Styrene butadiene rubber shoe material and preparation method thereof

Abstract

The invention provides a butadiene styrene rubber shoe material and a preparation method thereof. The butadiene styrene rubber shoe material is prepared from the following raw materials in parts by weight: 90-99 parts of lignin modified butadiene styrene rubber, 0.5-5 parts of tackifying resin, 0.1-2 parts of a cross-linking agent, 0.1-2 parts of filler and 0-2 parts of an auxiliary agent, the tackifying resin comprises styrene modified petroleum resin, and the auxiliary agent at least comprises at least one of an ultraviolet absorbent, a lubricant and an antioxidant. The styrene-butadiene rubber is modified by lignin, so that the tensile strength and the elongation at break can be improved. The styrene modified petroleum resin is selected as the tackifying resin, and the petroleum resin is added on the basis of the lignin modified styrene butadiene rubber, so that the free volume of molecular chains in the rubber can be reduced, the friction between chain segments, between fillers and between the chain segments and the fillers is increased, the hysteresis is enhanced, and the wet skid resistance can be improved. After the petroleum resin is modified by the styrene, the polarity and the softening point of the petroleum resin can be improved, so that the dipole moment and the crosslinking density are increased, and the hardness and the elasticity of the shoe material are improved.

Description

Technical Field

[0001] The invention relates to the technical field of styrene-butadiene rubber materials, in particular to styrene-butadiene rubber shoe materials and a preparation method thereof. Background Art

[0002] Styrene butadiene rubber (SBR), also known as polystyrene butadiene copolymer. Its physical properties, processing properties and product performance are close to those of natural rubber. Some properties such as wear resistance, heat resistance, aging resistance and vulcanization speed are better than those of natural rubber. It can be used in combination with natural rubber and various synthetic rubbers. It is widely used in the production of tires, tapes, hoses, wires and cables, medical devices and various rubber products. It is the largest general synthetic rubber variety and one of the earliest rubber varieties to achieve industrial production. It has the advantages of both rubber and plastic. It can be formed with plastic processing equipment. It does not require vulcanization at room temperature and has the elasticity of vulcanized rubber. After mixing with various additives, it can be made into various beautiful and comfortable soles. It is one of the most promising new materials in the shoemaking industry. The soles made by replacing vulcanized rubber and polyvinyl chloride with styrene butadiene rubber (SBR) have good elasticity (small force or residual deformation), are comfortable to wear, and do not cause stinky feet, so they are widely used in the shoemaking industry.

[0003] In order to meet the use requirements of shoe materials, most of the current styrene-butadiene rubber shoe materials will add reinforcing agents, such as carbon black, white carbon black, etc., to improve the mechanical properties. However, carbon black and white carbon black also have certain problems in industrial applications. For example, the high price makes the cost of rubber after filling increase significantly; due to the small particles, it is difficult to disperse in rubber and the price, so the filling amount cannot be too high. Therefore, the current styrene-butadiene rubber shoe materials are difficult to meet the strength requirements for long-term use. Summary of the invention

[0004] The object of the present invention is to provide a styrene-butadiene rubber shoe material and a preparation method thereof. The styrene-butadiene rubber shoe material not only has high elasticity, but also has good mechanical strength and anti-slip performance, which is conducive to its promotion and application in the shoe material market.

[0005] To achieve the above object, the present invention provides a styrene-butadiene rubber shoe material on one hand. The raw materials for preparing the styrene-butadiene rubber shoe material include 90 to 99 parts of lignin-modified styrene-butadiene rubber, 0.5 to 5 parts of tackifying resin, 0.1 to 2 parts of cross-linking agent, 0.1 to 2 parts of filler and 0 to 2 parts of auxiliary agent by weight, the tackifying resin includes styrene-modified petroleum resin, and the auxiliary agent includes at least one of a UV absorber, a lubricant and an antioxidant.

