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 comes into direct contact with the ground, the outsole of sports shoes has a decisive influence on the wear resistance, slip resistance, shock absorption and service life of the shoes. Currently, the materials used for outsoles of sports shoes have many limitations.

[0003] Vulcanized rubber materials are highly sought after in the athletic footwear market due to their excellent anti-slip, abrasion-resistant, and rebound properties, demonstrating unique advantages in athletic shoe outsoles. Vulcanized rubber's anti-slip properties ensure athletes maintain stability on a variety of surfaces, its abrasion resistance ensures sole durability, and its rebound properties enhance comfort and performance. However, the production process of vulcanized rubber presents several pressing challenges. For one thing, the low efficiency of the vulcanization process has limited its large-scale production and widespread application. Furthermore, the production process is prone to the generation of volatile organic compounds (VOCs). These not only pollute the production environment but also pose a potential health risk to workers. Furthermore, even with strict VOC emissions controls during production, VOCs are still released during packaging, storage, and use, particularly upon unpacking, impacting the quality inspection pass rate, sales, and purchasing experience of the finished shoes.

[0004] When used in athletic shoe outsoles, materials such as polyvinyl chloride (PVC), ethylene-vinyl acetate (EVA) resin, and thermoplastic polyurethane (TPP) exhibit relatively poor anti-slip properties, particularly wet-slip resistance. This means that on wet surfaces, these materials struggle to achieve optimal anti-slip performance, increasing the risk of injury to athletes. While PVC possesses good hardness and wear resistance, its wet-slip resistance is less than ideal. While EVA resin offers excellent flexibility and processing properties, its wet-slip resistance is suboptimal. TPU, while attracting attention for its excellent elasticity and wear resistance, still needs further improvement in wet-slip resistance.

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

[0006] The purpose of the present invention is to provide an anti-slip composite thermoplastic elastomer, a preparation method and application thereof, aiming to prepare a composite thermoplastic elastomer by blending surface-modified needle-shaped wollastonite, butyl rubber and liquid nitrile rubber through a dynamic vulcanization reaction, and directly injection-molding the obtained elastomer into a sports shoe outsole to solve the problems of poor wear resistance, poor rebound performance and poor anti-slip performance of the sports shoe outsole, as well as to solve the problems of complex production process, VOC emissions and recycling of scraps.

[0007] The technical solutions provided by the present invention are as follows: One of the objects of the present invention is to provide an anti-slip composite thermoplastic elastomer, comprising 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 a vulcanizing agent, 0.1-0.5 parts of a vulcanizing aid, 70-95 parts of thermoplastic polyurethane elastomer particles, and 1-5 parts of a compatibilizer.

[0008] Furthermore, the preparation method of the surface-modified needle-shaped wollastonite comprises the following steps: placing the needle-shaped wollastonite into a high-speed stirrer at 90-110° C., spraying a surface modifier into the high-speed stirrer, stirring at high speed for 10-30 minutes, and cooling to obtain the surface-modified needle-shaped wollastonite.

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

[0010] Furthermore, the mass of the surface modifier is 2-5% of the mass of the needle-shaped wollastonite.

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

[0012] Furthermore, 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.

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

[0014] A second object of the present invention is to provide a method for preparing the above-mentioned anti-slip composite thermoplastic elastomer, comprising the following steps: (1) Blending 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 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.

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

[0016] Furthermore, 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] A third object of the present invention is to provide an application of the above-mentioned anti-slip composite thermoplastic elastomer in the outsole of sports shoes.

[0018] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects: 1. The present invention prepares a composite thermoplastic elastomer by filling the prepared surface-modified needle-shaped wollastonite into a two-component rubber of butyl rubber and liquid nitrile rubber, and dynamically vulcanizing the composite thermoplastic elastomer, which can be directly injection-molded into sports shoe outsoles. The production process is simple, no VOC emissions are emitted, and scraps can be recycled. The sports shoe outsoles made using the composite thermoplastic elastomer have the characteristics of wear resistance, rebound resilience, anti-slip properties, especially excellent wet-slip resistance, are suitable for application in sports shoe outsoles, and have broad market application value.

