CN112625333B - High-wear-resistance and high-shock-absorption sports shoe sole material and preparation method thereof - Google Patents
High-wear-resistance and high-shock-absorption sports shoe sole material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
- A43B13/18—Resilient soles
- A43B13/187—Resiliency achieved by the features of the material, e.g. foam, non liquid materials
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/0066—Use of inorganic compounding ingredients
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2419/00—Characterised by the use of rubbers not provided for in groups C08J2407/00 - C08J2417/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
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- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/06—Polyurethanes from polyesters
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/14—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
Abstract
The invention discloses a high-wear-resistance and high-damping sole material of sports shoes and a preparation method thereof, and relates to the technical field of sports shoes. The invention discloses a high wear-resistant high-shock-absorption sports shoe sole material which is prepared by crosslinking and blending PBSs (Poly-butylenes-co-styrene) modified EVA to generate an EVA/PBSs copolymer under the action of a crosslinking agent and modified nano zinc oxide, then blending the EVA/PBSs copolymer with polyester type thermoplastic polyurethane elastomer, waste rubber powder, modified diatomite and other raw materials, and carrying out die pressing and foaming. The high-wear-resistance and high-shock-absorption sports shoe sole material provided by the invention has the advantages of simple preparation process, easiness in operation, low density, high elasticity, excellent wear resistance, shock absorption, weather resistance and corrosion resistance, the comfort level of sports shoes is improved, and the service life of the sports shoes is prolonged.
Description
Technical Field
The invention belongs to the technical field of sports shoes, and particularly relates to a high-wear-resistance and high-shock-absorption sole material of a sports shoe and a preparation method thereof.
Background
With the rapid development of modern society, people have changed greatly to the concept of wearing shoes, from protection and heat preservation in the last century to the pursuit of functions such as portability, comfort, beauty, shock absorption, wear resistance and the like. China is the first major country for producing and consuming sports shoes in the world, and research and development of the sports shoes are also in a change day by day. The existing sports shoe soles are divided into three categories, namely vulcanized rubber soles, air cushion filling soles and foaming soles, and with the continuous development of science and technology, the foaming soles have the advantages of excellent performance and low cost, so that the sports shoe soles have larger market share.
Currently, the bottom of the world's various brands of athletic shoes are mostly using foamed materials of EVA and its blends. The EVA and the blended foaming material thereof have light weight, warm keeping, comfort and low cost, but the existing EVA and the blended foaming material thereof have larger density and insufficient elasticity which is 30 to 42 percent, while the midsoles of basketball, running and other sports have the requirements of high elasticity (the rebound elasticity is more than 50 percent), and have poor wear resistance and slip resistance, and the existing EVA foaming material can not meet the requirements. The foaming rubber is widely used due to lightness, softness and comfort, but once the traditional rubber is foamed, the wear resistance and the skid resistance of the traditional rubber are obviously reduced, and the width of the foaming rubber are greatly reduced.
The good shock absorption performance can improve the wearing comfort of the sports shoes, buffer the shock of impact force to the body during sports, and protect the bones and joints of the human body from being damaged. At present, the shock absorption performance of sports shoes is mainly researched on materials and structures of soles, the structure shock absorption technology is mature, the material shock absorption is mainly concentrated on foamed midsoles and insoles of the sports shoes, and the shock absorption research on the materials of the soles is less. Therefore, the development of a foamed sole material with light weight, good elasticity, wear resistance and shock absorption becomes the main direction for the development and development of sports soles.
The Chinese invention patent CN201210408660.4 discloses a wide temperature range high damping sneaker sole rubber material and a preparation method thereof, the material mainly comprises brominated butyl rubber, butadiene rubber, a reinforcing agent, a vulcanizing agent, a vulcanization accelerator and petroleum resin, the material keeps good damping performance in a wide temperature range and has good wear resistance, but the tearing strength is general, the density is large, the sole is heavy, and the material does not meet the requirement of modern people on the lightness of shoes. Chinese invention patent CN201010248174.1 discloses a high shock-absorbing wear-resistant sports shoe sole material and a manufacturing method thereof, which is prepared by screening rubber composition proportion, coupling agent, accelerant and activator and reasonably controlling the process on the basis of rubber, softening oil and reinforcing agent, and has excellent shock absorption, wear resistance and wet skid resistance, but the density is larger, the rebound resilience is general, and the comfort level is general.
