Preparation method of high-elasticity shock-resistant SBS composite material for shoe soles

Abstract

The invention relates to the technical field of styrene-butadiene-styrene, and discloses a preparation method of a high-elasticity shock-resistant SBS (styrene-butadiene-styrene) composite material for soles, which comprises the following steps: mixing a grafted SBS modifier, graphene oxide, a styrene-butadiene-styrene copolymer, a polyurethane elastomer, K resin and the like, mixing, and carrying out mold pressing to obtain the high-elasticity shock-resistant SBS composite material for soles. The high-elasticity anti-seismic SBS composite material UVR for the shoe sole is obtained. The side chain of the grafted SBS modifier contains a phthalic acid group and a carbamate group which can interact with hydroxyl and carboxyl on the surface of the graphene oxide and the carbamate group of a polyurethane elastomer, so that the agglomeration of the graphene is reduced, and the service life of the graphene is prolonged. The compatibility between the graphene and the polyurethane elastomer and the styrene-butadiene-styrene copolymer is improved, and the tensile strength, the elongation at break, the rebound resilience and other properties of the SBS material are remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of styrene-butadiene-styrene, in particular to a method for preparing a high-elasticity shock-resistant SBS composite material for shoe soles. Background Art

[0002] Styrene-butadiene-styrene SBS is a thermoplastic elastomer with excellent performance, good tensile properties, weather resistance, low temperature resistance, electrical insulation and processing properties. It is widely used in the fields of footwear, toys and daily necessities, sports and medical equipment, etc. However, SBS has problems such as low strength and poor rebound performance, and its practical application is greatly limited.

[0003] Graphene is one of the nano materials with the highest strength at present, and it also has good toughness, bending, high temperature resistance and other properties. It is widely used in polymer materials, and usually needs to improve its agglomeration problem and enhance the compatibility with polymer materials. Polyurethane elastomer has the advantages of high strength, high elasticity, tear resistance, aging resistance, etc., and is widely used in the toughening modification of materials such as rubber and plastics. The Chinese invention patent with the announcement number CN112029295B discloses that the thermoplastic rubber sole obtained by using star-shaped styrene-butadiene polymer SBS, partially hydrogenated styrene-butadiene polymer, mixing type polyurethane elastomer, glass microbead powder, nano calcium carbonate, etc. as raw materials has good hardness, wear resistance and other properties. However, the patent does not improve the tensile strength, tear strength, resilience and other properties of SBS materials. Summary of the invention

[0004] (I) Technical problems to be solved: In view of the deficiencies in the prior art, the present invention provides a SBS composite material for shoe soles with high mechanical strength, high elasticity and shock resistance.

[0005] (II) Technical solution: A method for preparing a highly elastic and shock-resistant SBS composite material for shoe soles:

[0006] Step A, add styrene-butadiene-styrene copolymer to toluene, stir and dissolve, add 4-(methyl methacrylate urethane) phthalic acid grafting agent and dibenzoyl peroxide, heat to 65-85° C. in a nitrogen atmosphere, stir and carry out grafting reaction for 2-5 hours, add ethanol after cooling, filter the product, place it in a Soxhlet extractor, extract it with acetone, and dry it to obtain a grafted SBS modifier.

[0007] Step B, adding a grafted SBS modifier to toluene, heating to 50-65° C., stirring to dissolve, adding graphene oxide, stirring to perform surface modification for 1-4 hours, distilling under reduced pressure, drying, and then adding the mixture and styrene-butadiene-styrene copolymer, polyurethane elastomer, K resin, and additives to a high-speed mixer for mixing, and then adding the materials to a torque rheometer, mixing at 160-170° C. for 15-30 minutes, and finally in a flat vulcanizer, first hot pressing at 160-170° C. for 10-15 minutes at a pressure of 10-12 MPa; and then cold pressing for 15-30 minutes at a pressure of 7-10 MPa to obtain a high-elasticity shock-resistant SBS composite material for soles (abbreviated as UVR).

[0008] Preferably, in step A, the mass ratio of styrene-butadiene-styrene copolymer, 4-(methyl methacrylate urethane)phthalic acid grafting agent, and dibenzoyl peroxide is 100:(10-35):(0.4-1.5).

[0009] Preferably, in step B, the mass ratio of SBS modifier, graphene oxide, styrene-butadiene-styrene copolymer, polyurethane elastomer and K resin is (1.2-4):(0.05-0.5):100:(10-30):(6-15).