[0006] The raw materials for preparing the shoe material of the present invention are mainly styrene-butadiene rubber-like substances. Styrene-butadiene rubber has high elasticity, and the shoe material made of it as the main raw material has high resilience. In addition, styrene-butadiene rubber is modified by lignin. Since lignin has both rigid network and flexible side chain structure, styrene-butadiene rubber can be reinforced to improve the tensile strength and elongation at break of styrene-butadiene rubber, thereby overcoming the high cost and difficult dispersion problems of using carbon black and white carbon black reinforcing agents. However, the rolling resistance of styrene-butadiene rubber is reduced after being modified by lignin, and the anti-slip performance is reduced. Based on this, the inventor creatively selects styrene-modified petroleum resin as a tackifying resin, and adds petroleum resin on the basis of lignin-modified styrene-butadiene rubber, which can reduce the free volume of molecular chains in rubber, increase the friction between segments, between fillers, and between segments and fillers, and enhance the hysteresis, so that the anti-slip performance can be improved. In addition, after the petroleum resin is modified by styrene, the polarity and softening point of the petroleum resin can be improved, so the dipole moment and cross-linking density increase, thereby improving the hardness and elasticity of the shoe material. Therefore, the shoe material preparation raw material of the present invention is supplemented with styrene-modified petroleum resin as a tackifier based on lignin-modified styrene-butadiene rubber, so that the prepared shoe material has high resilience, better mechanical strength and anti-slip performance.

[0007] As a technical solution of the present invention, the lignin-modified styrene-butadiene rubber is styrene-butadiene rubber modified by lignin phenolic resin.

[0008] As a technical solution of the present invention, the lignin phenolic resin and the styrene butadiene rubber in the lignin-modified styrene butadiene rubber present an interpenetrating network structure.

[0009] As a technical solution of the present invention, the lignin phenolic resin accounts for 10-35% of the mass of the lignin-modified styrene-butadiene rubber.

[0010] As a technical solution of the present invention, the lignin phenolic resin is obtained by reacting lignin to replace part of phenol with formaldehyde, and the lignin accounts for 20-40% of the sum of the mass of the lignin and the phenol.

[0011] As a technical solution of the present invention, the cross-linking agent includes di-tert-butyl peroxide isopropylbenzene, and the filler includes at least one of silicon dioxide, talc, calcium carbonate, mica, kaolin, wollastonite and titanium dioxide.

[0012] As a technical solution of the present invention, the ultraviolet absorber includes at least one of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2,4-bis(2,4-xylyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine and 2-hydroxy-4-n-octyloxybenzophenone, and the lubricant includes at least one of calcium stearate, zinc stearate, magnesium stearate and stearic acid.

[0013] As a technical solution of the present invention, the antioxidant includes at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (1010), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (1076), 2,6-di-tert-butyl-p-methylphenol (T501), 1-hydroxy-4-methyl-2,6-di-tert-butylbenzene (264), tris(2,4-di-tert-butylphenyl) phosphite (168) and triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (2450).

[0014] As a technical solution of the present invention, the antioxidant includes tris(2,4-di-tert-butylphenyl)phosphite and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and the mass ratio of the two is 1 to 4:1.

[0015] Another aspect of the present invention provides a method for preparing styrene-butadiene rubber shoe materials, comprising the steps of:

[0016] (1) Lignin modified styrene butadiene rubber

[0017] Add lignin, phenol, formaldehyde, inorganic base and small molecule alcohol into a reactor, heat to 70-90°C for reaction, then cool and decompress to obtain lignin phenolic resin, mix the lignin phenolic resin and styrene-butadiene rubber, knead at room temperature, add a vulcanizing agent, heat to 150-180°C and knead;

[0018] (2) Styrene modified petroleum resin

[0019] Styrene and solvent are mixed, a catalyst is added and stirred to form a suspension, the suspension is placed in a constant temperature of 40-65°C and C5-C9 petroleum resin is added dropwise, after the addition is completed, the suspension is polymerized at a constant temperature and an alkali solution is used to terminate the reaction;

[0020] (3) Mixing and Injection Molding

[0021] The lignin-modified styrene-butadiene rubber, the styrene-modified petroleum resin, the tackifying resin, the crosslinking agent, the filler and the auxiliary agent in the formula amount are added into an internal mixer and heated and internally kneaded to obtain a mixture. After internal kneading, the mixture is injection molded by an injection molding machine.

[0022] The raw materials involved in the preparation method of the present invention are simple and easy to obtain, the operation is simple, and the prepared shoe material has higher resilience, better mechanical strength and anti-slip performance.

[0023] As a technical solution of the present invention, the inorganic base is sodium hydroxide, potassium hydroxide or ammonium hydroxide.

