High-weather-resistance wear-resistant composite material for shoe soles and preparation method of high-weather-resistance wear-resistant composite material

Abstract

The invention relates to the technical field of shoe soles, in particular to a high-weather-resistance wear-resistant composite material for shoe soles. The high-weather-resistance wear-resistant composite material is prepared from 65-75 parts of nitrile rubber, 18-25 parts of chloroprene rubber, 25-35 parts of thermoplastic polyurethane elastomer, 20-30 parts of modified polytetrafluoroethylene, 1-2 parts of anti-aging agent, 8-12 parts of reinforcing carbon black and 5-10 parts of plasticizer. The high-weatherability wear-resistant composite material for the shoe sole has the advantages of strong tensile strength, high elongation at break, strong tear strength, wear resistance and aging resistance, and is not easy to dissolve by an organic solvent in a paint spraying operation environment and adhere to the ground.

Description

Technical Field

[0001] The present invention relates to the technical field of shoe soles, and particularly relates to a high weather resistance and wear-resistant composite material for shoe soles and a preparation method thereof. Background Art

[0002] In the existing spray painting operation environment, the air will be mixed with more organic solvents, and there will also be a small amount of liquid organic solvents on the ground. If the staff wears shoe materials with rubber soles in the spray painting workshop, it is extremely easy to be dissolved by organic solvents (such as acetone, methyl ethyl ketone, cyclohexanone, benzene, n-butanol, styrene, etc.) and adhered to the ground, resulting in damage to the shoe materials and affecting the normal walking of the staff. Summary of the Invention

[0003] In order to overcome the disadvantages and deficiencies existing in the prior art, the purpose of the present invention is to provide a high weather resistance and wear-resistant composite material for shoe soles. The prepared composite material has strong tensile strength, high elongation at break, strong tear strength, wear resistance and anti-aging performance, and is not easily dissolved by organic solvents and adhered to the ground.

[0004] Another purpose of the present invention is to provide a preparation method of a high weather resistance and wear-resistant composite material for shoe soles. The preparation method is simple in operation, convenient to control, high in production efficiency, low in production cost, and can be used for large-scale production.

[0005] The purpose of the present invention is achieved by the following technical solutions: A high weather resistance and wear-resistant composite material for shoe soles, comprising the following raw materials in parts by weight: 65-75 parts of nitrile rubber, 18-25 parts of chloroprene rubber, 25-35 parts of thermoplastic polyurethane elastomer, 20-30 parts of modified polytetrafluoroethylene, 1-2 parts of anti-aging agent, 8-12 parts of reinforcing carbon black, and 5-10 parts of plasticizer.

[0006] The high weather resistance and wear-resistant composite material for shoe soles of the present invention uses nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer and modified polytetrafluoroethylene as the main rubber materials, and adds anti-aging agent, reinforcing carbon black, dispersant and plasticizer. The prepared composite material has strong tensile strength, high elongation at break, strong tear strength, wear resistance and anti-aging performance, and is not easily dissolved by organic solvents and adhered to the ground in the spray painting operation environment.

[0007] Further, the preparation method of the modified polytetrafluoroethylene comprises the following steps:

[0008] A1. Add deionized water to polytetrafluoroethylene to obtain a polytetrafluoroethylene dispersion with a solid content of 75-85%.

[0009] A2. Add titanium dioxide sol and polytetrafluoroethylene dispersion into a reactor, stir evenly, then perform ultrasonic dispersion at a temperature of 80 - 110°C for 1 - 2 h. After natural cooling, put the precipitate in the reactor into a drying oven and dry for 12 h. Grind the dried powder for standby;

[0010] A3. Add the ground powder into a crucible, and then transfer it to a sintering furnace with nitrogen protection. The sintering temperature is 550 - 650°C, and the sintering time is 30 - 45 min. After heating is completed and natural cooling, titanium dioxide-polytetrafluoroethylene mixture can be obtained;