[0010] Preferably, the auxiliary agent in step B is any one or a combination of white mineral oil, paraffin, and antioxidant.

[0011] Preferably, the preparation method of 4-(urethane methacrylate)phthalic acid grafting agent is as follows: add isocyanoethyl methacrylate, 4-hydroxyphthalic acid, and dibutyltin dilaurate in a mass ratio of 100:(118-130):(1.8-2.6) to dichloromethane, toluene or tetrahydrofuran solvent, stir and react at 20-40°C for 2-5h, distill under reduced pressure, wash with petroleum ether, and recrystallize the product in ethanol to obtain 4-(urethane methacrylate)phthalic acid grafting agent. The reaction formula is:

[0012]

[0013] (III) Technical effect of the present invention: The present invention uses 4-(methacrylate urethane) phthalic acid grafting agent to add solution to styrene-butadiene-styrene copolymer for grafting modification to obtain a grafted SBS modifier, thereby introducing a carbamate group and a phthalic acid structure into the side chain of SBS. Then, styrene-butadiene-styrene copolymer is used as a substrate, graphene oxide is used as a reinforcing filler, and polyurethane elastomer is used as a toughening agent, and mixed and molded with K resin, white mineral oil, etc. to obtain a high-elasticity and shock-resistant SBS composite material UVR for soles.

[0014] The side chain of the grafted SBS modifier of the invention contains a phthalic acid group, which can interact with a hydroxyl group, a carboxyl group, etc. on the surface of graphene oxide, thereby modifying the grafted SBS modifier to the surface of graphene, which is beneficial to reducing the agglomeration of graphene. At the same time, the grafted SBS modifier has good compatibility with the styrene-butadiene-styrene copolymer, thereby improving the compatibility between the graphene and the styrene-butadiene-styrene copolymer, making the graphene have a better reinforcement effect, and significantly improving the tensile strength, elongation at break, tear strength and other properties of SBS.

[0015] The side chain of the grafted SBS modifier of the present invention contains a large number of carbamate groups, which can form hydrogen bonds and other interactions with the carbamate groups in the polyurethane elastomer, so that the grafted SBS modifier can be used as a compatibilizer to improve the compatibility between the polyurethane elastomer and the styrene-butadiene-styrene copolymer, so that the polyurethane elastomer can play a better reinforcement effect, and significantly improve the elongation at break, resilience and other properties of the SBS material. DETAILED DESCRIPTION

[0016] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0017] The styrene-butadiene-styrene copolymer SBS of the present invention, model YH-188, Dongguan Longsheng Engineering Plastics Co., Ltd. Graphene oxide, product specification 0.5-3 μm, Zhongke Leiming (Beijing) Technology Co., Ltd. White mineral oil, model 10#, Jinan Xinhuihuang Chemical Co., Ltd. K resin, model PB-5903, Dongguan Huayun Plastic Raw Materials Co., Ltd. Polyurethane elastomer, model 3695AU, Dongguan Huayun Plastic Raw Materials Co., Ltd.

[0018] Embodiment 1:

[0019] (1) Add 5 g of isocyanoethyl methacrylate, 6.5 g of 4-hydroxyphthalic acid, and 90 mg of dibutyltin dilaurate to 50 mL of toluene solvent, stir and react at 25° C. for 5 h, distill under reduced pressure, wash with petroleum ether, and recrystallize the product in ethanol to obtain 4-(urethane methacrylate)phthalic acid grafting agent.

[0020] (2) Add 20 g of styrene-butadiene-styrene copolymer to 250 mL of toluene, stir to dissolve, then add 2 g of 4-(methyl methacrylate urethane)phthalic acid grafting agent and 0.08 g of dibenzoyl peroxide, heat to 85 ° C in a nitrogen atmosphere, stir to carry out grafting reaction for 2 h, cool and add ethanol, filter the product, place it in a Soxhlet extractor, extract it with acetone for 24 h, and dry it to obtain a grafted SBS modifier.

[0021] (3) Add 12 g of grafted SBS modifier to 80 mL of toluene, heat to 60°C, stir to dissolve, add 0.5 g of graphene oxide, stir for surface modification for 1 h, distill under reduced pressure, dry, and then add the mixture and 1000 g of styrene-butadiene-styrene copolymer, 100 g of polyurethane elastomer, 120 g of K resin, 100 g of white mineral oil, 8 g of paraffin, and 5 g of antioxidant 1010 into a high-speed mixer for mixing. Then add the materials to a torque rheometer, mix at 170°C for 20 min, and finally hot press at 170°C for 10 min at a pressure of 10 MPa in a flat vulcanizer; then cold press for 30 min at a pressure of 8 MPa to obtain a high-elasticity and shock-resistant SBS composite material UVR for soles.

