Wear-resistant thermoplastic rubber particles for shoe soles and method for producing same

Abstract

The application discloses a kind of wear-resistant thermoplastic rubber particles for shoe sole and preparation method thereof, after polyurethane prepolymer, benzophenone, functionalized carbon black and 1,4-butanediol are mixed and reacted, then using ultraviolet light irradiation treatment, wear-resistant thermoplastic rubber particles for shoe sole are prepared, polyurethane molecule is hyperbranched structure, hyperbranched structure has high degree of branching and rich end group, can effectively disperse stress, reduce local stress concentration, to reduce the wear of shoe sole in friction process, also can the flexibility and resilience of shoe sole, so that it can better restore original shape when being rubbed, reduce the loss of material, after ultraviolet light irradiation treatment, sulfydryl on functionalized carbon black can be grafted with polyurethane prepolymer, and then form crosslinking lattice structure, can effectively resist external stress effect, improve the tensile strength and tear resistance of shoe sole, and the high adsorption performance of carbon black itself can prevent polyurethane molecular chain from slipping, further enhance the mechanical properties of material.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of wear-resistant thermoplastic rubber particles, in particular to a wear-resistant thermoplastic rubber particle for shoe soles and a preparation method thereof. BACKGROUND

[0002] In modern shoe manufacturing, the selection of shoe sole material plays a crucial role in the performance, comfort and durability of the shoes. Traditional shoe sole materials are mostly rubber, EVA and PVC. These materials are mostly rigid and have low elasticity or have high elasticity and low rigidity, which cannot meet the demand for comfort and durability at the same time. Thermoplastic polyurethane elastomer, as a high-performance polymer material, occupies an irreplaceable position in the field of shoe sole manufacturing. Its unique micro-phase separation structure is composed of hard segments (rigid segments, providing mechanical strength) and soft segments (flexible segments, imparting elasticity). This structure enables it to have both the high elasticity of rubber and the rigidity characteristics of plastic, but its wear resistance is limited, and it will show obvious wear after long-term use, thereby reducing the service life of the shoe sole. SUMMARY

[0003] The present application relates to the field of wear-resistant thermoplastic rubber particles, in particular to a wear-resistant thermoplastic rubber particle for shoe soles and a preparation method thereof.

[0004] The object of the present application can be achieved by the following technical solutions:

[0005] A preparation method of a wear-resistant thermoplastic rubber particle for shoe soles, specifically comprising the following steps:

[0006] Step A1: Mix carbon black and hydrogen peroxide, and react for 1-1.5 h under the conditions of a rotation speed of 300-500 r / min and a temperature of 80-85℃, to obtain pretreated carbon black. Disperse the pretreated carbon black in ethanol, and stir under the conditions of a rotation speed of 200-300 r / min and a temperature of 75-80℃, and then add deionized water and KH550, and react for 30-40 min, to obtain modified carbon black;

[0007] Step A2: Mix the modified carbon black, 4-mercaptobenzaldehyde, p-toluenesulfonic acid and tetrahydrofuran uniformly, and react for 1-2 h under the conditions of a rotation speed of 120-150 r / min and a temperature of 40-50℃, to obtain functionalized carbon black. Mix polytetrahydrofuran ether diol, modified monomer and diphenyl methane diisocyanate, and protect under nitrogen atmosphere, and react for 1-1.5 h under the conditions of a rotation speed of 90-120 r / min and a temperature of 80-85℃, to obtain a polyurethane prepolymer;

[0008] Step A3: the polyurethane prepolymer, benzophenone, functionalized carbon black and DMF were mixed, and then the mixture was reacted for 30-40 min under the protection of nitrogen at a rotation speed of 120-150 r / min and a temperature of 80-85℃, after which 1,4-butanediol was added, and the reaction was continued for 20-30 min, and then the mixture was treated with 365 nm ultraviolet light for 10-15 s to obtain the wear-resistant thermoplastic rubber particles for shoe soles.

[0009] Further, the mass ratio of the carbon black to hydrogen peroxide in step A1 is 1:4, the mass fraction of hydrogen peroxide is 30%, and the amount of KH550 is 3% of the mass of the pretreated carbon black.