Disclosure of Invention
The sole material for the sports shoes is simple in preparation process, easy to operate, low in density, high in elasticity, excellent in wear resistance, shock absorption, weather resistance and corrosion resistance, improves comfort of the sports shoes and prolongs service life of the sports shoes.
In order to realize the aim of the invention, the invention provides a high-wear-resistance and high-shock-absorption sports shoe sole material which is prepared from the following raw materials in parts by weight: 40-60 parts of ethylene-vinyl acetate copolymer, 2-5 parts of modified nano zinc oxide, 10-20 parts of Polyborosiloxane (PBSs), 25-40 parts of polyester type thermoplastic polyurethane elastomer, 5-10 parts of waste rubber powder, 8-12 parts of modified diatomite, 1-3 parts of ligand type titanate coupling agent, 2-5 parts of foaming agent, 1-2 parts of cross-linking agent, 1-3 parts of vulcanizing agent and 0.3-0.8 part of anti-aging agent.
Furthermore, the VA content in the ethylene-vinyl acetate copolymer is 22-36%.
Further, the preparation method of the modified nano zinc oxide comprises the following steps: adding nano zinc oxide into stearic acid at 70 ℃, stirring for 30min, then cooling to normal temperature, adding a silane coupling agent, and stirring for 30-40min to obtain the modified nano zinc oxide.
Further, the mass ratio of the nano zinc oxide to the stearic acid is 1: (0.5-0.8), wherein the mass ratio of the nano zinc oxide to the silane coupling agent is 1: (0.1-0.2).
Further, the preparation method of the polyborosiloxane comprises the following steps: vacuumizing a reaction kettle, adding hydroxyl polydimethylsiloxane (PDMS-OH) and boric acid, uniformly stirring, heating to 200 ℃ at the speed of 5 ℃/min, reacting for 30min at the temperature, and naturally cooling to room temperature to obtain PBSs, wherein the mass ratio of the hydroxyl polydimethylsiloxane to the boric acid is 1: (0.02-0.04).
Further, the polyester type thermoplastic polyurethane elastomer is Elastollan C64D from Pasteur, Germany.
Further, the modified diatomite is prepared by stirring diatomite and alkyl phosphorus carboxylate for 1 hour at 50-60 ℃, and the mass ratio of the diatomite to the alkyl phosphorus carboxylate is 1: (0.3-0.5).
Further, the foaming agent is azodicarboxylate, the crosslinking agent is dicumyl peroxide, the vulcanizing agent is benzoyl peroxide, and the anti-aging agent is anti-aging agent AW.
A preparation method of a high-wear-resistance high-shock-absorption sports shoe sole material specifically comprises the following steps:
(1) EVA/PBSs copolymer: adding EVA into a double-roll open mill, heating to 100 ℃, adding PBSs after the EVA is completely molten, mixing for 30min, then heating to 160 ℃, adding modified nano zinc oxide and a cross-linking agent, mixing for 1h, and taking down a material sheet to prepare an EVA/PBSs copolymer;
(2) uniformly mixing the EVA/PBSs copolymer, the polyester thermoplastic polyurethane elastomer, the waste rubber powder and the modified diatomite in a double-roll mill, heating to 100-120 ℃, mixing for 20-30min, then adding a coordination type titanate coupling agent and a vulcanizing agent, and mixing for 10-20min to obtain a mixture;
(3) adding a foaming agent and an anti-aging agent into the mixed mixture, mixing for 5min at 70-80 ℃, discharging sheets, then placing the obtained sheets on a flat vulcanization instrument, preheating for 5min at 160-180 ℃, and foaming under the condition of mould pressing of 10-12MPa to obtain the sole material.