[0019] 2. The present invention innovatively uses the prepared anti-slip composite thermoplastic elastomer in the outsole of sports shoes. The composite rubber material of butyl rubber and liquid nitrile rubber is used to improve the anti-slip performance of the material on the surface of polar and non-polar media. The composite rubber material is filled with surface-modified acicular wollastonite. The synergistic effect of the three substances of surface-modified acicular wollastonite, butyl rubber and liquid nitrile rubber is utilized to exhibit excellent anti-slip performance, improve the grip and stability of sports shoes, thereby effectively preventing athletes from slipping during exercise, especially in humid or rainy environments, providing athletes with more reliable safety protection and a comfortable wearing experience.

[0020] 3. The vulcanized butyl rubber dispersed phase in the present invention has a high-density structure of the isobutylene segment in its molecular chain, which gives the dispersed phase low surface polarity and dense properties. This can effectively reduce the adsorption of water on the material surface, thereby reducing the decrease in the friction coefficient caused by the formation of water film under wet conditions. This helps to maintain the stability of the material's microscopic surface deformation during dynamic contact, further improving the grip in wet environments. The vulcanized nitrile rubber dispersed phase contains acrylonitrile polar groups, which can reduce slip through intermolecular forces with polar media. Surface-modified acicular wollastonite, a high-modulus inorganic filler, is incorporated into the composite rubber material. The filler and the rubber matrix form a physical crosslinking network, increasing the material's hardness, inhibiting dynamic deformation, and reducing friction losses caused by elastic hysteresis. Furthermore, the microscopic protrusions of the surface-modified acicular wollastonite disrupt the continuity of the water film, increasing the actual friction area of ​​the contact surface and enhancing friction in wet conditions. This allows the outsoles of athletic shoes made with this composite rubber material to maintain excellent anti-slip properties even on wet or oily surfaces. Furthermore, the surface-modified acicular wollastonite exhibits excellent dispersibility and processing properties, allowing it to be evenly dispersed in a rubber or thermoplastic elastomer matrix to form a stable composite material system. Furthermore, during processing, the filler does not adversely affect the composite's fluidity and formability, thereby ensuring production efficiency and product quality. DETAILED DESCRIPTION

[0021] The principles and features of the present invention are described below with reference to examples. The examples are only used to explain the present invention and are not used to limit the scope of the present invention.

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

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

[0024] Liquid nitrile rubber: purchased from Hengshui Ruien Rubber & Plastic Technology Co., Ltd., product model: LNBR-29-1E. The viscosity of LNBR-29-1E is generally in the range of 800–1000 Pa·s (at 23°C).

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

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

[0027] SEBS grafted maleic anhydride was purchased from Kraton, USA, 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 for 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 a surface modifier, a silane coupling agent Si-69, into the stirrer using a spray bottle, starting a high-speed stirring mode, and mixing for 25 minutes to obtain the surface-modified needle-shaped wollastonite.

[0031] Preparation Example 2 A method for preparing 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 a surface modifier, a silane coupling agent KH560, into the stirrer using a spray bottle, starting a high-speed stirring mode, and mixing for 20 minutes to obtain the surface-modified needle-shaped wollastonite.

[0032] Preparation Example 3 A preparation method for 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 a surface modifier silane coupling agent KH570 and 60g of a surface modifier silane coupling agent Si-69 with a spray bottle, starting a high-speed stirring mode, and mixing for 30 minutes to obtain the surface-modified needle-shaped wollastonite.

[0033] Example 1: A wet and slip-resistant composite thermoplastic elastomer comprising the following components in parts by weight: 15 parts of butyl rubber, 5 parts of liquid nitrile rubber, 5.263 parts of surface-modified needle-shaped wollastonite obtained in Preparation Example 1, 1 part of vulcanizing agent phenolic resin, 0.3 part of vulcanizing aid stannous chloride, 85 parts of thermoplastic polyurethane elastomer particles, and 3 parts of compatibilizer 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 mixed in a 6 L internal mixer to obtain a mixed material; during the mixing process, the material temperature was controlled to be below 70°C; (2) The mixed material was placed in a conical twin-screw forced-feed rubber pelletizer, and while pelletizing, the surface-modified needle-shaped wollastonite obtained in Preparation Example 1, accounting for 1% of the weight of the mixed material, was mixed in for isolation to prepare mixed material pellets; (3) The mixed material pellets, thermoplastic polyurethane elastomer pellets and POE grafted maleic anhydride were fed into a twin-screw extruder at a ratio of 26.563:85:3 through a loss-in-weight scale. The temperature of each section of the twin-screw extruder was set at 160-190°C and the screw speed was set at 400 rpm. Dynamic vulcanization and granulation were carried out. After cooling, the anti-slip composite thermoplastic elastomer was obtained.

