparative Example 5 A wet-slip resistant composite thermoplastic elastomer, comprising the following components by weight: 15 parts of butyl rubber, 5 parts of liquid nitrile rubber, 5 parts of acicular wollastonite, 1 part of phenolic resin as vulcanizing agent, 0.3 part of stannous chloride as vulcanization aid, 85 parts of thermoplastic polyurethane elastomer particles, and 3 parts of POE grafted maleic anhydride as compatibilizer.

[0047] A preparation method of a wet-slip resistant composite thermoplastic elastomer, comprising the following steps: (1)At room temperature, 1000 g of acicular wollastonite, 3000 g of butyl rubber, 1000 g of liquid nitrile rubber, 200 g of phenolic resin and 60 g of stannous chloride were put into a 6L internal mixer for blending to obtain a blended material, and the temperature of the material was controlled below 70 °C during the blending process; (2)The blended material was put into a rubber granulator with a conical twin-screw forced feeding, and 1% of acicular wollastonite by weight of the blended material was mixed in during pelletizing for isolation to prepare blended material pellets; (3)The blended material pellets, thermoplastic polyurethane elastomer pellets, and POE-grafted maleic anhydride were fed into a twin-screw extruder by a loss-in-weight feeder in a ratio of 15:85:3. The temperature of each section of the twin-screw extruder was set at 160 - 190 °C, and the screw speed was 400 revolutions per minute for dynamic vulcanization and pelletizing. After cooling, the composite thermoplastic elastomer was obtained.

[0048] Comparative Example 6 A wet-slip resistant composite thermoplastic elastomer, comprising the following components by weight: 3 parts of butyl rubber, 15 parts of liquid nitrile rubber, 7 parts of surface-modified acicular wollastonite obtained in Preparation Example 1, 1 part of vulcanizing agent phenolic resin, 0.3 part of vulcanization aid stannous chloride, 85 parts of thermoplastic polyurethane elastomer pellets, and 3 parts of compatibilizer POE-grafted maleic anhydride.

[0049] A preparation method of a wet-slip resistant composite thermoplastic elastomer, comprising the following steps: (1)At room temperature, 1400 g of surface-modified acicular wollastonite obtained in Preparation Example 1, 600 g of butyl rubber, 3000 g of liquid nitrile rubber, 200 g of phenolic resin and 60 g of stannous chloride were put into a 6L internal mixer for blending to obtain a blended material; the temperature of the material was controlled below 70 °C during the blending process; (2)The blended material was put into a rubber granulator with a conical twin-screw forced feeding, and 1% of surface-modified acicular wollastonite obtained in Preparation Example 1 by weight of the blended material was mixed in during pelletizing for isolation to prepare blended material pellets; (3)The blended material pellets, thermoplastic polyurethane elastomer pellets and POE-grafted maleic anhydride were fed into a twin-screw extruder by a loss-in-weight feeder in a ratio of 15:85:3. The temperature of each section of the twin-screw extruder was set at 160 - 190 °C, and the screw speed was 400 revolutions per minute for dynamic vulcanization and pelletizing. After cooling, the wet-slip resistant composite thermoplastic elastomer was obtained.

[0050] Comparative Example 7 A wet-slip resistant composite thermoplastic elastomer, comprising the following components by weight: 12.5 parts of butyl rubber, 0.5 parts of liquid nitrile rubber, 12 parts of surface-modified acicular wollastonite obtained in Preparation Example 1, 1 part of vulcanizing agent phenolic resin, 0.3 part of vulcanization aid stannous chloride, 85 parts of thermoplastic polyurethane elastomer pellets, and 3 parts of compatibilizer POE-grafted maleic anhydride.

[0051] A preparation method of a moisture-resistant slip composite thermoplastic elastomer, comprising the following steps: (1) At room temperature, 2400 g of the surface-modified acicular wollastonite obtained in Preparation Example 1, 2500 g of butyl rubber, 100 g of liquid nitrile rubber, 200 g of phenolic resin, and 60 g of stannous chloride were put into a 6L internal mixer for blending to obtain a kneaded material; during the kneading process, the temperature of the material was controlled below 70 °C; (2) The kneaded material was put into a rubber granulator with a conical twin-screw forced feeding, and during pelletizing, 1% by weight of the surface-modified acicular wollastonite obtained in Preparation Example 1 was mixed in for isolation to prepare kneaded material pellets; (3) The kneaded material pellets, thermoplastic polyurethane elastomer pellets, and POE-grafted maleic anhydride were put into a twin-screw extruder by a loss-in-weight feeder in a ratio of 15:85:3. The temperature of each section of the twin-screw extruder was set at 160 - 190 °C, and the screw speed was 400 revolutions per minute for dynamic vulcanization and pelletizing. After cooling, the moisture-resistant slip composite thermoplastic elastomer was obtained.

[0052] Comparative Example 8 A moisture-resistant slip composite thermoplastic elastomer, comprising the following components by weight: 4 parts of butyl rubber, 8 parts of liquid nitrile rubber, 13 parts of the surface-modified acicular wollastonite obtained in Preparation Example 1, 1 part of the vulcanizing agent phenolic resin, 0.3 part of the vulcanization aid stannous chloride, 85 parts of thermoplastic polyurethane elastomer pellets, and 3 parts of the compatibilizer POE-grafted maleic anhydride.