[0024] As a technical solution of the present invention, the small molecule alcohol is a small molecule monohydric alcohol or dihydric alcohol having 2 to 5 carbon atoms.

[0025] As a technical solution of the present invention, the solvent is at least one of ethanol, propanol, isoprene glycol, acetone, methanol, n-butanol, ethyl acetate, ether, chloroform, dichloromethane and petroleum ether.

[0026] As a technical solution of the present invention, the catalyst may be aluminum trichloride. DETAILED DESCRIPTION

[0027] The raw materials for preparing the styrene-butadiene rubber shoe material of the present invention include lignin-modified styrene-butadiene rubber, tackifying resin, cross-linking agent, filler and auxiliary agent.

[0028] Among them, lignin modified styrene butadiene rubber is used as the main raw material, accounting for 90-99 parts of the raw materials for preparation, and its content can be but not limited to 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, and 99 parts of the raw materials for preparation. Lignin modified styrene butadiene rubber is styrene butadiene rubber modified by lignin phenolic resin. The introduction of phenolic hydroxyl groups on the basis of styrene butadiene rubber can delay the vulcanization of the rubber material, thereby prolonging the time for the tensile strength to reach the maximum value, so as to improve its mechanical strength. In the lignin modified styrene butadiene rubber, lignin phenolic resin and styrene butadiene rubber present an interpenetrating network structure.

[0029] The synthesis of lignin-modified styrene-butadiene rubber may include: adding lignin, phenol, formaldehyde, inorganic base and small molecule alcohol into a reactor, heating to 70-90°C for reaction and then cooling and decompressing to dehydrate to obtain lignin phenolic resin, mixing the lignin phenolic resin and styrene-butadiene rubber and kneading them at room temperature first, adding a vulcanizing agent after kneading at room temperature and heating to 150-180°C for kneading.

[0030] The inorganic base is sodium hydroxide, potassium hydroxide or ammonium hydroxide. The molecular alcohol is a small molecular monohydric alcohol or dihydric alcohol with 2 to 5 carbon atoms, such as methanol, ethanol, ethylene glycol, propanol, isoprene glycol, and n-butanol. The molar ratio of phenol to formaldehyde is 1:1.1 to 1.8. Ethanol is 90 to 120% of the mass of phenol. The temperature of cooling and decompression can be 50 to 65°C. The lignin phenolic resin is obtained by reacting part of phenol with formaldehyde by replacing lignin, and lignin accounts for 20 to 40% of the sum of the mass of lignin and phenol. The content of lignin is controlled to make the comprehensive performance of the shoe material better. The lignin phenolic resin accounts for 10 to 35% of the mass of the lignin-modified styrene-butadiene rubber. The content of lignin phenolic resin should not be too low, otherwise the strength of styrene-butadiene rubber cannot be effectively improved. The content of lignin phenolic resin should not be too high, otherwise the phase separation of lignin phenolic resin and styrene-butadiene rubber will be caused. The lignin phenolic resin and styrene-butadiene rubber are mixed and then vulcanized with a vulcanizing agent. The vulcanizing agent may be a conventional vulcanizing agent, such as sulfur, organic disulfide and polysulfide, thiazoles, diphenylguanidines, alkylphenolic resins, polyhalides, and the like.

[0031] The tackifying resin accounts for 0.5 to 5 parts of the raw materials, and its content can be but not limited to 0.5, 1, 2, 3, 4, and 5 parts of the raw materials. The tackifying resin is styrene-modified petroleum resin.

[0032] The synthesis of styrene-modified petroleum resin may include: mixing styrene and solvent, adding catalyst and stirring to form suspension, placing the suspension in a constant temperature of 40-65°C and then adding C5-C9 petroleum resin dropwise, polymerizing at constant temperature after the addition is completed and terminating the reaction with alkali solution. The solvent is at least one of ethanol, propanol, isoprene glycol, acetone, methanol, n-butanol, ethyl acetate, ether, chloroform, dichloromethane and petroleum ether. The catalyst may be aluminum chloride. The alkali solution may be sodium hydroxide or potassium hydroxide solution.