[0022] Embodiment 2:

[0023] (1) Add 5 g of isocyanoethyl methacrylate, 5.9 g of 4-hydroxyphthalic acid, and 130 mg of dibutyltin dilaurate to 50 mL of tetrahydrofuran solvent, stir and react at 20° C. for 5 h, distill under reduced pressure, wash with petroleum ether, and recrystallize the product in ethanol to obtain 4-(urethane methacrylate)phthalic acid grafting agent.

[0024] (2) Add 20 g of styrene-butadiene-styrene copolymer to 300 mL of toluene, stir to dissolve, then add 5 g of 4-(methyl methacrylate urethane)phthalic acid grafting agent and 0.2 g of dibenzoyl peroxide, heat to 65 ° C in a nitrogen atmosphere, stir to carry out grafting reaction for 5 hours, cool and add ethanol, filter the product, place it in a Soxhlet extractor, extract it with acetone for 24 hours, and dry it to obtain a grafted SBS modifier.

[0025] (3) Add 25 g of grafted SBS modifier to 100 mL of toluene, heat to 50°C, stir to dissolve, add 3 g of graphene oxide, stir for surface modification for 4 h, distill under reduced pressure, dry, then add the mixture and 1000 g of styrene-butadiene-styrene copolymer, 200 g of polyurethane elastomer, 60 g of K resin, 120 g of white mineral oil, 4 g of paraffin, and 8 g of antioxidant 1010 into a high-speed mixer for mixing, then add the materials into a torque rheometer, mix at 160°C for 30 min, and finally hot press at 160°C for 15 min at a pressure of 12 MPa in a flat vulcanizer; then cold press for 15 min at a pressure of 10 MPa to obtain a high-elasticity and shock-resistant SBS composite material UVR for soles.

[0026] Embodiment 3:

[0027] (1) Add 5 g of isocyanoethyl methacrylate, 6.5 g of 4-hydroxyphthalic acid, and 110 mg of dibutyltin dilaurate to 40 mL of dichloromethane solvent, stir and react at 40° C. for 2 h, distill under reduced pressure, wash with petroleum ether, and recrystallize the product in ethanol to obtain 4-(urethane methacrylate)phthalic acid grafting agent.

[0028] (2) Add 20 g of styrene-butadiene-styrene copolymer to 300 mL of toluene, stir to dissolve, then add 7 g of 4-(methyl methacrylate urethane)phthalic acid grafting agent and 0.3 g of dibenzoyl peroxide, heat to 80 ° C in a nitrogen atmosphere, stir to carry out grafting reaction for 5 hours, cool and add ethanol, filter the product, place it in a Soxhlet extractor, extract it with acetone for 24 hours, and dry it to obtain a grafted SBS modifier.

[0029] (3) Add 40 g of grafted SBS modifier to 150 mL of toluene, heat to 65° C., stir to dissolve, add 5 g of graphene oxide, stir to perform surface modification for 3 h, distill under reduced pressure, dry, then add the mixture and 1000 g of styrene-butadiene-styrene copolymer, 300 g of polyurethane elastomer, 150 g of K resin, 50 g of white mineral oil, 6 g of paraffin, and 5 g of antioxidant 1010 into a high-speed mixer for mixing, then add the materials into a torque rheometer, mix at 170° C. for 20 min, and finally hot press at 170° C. for 10 min at a pressure of 10 MPa in a flat vulcanizer; then cold press for 20 min at a pressure of 7 MPa to obtain a high-elasticity and shock-resistant SBS composite material UVR for soles.

[0030] Comparative Example 1: The difference between this comparative example and Example 1 is that no grafted SBS modifier, graphene oxide and polyurethane elastomer are added.

[0031] (1) 1000 g of styrene-butadiene-styrene copolymer, 120 g of K resin, 100 g of white mineral oil, 8 g of paraffin wax, and 5 g of antioxidant 1010 were added to a high-speed mixer for mixing, and then the materials were added to a torque rheometer, kneaded at 170° C. for 20 min, and finally hot-pressed at 170° C. for 10 min at a pressure of 10 MPa in a flat vulcanizer; and then cold-pressed for 30 min at a pressure of 8 MPa to obtain an SBS composite material for shoe soles.