[0010] Further, the molar ratio of the amino group on the modified carbon black to 4-mercaptobenzaldehyde in step A2 is 1:1, the amount of p-toluenesulfonic acid is 1‰ of the amount of 4-mercaptobenzaldehyde, the molar ratio of polytetrahydrofurfuryl ether glycol to diphenyl methane diisocyanate is 1:2, and the amount of the modified monomer is 10% of the mass of the polytetrahydrofurfuryl ether glycol, and the molecular weight of the polytetrahydrofurfuryl ether glycol is 2000.

[0011] Further, the amount of the functionalized carbon black in step A3 is 3% of the mass of the polyurethane prepolymer, and the amount of benzophenone is 1% of the mass of the functionalized carbon black, and the molar ratio of the isocyanate group on the polyurethane prepolymer to 1,4-butanediol is 1:1.5.

[0012] Further, the modified monomer is prepared by the following steps:

[0013] Step B1: 3,4-epoxy-1-butene, trichlorosilane, chloroplatinic acid and DMF were uniformly mixed, and then the mixture was reacted for 6-8 h under the protection of nitrogen at a rotation speed of 120-150 r / min and a temperature of 70-80℃ to obtain an intermediate, dimethylvinylsilicon lithium and tetrahydrofuran were uniformly mixed, and then the mixture was stirred at a rotation speed of 150-200 r / min and a temperature of 0℃, and then hexamethylcyclotrisiloxane was added, and the mixture was heated to 25-30℃ and reacted for 7-9 h, and then the intermediate was added, and the reaction was continued for 1-1.5 h to obtain pretreated polysiloxane;

[0014] Step B2: 4,4'-diaminodiphenylmethane, pretreated polysiloxane and DMF were uniformly mixed, and then the mixture was reacted for 3-5 h at a rotation speed of 200-300 r / min, a temperature of 60-65℃ and a pH value of 11-12 to obtain modified polysiloxane, maleic anhydride and DMF were mixed, and then the mixture was stirred at a rotation speed of 200-300 r / min and a temperature of 5-10℃, and then p-aminobenzoic acid was added, and the mixture was heated to 55-60℃ and reacted for 30-40 min, and then triethylamine, acetic anhydride and nickel acetate were added, and the reaction was continued for 2-3 h to obtain a modifier;

[0015] Step B3: the modified polysiloxane, modifier, p-toluenesulfonic acid, 4A molecular sieve and DMF are mixed, and the reaction is carried out at a rotation speed of 120-150 r / min and a temperature of 110-115 DEG C for 4-6 h to obtain a functionalized polysiloxane; the diethanolamine, triethylamine and tetrahydrofuran are mixed, and the stirring is carried out at a rotation speed of 300-500 r / min and a temperature of 0 DEG C, and the furanoyl chloride is added, and the temperature is raised to 20-25 DEG C, and the reaction is carried out for 2-4 h to obtain a linker; the functionalized polysiloxane, linker and DMF are uniformly mixed, and the reaction is carried out at a rotation speed of 150-200 r / min and a temperature of 20-25 DEG C for 20-25 h to obtain a modified monomer.

[0016] Further, the molar ratio of 3,4-epoxy-1-butene to trichlorosilane in step B1 is 1:1, the amount of chloroplatinic acid is 1 ‰ of the mass of trichlorosilane, and the molar ratio of lithium dimethylvinylsilanol, hexamethylcyclotrisiloxane and Si-Cl bond on the intermediate is 1:4:1.

[0017] Further, the molar ratio of amino group on 4,4'-diaminodiphenyl methane to epoxy group on the pretreated polysiloxane in step B2 is 1:2, and the amount of maleic anhydride, p-aminobenzoic acid, triethylamine, acetic anhydride and nickel acetate is 50 mmol:25 mmol:5 mL:10 mL:3.5 g.

[0018] Further, the amount of modified polysiloxane, modifier and 4A molecular sieve in step B3 is 1 mol:2 mol:20 g, the amount of p-toluenesulfonic acid is 1 ‰ of the mass of modified polysiloxane, the molar ratio of diethanolamine, triethylamine and furanoyl chloride is 1.1:1.2:1, and the molar ratio of functionalized polysiloxane to linker is 1:2.