[0011] A4. Dry the titanium dioxide-polytetrafluoroethylene mixture and benzyl alcohol at 100 - 120°C for 2 - 4 h, then disperse the titanium dioxide-polytetrafluoroethylene mixture in acetone and perform ultrasonic treatment for 10 - 20 minutes to obtain a titanium dioxide-polytetrafluoroethylene mixture dispersion;

[0012] A5. Under nitrogen protection, add isocyanate crosslinking agent and catalyst into the titanium dioxide-polytetrafluoroethylene mixture dispersion, stir evenly, and react at 70 - 80°C for 2 - 4 h. Cool down to 50 - 60°C and then add benzyl alcohol to continue the reaction for 1 - 2 h. Use a vacuum pump to filter out acetone to obtain modified polytetrafluoroethylene.

[0013] Further, in step A2, the ultrasonic treatment frequency is 2000 - 5000 Hz; in step A4, the ultrasonic treatment frequency is 1000 - 2000 Hz.

[0014] Further, the addition amount of the titanium dioxide sol is 25 - 35% of the mass of polytetrafluoroethylene.

[0015] Further, the addition amount of the benzyl alcohol is 10 - 14% of the mass of the titanium dioxide-polytetrafluoroethylene mixture.

[0016] Specifically, the preparation method of the titanium dioxide sol is as follows: Dissolve 50 - 100 g of tetrabutyl titanate in 1 L of anhydrous acetaldehyde, add 1 - 2 g of acetylacetone, and under strong stirring, dropwise add a mixed solution of 0.1 - 0.5 mol / L nitric acid, deionized water, and anhydrous ethanol to form a white gel-like precipitate, thus obtaining titanium dioxide sol. Among them, the molar ratio of the nitric acid, deionized water, and anhydrous ethanol is 1:0.2:0.3.

[0017] Further, the molar ratio of the benzyl alcohol to the isocyanate crosslinking agent is 1.5 - 2.5:0.5 - 1.5.

[0018] Further, the isocyanate crosslinking agent is at least one of hexamethylene diisocyanate, toluene diisocyanate, or isophorone diisocyanate.

[0019] Further, the addition amount of the catalyst is 2-3% of the total mass of the titanium dioxide-polytetrafluoroethylene mixture, benzyl alcohol and isocyanate crosslinking agent, and the catalyst is at least one of dibutyltin dilaurate and stannous octoate.

[0020] Further, the reinforcing carbon black is a mixture of carbon black 550 and carbon black 330 mixed at a weight ratio of 10-12:20-25.

[0021] Further, the anti-aging agent is anti-aging agent RD.

[0022] Further, the dispersant is dispersant WB212.

[0023] Further, the plasticizer is at least one of bis(2-ethylhexyl) phthalate, dibutyl phthalate and diethyl phthalate.

[0024] Another object of the present invention is achieved by the following technical solution: The preparation method of the above-mentioned high weather resistance and wear-resistant composite material for soles includes the following steps:

[0025] (S1), Take nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, modified polytetrafluoroethylene, anti-aging agent, reinforcing carbon black, plasticizer and dispersant by weight parts, and set aside;

[0026] (S2), Mix and knead nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, modified polytetrafluoroethylene, anti-aging agent, reinforcing carbon black, plasticizer and dispersant in a kneader, then pour out the material, open mill and granulate to obtain pellets;

[0027] (S3), Melt the pellets in step (S2) in an injection molding machine and then inject them into a sealed sole mold, and cool and mold to obtain the high weather resistance and wear-resistant composite material for soles.

[0028] Further, the operating temperature of the kneader is 165-190 °C; the operating temperature of the injection molding machine is 165-190 °C.

[0029] The preparation method of the high weather resistance and wear-resistant composite material for soles is simple in operation, convenient to control, high in production efficiency, low in production cost, and can be used for large-scale production.