[0032] Comparative Example 2: The difference between this comparative example and Example 1 is that graphene oxide and polyurethane elastomer are not added.

[0033] (1) 12 g of grafted SBS modifier, 1000 g of styrene-butadiene-styrene copolymer, 120 g of K resin, 100 g of white mineral oil, 8 g of paraffin wax, and 5 g of antioxidant 1010 were added to a high-speed mixer for mixing, and then the materials were added to a torque rheometer, mixed at 170° C. for 20 min, and finally hot-pressed at 170° C. for 10 min at a pressure of 10 MPa in a flat vulcanizer; and then cold-pressed for 30 min at a pressure of 8 MPa to obtain an SBS composite material for shoe soles.

[0034] Comparative Example 3: The difference between this comparative example and Example 1 is that no grafted SBS modifier and polyurethane elastomer are added.

[0035] (1) 0.5 g of graphene oxide, 1000 g of styrene-butadiene-styrene copolymer, 120 g of K resin, 100 g of white mineral oil, 8 g of paraffin wax, and 5 g of antioxidant 1010 were added to a high-speed mixer for mixing, and then the materials were added to a torque rheometer, mixed at 170° C. for 20 min, and finally hot-pressed at 170° C. for 10 min at a pressure of 10 MPa in a flat vulcanizer; and then cold-pressed for 30 min at a pressure of 8 MPa to obtain an SBS composite material for soles.

[0036] Comparative Example 4: The difference between this comparative example and Example 1 is that no polyurethane elastomer is added.

[0037] (1) Add 12 g of grafted SBS modifier to 80 mL of toluene, heat to 60° C., stir to dissolve, add 0.5 g of graphene oxide, stir to perform surface modification for 1 h, distill under reduced pressure, dry, then add the mixture and 1000 g of styrene-butadiene-styrene copolymer, 120 g of K resin, 100 g of white mineral oil, 8 g of paraffin, and 5 g of antioxidant 1010 into a high-speed mixer for mixing, then add the materials into a torque rheometer, mix at 170° C. for 20 min, and finally hot press at 170° C. for 10 min at a pressure of 10 MPa in a flat vulcanizer; then cold press for 30 min at a pressure of 8 MPa to obtain an SBS composite material for shoe soles.

[0038] Comparative Example 5: The difference between this comparative example and Example 1 is that no grafted SBS modifier and graphene oxide are added.

[0039] (1) 1000 g of styrene-butadiene-styrene copolymer, 100 g of polyurethane elastomer, 120 g of K resin, 100 g of white mineral oil, 8 g of paraffin wax, and 5 g of antioxidant 1010 were added to a high-speed mixer for mixing, and then the materials were added to a torque rheometer, mixed at 170° C. for 20 min, and finally hot-pressed at 170° C. for 10 min at a pressure of 10 MPa in a flat vulcanizer; and then cold-pressed for 30 min at a pressure of 8 MPa to obtain an SBS composite material for shoe soles.

[0040] Comparative Example 6: The difference between this comparative example and Example 1 is that graphene oxide is not added.

[0041] (1) 12 g of grafted SBS modifier, 1000 g of styrene-butadiene-styrene copolymer, 100 g of polyurethane elastomer, 120 g of K resin, 100 g of white mineral oil, 8 g of paraffin wax, and 5 g of antioxidant 1010 were added to a high-speed mixer for mixing, and then the materials were added to a torque rheometer, mixed at 170° C. for 20 min, and finally hot-pressed at 170° C. for 10 min at a pressure of 10 MPa in a flat vulcanizer; and then cold-pressed for 30 min at a pressure of 8 MPa to obtain an SBS composite material for shoe soles.

[0042] Comparative Example 7: The difference between this comparative example and Example 1 is that no grafted SBS modifier is added.

[0043] (1) 0.5 g of graphene oxide, 1000 g of styrene-butadiene-styrene copolymer, 100 g of polyurethane elastomer, 120 g of K resin, 100 g of white mineral oil, 8 g of paraffin wax, and 5 g of antioxidant 1010 were added to a high-speed mixer for mixing, and then the materials were added to a torque rheometer, mixed at 170° C. for 20 min, and finally hot-pressed at 170° C. for 10 min at a pressure of 10 MPa in a flat vulcanizer; and then cold-pressed for 30 min at a pressure of 8 MPa to obtain an SBS composite material for shoe soles.