[0035] Example 2: A wet and slip-resistant composite thermoplastic elastomer comprising the following components in parts by weight: 25 parts of butyl rubber, 10 parts of liquid nitrile rubber, 9.46 parts of surface-modified needle-shaped wollastonite obtained in Preparation Example 2, 1.5 parts of phenolic resin as a vulcanizing agent, 0.5 parts of stannous chloride as a vulcanizing aid, 70 parts of thermoplastic polyurethane elastomer particles, and 5 parts of polypropylene grafted maleic anhydride as a compatibilizer.

[0036] A method for preparing an anti-slip composite thermoplastic elastomer comprises the following steps: (1) At room temperature, 900 g of the surface-modified needle-shaped 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 were put into a 6 L internal mixer and blended to obtain a mixed material. During the mixing process, the material temperature was controlled to be below 70°C. (2) The mixed material was placed in a conical twin-screw forced-feed rubber pelletizer, and while pelletizing, the surface-modified needle-shaped wollastonite obtained in Preparation Example 2, accounting for 1% by weight of the mixed material, was mixed in for isolation to prepare mixed material pellets; (3) The mixed material pellets, thermoplastic polyurethane elastomer pellets, and polypropylene grafted maleic anhydride were fed into a twin-screw extruder at a ratio of 46.46:70:5 using a loss-in-weight scale. The temperature of each section of the twin-screw extruder was set at 160-200°C and the screw speed was set at 450 rpm. Dynamic vulcanization and granulation were performed. After cooling, the anti-slip composite thermoplastic elastomer was obtained.

[0037] Example 3: A wet and slip-resistant composite thermoplastic elastomer comprising the following components in parts by weight: 5 parts of butyl rubber, 1 part of liquid nitrile rubber, 1.073 parts of surface-modified needle-shaped wollastonite obtained in Preparation Example 3, 0.2 parts of phenolic resin as a vulcanizing agent, 0.1 parts of stannous chloride as a vulcanizing aid, 95 parts of thermoplastic polyurethane elastomer particles, and 1 part of SEBS grafted maleic anhydride as a compatibilizer.

[0038] A method for preparing an anti-slip composite thermoplastic elastomer comprises the following steps: (1) At room temperature, 700 g of the surface-modified needle-shaped 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 were put into a 6 L internal mixer and blended to obtain a mixed material. During the mixing process, the material temperature was controlled to be below 70°C; (2) The mixed material was placed in a conical twin-screw forced-feed rubber pelletizer, and while pelletizing, the surface-modified needle-shaped wollastonite obtained in Preparation Example 3, accounting for 1% of the weight of the mixed material, was mixed in for isolation to prepare mixed material pellets; (3) The mixed material pellets, thermoplastic polyurethane elastomer pellets, and SEBS grafted maleic anhydride were fed into a twin-screw extruder at a ratio of 7.373:95:1 through a loss-in-weight scale. The temperature of each section of the twin-screw extruder was set at 160-190°C and the screw speed was set at 350 rpm. Dynamic vulcanization and granulation were carried out. After cooling, the anti-slip composite thermoplastic elastomer was obtained.

[0039] Comparative Example 1 Pure thermoplastic polyurethane elastomer granules are used.

[0040] Comparative Example 2 A wet and slip-resistant composite thermoplastic elastomer comprises the following components in parts by weight: 20 parts of butyl rubber, 5.263 parts of surface-modified acicular wollastonite obtained in Preparation Example 1, 1 part of a vulcanizing agent, 1 part of phenolic resin, 0.3 parts of a vulcanizing aid, stannous chloride, 85 parts of thermoplastic polyurethane elastomer particles, and 3 parts of POE-grafted maleic anhydride, a compatibilizer.

[0041] 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, 4000 g of butyl rubber, 200 g of phenolic resin, and 60 g of stannous chloride were put into a 6 L internal mixer and blended to obtain a mixed material. During the mixing process, the material temperature was controlled to be below 70°C; (2) The mixed material is placed in a conical twin-screw forced feeding rubber pelletizer, and while pelletizing, surface-modified needle-shaped wollastonite accounting for 1% of the weight of the mixed material is mixed in for isolation to prepare mixed material pellets; (3) The mixed material pellets, thermoplastic polyurethane elastomer pellets, and POE grafted maleic anhydride were fed into a twin-screw extruder at a ratio of 26.563:85:3 using a loss-in-weight scale. The temperature of each section of the twin-screw extruder was set at 160-190°C and the screw speed was set at 400 rpm. Dynamic vulcanization and granulation were performed, and the composite thermoplastic elastomer was obtained after cooling.