The invention achieves the following beneficial effects:
1. the invention is prepared by foaming ethylene-vinyl acetate copolymer (EVA) serving as a matrix, and the EVA has excellent flexibility, high resilience, good ductility and processability, so that the foaming material has better compression resilience resistance, toughness and lower hardness, and has better comprehensive physical properties.
2. The PBSs are synthesized by the reaction of hydroxyl-terminated polydimethylsiloxane (PDMS-OH) and boric acid, the molecular chain of PDMS-OH is randomly broken in the reaction process, and polydisperse polar end groups are converted into boron and-Si-O-B (OH) through the hydrolysis of boron-oxygen bond and B-O-B and boric acid2Due to the hydrogen bonds formed between the end groups, the synthesized PBSs form a supramolecular elastomer and have strong viscoelasticity. The invention cross-links and blends the PBSs with the EVA under the action of the cross-linking agent and the modified nano zinc oxide to ensure that strong interaction exists between molecular chain ends, so that the EVA/PBSs copolymerThe high-adhesion high-strength polyurethane foam material has high adhesion and excellent strength and toughness, so that the pore diameter of the cells of the foam material is increased, the density of the cells is reduced, and the wear resistance, the damping property, the tearing strength and the resilience of the sole foam material are improved.
3. The modified nano zinc oxide is used as a catalyst to be added into the reaction process of the EVA and the PBSs, so that the crosslinking effect of the EVA and the PBSs is improved, the wear resistance, the mechanical strength and the aging resistance of the EVA/PBSs copolymer are improved due to the excellent performance of the modified nano zinc oxide, and the wear resistance, the mechanical strength and the aging resistance of a sole material are further improved. The modified wear-resistant zinc oxide is also used as an active agent of the sole foaming material, so that the decomposition temperature of the foaming agent is reduced, the foaming effect of the invention is improved, the cell density is high, the expansion rate is high, the cells are uniform, and the density of the sole material is reduced.
The surface polarity of the nano zinc oxide is strong, and the nano zinc oxide is not easy to be uniformly dispersed in an organic medium, so that the nano zinc oxide is subjected to surface modification by the method. If the silane coupling agent is used singly for carrying out surface treatment on the nano zinc oxide, more silane coupling agents are needed, but the method firstly carries out pre-activation treatment on the nano zinc oxide by stearic acid and then carries out surface treatment by the silane coupling agent, so that the modification effect of the nano zinc oxide is improved, and the cost is reduced.
4. The polyester type thermoplastic polyurethane elastomer added in the invention has very good damping performance, good rebound, excellent wear resistance and corrosion resistance, and the interface bonding force with other components in the sole material is increased through the ligand type titanate coupling agent, so that the shock absorption, rebound resilience, wear resistance and corrosion resistance of the invention are improved.
5. The diatomite modified by the alkyl phosphorus carboxylate improves the compatibility with each component of a sole material, reduces the viscosity of a system, increases the fluidity of the system, improves the processability of the system, reduces the deformation and improves the dimensional stability of the diatomite. The modified diatomite can be used as a nucleating agent of the EVA/PBSs copolymer, so that the foaming performance of the EVA/PBSs copolymer is improved, the cell density of the invention is larger, and the cell distribution is more uniform. The modified diatomite also improves the wear resistance and aging resistance of the invention.
6. The waste rubber powder is wide in source and low in price, and is added into the sole material, so that the use amount of EVA is reduced, the cost is reduced, the waste resources are reasonably utilized, the energy is saved, the environment is protected, and the tensile strength, the elongation at break and the resilience of the sole material are improved.