[0019] The present application has the following beneficial effects: the wear-resistant thermoplastic rubber particles for shoe soles are prepared by mixing and reacting polyurethane prepolymer, benzophenone, functionalized carbon black and 1,4-butanediol, and then treating by ultraviolet light, the functionalized carbon black is prepared by treating carbon black with hydrogen peroxide to graft hydroxyl groups on the surface, and then treating with KH550 to graft amino groups on the surface, the modified carbon black is prepared by reacting the modified carbon black with mercaptobenzaldehyde, the aldehyde groups on the mercaptobenzaldehyde and the amino groups on the modified carbon black are reacted to form imine bonds, and the functionalized carbon black is prepared.

[0020] The modified prepolymer is prepared by reacting polytetrahydrofuran ether glycol, modified monomer and diphenyl methane diisocyanate, the modified monomer is prepared by reacting 3,4-epoxy-1-butene and trichlorosilane, the double bond on 3,4-epoxy-1-butene reacts with the Si-H bond on trichlorosilane to prepare an intermediate, dimethylvinylsilanol lithium is used as an initiator, hexamethylcyclotrisiloxane is used as a polymerization monomer, and the intermediate is added again, so that the Si-Cl bond on the intermediate reacts with the silanol lithium to prepare a pretreated polysiloxane, 4,4'-diaminodiphenyl methane reacts with the pretreated polysiloxane, so that the amino group on 4,4'-diaminodiphenyl methane reacts with the epoxy group on the pretreated polysiloxane to form a new hydroxyl group, and a modified polysiloxane is prepared, maleic anhydride reacts with p-aminobenzoic acid, so that maleic anhydride ring-opening reacts with the amino group on p-aminobenzoic acid to form a maleimide, and a modifier is prepared, the modified polysiloxane reacts with the modifier, so that the diol on the modified polysiloxane reacts with the boric acid on the modifier to form a boric acid ester structure, and a functionalized polysiloxane is prepared, diethanolamine reacts with furanoyl chloride, so that the secondary amine on diethanolamine reacts with the acid chloride on furanoyl chloride to prepare a linking agent, and the linking agent reacts with the functionalized polysiloxane, so that the furan group on the linking agent reacts with the maleimide DA on the functionalized polysiloxane to prepare a modified monomer.

[0021] The addition of the modified monomer makes the prepared polyurethane molecule have a hyperbranched structure, the hyperbranched structure has a high degree of branching and a large number of end groups, such a structure can effectively disperse stress and reduce local stress concentration, thereby reducing the wear of the shoe sole during friction, and also improving the flexibility and resilience of the shoe sole, so that the shoe sole can better restore its original state when subjected to friction and reduce material loss, after ultraviolet light irradiation treatment, the mercapto group on the functionalized carbon black can be grafted with the polyurethane prepolymer to form a crosslinked network structure, which can effectively resist external stress and improve the tensile strength and tear resistance of the shoe sole, and the high adsorption performance of the carbon black can prevent the slippage of the polyurethane molecular chain, further enhancing the mechanical properties of the material. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0023] Embodiment 1, a preparation method of a wear-resistant thermoplastic rubber particle for shoe soles, specifically comprising the following steps:

[0024] Step A1: mixing carbon black and hydrogen peroxide, under the condition of 300 r / min rotation speed and 80℃ temperature, reacting for 1h to obtain pretreated carbon black, dispersing the pretreated carbon black in ethanol, under the condition of 200 r / min rotation speed and 75℃ temperature, stirring and adding deionized water and KH550, and reacting for 30 min to obtain modified carbon black;

[0025] Step A2: mixing the modified carbon black, 4-mercaptobenzaldehyde, p-toluenesulfonic acid and tetrahydrofuran uniformly, under the condition of 120 r / min rotation speed and 40℃ temperature, reacting for 1h to obtain functionalized carbon black, mixing polytetrahydrofuran ether diol, modified monomer and diphenyl methane diisocyanate, and introducing nitrogen protection, under the condition of 90 r / min rotation speed and 80℃ temperature, reacting for 1h to obtain polyurethane prepolymer;

[0026] Step A3: mixing the polyurethane prepolymer, benzophenone, functionalized carbon black and DMF, under the condition of introducing nitrogen protection, 120 r / min rotation speed and 80℃ temperature, reacting for 30 min, then adding 1,4-butanediol, continuing to react for 20 min, and then irradiating with 365 nm ultraviolet light for 10 s to obtain the wear-resistant thermoplastic rubber particles for shoe sole.