[0042] Comparative Example 3 A wet and slip-resistant composite thermoplastic elastomer comprises the following components in parts by weight: 20 parts of liquid nitrile rubber, 5.263 parts of surface-modified needle-shaped wollastonite obtained in Preparation Example 1, 1 part of a vulcanizing agent, 0.3 parts of stannous chloride, a vulcanizing aid, 85 parts of thermoplastic polyurethane elastomer particles, and 3 parts of POE-grafted maleic anhydride, a compatibilizer.

[0043] 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, 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 and blended to obtain a mixed material. During the mixing process, the material temperature was controlled to be below 70° C.; (2) The mixed material is placed in a conical twin-screw forced feeding rubber pelletizer, and while pelletizing, surface-modified needle-shaped wollastonite accounting for 1% of the weight of the mixed material is mixed in for isolation to prepare mixed material pellets; (3) The mixed material pellets, thermoplastic polyurethane elastomer pellets, and POE grafted maleic anhydride were fed into a twin-screw extruder at a ratio of 26.563:85:3 using a loss-in-weight scale. The temperature of each section of the twin-screw extruder was set at 160-190°C and the screw speed was set at 400 rpm. Dynamic vulcanization and granulation were performed, and the composite thermoplastic elastomer was obtained after cooling.

[0044] Comparative Example 4 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, 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.

[0045] A method for preparing an anti-slip composite thermoplastic elastomer comprises 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 6L internal mixer for blending to obtain a mixed material. During the mixing process, the material temperature was controlled below 70°C; (2) The compounded material is placed in a conical twin-screw forced feeding rubber granulator to prepare compounded material pellets; (3) The mixed material pellets, thermoplastic polyurethane elastomer pellets, and POE grafted maleic anhydride were fed into a twin-screw extruder at a ratio of 21.3:85:3 using a loss-in-weight scale. The temperature of each section of the twin-screw extruder was set at 160-190°C and the screw speed was set at 400 rpm. Dynamic vulcanization and granulation were performed. After cooling, an anti-slip composite thermoplastic elastomer was obtained.

[0046] Comparative Example 5 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, 5.263 parts of needle-shaped wollastonite, 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 compatibilizer (POE grafted maleic anhydride).

[0047] A method for preparing an anti-slip composite thermoplastic elastomer comprises the following steps: (1) At room temperature, 1000 g of needle-shaped 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 6 L internal mixer for blending to obtain a mixed material. During the mixing process, the material temperature was controlled to be below 70°C; (2) The mixed material is placed in a conical twin-screw forced feeding rubber pelletizer, and while pelletizing, needle-shaped wollastonite accounting for 1% of the weight of the mixed material is mixed in for isolation to prepare mixed material pellets; (3) The mixed material pellets, thermoplastic polyurethane elastomer pellets, and POE grafted maleic anhydride were fed into a twin-screw extruder at a ratio of 26.563:85:3 using a loss-in-weight scale. The temperature of each section of the twin-screw extruder was set at 160-190°C and the screw speed was set at 400 rpm. Dynamic vulcanization and granulation were performed, and the composite thermoplastic elastomer was obtained after cooling.

[0048] Comparative Example 6 A wet and slip-resistant composite thermoplastic elastomer comprises the following components in parts by weight: 3 parts of butyl rubber, 15 parts of liquid nitrile rubber, 7.263 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 POE-grafted maleic anhydride as a compatibilizer.

[0049] A method for preparing an anti-slip composite thermoplastic elastomer comprises the following steps: (1) At room temperature, 1400 g of the surface-modified needle-shaped 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 6 L internal mixer and blended to obtain a mixed material; during the mixing process, the material temperature was controlled to be below 70°C; (2) The mixed material was placed in a conical twin-screw forced-feed rubber pelletizer, and while pelletizing, the surface-modified needle-shaped wollastonite obtained in Preparation Example 1, accounting for 1% of the weight of the mixed material, was mixed in for isolation to prepare mixed material pellets; (3) The mixed material pellets, thermoplastic polyurethane elastomer pellets and POE grafted maleic anhydride were fed into a twin-screw extruder at a ratio of 26.563:85:3 through a loss-in-weight scale. The temperature of each section of the twin-screw extruder was set at 160-190°C and the screw speed was set at 400 rpm. Dynamic vulcanization and granulation were carried out. After cooling, the anti-slip composite thermoplastic elastomer was obtained.