[0033] The raw materials for preparing the styrene-butadiene rubber shoe material of the present invention may further include a crosslinking agent, and the content of the crosslinking agent in the raw materials may be, but is not limited to, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 part, 1.1 part, 1.2 part, 1.3 part, 1.4 part, 1.5 part, 1.6 part, 1.7 part, 1.8 part, 1.9 part, 2.0 part. The crosslinking agent includes di-tert-butyl peroxide isopropylbenzene.

[0034] The raw materials for preparing the styrene-butadiene rubber shoe material of the present invention may further include fillers, and the content of the fillers in the raw materials may be, but is not limited to, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2.0 parts. The filler includes at least one of silicon dioxide, talc, calcium carbonate, mica, kaolin, wollastonite and titanium dioxide.

[0035] The raw materials for preparing the styrene-butadiene rubber shoe material of the present invention may further include auxiliary agents, which include at least one of ultraviolet absorbers, lubricants and antioxidants. The content of the auxiliary agents in the raw materials may be, but is not limited to, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0. The ultraviolet absorber includes at least one of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2,4-bis(2,4-xylyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine and 2-hydroxy-4-n-octyloxybenzophenone. The lubricant includes at least one of calcium stearate, zinc stearate, magnesium stearate and stearic acid. The antioxidant includes at least one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester (antioxidant 1010), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester (antioxidant 1076), 2,6-di-tert-butyl-p-methylphenol (antioxidant T501), 1-hydroxy-4-methyl-2,6-bis-tertiary butylbenzene (antioxidant 264), tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168) and triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (antioxidant 2450). More preferably, the antioxidant includes tris(2,4-di-tert-butylphenyl) phosphite (Antioxidant 168) and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Antioxidant 1076), and the mass ratio of the two is 1 to 4:1.

[0036] The preparation method of the styrene-butadiene rubber shoe material of the present invention comprises adding a formula amount of lignin-modified styrene-butadiene rubber, styrene-modified petroleum resin, tackifying resin, crosslinking agent, filler and auxiliary agent into an internal mixer, heating and internal mixing to obtain a mixture, and after internal mixing, injection molding the mixture by an injection molding machine.

[0037] In order to better illustrate the purpose, technical scheme and beneficial effects of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be noted that the following implementation method is a further explanation of the present invention and should not be used as a limitation of the present invention.

[0038] Synthesis of lignin modified styrene butadiene rubber A1:

[0039] Add lignin, phenol, formaldehyde, sodium hydroxide and ethanol to a reactor, heat to 80°C for reaction for 1 hour, then cool to 60°C for dehydration under reduced pressure to obtain lignin phenolic resin, mix lignin phenolic resin and styrene-butadiene rubber (the mass ratio of lignin phenolic resin to styrene-butadiene rubber is 25:75) and knead at room temperature for 1 hour, then add an organic disulfide vulcanizing agent and heat to 170°C for kneading for 60 minutes. Among them, the molar ratio of phenol to formaldehyde is 1:1.6, the amount of sodium hydroxide is 5% of the mass of phenol, the amount of ethanol is 120% of the mass of phenol, and the mass ratio of lignin to phenol is 25:75.

[0040] Synthesis of lignin modified styrene butadiene rubber A2:

[0041] Add lignin, phenol, formaldehyde, potassium hydroxide and n-butanol into a reactor, heat to 75°C for reaction for 2h, then cool to 55°C for dehydration under reduced pressure to obtain lignin phenolic resin, mix lignin phenolic resin and styrene-butadiene rubber (the mass ratio of lignin phenolic resin to styrene-butadiene rubber is 30:70) and knead at room temperature for 1h, then add an organic disulfide vulcanizing agent and heat to 180°C for kneading for 50min. Among them, the molar ratio of phenol to formaldehyde is 1:1.5, the amount of sodium hydroxide is 7% of the mass of phenol, the amount of n-butanol is 100% of the mass of phenol, and the mass ratio of lignin to phenol is 30:70.

[0042] Synthesis of lignin modified styrene butadiene rubber A3:

[0043] Lignin and styrene-butadiene rubber (the mass ratio of lignin to styrene-butadiene rubber is 25:75) are mixed and kneaded at room temperature for 1 hour, and then an organic disulfide vulcanizing agent is added and the temperature is raised to 170°C for kneading for 60 minutes. Among them, the molar ratio of phenol to formaldehyde is 1:1.6, the amount of sodium hydroxide is 5% of the mass of phenol, the amount of ethanol is 120% of the mass of phenol, and the mass ratio of lignin to phenol is 25:75.