[0030] The beneficial effects of the present invention are as follows: The high weather resistance and wear-resistant composite material for soles of the present invention uses nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer and modified polytetrafluoroethylene as the main rubber materials, and adds anti-aging agent, reinforcing carbon black, dispersant and plasticizer. The prepared composite material has strong tensile strength, high elongation at break, strong tear strength, wear resistance and anti-aging performance, and is not easily dissolved by organic solvents and adhered to the ground in the spray painting operation environment.

[0031] The preparation method of the high weather resistance and wear resistance composite material for shoe soles of the present invention is simple to operate, convenient to control, high in production efficiency and low in production cost, and can be used for large-scale production. Detailed implementation manners

[0032] For the convenience of those skilled in the art to understand, the present invention will be further described below in conjunction with embodiments. The content mentioned in the implementation manners does not limit the present invention.

[0033] Embodiment 1

[0034] A high weather resistance and wear resistance composite material for shoe soles, comprising the following raw materials in parts by weight: 65 parts of nitrile rubber, 18 parts of chloroprene rubber, 25 parts of thermoplastic polyurethane elastomer, 20 parts of modified polytetrafluoroethylene, 1 part of antioxidant, 8 parts of reinforcing carbon black, and 5 parts of plasticizer.

[0035] In this embodiment, the nitrile rubber is selected from NBR-3306, the chloroprene rubber is selected from Neoprene W, and the thermoplastic polyurethane elastomer is selected from Elastollan V2905.

[0036] Further, the preparation method of the modified polytetrafluoroethylene comprises the following steps:

[0037] A1. Add deionized water to polytetrafluoroethylene to obtain a polytetrafluoroethylene dispersion with a solid content of 80%;

[0038] A2. Add titanium dioxide sol and polytetrafluoroethylene dispersion to a reactor, stir evenly, then perform ultrasonic dispersion at a temperature of 100°C for 1.5 h. After natural cooling, put the precipitate in the reactor into a drying oven and dry for 12 h. Grind the dried powder for standby;

[0039] A3. Add the ground powder to a crucible, and then transfer it to a sintering furnace with nitrogen protection. The sintering temperature is 600°C and the sintering time is 40 min. After heating is completed and natural cooling, titanium dioxide-polytetrafluoroethylene mixture can be obtained;

[0040] A4. Dry the titanium dioxide-polytetrafluoroethylene mixture and benzyl alcohol at 110°C for 3 h, then disperse the titanium dioxide-polytetrafluoroethylene mixture in acetone and perform ultrasonic treatment for 15 minutes to obtain a titanium dioxide-polytetrafluoroethylene mixture dispersion;

[0041] A5. Under nitrogen protection, add isocyanate crosslinking agent and catalyst to the titanium dioxide-polytetrafluoroethylene mixture dispersion, stir evenly, react at 75°C for 3 h, cool down to 55°C, add benzyl alcohol and continue to react for 1.5 h, and use a vacuum pump to filter out acetone to obtain modified polytetrafluoroethylene.

[0042] Further, the polytetrafluoroethylene is selected from 7A.

[0043] Further, in step A2, the frequency of ultrasonic treatment is 3000 Hz; in step A4, the frequency of ultrasonic treatment is 1500 Hz.

[0044] Further, the addition amount of the titanium dioxide sol is 30% of the mass of the polytetrafluoroethylene.

[0045] Further, the addition amount of the benzyl alcohol is 12% of the mass of the titanium dioxide-polytetrafluoroethylene mixture.

[0046] Specifically, the preparation method of the titanium dioxide sol is as follows: 75 g of tetrabutyl titanate is dissolved in 1 L of absolute acetaldehyde, 1.5 g of acetylacetone is added, and under strong stirring, a mixed solution of 0.3 mol / L nitric acid, deionized water and absolute ethanol is dropped in, and a white gel-like precipitate appears to obtain the titanium dioxide sol. Among them, the molar ratio of the nitric acid, deionized water and absolute ethanol is 1:0.2:0.3.

[0047] Further, the molar ratio of the benzyl alcohol to the isocyanate crosslinking agent is 1.8:0.8.