[0050] Comparative Example 7 A wet and slip-resistant composite thermoplastic elastomer comprises the following components in parts by weight: 12.5 parts of butyl rubber, 0.5 parts of liquid nitrile rubber, 12.263 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, 85 parts of thermoplastic polyurethane elastomer particles, and 3 parts of POE grafted maleic anhydride, a compatibilizer.

[0051] A method for preparing an anti-slip composite thermoplastic elastomer comprises the following steps: (1) At room temperature, 2400 g of the surface-modified needle-shaped 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 6 L internal mixer and blended to obtain a mixed material; during the mixing process, the material temperature was controlled to be below 70°C; (2) The mixed material was placed in a conical twin-screw forced-feed rubber pelletizer, and while pelletizing, the surface-modified needle-shaped wollastonite obtained in Preparation Example 1, accounting for 1% of the weight of the mixed material, was mixed in for isolation to prepare mixed material pellets; (3) The mixed material pellets, thermoplastic polyurethane elastomer pellets and POE grafted maleic anhydride were fed into a twin-screw extruder at a ratio of 26.563:85:3 through a loss-in-weight scale. The temperature of each section of the twin-screw extruder was set at 160-190°C and the screw speed was set at 400 rpm. Dynamic vulcanization and granulation were carried out. After cooling, the anti-slip composite thermoplastic elastomer was obtained.

[0052] Comparative Example 8 A wet and slip-resistant composite thermoplastic elastomer comprises the following components in parts by weight: 4 parts of butyl rubber, 8 parts of liquid nitrile rubber, 13.263 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 POE grafted maleic anhydride, a compatibilizer.

[0053] A method for preparing an anti-slip composite thermoplastic elastomer comprises the following steps: (1) At room temperature, 2600 g of the surface-modified needle-shaped 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 mixed in a 6 L internal mixer to obtain a mixed material; during the mixing process, the material temperature was controlled to be below 70°C; (2) The mixed material was placed in a conical twin-screw forced-feed rubber pelletizer, and while pelletizing, the surface-modified needle-shaped wollastonite obtained in Preparation Example 1, accounting for 1% of the weight of the mixed material, was mixed in for isolation to prepare mixed material pellets; (3) The mixed material pellets, thermoplastic polyurethane elastomer pellets and POE grafted maleic anhydride were fed into a twin-screw extruder at a ratio of 26.563:85:3 through a loss-in-weight scale. The temperature of each section of the twin-screw extruder was set at 160-190°C and the screw speed was set at 400 rpm. Dynamic vulcanization and granulation were carried out. After cooling, the anti-slip composite thermoplastic elastomer was obtained.

[0054] Performance testing: 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 injection molded into the forefoot and heel of outsoles, respectively, and tested according to the standard GB / T9867-2008.

[0056] 3. Dry and wet anti-slip testing: The injection-molded forefoot and heel of the outsole are affixed to the corresponding midsole and tested for dry and wet anti-slip properties in accordance with standard GB / T3903.6-2017.

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

[0058] Table 1 Performance test results

[0059] It can be seen from the data in Table 1 that the sports shoe outsole prepared with pure TPU material in Comparative Example 1 has high mechanical strength, but poor dry and wet anti-slip effects; the forefoot and heel of the outsoles prepared in Examples 1-3 have obvious advantages in wear resistance, and the dry and wet anti-slip properties of Examples 1-3 are better than those of Comparative Examples 1-8, indicating that the sports shoe outsoles prepared by the present invention have better comprehensive performance in anti-slip performance, wear resistance, mechanical strength and rebound, and have 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 utilizing the synergistic effect of these three species. The advantages of the above-mentioned mixed rubber and thermoplastic polyurethane as matrix materials are better combined through dynamic vulcanization reaction processing, so that the prepared composite thermoplastic elastomer exhibits excellent anti-slip performance when used in sports shoe outsoles, and also has good wear resistance and resilience.

[0061] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection 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 auxiliary agent, 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: placing 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 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 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 an 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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