[0044] Synthesis of styrene-modified petroleum resin B1: Styrene and ethanol are mixed, aluminum chloride is added and stirred to form a suspension, the suspension is placed in a constant temperature of 60°C and C5 petroleum resin is added dropwise, after the addition is completed, the polymerization is carried out at a constant temperature and sodium hydroxide is used to terminate the reaction.

[0045] Synthesis of styrene-modified petroleum resin B2: Styrene and n-butanol are mixed, aluminum chloride is added and stirred to form a suspension, the suspension is placed in a constant temperature of 50°C and C9 petroleum resin is added dropwise. After the addition is completed, the suspension is polymerized at a constant temperature and sodium hydroxide is used to terminate the reaction.

[0046] Example 1

[0047] This embodiment is a styrene-butadiene rubber shoe material and a preparation method thereof.

[0048] The raw materials for preparing styrene-butadiene rubber shoe materials include, in parts by weight, 97 parts of lignin-modified styrene-butadiene rubber A1, 1 part of styrene-modified petroleum resin B1, 0.5 parts of di-tert-butyl peroxide isopropylbenzene, 0.8 parts of silicon dioxide, 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0.2 parts of tris(2,4-di-tert-butylphenyl) phosphite, 0.1 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.2 parts of calcium stearate.

[0049] The preparation method of the styrene-butadiene rubber shoe material of the present embodiment can be as follows: lignin-modified styrene-butadiene rubber A1, ethylene-modified petroleum resin B1, di-tert-butyl peroxide isopropylbenzene, silicon dioxide, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, tris(2,4-di-tert-butylphenyl) phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester and calcium stearate are added into an internal mixer, heated and internally kneaded to obtain a mixture, and after internal kneading, the mixture is injection molded by an injection molding machine.

[0050] Example 2

[0051] This embodiment is a styrene-butadiene rubber shoe material and a preparation method thereof.

[0052] The raw materials for preparing styrene-butadiene rubber shoe materials include, in parts by weight, 97 parts of lignin-modified styrene-butadiene rubber A2, 1 part of styrene-modified petroleum resin B1, 0.5 parts of di-tert-butyl peroxide isopropylbenzene, 0.8 parts of silicon dioxide, 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0.2 parts of tris(2,4-di-tert-butylphenyl) phosphite, 0.1 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.2 parts of calcium stearate.

[0053] The preparation method of the styrene-butadiene rubber shoe material of the present embodiment can be as follows: lignin-modified styrene-butadiene rubber A2, ethylene-modified petroleum resin B1, di-tert-butyl peroxide isopropylbenzene, silicon dioxide, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, tris(2,4-di-tert-butylphenyl) phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol and calcium stearate are added into an internal mixer, heated and internally kneaded to obtain a mixture, and after internal kneading, the mixture is injection molded by an injection molding machine.

[0054] Example 3

[0055] This embodiment is a styrene-butadiene rubber shoe material and a preparation method thereof.

[0056] The raw materials for preparing styrene-butadiene rubber shoe materials include, in parts by weight, 97 parts of lignin-modified styrene-butadiene rubber A3, 1 part of styrene-modified petroleum resin B1, 0.5 parts of di-tert-butyl peroxide isopropylbenzene, 0.8 parts of silicon dioxide, 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0.2 parts of tris(2,4-di-tert-butylphenyl) phosphite, 0.1 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.2 parts of calcium stearate.

[0057] The preparation method of the styrene-butadiene rubber shoe material of the present embodiment can be as follows: lignin-modified styrene-butadiene rubber A3, ethylene-modified petroleum resin B1, di-tert-butyl peroxide isopropylbenzene, silicon dioxide, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, tris(2,4-di-tert-butylphenyl) phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol and calcium stearate are added into an internal mixer, heated and internally kneaded to obtain a mixture, and after internal kneading, the mixture is injection molded by an injection molding machine.

[0058] Example 4

[0059] This embodiment is a styrene-butadiene rubber shoe material and a preparation method thereof.