[0027] The mass ratio of carbon black to hydrogen peroxide in step A1 is 1:4, the mass fraction of hydrogen peroxide is 30%, and the amount of KH550 is 3% of the mass of pretreated carbon black.

[0028] The molar ratio of amino group on the modified carbon black to 4-mercaptobenzaldehyde in step A2 is 1:1, the amount of p-toluenesulfonic acid is 1‰ of the amount of 4-mercaptobenzaldehyde, the molar ratio of polytetrahydrofuran ether diol to diphenyl methane diisocyanate is 1:2, the amount of modified monomer is 10% of the mass of polytetrahydrofuran ether diol, and the molecular weight of polytetrahydrofuran ether diol is 2000.

[0029] The amount of functionalized carbon black in step A3 is 3% of the mass of polyurethane prepolymer, the amount of benzophenone is 1% of the mass of functionalized carbon black, and the molar ratio of isocyanate group on the polyurethane prepolymer to 1,4-butanediol is 1:1.5.

[0030] The modified monomer is prepared by the following steps:

[0031] Step B1: 3,4-epoxy-1-butene, trichlorosilane, chloroplatinic acid and DMF were mixed uniformly, protected by nitrogen, reacted at 70℃ and 120r / min for 6h to obtain an intermediate, lithium dimethylvinylsilanolate and tetrahydrofuran were mixed uniformly, stirred at 0℃ and 150r / min, then hexamethylcyclotrisiloxane was added, the temperature was raised to 25℃, reacted for 7h, then the intermediate was added, and reacted for 1h to obtain a pretreated polysiloxane;

[0032] Step B2: 4,4'-diaminodiphenylmethane, the pretreated polysiloxane and DMF were mixed uniformly, reacted at 60℃, 200r / min and pH 11 for 3h to obtain a modified polysiloxane, maleic anhydride and DMF were mixed, stirred at 5℃ and 200r / min, then p-aminobenzoic acid was added, the temperature was raised to 55℃, reacted for 30min, then triethylamine, acetic anhydride and nickel acetate were added, and reacted for 2h to obtain a modifier;

[0033] Step B3: the modified polysiloxane, the modifier, p-toluenesulfonic acid, 4A molecular sieve and DMF were mixed, reacted at 110℃ and 120r / min for 4h to obtain a functionalized polysiloxane, diethanolamine, triethylamine and tetrahydrofuran were mixed, stirred at 0℃ and 300r / min, then furanoyl chloride was added, the temperature was raised to 20℃, reacted for 2h to obtain a linker, the functionalized polysiloxane, the linker and DMF were mixed uniformly, reacted at 20℃ and 150r / min for 20h to obtain a modified monomer.

[0034] The molar ratio of 3,4-epoxy-1-butene to trichlorosilane in step B1 was 1:1, the amount of chloroplatinic acid was 1‰ of the mass of trichlorosilane, and the molar ratio of lithium dimethylvinylsilanolate, hexamethylcyclotrisiloxane and Si-Cl bond on the intermediate was 1:4:1.

[0035] The molar ratio of amino group on 4,4'-diaminodiphenylmethane to epoxy group on the pretreated polysiloxane in step B2 was 1:2, and the amount of maleic anhydride, p-aminobenzoic acid, triethylamine, acetic anhydride and nickel acetate was 50mmol:25mmol:5mL:10mL:3.5g.

[0036] The amount of the modified polysiloxane, the modifier and 4A molecular sieve in step B3 was 1mol:2mol:20g, the amount of p-toluenesulfonic acid was 1‰ of the mass of the modified polysiloxane, the molar ratio of diethanolamine, triethylamine and furanoyl chloride was 1.1:1.2:1, and the molar ratio of the functionalized polysiloxane to the linker was 1:2.