7. The invention utilizes PBSs modified EVA to crosslink and blend under the action of a crosslinking agent and modified nano zinc oxide to generate an EVA/PBSs copolymer, then blends the copolymer with polyester thermoplastic polyurethane elastomer, waste rubber powder, modified diatomite and other raw materials, and obtains a sole material after mould pressing and foaming, wherein the sole material has low density, high elasticity, excellent wear resistance, shock absorption, weather resistance, corrosion resistance and wet skid resistance, thereby ensuring the portability, comfort and wear resistance of sports shoes, prolonging the service life of the sports shoes and ensuring the use effect of the sports shoes. The sole material of the sports shoe prepared by the invention has strong binding force among raw materials, and the raw materials are not easy to separate out of the product, thereby ensuring the stable performance of the sole, not polluting the environment and prolonging the service life of the sports shoe. The preparation method is simple, the raw materials are easy to obtain, and the sole material can be recycled, so that the aims of energy conservation and environmental protection can be fulfilled.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The Polyborosiloxanes (PBSs) in the examples of the present invention can be prepared by the methods of the examples, and can also be prepared according to the prior art documents derived from: liu Z, Picken S J, Besseling N A M. Polybosisiloxanes (PBSs), Synthetic Kinetics [ J ] Macromolecules 2014,47(14): 4531-.
The sole material for sports shoes with high wear resistance and high shock absorption and the preparation method thereof according to the present invention will be described with reference to the following embodiments.
Example 1
A high wear-resistant high-damping sports shoe sole material is composed of the following raw materials in parts by weight: 40 parts of ethylene-vinyl acetate copolymer, 2 parts of modified nano zinc oxide, 20 parts of PBSs, 40 parts of polyester type thermoplastic polyurethane elastomer, 8 parts of waste rubber powder, 8 parts of modified diatomite, 3 parts of coordination type titanate coupling agent, 3 parts of foaming agent, 1 part of crosslinking agent, 3 parts of vulcanizing agent and 0.8 part of anti-aging agent. The preparation method of the sole material consisting of the materials comprises the following steps:
(1) EVA/PBSs copolymer: adding EVA into a double-roll open mill, heating to 100 ℃, adding PBSs after the EVA is completely molten, mixing for 30min, then heating to 160 ℃, adding modified nano zinc oxide and a cross-linking agent, mixing for 1h, and taking down a material sheet to obtain the EVA/PBSs copolymer.
(2) Uniformly mixing the EVA/PBSs copolymer, the polyester thermoplastic polyurethane elastomer, the waste rubber powder and the modified diatomite in a double-roll mill, heating to 100-120 ℃, mixing for 20-30min, then adding the coordination type titanate coupling agent and the vulcanizing agent, and mixing for 10-20min to obtain a mixture.
(3) Adding a foaming agent and an anti-aging agent into the mixed mixture, mixing for 5min at 70-80 ℃, discharging sheets, then placing the obtained sheets on a flat-plate vulcanizing instrument, preheating for 5min at 160-180 ℃, and foaming under the condition that the mould pressing is 10-12MPa to prepare the sole material.
The ethylene-vinyl acetate copolymer contains 22-36% of VA, the polyester thermoplastic polyurethane elastomer is Elastollan C64D from Pasteur Germany, the foaming agent is azodicarboxylate, the crosslinking agent is dicumyl peroxide, the vulcanizing agent is benzoyl peroxide, and the anti-aging agent is AW.
The preparation method of the modified nano zinc oxide comprises the following steps: adding nano zinc oxide into stearic acid at 70 ℃, stirring for 30min, then cooling to normal temperature, adding a silane coupling agent, and stirring for 30-40min to obtain the modified nano zinc oxide. Wherein the mass ratio of the nano zinc oxide to the stearic acid is 1: 0.8, the mass ratio of the nano zinc oxide to the silane coupling agent is 1: 0.1.
the preparation method of the polyborosiloxane comprises the following steps: vacuumizing the reaction kettle, adding hydroxyl polydimethylsiloxane (PDMS-OH) and boric acid, stirring uniformly, heating to 200 ℃ at the speed of 5 ℃/min, reacting for 30min at the temperature, and naturally cooling to room temperature to obtain the PBSs. Wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the boric acid is 1: 0.02.