[0048] Further, the isocyanate crosslinking agent is toluene diisocyanate.

[0049] Further, the addition amount of the catalyst is 2.5% of the total mass of the titanium dioxide-polytetrafluoroethylene mixture, the benzyl alcohol and the isocyanate crosslinking agent, and the catalyst is dibutyltin dilaurate.

[0050] Further, the reinforcing carbon black is a mixture of carbon black 550 and carbon black 330 in a weight ratio of 11:22.

[0051] Further, the anti-aging agent is anti-aging agent RD.

[0052] Further, the dispersant is dispersant WB212.

[0053] Further, the plasticizer is dibutyl phthalate.

[0054] A preparation method of a high weather resistance and wear-resistant composite material for shoe soles includes the following steps:

[0055] (S1), take acrylonitrile-butadiene rubber, chloroprene rubber, thermoplastic polyurethane elastomer, modified polytetrafluoroethylene, anti-aging agent, reinforcing carbon black, plasticizer and dispersant by weight parts for standby;

[0056] (S2), Mix and knead nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, modified polytetrafluoroethylene, anti-aging agent, reinforcing carbon black, plasticizer and dispersant in a mixer, then discharge the material, open mill and granulate to obtain granulated materials;

[0057] (S3), Melt the granulated materials obtained in step (S2) in an injection molding machine and then inject them into a sealed sole mold, and cool and form to obtain a highly weather-resistant and wear-resistant composite material for soles.

[0058] Furthermore, the operating temperature of the mixer is 180 °C; the operating temperature of the injection molding machine is 180 °C.

[0059] Example 2

[0060] Different from Example 1, a highly weather-resistant and wear-resistant composite material for soles comprises the following raw materials in parts by weight: 70 parts of nitrile rubber, 22 parts of chloroprene rubber, 30 parts of thermoplastic polyurethane elastomer, 25 parts of modified polytetrafluoroethylene, 1.5 parts of anti-aging agent, 10 parts of reinforcing carbon black, and 8 parts of plasticizer.

[0061] A preparation method of a highly weather-resistant and wear-resistant composite material for soles comprises the following steps:

[0062] (S1), Weigh nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, modified polytetrafluoroethylene, anti-aging agent, reinforcing carbon black, plasticizer and dispersant according to parts by weight and set aside;

[0063] (S2), Mix and knead nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, modified polytetrafluoroethylene, anti-aging agent, reinforcing carbon black, plasticizer and dispersant in a mixer, then discharge the material, open mill and granulate to obtain granulated materials;

[0064] (S3), Melt the granulated materials obtained in step (S2) in an injection molding machine and then inject them into a sealed sole mold, and cool and form to obtain a highly weather-resistant and wear-resistant composite material for soles.

[0065] Example 3

[0066] Different from Example 1, a highly weather-resistant and wear-resistant composite material for soles comprises the following raw materials in parts by weight: 75 parts of nitrile rubber, 25 parts of chloroprene rubber, 35 parts of thermoplastic polyurethane elastomer, 30 parts of modified polytetrafluoroethylene, 2 parts of anti-aging agent, 12 parts of reinforcing carbon black, and 10 parts of plasticizer.

[0067] A preparation method of a highly weather-resistant and wear-resistant composite material for soles comprises the following steps:

[0068] (S1), Weigh nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, modified polytetrafluoroethylene, anti-aging agent, reinforcing carbon black, plasticizer and dispersant according to parts by weight and set aside;

[0069] (S2), Mix and knead nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, modified polytetrafluoroethylene, anti-aging agent, reinforcing carbon black, plasticizer and dispersant in a kneader, then discharge the material, open mill and granulate to obtain granular materials;

[0070] (S3), Melt the granular materials in step (S2) in an injection molding machine and then inject them into a sealed sole mold, and cool and form to obtain a highly weather-resistant and wear-resistant composite material for soles.