[0037] Embodiment 2, a method for preparing a wear-resistant thermoplastic rubber particle for shoe sole, specifically comprising the following steps:

[0038] Step A1: mixing carbon black and hydrogen peroxide, and reacting for 1.3 h under the condition of 300 r / min rotation speed and 85℃ temperature to prepare pretreated carbon black, and dispersing the pretreated carbon black in ethanol, and stirring under the condition of 200 r / min rotation speed and 78℃ temperature, and adding deionized water and KH550, and reacting for 35 min to prepare modified carbon black;

[0039] Step A2: uniformly mixing the modified carbon black, 4-mercaptobenzaldehyde, p-toluenesulfonic acid and tetrahydrofuran, and reacting for 1.5 h under the condition of 120 r / min rotation speed and 45℃ temperature to prepare functionalized carbon black, and mixing polytetrahydrofuran ether diol, modified monomer and diphenyl methane diisocyanate, and protecting under nitrogen atmosphere, and reacting for 1.5 h under the condition of 90 r / min rotation speed and 85℃ temperature to prepare polyurethane prepolymer;

[0040] Step A3: mixing the polyurethane prepolymer, benzophenone, functionalized carbon black and DMF, and protecting under nitrogen atmosphere, and reacting for 35 min under the condition of 120 r / min rotation speed and 85℃ temperature, and then adding 1,4-butanediol, and continuing to react for 25 min, and then treating with 365 nm ultraviolet light for 13 s to prepare the wear-resistant thermoplastic rubber particle for shoe sole.

[0041] The mass ratio of the carbon black to hydrogen peroxide in step A1 is 1:4, the mass fraction of hydrogen peroxide is 30%, and the amount of KH550 is 3% of the mass of the pretreated carbon black.

[0042] The molar ratio of the amino group on the modified carbon black to 4-mercaptobenzaldehyde in step A2 is 1:1, the amount of p-toluenesulfonic acid is 1‰ of the amount of 4-mercaptobenzaldehyde, the molar ratio of polytetrahydrofuran ether diol to diphenyl methane diisocyanate is 1:2, the amount of modified monomer is 10% of the mass of polytetrahydrofuran ether diol, and the molecular weight of polytetrahydrofuran ether diol is 2000.

[0043] The amount of functionalized carbon black in step A3 is 3% of the mass of the polyurethane prepolymer, the amount of benzophenone is 1% of the mass of the functionalized carbon black, and the molar ratio of the isocyanate group on the polyurethane prepolymer to 1,4-butanediol is 1:1.5.

[0044] The modified monomer is prepared by the following steps:

[0045] Step B1: 3,4-epoxy-1-butene, trichlorosilane, chloroplatinic acid and DMF were mixed uniformly, protected by nitrogen, reacted at 75℃ and 150r / min for 7h to obtain an intermediate, dimethylvinylsilanol lithium and tetrahydrofuran were mixed uniformly, stirred at 0℃ and 150r / min, then hexamethylcyclotrisiloxane was added, the temperature was raised to 28℃, reacted for 8h, then the intermediate was added, and reacted for 1.3h to obtain a pretreated polysiloxane;

[0046] Step B2: 4,4'-diaminodiphenylmethane, the pretreated polysiloxane and DMF were mixed uniformly, reacted at 65℃, 200r / min and pH 11 for 4h to obtain a modified polysiloxane, maleic anhydride and DMF were mixed, stirred at 10℃ and 200r / min, then p-aminobenzoic acid was added, the temperature was raised to 58℃, reacted for 35min, then triethylamine, acetic anhydride and nickel acetate were added, and reacted for 3h to obtain a modifier;

[0047] Step B3: the modified polysiloxane, the modifier, p-toluenesulfonic acid, 4A molecular sieve and DMF were mixed, reacted at 115℃ and 120r / min for 5h to obtain a functionalized polysiloxane, diethanolamine, triethylamine and tetrahydrofuran were mixed, stirred at 0℃ and 300r / min, then furanoyl chloride was added, the temperature was raised to 25℃, reacted for 3h to obtain a linker, the functionalized polysiloxane, the linker and DMF were mixed uniformly, reacted at 25℃ and 150r / min for 20h to obtain a modified monomer.