[0060] The raw materials for preparing styrene-butadiene rubber shoe materials include, in parts by weight, 97 parts of lignin-modified styrene-butadiene rubber A1, 1 part of styrene-modified petroleum resin B2, 0.5 parts of di-tert-butyl peroxide isopropylbenzene, 0.8 parts of silicon dioxide, 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0.2 parts of tris(2,4-di-tert-butylphenyl) phosphite, 0.1 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.2 parts of calcium stearate.

[0061] The preparation method of the styrene-butadiene rubber shoe material of the present embodiment can be as follows: lignin-modified styrene-butadiene rubber A1, ethylene-modified petroleum resin B2, di-tert-butyl peroxide isopropylbenzene, silicon dioxide, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, tris(2,4-di-tert-butylphenyl) phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol and calcium stearate are added into an internal mixer, heated and internally kneaded to obtain a mixture, and after internal kneading, the mixture is injection molded by an injection molding machine.

[0062] Example 5

[0063] This embodiment is a styrene-butadiene rubber shoe material and a preparation method thereof.

[0064] The raw materials for preparing styrene-butadiene rubber shoe materials include, in parts by weight, 97 parts of lignin-modified styrene-butadiene rubber A2, 1 part of styrene-modified petroleum resin B2, 0.5 parts of di-tert-butyl peroxide isopropylbenzene, 0.8 parts of silicon dioxide, 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0.2 parts of tris(2,4-di-tert-butylphenyl) phosphite, 0.1 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.2 parts of calcium stearate.

[0065] The preparation method of the styrene-butadiene rubber shoe material of the present embodiment can be as follows: lignin-modified styrene-butadiene rubber A2, ethylene-modified petroleum resin B2, di-tert-butyl peroxide isopropylbenzene, silicon dioxide, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, tris(2,4-di-tert-butylphenyl) phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester and calcium stearate are added into an internal mixer, heated and internally kneaded to obtain a mixture, and after internal kneading, the mixture is injection molded by an injection molding machine.

[0066] Example 6

[0067] This embodiment is a styrene-butadiene rubber shoe material and a preparation method thereof.

[0068] The raw materials for preparing styrene-butadiene rubber shoe materials include, in parts by weight, 95 parts of lignin-modified styrene-butadiene rubber A1, 2 parts of styrene-modified petroleum resin B1, 1 part of di-tert-butyl peroxide isopropylbenzene, 1 part of silicon dioxide, 0.3 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0.3 parts of tris(2,4-di-tert-butylphenyl) phosphite, 0.1 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.3 parts of calcium stearate.

[0069] The preparation method of the styrene-butadiene rubber shoe material of the present embodiment can be as follows: lignin-modified styrene-butadiene rubber A1, ethylene-modified petroleum resin B1, di-tert-butyl peroxide isopropylbenzene, silicon dioxide, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, tris(2,4-di-tert-butylphenyl) phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester and calcium stearate are added into an internal mixer, heated and internally kneaded to obtain a mixture, and after internal kneading, the mixture is injection molded by an injection molding machine.

[0070] Example 7

[0071] This embodiment is a styrene-butadiene rubber shoe material and a preparation method thereof.

[0072] Measured in parts by weight, the raw materials for preparing styrene-butadiene rubber shoe materials include 97 parts of lignin-modified styrene-butadiene rubber A1, 1 part of styrene-modified petroleum resin B1, 0.5 parts of di-tert-butyl peroxide isopropylbenzene, 0.8 parts of mica, 0.2 parts of 2-hydroxy-4-n-octyloxybenzophenone, 0.4 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and 0.2 parts of magnesium stearate.

[0073] The preparation method of the styrene-butadiene rubber shoe material of the present embodiment can be as follows: adding lignin-modified styrene-butadiene rubber A1, ethylene-modified petroleum resin B1, di-tert-butyl peroxide isopropylbenzene, mica, 2-hydroxy-4-n-octyloxybenzophenone, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and magnesium stearate into an internal mixer, heating and internal mixing to obtain a mixture, and after internal mixing, injection molding the mixture using an injection molding machine.

[0074] Comparative Example 1

[0075] This comparative example is a styrene-butadiene rubber shoe material and a preparation method thereof.

[0076] Measured in parts by weight, the raw materials for preparing styrene-butadiene rubber shoe materials include 98 parts of lignin-modified styrene-butadiene rubber A1, 0.5 parts of di-tert-butyl peroxide isopropylbenzene, 0.8 parts of silicon dioxide, 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0.2 parts of tris(2,4-di-tert-butylphenyl) phosphite, 0.1 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.2 parts of calcium stearate.