[0053] A preparation method of a moisture-resistant slip composite thermoplastic elastomer, comprising the following steps: (1) At room temperature, 2600 g of the surface-modified acicular wollastonite obtained in Preparation Example 1, 800 g of butyl rubber, 1600 g of liquid nitrile rubber, 200 g of phenolic resin, and 60 g of stannous chloride were put into a 6L internal mixer for blending to obtain a kneaded material; during the kneading process, the temperature of the material was controlled below 70 °C; (2) The kneaded material was put into a rubber granulator with a conical twin-screw forced feeding, and during pelletizing, 1% by weight of the surface-modified acicular wollastonite obtained in Preparation Example 1 was mixed in for isolation to prepare kneaded material pellets; (3) The kneaded material pellets, thermoplastic polyurethane elastomer pellets, and POE-grafted maleic anhydride were put into a twin-screw extruder by a loss-in-weight feeder in a ratio of 15:85:3. The temperature of each section of the twin-screw extruder was set at 160 - 190 °C, and the screw speed was 400 revolutions per minute for dynamic vulcanization and pelletizing. After cooling, the moisture-resistant slip composite thermoplastic elastomer was obtained.

[0054] Performance test: 1. The Shore A hardness, tensile strength, and elongation at break of the elastomers obtained in Examples 1-3 and Comparative Examples 1-8 were measured according to Standards GB / T531.1-2008, GB / T528-2009, and GB / T528-2009, respectively.

[0055] 2. DIN abrasion test: The elastomers obtained in Examples 1-3 and Comparative Examples 1-8 were respectively injection-molded into the forefoot and heel of the outsole, and measured according to Standard GB / T9867-2008.

[0056] 3. Dry and wet skid resistance tests: The injection-molded forefoot and heel of the outsole were pasted onto the corresponding midsole, and the dry and wet skid resistances were respectively tested according to Standard GB / T3903.6-2017.

[0057] The performance test results are shown in Table 1.

[0058] Table 1 Performance Test Results Table

[0059] From the data in Table 1, it can be seen that for the outsole of the sports shoes prepared with pure TPU material in Comparative Example 1, although the mechanical strength is relatively high, the dry and wet skid resistance effects are very poor; the outsole forefoot and heel prepared in Examples 1-3 have obvious advantages in wear resistance, and the dry and wet skid resistance performances of Examples 1-3 are better than those of Comparative Examples 1-8, indicating that the outsole of the sports shoes prepared by the present invention has better comprehensive performances in skid resistance, wear resistance, mechanical strength, and resilience, and has better market application value.

[0060] From the performance test data of the examples and comparative examples in Table 1, it can be seen that the present invention innovatively fills surface-modified acicular wollastonite into butyl rubber and liquid nitrile rubber, effectively utilizes the synergistic effect of these three species, and better combines the advantages of the above-mentioned blended rubber and thermoplastic polyurethane as the matrix material through dynamic vulcanization reaction processing, so that the prepared composite thermoplastic elastomer shows excellent anti-wet skid performance when used in the outsole of sports shoes, and at the same time has good abrasion resistance and resilience.

[0061] The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An anti-slip composite thermoplastic elastomer, characterized in that: The invention comprises the following components in parts by weight: 5-25 parts of butyl rubber, 1-10 parts of liquid nitrile rubber, 1-10 parts of surface-modified needle-shaped wollastonite, 0.2-1.5 parts of vulcanizing agent, 0.1-0.5 parts of vulcanizing aid, 70-95 parts of thermoplastic polyurethane elastomer particles and 1-5 parts of compatibilizer.

2. The anti-slip composite thermoplastic elastomer according to claim 1, characterized in that: The preparation method of the surface-modified needle-shaped wollastonite comprises the following steps: putting the needle-shaped wollastonite into a high-speed stirrer at 90-110° C., spraying a surface modifier into the high-speed stirrer, stirring for 10-30 minutes, and cooling to obtain the surface-modified needle-shaped wollastonite.

3. The anti-slip composite thermoplastic elastomer according to claim 2, characterized in that: The surface modifier is one or more of silane coupling agents Si-69, KH550, KH560, and KH570.

4. The anti-slip composite thermoplastic elastomer according to claim 2, characterized in that: The mass of the surface modifier is 2-5% of the mass of the needle-shaped wollastonite.

5. The anti-slip composite thermoplastic elastomer according to claim 1, characterized in that: The viscosity of the liquid nitrile rubber is 100-3000 Pa·s.

6. The anti-slip composite thermoplastic elastomer according to claim 1, characterized in that: The vulcanizing agent is phenolic resin or brominated phenolic resin, the vulcanizing aid is stannous chloride or zinc oxide, and the compatibilizer is one or more of polypropylene grafted maleic anhydride, POE grafted maleic anhydride, and SEBS grafted maleic anhydride.

7. A method for preparing the anti-slip composite thermoplastic elastomer according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) Blending the surface-modified needle-shaped wollastonite, butyl rubber, liquid nitrile rubber, a vulcanizing agent, and a vulcanizing aid to obtain a compound; (2) placing the mixed material into a rubber pelletizer, and mixing 0.8-1.2% of the surface-modified needle-shaped wollastonite by weight of the mixed material into the mixed material while pelletizing the mixed material to obtain mixed material particles; (3) The mixed material particles, thermoplastic polyurethane elastomer particles and compatibilizer are put into a twin-screw extruder for dynamic vulcanization and granulation, and the anti-slip composite thermoplastic elastomer is obtained after cooling.

8. The method for preparing the anti-slip composite thermoplastic elastomer according to claim 7, characterized in that: The blending in step (1) is carried out in a rubber open mixer or internal mixer.

9. The method for preparing the anti-slip composite thermoplastic elastomer according to claim 7, characterized in that: The screw speed of the twin-screw extruder in step (3) is 250-450 rpm, and the temperature of each section of the twin-screw extruder is 160-200°C.

10. Use of the anti-slip composite thermoplastic elastomer according to any one of claims 1 to 6 in the outsole of sports shoes.

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