[0048] The molar ratio of 3,4-epoxy-1-butene to trichlorosilane in step B1 was 1:1, the amount of chloroplatinic acid was 1‰ of the mass of trichlorosilane, and the molar ratio of dimethylvinylsilanol lithium, hexamethylcyclotrisiloxane and Si-Cl bond on the intermediate was 1:4:1.

[0049] The molar ratio of amino group on 4,4'-diaminodiphenylmethane to epoxy group on the pretreated polysiloxane in step B2 was 1:2, and the amount of maleic anhydride, p-aminobenzoic acid, triethylamine, acetic anhydride and nickel acetate was 50mmol:25mmol:5mL:10mL:3.5g.

[0050] The amount of the modified polysiloxane, the modifier and 4A molecular sieve in step B3 was 1mol:2mol:20g, the amount of p-toluenesulfonic acid was 1‰ of the mass of the modified polysiloxane, the molar ratio of diethanolamine, triethylamine and furanoyl chloride was 1.1:1.2:1, and the molar ratio of the functionalized polysiloxane to the linker was 1:2.

[0051] Embodiment 3, a method for preparing the wear-resistant thermoplastic rubber particles for shoe soles, specifically comprising the following steps:

[0052] Step A1: mixing carbon black and hydrogen peroxide, and reacting for 1.5 h under the conditions of a rotation speed of 500 r / min and a temperature of 85℃ to prepare pretreated carbon black, and dispersing the pretreated carbon black in ethanol, stirring under the conditions of a rotation speed of 300 r / min and a temperature of 80℃, and adding deionized water and KH550, and reacting for 40 min to prepare modified carbon black;

[0053] Step A2: uniformly mixing the modified carbon black, 4-mercaptobenzaldehyde, p-toluenesulfonic acid and tetrahydrofuran, and reacting for 2 h under the conditions of a rotation speed of 150 r / min and a temperature of 50℃ to prepare functionalized carbon black, and mixing polytetrahydrofuran ether diol, modified monomer and diphenyl methane diisocyanate, and protecting under nitrogen, and reacting for 1.5 h under the conditions of a rotation speed of 120 r / min and a temperature of 85℃ to prepare polyurethane prepolymer;

[0054] Step A3: mixing the polyurethane prepolymer, benzophenone, functionalized carbon black and DMF, protecting under nitrogen, and reacting for 40 min under the conditions of a rotation speed of 150 r / min and a temperature of 85℃, and then adding 1,4-butanediol, and continuing to react for 30 min, and then irradiating with 365 nm ultraviolet light for 15 s to prepare the wear-resistant thermoplastic rubber particles for shoe soles.

[0055] The mass ratio of the carbon black to hydrogen peroxide in step A1 is 1:4, the mass fraction of hydrogen peroxide is 30%, and the amount of KH550 is 3% of the mass of the pretreated carbon black.

[0056] The molar ratio of the amino group on the modified carbon black to 4-mercaptobenzaldehyde in step A2 is 1:1, the amount of p-toluenesulfonic acid is 1‰ of the amount of 4-mercaptobenzaldehyde, the molar ratio of polytetrahydrofuran ether diol to diphenyl methane diisocyanate is 1:2, the amount of modified monomer is 10% of the mass of polytetrahydrofuran ether diol, and the molecular weight of polytetrahydrofuran ether diol is 2000.

[0057] The amount of functionalized carbon black in step A3 is 3% of the mass of the polyurethane prepolymer, the amount of benzophenone is 1% of the mass of the functionalized carbon black, and the molar ratio of the isocyanate group on the polyurethane prepolymer to 1,4-butanediol is 1:1.5.