[0077] The preparation method of the styrene-butadiene rubber shoe material of the comparative example can be as follows: lignin-modified styrene-butadiene rubber A1, di-tert-butyl peroxide isopropylbenzene, silicon dioxide, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, tris(2,4-di-tert-butylphenyl) phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol and calcium stearate are added into an internal mixer, heated and internally kneaded to obtain a mixture, and after internal kneading, the mixture is injection molded by an injection molding machine.

[0078] Comparative Example 2

[0079] This comparative example is a styrene-butadiene rubber shoe material and a preparation method thereof.

[0080] The raw materials for preparing styrene-butadiene rubber shoe materials include, in parts by weight, 97 parts of styrene-butadiene rubber, 1 part of styrene-modified petroleum resin B1, 0.5 parts of di-tert-butyl peroxide isopropylbenzene, 0.8 parts of silicon dioxide, 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0.2 parts of tris(2,4-di-tert-butylphenyl) phosphite, 0.1 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.2 parts of calcium stearate.

[0081] The preparation method of the styrene-butadiene rubber shoe material of the comparative example can be as follows: styrene-butadiene rubber, ethylene-modified petroleum resin B1, di-tert-butyl peroxide isopropylbenzene, silicon dioxide, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, tris(2,4-di-tert-butylphenyl) phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol and calcium stearate are added into an internal mixer, heated and internally kneaded to obtain a mixture, and after internal kneading, the mixture is injection molded by an injection molding machine.

[0082] Comparative Example 3

[0083] This comparative example is a styrene-butadiene rubber shoe material and a preparation method thereof.

[0084] The raw materials for preparing styrene-butadiene rubber shoe materials include, in parts by weight, 97 parts of lignin-modified styrene-butadiene rubber A1, 1 part of C5 petroleum resin, 0.5 parts of di-tert-butyl peroxide isopropylbenzene, 0.8 parts of silicon dioxide, 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0.2 parts of tris(2,4-di-tert-butylphenyl) phosphite, 0.1 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.2 parts of calcium stearate.

[0085] The preparation method of the styrene-butadiene rubber shoe material of the comparative example can be as follows: lignin-modified styrene-butadiene rubber A1, C5 petroleum resin, di-tert-butyl peroxide isopropylbenzene, silicon dioxide, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, tris(2,4-di-tert-butylphenyl) phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol and calcium stearate are added into an internal mixer, heated and internally kneaded to obtain a mixture, and after internal kneading, the mixture is injection molded by an injection molding machine.

[0086] Comparative Example 4

[0087] This comparative example is a styrene-butadiene rubber shoe material and a preparation method thereof.

[0088] The raw materials for preparing styrene-butadiene rubber shoe materials include 97 parts of styrene-butadiene rubber, 1 part of C5 petroleum resin, 0.5 parts of di-tert-butyl peroxide isopropylbenzene, 0.8 parts of silicon dioxide, 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0.2 parts of tris(2,4-di-tert-butylphenyl) phosphite, 0.1 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.2 parts of calcium stearate.

[0089] The preparation method of the styrene-butadiene rubber shoe material of the comparative example can be as follows: styrene-butadiene rubber, C5 petroleum resin, di-tert-butyl peroxide isopropylbenzene, silicon dioxide, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, tris(2,4-di-tert-butylphenyl) phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol and calcium stearate are added into an internal mixer, heated and internally kneaded to obtain a mixture, and after internal kneading, the mixture is injection molded by an injection molding machine.

[0090] The styrene-butadiene rubber shoe materials prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were subjected to performance tests. The test methods are as follows. The test results are shown in Table 1.

[0091] Anti-slip test: Anti-slip test is carried out according to ASTM-F1677 standard.

[0092] Shore hardness: Tested in accordance with the national standard "GB / T 531.1-2008 Test method for indentation hardness of vulcanized rubber or thermoplastic rubber Part 1_Shore durometer method (Shore hardness) Shore hardness".

[0093] Tensile strength and elongation at break: tested in accordance with the national standard GB / T 528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber.