[0071] Comparative Example 1

[0072] The difference between this comparative example and Example 2 is that an equal amount of polytetrafluoroethylene is replaced with modified polytetrafluoroethylene.

[0073] A highly weather-resistant and wear-resistant composite material for soles, comprising the following raw materials in parts by weight: 70 parts of nitrile rubber, 22 parts of chloroprene rubber, 30 parts of thermoplastic polyurethane elastomer, 25 parts of polytetrafluoroethylene, 1.5 parts of anti-aging agent, 10 parts of reinforcing carbon black, and 8 parts of plasticizer.

[0074] A preparation method of a highly weather-resistant and wear-resistant composite material for soles, comprising the following steps:

[0075] (S1), Weigh and take nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, polytetrafluoroethylene, anti-aging agent, reinforcing carbon black, plasticizer and dispersant according to parts by weight, and set aside;

[0076] (S2), Mix and knead nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, polytetrafluoroethylene, anti-aging agent, reinforcing carbon black, plasticizer and dispersant in a kneader, then discharge the material, open mill and granulate to obtain granular materials;

[0077] (S3), Melt the granular materials in step (S2) in an injection molding machine and then inject them into a sealed sole mold, and cool and form to obtain a highly weather-resistant and wear-resistant composite material for soles.

[0078] Comparative Example 2

[0079] The difference between this comparative example and Example 3 is that 26 parts by weight of nitrile rubber and 9 parts by weight of chloroprene rubber are replaced with thermoplastic polyurethane elastomer.

[0080] A highly weather-resistant and wear-resistant composite material for soles, comprising the following raw materials in parts by weight: 101 parts of nitrile rubber, 34 parts of chloroprene rubber, 30 parts of modified polytetrafluoroethylene, 2 parts of anti-aging agent, 12 parts of reinforcing carbon black, and 10 parts of plasticizer.

[0081] A preparation method of a highly weather-resistant and wear-resistant composite material for soles, comprising the following steps:

[0082] (S1) Take nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, modified polytetrafluoroethylene, anti-aging agent, reinforcing carbon black, plasticizer and dispersant by weight parts for standby;

[0083] (S2) Mix and knead nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, modified polytetrafluoroethylene, anti-aging agent, reinforcing carbon black, plasticizer and dispersant in an internal mixer, then discharge, open mill and granulate to obtain granular materials;

[0084] (S3) Melt the granular materials in step (S2) in an injection molding machine and then inject them into a sealed sole mold for cooling and molding to obtain a high weather resistance and wear-resistant composite material for soles.

[0085] Performance Test

[0086] Take the composite materials of Examples 1-3 and Comparative Examples 1-2, and test their tensile strength, elongation at break, tear strength, wear resistance and resistance to organic solvent corrosion. The test methods are as follows:

[0087] Tensile strength and elongation at break: Test according to "GB / T 3903.22-2008 Footwear - Test methods for outsoles - Tensile strength and elongation";

[0088] Tear strength and wear resistance: Test according to "GB 21148-2007 Personal protective equipment - Safety shoes";

[0089] Resistance to organic solvent corrosion: Contact the bottom of the composite material with acetone in a closed environment for 1 h, and then observe the change of the bottom of the outsole.

[0090] The test results are shown in the following table:

[0091]

[0092]

[0093] The above embodiments are preferred implementation solutions of the present invention. In addition, the present invention can also be implemented in other ways. Any obvious replacements without departing from the concept of the present invention are within the protection scope of the present invention.

Claims

1. A highly weather-resistant and wear-resistant composite material for shoe soles, characterized in that: The invention comprises the following raw materials in parts by weight: 65-75 parts of nitrile rubber, 18-25 parts of chloroprene rubber, 25-35 parts of thermoplastic polyurethane elastomer, 20-30 parts of modified polytetrafluoroethylene, 1-2 parts of antioxidant, 1-2 parts of dispersant, 8-12 parts of reinforcing carbon black and 5-10 parts of plasticizer.