[0058] The modified monomer is prepared by the following steps:

[0059] Step B1: 3,4-epoxy-1-butene, trichlorosilane, chloroplatinic acid and DMF were mixed uniformly, protected by nitrogen, reacted at 80℃ and 150r / min for 8h to obtain an intermediate, lithium dimethylvinylsilanolate and tetrahydrofuran were mixed uniformly, stirred at 0℃ and 200r / min, then hexamethylcyclotrisiloxane was added, the temperature was raised to 30℃, reacted for 9h, then the intermediate was added, and reacted for 1.5h to obtain a pretreated polysiloxane;

[0060] Step B2: 4,4'-diaminodiphenylmethane, the pretreated polysiloxane and DMF were mixed uniformly, reacted at 65℃, 300r / min and pH 12 for 5h to obtain a modified polysiloxane, maleic anhydride and DMF were mixed, stirred at 10℃ and 300r / min, then p-aminobenzoic acid was added, the temperature was raised to 60℃, reacted for 40min, then triethylamine, acetic anhydride and nickel acetate were added, and reacted for 3h to obtain a modifier;

[0061] Step B3: the modified polysiloxane, the modifier, p-toluenesulfonic acid, 4A molecular sieve and DMF were mixed, reacted at 115℃ and 150r / min for 6h to obtain a functionalized polysiloxane, diethanolamine, triethylamine and tetrahydrofuran were mixed, stirred at 0℃ and 500r / min, then furanoyl chloride was added, the temperature was raised to 25℃, reacted for 4h to obtain a linker, the functionalized polysiloxane, the linker and DMF were mixed uniformly, reacted at 25℃ and 200r / min for 25h to obtain a modified monomer.

[0062] The molar ratio of 3,4-epoxy-1-butene to trichlorosilane in step B1 was 1:1, the amount of chloroplatinic acid was 1‰ of the mass of trichlorosilane, and the molar ratio of lithium dimethylvinylsilanolate, hexamethylcyclotrisiloxane and Si-Cl bond on the intermediate was 1:4:1.

[0063] The molar ratio of amino group on 4,4'-diaminodiphenylmethane to epoxy group on the pretreated polysiloxane in step B2 was 1:2, and the amount of maleic anhydride, p-aminobenzoic acid, triethylamine, acetic anhydride and nickel acetate was 50mmol:25mmol:5mL:10mL:3.5g.

[0064] The amount of the modified polysiloxane, the modifier and 4A molecular sieve in step B3 was 1mol:2mol:20g, the amount of p-toluenesulfonic acid was 1‰ of the mass of the modified polysiloxane, the molar ratio of diethanolamine, triethylamine and furanoyl chloride was 1.1:1.2:1, and the molar ratio of the functionalized polysiloxane to the linker was 1:2.

[0065] Comparative Example 1, in this comparative example, the pre-treated carbon black was dispersed in ethanol, and then deionized water and 3-mercaptopropyltrimethoxysilane were added and stirred at 200 r / min and 75℃ for 30 min to produce a product instead of the functionalized carbon black, and the remaining steps were the same as in Example 1.

[0066] Comparative Example 2, in this comparative example, the functionalized carbon black was replaced by carbon black, and the remaining steps were the same as in Example 1.

[0067] Comparative Example 3, in this comparative example, no modified monomer was added, and the remaining steps were the same as in Example 1.

[0068] Comparative Example 4, in this comparative example, the linking agent was replaced by furfuryl alcohol, and the remaining steps were the same as in Example 1.

[0069] The rubber particles prepared in Examples 1-3 and Comparative Examples 1-4 were made into flat samples with a thickness of 4 mm, and a wear testing machine was used, with an H-18 grinding wheel, an applied load of 800 g, a rotation speed of 60 r / min, and a total rotation of 1000 revolutions. The weight loss rate was calculated by weighing the sample before and after the test. The rubber particles were made into standard dumbbell-shaped tensile samples with a thickness of 2 mm, and the tensile strength was detected under the conditions of a tensile rate of 10 mm / min and a gauge length of 20 mm. The detection results are shown in Table 1.

[0070] Table 1

[0071]

[0072] As can be seen from Table 1, the application has good wear resistance.

[0073] The above content is only an example and description of the concept of the application. Those skilled in the art can make various modifications or supplements to the described specific examples or use similar ways to replace them, as long as they do not deviate from the concept of the application or exceed the scope defined by the claims, and they should belong to the protection scope of the application.