[0094] Tear strength: Tested in accordance with the national standard "GB / T 529-2008 Determination of tear strength of vulcanized rubber or thermoplastic rubber".

[0095] Table 1 Performance test results of styrene-butadiene rubber shoe materials of Examples 1 to 7 and Comparative Examples 1 to 4

[0096]

[0097]

[0098] From the results in Table 1, it can be seen that in the raw materials for preparing the styrene-butadiene rubber shoe material of the present invention, styrene-modified petroleum resin is used as a tackifier on the basis of lignin-modified styrene-butadiene rubber, so that the prepared shoe material has not only higher resilience, but also better mechanical strength and anti-slip performance.

[0099] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, it is not limited to those listed in the embodiments. Those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A styrene-butadiene rubber shoe material, characterized in that: The raw materials include 90-99 parts of lignin-modified styrene-butadiene rubber, 0.5-5 parts of tackifying resin, 0.1-2 parts of cross-linking agent, 0.1-2 parts of filler and 0-2 parts of auxiliary agent in parts by weight, wherein the tackifying resin includes styrene-modified petroleum resin, and the auxiliary agent includes at least one of ultraviolet absorber, lubricant and antioxidant.

2. The styrene-butadiene rubber shoe material according to claim 1, characterized in that: The lignin-modified styrene-butadiene rubber is styrene-butadiene rubber modified by lignin phenolic resin.

3. The styrene-butadiene rubber shoe material according to claim 2, characterized in that: The lignin phenolic resin and the styrene butadiene rubber in the lignin-modified styrene butadiene rubber present an interpenetrating network structure.

4. The styrene-butadiene rubber shoe material according to claim 3, characterized in that: The lignin phenolic resin accounts for 10-35% of the mass of the lignin modified styrene-butadiene rubber.

5. The styrene-butadiene rubber shoe material according to claim 2, characterized in that: The lignin phenolic resin is obtained by reacting lignin to replace part of phenol with formaldehyde, and the lignin accounts for 20-40% of the sum of the mass of the lignin and the phenol.

6. The styrene-butadiene rubber shoe material according to claim 1, characterized in that: The cross-linking agent includes di-tert-butyl peroxide isopropylbenzene, and the filler includes at least one of silicon dioxide, talc, calcium carbonate, mica, kaolin, wollastonite and titanium dioxide.

7. The styrene-butadiene rubber shoe material according to claim 1, characterized in that: The ultraviolet absorber includes at least one of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2,4-bis(2,4-xylyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine and 2-hydroxy-4-n-octyloxybenzophenone, and the lubricant includes at least one of calcium stearate, zinc stearate, magnesium stearate and stearic acid.

8. The styrene-butadiene rubber shoe material according to claim 1, characterized in that: The antioxidant includes at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-p-methylphenol, 1-hydroxy-4-methyl-2,6-di-tert-butylbenzene, tris(2,4-di-tert-butylphenyl) phosphite and triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate.

9. The styrene-butadiene rubber shoe material according to claim 8, characterized in that: The antioxidant comprises tris(2,4-di-tert-butylphenyl)phosphite and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol, and the mass ratio of the two is 1-4:

1.

10. The method for preparing styrene-butadiene rubber shoe material according to claims 1 to 9, characterized in that: Includes steps: (1) Lignin modified styrene butadiene rubber Add lignin, phenol, formaldehyde, inorganic base and small molecule alcohol into a reactor, heat to 70-90°C for reaction, then cool and decompress to obtain lignin phenolic resin, mix the lignin phenolic resin and styrene-butadiene rubber, knead at room temperature, add a vulcanizing agent, heat to 150-180°C and knead; (2) Styrene modified petroleum resin Styrene and solvent are mixed, a catalyst is added and stirred to form a suspension, the suspension is placed in a constant temperature of 40-65°C and C5-C9 petroleum resin is added dropwise, after the addition is completed, the suspension is polymerized at a constant temperature and an alkali solution is used to terminate the reaction; (3) Mixing and Injection Molding The lignin-modified styrene-butadiene rubber, the styrene-modified petroleum resin, the tackifying resin, the crosslinking agent, the filler and the auxiliary agent in the formula amount are added into an internal mixer and heated and internally kneaded to obtain a mixture. After internal kneading, the mixture is injection molded by an injection molding machine.

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