the modified diatomite is prepared by stirring diatomite and alkyl phosphorus carboxylate at 50-60 ℃ for 1 h. Wherein the mass ratio of the diatomite to the alkyl phosphorus carboxylate is 1: 0.5.
example 2
A high-wear-resistance high-shock-absorption sports shoe sole material is composed of the following raw materials in parts by weight: 60 parts of ethylene-vinyl acetate copolymer, 5 parts of modified nano zinc oxide, 10 parts of PBSs, 25 parts of polyester thermoplastic polyurethane elastomer, 10 parts of waste rubber powder, 12 parts of modified diatomite, 1 part of coordination type titanate coupling agent, 5 parts of azodicarboxylate, 2 parts of dicumyl peroxide, 1 part of benzoyl peroxide and 0.3 part of anti-aging agent AW. The preparation method of the sole material composed of the material is the same as that of the embodiment 1, and the embodiment 1 is specifically referred to.
The EVA ethylene-vinyl acetate copolymer has VA content of 22-36%, and the polyester type thermoplastic polyurethane elastomer is Elastollan C64D from Pasteur Germany.
The preparation method of the modified nano-zinc oxide is the same as that in the embodiment 1, except that the mass ratio of the nano-zinc oxide to the stearic acid is 1: 0.5, the mass ratio of the nano zinc oxide to the silane coupling agent is 1: 0.2.
the preparation method of the polyborosiloxane is the same as that of the polyborosiloxane in example 1, except that the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the boric acid is 1: 0.04.
the modified diatomite is prepared by stirring diatomite and alkyl phosphorus carboxylate at 50-60 ℃ for 1 h. Wherein the mass ratio of the diatomite to the alkyl phosphorus carboxylate is 1: 0.3.
example 3
A high-wear-resistance high-shock-absorption sports shoe sole material is composed of the following raw materials in parts by weight: 50 parts of ethylene-vinyl acetate copolymer, 3 parts of modified nano zinc oxide, 15 parts of PBSs, 34 parts of polyester type thermoplastic polyurethane elastomer, 8 parts of waste rubber powder, 10 parts of modified diatomite, 2 parts of coordination type titanate coupling agent, 4 parts of azodicarbonic diformate, 1.5 parts of dicumyl peroxide, 2 parts of benzoyl peroxide and 0.5 part of anti-aging agent AW. The preparation method of the sole material composed of the material is the same as that in example 1, and the specific reference is made to example 1.
The EVA ethylene-vinyl acetate copolymer has VA content of 22-36%, and the polyester type thermoplastic polyurethane elastomer is Elastollan C64D from Pasteur Germany.
The preparation method of the modified nano-zinc oxide is the same as that in the embodiment 1, except that the mass ratio of the nano-zinc oxide to the stearic acid is 1: 0.7, the mass ratio of the nano zinc oxide to the silane coupling agent is 1: 0.1.
the preparation method of the polyborosiloxane is the same as that of example 1, except that the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the boric acid is 1: 0.03.
the modified diatomite is prepared by stirring diatomite and alkyl phosphorus carboxylate at 50-60 ℃ for 1 h. Wherein the mass ratio of the diatomite to the alkyl phosphorus carboxylate is 1: 0.4.
example 4
A high wear-resistant high-damping sports shoe sole material is composed of the following raw materials in parts by weight: 55 parts of ethylene-vinyl acetate copolymer, 4 parts of modified nano zinc oxide, 15 parts of PBSs, 31 parts of polyester type thermoplastic polyurethane elastomer, 5 parts of waste rubber powder, 11 parts of modified diatomite, 2 parts of coordination type titanate coupling agent, 2 parts of azodicarboxylate, 2 parts of dicumyl peroxide, 2 parts of benzoyl peroxide and 0.6 part of anti-aging agent AW. The preparation method of the sole material composed of the material is the same as that of the embodiment 1, and the embodiment 1 is specifically referred to.