Claims

1. A method for preparing wear-resistant thermoplastic granules for shoe soles, characterized in that: Specifically, the steps include the following: Step A1: Mix carbon black and hydrogen peroxide to react and obtain pretreated carbon black. Disperse the pretreated carbon black in ethanol, stir and add deionized water and KH550 to react and obtain modified carbon black. Step A2: Modified carbon black, 4-mercaptobenzaldehyde, p-toluenesulfonic acid and tetrahydrofuran are mixed and reacted to obtain functionalized carbon black. Polytetrahydrofuran ether diol, modified monomer and diphenylmethane diisocyanate are mixed and reacted under nitrogen protection to obtain polyurethane prepolymer. Step A3: Mix polyurethane prepolymer, benzophenone, functionalized carbon black and DMF, and react under nitrogen protection. Then add 1,4-butanediol and continue the reaction. Finally, treat with 365nm ultraviolet light to obtain wear-resistant thermoplastic granules for shoe soles. The modified monomer is prepared by the following steps: Step B1: Mix 3,4-epoxy-1-butene, trichlorosilane, chloroplatinic acid and DMF evenly, purge with nitrogen, and react to obtain an intermediate. Mix and stir dimethylvinylsilyl alcohol lithium and tetrahydrofuran and add hexamethylcyclotrisiloxane. After heating and reacting, add the intermediate and continue the reaction to obtain pretreated polysiloxane. Step B2: Mix 4,4'-diaminodiphenylmethane, pretreated polysiloxane and DMF to prepare modified polysiloxane. Mix maleic anhydride and DMF and stir, then add p-aminophenylboronic acid. After heating and reacting, add triethylamine, acetic anhydride and nickel acetate and continue the reaction to obtain the modifier. Step B3: The modified polysiloxane, modifier, p-toluenesulfonic acid, 4A molecular sieve and DMF are mixed and reacted to obtain the functionalized polysiloxane. Diethanolamine, triethylamine and tetrahydrofuran are mixed and stirred and furanyl chloride is added. The mixture is heated and reacted to obtain the linker. The functionalized polysiloxane, linker and DMF are mixed and reacted to obtain the modified monomer.

2. The method for preparing wear-resistant thermoplastic granules for shoe soles according to claim 1, characterized in that: The mass ratio of carbon black to hydrogen peroxide in step A1 is 1:4, and the amount of KH550 used is 3% of the mass of the pretreated carbon black.

3. The method for preparing wear-resistant thermoplastic granules for shoe soles according to claim 1, characterized in that: The molar ratio of amino groups and 4-mercaptobenzaldehyde on the modified carbon black described in step A2 is 1:1, the molar ratio of polytetrahydrofuran ether diol and diphenylmethane diisocyanate is 1:2, and the amount of modified monomer is 10% of the mass of polytetrahydrofuran ether diol.

4. The method for preparing wear-resistant thermoplastic granules for shoe soles according to claim 1, characterized in that: The amount of functionalized carbon black used in step A3 is 3% of the mass of the polyurethane prepolymer, and the molar ratio of isocyanate groups and 1,4-butanediol on the polyurethane prepolymer is 1:1.

5.

5. The method for preparing wear-resistant thermoplastic granules for shoe soles according to claim 1, characterized in that: The molar ratio of 3,4-epoxy-1-butene and trichlorosilane in step B1 is 1:1, and the molar ratio of lithium dimethylvinylsilanolate, hexamethylcyclotrisiloxane and the Si-Cl bond on the intermediate is 1:4:

1.

6. The method for preparing wear-resistant thermoplastic granules for shoe soles according to claim 1, characterized in that: In step B2, the molar ratio of the amino group on the 4,4'-diaminodiphenylmethane to the epoxy group on the pretreated polysiloxane is 1:2, and the amounts of maleic anhydride, p-aminophenylboronic acid, triethylamine, acetic anhydride, and nickel acetate are 50 mmol: 25 mmol: 5 mL: 10 mL: 3.5 g.

7. The method for preparing wear-resistant thermoplastic granules for shoe soles according to claim 1, characterized in that: The amounts of modified polysiloxane, modifier and 4A molecular sieve mentioned in step B3 are 1mol:2mol:20g, the molar ratio of diethanolamine, triethylamine and furanyl chloride is 1.1:1.2:1, and the molar ratio of functionalized polysiloxane and binder is 1:

2.

8. A type of wear-resistant thermoplastic granules for shoe soles, characterized in that: Prepared according to any one of the preparation methods described in claims 1-7.

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