2. The highly weather-resistant and wear-resistant composite material for shoe soles according to claim 1, characterized in that: The preparation method of the modified polytetrafluoroethylene comprises the following steps: A1. Add deionized water to polytetrafluoroethylene to prepare a polytetrafluoroethylene dispersion having a solid content of 75-85%; A2, adding titanium dioxide sol and polytetrafluoroethylene dispersion into the reactor and stirring evenly, ultrasonically dispersing at 80-110°C for 1-2h, and after natural cooling, placing the precipitate in the reactor in a drying oven for 12h, grinding the dried powder for standby use; A3. Add the ground powder into a crucible, and then transfer it to a sintering furnace protected by nitrogen. The sintering temperature is 550-650°C and the sintering time is 30-45 minutes. After heating is completed and naturally cooled, a titanium dioxide-polytetrafluoroethylene mixture can be obtained. A4, drying the titanium dioxide-polytetrafluoroethylene mixture and benzyl alcohol at 100-120° C. for 2-4 hours, dispersing the titanium dioxide-polytetrafluoroethylene mixture in acetone, and ultrasonically treating for 10-20 minutes to obtain a titanium dioxide-polytetrafluoroethylene mixture dispersion; A5. Under nitrogen protection, add isocyanate crosslinker and catalyst to the titanium dioxide-polytetrafluoroethylene mixture dispersion, stir evenly, and react at 70-80°C for 2-4h, cool to 50-60°C, add benzyl alcohol and continue to react for 1-2h, use a vacuum pump to filter out acetone to obtain modified polytetrafluoroethylene.

3. The highly weather-resistant and wear-resistant composite material for shoe soles according to claim 2, characterized in that: The added amount of the catalyst is 2-3% of the total mass of the titanium dioxide-polytetrafluoroethylene mixture, benzyl alcohol and isocyanate crosslinking agent, and the catalyst is at least one of dibutyltin dilaurate and stannous octoate.

4. The highly weather-resistant and wear-resistant composite material for shoe soles according to claim 2, characterized in that: The isocyanate crosslinking agent is at least one of hexamethylene diisocyanate, toluene diisocyanate or isophorone diisocyanate.

5. The highly weather-resistant and wear-resistant composite material for shoe soles according to claim 2, characterized in that: The added amount of the titanium dioxide sol is 25-35% of the mass of the polytetrafluoroethylene.

6. The highly weather-resistant and wear-resistant composite material for shoe soles according to claim 1, characterized in that: The reinforcing carbon black is a mixture of carbon black 550 and carbon black 330 in a weight ratio of 10-12:20-25.

7. The highly weather-resistant and wear-resistant composite material for shoe soles according to claim 2, characterized in that: The molar ratio of the benzyl alcohol to the isocyanate crosslinking agent is 1.5-2.5:0.5-1.

5.

8. The highly weather-resistant and wear-resistant composite material for shoe soles according to claim 1, characterized in that: The plasticizer is at least one of di(2-ethylhexyl) phthalate, dibutyl phthalate and diethyl phthalate.

9. A method for preparing a highly weather-resistant and wear-resistant composite material for shoe soles according to any one of claims 1 to 8, characterized in that: The steps include: (S1), taking nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, modified polytetrafluoroethylene, antioxidant, reinforcing carbon black, plasticizer and dispersant by weight, and set aside; (S2), mixing nitrile rubber, chloroprene rubber, thermoplastic polyurethane elastomer, modified polytetrafluoroethylene, antioxidant, reinforcing carbon black, plasticizer and dispersant in an internal mixer, and then pouring, refining and granulating to obtain pellets; (S3), melting the pellets of step (S2) in an injection molding machine and then injecting them into a sealed sole mold, cooling and molding, thereby obtaining a highly weather-resistant and wear-resistant composite material for soles.

10. The method for preparing a highly weather-resistant and wear-resistant composite material for shoe soles according to claim 9, characterized in that: The operating temperature of the internal mixer is 165-190°C; the operating temperature of the injection molding machine is 165-190°C.

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