The EVA ethylene-vinyl acetate copolymer has VA content of 22-36%, and the polyester type thermoplastic polyurethane elastomer is Elastollan C64D from Pasteur Germany.
The preparation method of the modified nano-zinc oxide is the same as that in the embodiment 1, except that the mass ratio of the nano-zinc oxide to the stearic acid is 1: 0.6, the mass ratio of the nano zinc oxide to the silane coupling agent is 1: 0.1.
the preparation method of the polyborosiloxane is the same as that of example 1, except that the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the boric acid is 1: 0.03.
the modified diatomite is prepared by stirring diatomite and alkyl phosphorus carboxylate at 50-60 ℃ for 1 h. Wherein the mass ratio of the diatomite to the alkyl phosphorus carboxylate is 1: 0.5.
comparative example 1
The raw materials and the preparation method of the sole material for the sports shoes are the same as those in the embodiment 3, and the specific reference is made to the embodiment 3. Except that PBSs were not added in this comparative example.
Comparative example 2
The raw materials and the preparation method of the sole material for the sports shoes are the same as those in the embodiment 3, and the specific reference is made to the embodiment 3. Except that the modified nano zinc oxide was not added in this comparative example.
Comparative example 3
A sole material for sports shoes, the raw materials and the preparation method thereof are the same as those in example 3, and the specific reference is made to example 3. Except that the polyester type thermoplastic polyurethane elastomer was not added in this comparative example.
Comparative example 4
The raw materials and the preparation method of the sole material for the sports shoes are the same as those in the embodiment 3, and the specific reference is made to the embodiment 3. Except that in this comparative example, no modified diatomaceous earth was added.
The sole materials of the sports shoes prepared in the above examples 1 to 4 and comparative examples 1 to 4 were compared and tested for their mechanical properties, and the test results are shown in table 1 below.
TABLE 1 detection result of mechanical properties of sole material of sports shoes
As can be seen from the test results in Table 1, the sole material for sports shoes has high impact strength, elongation at break and right-angle tear strength, and has excellent toughness and impact resistance. After the PBSs are added into the sole material, the tensile strength, the impact strength, the tearing strength and the toughness of the sole material are greatly enhanced; after the polyester type thermoplastic polyurethane elastomer or the modified diatomite is added into the sole material, the strength and the toughness of the sole material are improved.
The abrasion resistance, hardness, density, shock absorption and rebound resilience of the pedal materials prepared in examples 1 to 4 and comparative examples 1 to 4 were measured by comparison, and the results are shown in Table 2 below.
Shock absorption: the dynamic thermomechanical analysis test conditions, the instrument names and the model details are as follows:
(1) sample size: 10 mm. times.10 mm. times.2 mm
(2) Testing the instrument: a Dynamic Mechanical Thermal Spectrometer (DMTS); the model is as follows: eplex or 500n
(3) A test mode: compression mode
And (3) testing conditions are as follows: frequency: 10 Hz; static strain: 5 percent; dynamic strain: 0.5 percent; the heating rate is 2 ℃/min, and the heating range is as follows: -130 ℃ to 100 ℃.
Table 2 table of performance test results of sole material of sports shoes
As can be seen from the test results in Table 2, the sole material for sports shoes according to the present invention is light in weight, low in hardness, and excellent in wear resistance, shock absorption and rebound resilience. After the PBSs are added, the wear resistance, the shock absorption and the rebound resilience of the rubber composition are greatly improved, and the density and the hardness are reduced; after the modified nano zinc oxide is added, the wear resistance, the rebound resilience and the shock absorption of the invention are all improved; when the polyester type thermoplastic polyurethane elastomer is added, the wear resistance, the rebound resilience and the shock absorption of the invention are improved; after the modified diatomite is added, the density of the wear-resistant brick is reduced, and the wear resistance is improved.