[0044] Comparative Example 8: The difference between this comparative example and Example 1 is that acrylic acid is used instead of 4-(methyl methacrylate urethane)phthalic acid grafting agent.

[0045] (1) Add 20 g of styrene-butadiene-styrene copolymer to 250 mL of toluene, stir to dissolve, then add 2 g of acrylic acid and 0.08 g of dibenzoyl peroxide, heat to 85 ° C in a nitrogen atmosphere, stir to carry out grafting reaction for 2 h, cool and add ethanol, filter the product, place it in a Soxhlet extractor, extract it with acetone for 24 h, and dry it to obtain a grafted SBS modifier.

[0046] (2) Add 12 g of grafted SBS modifier to 80 mL of toluene, heat to 60° C., stir to dissolve, add 0.5 g of graphene oxide, stir for surface modification for 1 h, distill under reduced pressure, dry, then add the mixture and 1000 g of styrene-butadiene-styrene copolymer, 100 g of polyurethane elastomer, 120 g of K resin, 100 g of white mineral oil, 8 g of paraffin, and 5 g of antioxidant 1010 into a high-speed mixer for mixing, then add the materials into a torque rheometer, mix at 170° C. for 20 min, and finally hot press at 170° C. for 10 min at a pressure of 10 MPa in a flat vulcanizer; then cold press for 30 min at a pressure of 8 MPa to obtain an SBS composite material for soles.

[0047] The tensile properties are tested according to GB / T 528-2009. The tear strength is tested according to GB / T 529-2008. The rebound performance is tested according to GB / T 1681-2009.

[0048] Table 1: Test results

[0049]

[0050]

[0051] It can be seen from Table 1 that the tensile strength, elongation at break, tear strength and rebound rate of the SBS composite material of Comparative Example 1 are low, and the mechanical properties and elasticity are not good.

[0052] Comparative Example 2 adds a grafted SBS modifier, which contains a styrene-butadiene-styrene main chain and has good compatibility with the styrene-butadiene-styrene copolymer. When added to the SBS material, it has almost no effect on the mechanical properties of the material. The tensile strength and other properties of the SBS material are very similar to those of Comparative Example 1.

[0053] Example 1-3 adds graphene oxide, polyurethane elastomer and grafted SBS modifier, the side chain of the modifier contains phthalic acid group It can interact with the hydroxyl and carboxyl groups on the surface of graphene oxide, thereby modifying the grafted SBS modifier to the graphene surface, which is beneficial to reduce the agglomeration of graphene. At the same time, the grafted SBS modifier has good compatibility with styrene-butadiene-styrene copolymer, thereby improving the compatibility between graphene and styrene-butadiene-styrene copolymer, making graphene have a better reinforcement effect, and significantly improving the tensile strength, elongation at break, tear strength and other properties of SBS. At the same time, the side chain of the modifier contains a large number of carbamate groups It can form hydrogen bonds and other interactions with the carbamate groups in the polyurethane elastomer, so that the grafted SBS modifier can act as a compatibilizer to improve the compatibility between the polyurethane elastomer and the styrene-butadiene-styrene copolymer, so that the polyurethane elastomer can play a better reinforcement effect, and significantly improve the elongation at break, resilience and other properties of the SBS material.

[0054] In Comparative Example 3, only graphene oxide is added, which has poor compatibility with styrene-butadiene-styrene copolymer, and graphene oxide is easily agglomerated, and has poor reinforcing effect on the SBS material, and does not significantly improve the mechanical properties of the SBS material, such as tensile strength.

[0055] Comparative Example 4 added graphene oxide and grafted SBS modifier, the modifier improved the compatibility between graphene and styrene-butadiene-styrene copolymer, so that graphene has a better reinforcement effect, which is beneficial to improve the tensile strength, elongation at break, tear strength and other properties of SBS.

[0056] In Comparative Example 5, only polyurethane elastomer is added, which has poor compatibility with styrene-butadiene-styrene copolymer, has low reinforcement effect, and fails to effectively improve the tensile strength, resilience and other properties of SBS.

[0057] In Comparative Example 6, polyurethane elastomer and grafted SBS modifier were added. The modifier can improve the compatibility between polyurethane elastomer and styrene-butadiene-styrene copolymer, so that polyurethane elastomer can play a better reinforcement effect, which is beneficial to improve the elongation at break, resilience and other properties of SBS material.