The technical features of the embodiments described above can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (7)
1. The high-wear-resistance and high-shock-absorption sports shoe sole material is characterized by being prepared from the following raw materials in parts by weight: 40-60 parts of ethylene-vinyl acetate copolymer, 2-5 parts of modified nano zinc oxide, 10-20 parts of PBSs, 25-40 parts of polyester thermoplastic polyurethane elastomer, 5-10 parts of waste rubber powder, 8-12 parts of modified diatomite, 1-3 parts of ligand titanate coupling agent, 2-5 parts of foaming agent, 1-2 parts of crosslinking agent, 1-3 parts of vulcanizing agent and 0.3-0.8 part of anti-aging agent;
the preparation method of the modified nano zinc oxide comprises the following steps: adding nano zinc oxide into stearic acid at 70 ℃, stirring for 30min, then cooling to normal temperature, adding a silane coupling agent, and stirring for 30-40min to obtain modified nano zinc oxide;
the preparation method of the sole material specifically comprises the following steps:
(1) EVA/PBSs copolymer: adding EVA into a double-roll open mill, heating to 100 ℃, adding PBSs after the EVA is completely molten, mixing for 30min, then heating to 160 ℃, adding modified nano zinc oxide and a cross-linking agent, mixing for 1h, taking down a material sheet, and preparing an EVA/PBSs copolymer;
(2) uniformly mixing the EVA/PBSs copolymer, the polyester thermoplastic polyurethane elastomer, the waste rubber powder and the modified diatomite in a double-roll mill, heating to 100-120 ℃, mixing for 20-30min, then adding a coordination type titanate coupling agent and a vulcanizing agent, and mixing for 10-20min to obtain a mixture;
(3) adding a foaming agent and an anti-aging agent into the mixed mixture, mixing for 5min at 70-80 ℃, discharging sheets, then placing the obtained sheets on a flat vulcanization instrument, preheating for 5min at 160-180 ℃, and foaming under the condition of mould pressing of 10-12MPa to obtain the sole material.
2. The high wear-resistant high damping athletic shoe sole material of claim 1, wherein the ethylene-vinyl acetate copolymer has a VA content of 22-36%.
3. The high-wear-resistance high-shock-absorption sports shoe sole material according to claim 1, wherein the mass ratio of the nano zinc oxide to the stearic acid is 1: (0.5-0.8), wherein the mass ratio of the nano zinc oxide to the silane coupling agent is 1: (0.1-0.2).
4. The high wear-resistant high shock-absorbing sports shoe sole material according to claim 1, wherein the PBSs are prepared by a method comprising the following steps: vacuumizing a reaction kettle, adding hydroxyl-terminated polydimethylsiloxane and boric acid, uniformly stirring, heating to 200 ℃ at the speed of 5 ℃/min, reacting at the temperature for 30min, and naturally cooling to room temperature to obtain PBSs, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the boric acid is 1: (0.02-0.04).
5. The high abrasion-resistant high damping sneaker sole material according to claim 1, wherein said polyester-type thermoplastic polyurethane elastomer is ElastollanC64D from Pasteur, Germany.
6. The high wear-resistant high damping sneaker sole material according to claim 1, wherein the modified diatomaceous earth is prepared by stirring diatomaceous earth and alkyl phosphorus carboxylate at 50-60 ℃ for 1 hour, and the mass ratio of the diatomaceous earth to the alkyl phosphorus carboxylate is 1: (0.3-0.5).
7. The sole material for sports shoes with high wear resistance and high shock absorption according to claim 1, wherein the foaming agent is azodicarboxylate, the crosslinking agent is dicumyl peroxide, the vulcanizing agent is benzoyl peroxide, and the anti-aging agent is anti-aging agent AW.
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| CN115044157A (en) * | 2022-06-22 | 2022-09-13 | 东莞市兴胜新材料有限公司 | Shock-absorbing and energy-absorbing recyclable material and preparation method thereof |
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