[0058] In Comparative Example 7, no grafted SBS modifier was added, and the added polyurethane elastomer and graphene oxide had poor compatibility with the styrene-butadiene-styrene copolymer, resulting in the mechanical properties of the SBS material being lower than those in Example 1.

[0059] In Comparative Example 8, styrene-butadiene-styrene copolymer is grafted and modified with acrylic acid. The obtained grafted SBS modifier contains only carboxyl groups but no phthalic acid groups. The interaction force between the grafted SBS modifier and the hydroxyl and carboxyl groups on the surface of graphene oxide is low. The grafted SBS modifier does not contain carbamate groups and the interaction force between the grafted SBS modifier and the polyurethane elastomer is low. The compatibility between graphene oxide, polyurethane elastomer and styrene-butadiene-styrene copolymer is not improved well, resulting in the tensile strength and resilience of the SBS material being lower than those in Example 1.

Claims

1. A method for preparing a high elastic shock-resistant SBS composite material for soles, characterized in that: The preparation method comprises the following steps: Step A, adding styrene-butadiene-styrene copolymer to toluene, stirring and dissolving, adding 4-(methyl methacrylate urethane) phthalic acid grafting agent and dibenzoyl peroxide, stirring in a nitrogen atmosphere for grafting reaction, adding ethanol after cooling, filtering the product, placing it in a Soxhlet extractor for extraction, and drying to obtain a grafted SBS modifier; Step B, adding a grafted SBS modifier to toluene, heating and stirring to dissolve, adding graphene oxide, stirring to perform surface modification, distilling under reduced pressure, drying, and then adding the mixture, styrene-butadiene-styrene copolymer, polyurethane elastomer, K resin, and additives to a high-speed mixer for mixing, and then adding the materials to a torque rheometer for kneading, and finally performing molding in a flat vulcanizer to obtain a high-elasticity and shock-resistant SBS composite material for soles.

2. The method for preparing the high elastic shock-resistant SBS composite material for soles according to claim 1, characterized in that: In the step A, the mass ratio of styrene-butadiene-styrene copolymer, 4-(methyl methacrylate urethane) phthalic acid grafting agent, and dibenzoyl peroxide is 100:(10-35):(0.4-1.5).

3. The method for preparing the high elasticity and shock resistant SBS composite material for soles according to claim 1, characterized in that: The temperature of the grafting reaction in step A is 65-85° C., and the reaction time is 2-5 hours.

4. The method for preparing the high elastic shock-resistant SBS composite material for soles according to claim 1, characterized in that: In the step B, the mass ratio of the SBS modifier, graphene oxide, styrene-butadiene-styrene copolymer, polyurethane elastomer and K resin is (1.2-4):(0.05-0.5):100:(10-30):(6-15).

5. The method for preparing the high elasticity and shock resistant SBS composite material for soles according to claim 1, characterized in that: The temperature during heating and stirring in step B is 50-65° C., and the time for surface modification is 1-4 hours.

6. The method for preparing the high elasticity and shock resistant SBS composite material for soles according to claim 1, characterized in that: The mixing temperature in step B is 160-170° C. and the mixing time is 15-30 min.

7. The method for preparing the high elasticity and shock resistant SBS composite material for soles according to claim 1, characterized in that: The auxiliary agent in step B is any one or a combination of white mineral oil, paraffin, and antioxidant; And / or, the solvent is dichloromethane, toluene or tetrahydrofuran.

8. The method for preparing the high elasticity and shock resistant SBS composite material for soles according to claim 1, characterized in that: In the step B, the molding is first hot pressed at 160-170° C. for 10-15 minutes at a pressure of 10-12 MPa, and then cold pressed for 15-30 minutes at a pressure of 7-10 MPa.

9. The method for preparing the high elastic shock-resistant SBS composite material for soles according to claim 2, characterized in that: The preparation method of the 4-(urethane methacrylate)phthalic acid grafting agent is as follows: adding isocyanoethyl methacrylate, 4-hydroxyphthalic acid and dibutyltin dilaurate in a mass ratio of 100:(118-130):(1.8-2.6) into a solvent, stirring and reacting at 20-40° C. for 2-5 hours, distilling under reduced pressure, washing and recrystallizing to obtain the 4-(urethane methacrylate)phthalic acid grafting agent.

10. A high elasticity and shock resistant SBS composite material for soles prepared by the preparation method according to any one of claims 1 to 9.

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