阅读说明：本技术 快速成型耐低温鞋材用聚氨酯弹性体及其制备方法 (Polyurethane elastomer for quickly-formed low-temperature-resistant shoe material and preparation method thereof ) 是由 李英乾 刘兆阳 李涛 张雪峰 于 2021-09-27 设计创作，主要内容包括：本发明属于聚氨酯应用技术领域,具体涉及一种快速成型耐低温鞋材用聚氨酯弹性体及其制备方法,所述弹性体由聚合物A组分和预聚物B组分制成,其中,A组分由多元醇A、扩链剂、催化剂、抗氧化剂和抗紫外线吸收剂制成；B组分由二异氰酸酯和多元醇B制成,其NCO含量为18～25％。本发明所述的聚氨酯产品,操作温度低、粘度小、易混合、压模2～5分钟可开模,生产效率高；硬度可在60～95A范围内调节,且综合性能优异,拉伸强度≥25MPa,扯断伸长率≥450％、裤型撕裂强度≥15KN/m、耐低温性能优异,适合不同硬度鞋面、鞋底等鞋材配件的工业化生产。(The invention belongs to the technical field of polyurethane application, and particularly relates to a polyurethane elastomer for a rapid-forming low-temperature-resistant shoe material and a preparation method thereof, wherein the elastomer is prepared from a polymer A component and a prepolymer B component, wherein the A component is prepared from a polyol A, a chain extender, a catalyst, an antioxidant and an anti-ultraviolet absorber; the component B is prepared from diisocyanate and polyol B, and the NCO content of the component B is 18-25%. The polyurethane product disclosed by the invention is low in operation temperature, small in viscosity, easy to mix, capable of being subjected to die sinking for 2-5 minutes during die pressing and high in production efficiency; the hardness can be adjusted within the range of 60-95A, the comprehensive performance is excellent, the tensile strength is not less than 25MPa, the elongation at break is not less than 450%, the pant-type tearing strength is not less than 15KN/m, the low-temperature resistance is excellent, and the method is suitable for industrial production of shoe material accessories such as vamps, soles and the like with different hardness.)

1. The utility model provides a polyurethane elastomer for quick shaping low temperature resistant shoes material which characterized in that: is prepared from a component A and a component B, wherein:

the component A is prepared from the following raw materials in percentage by weight:

82-96% of polyol A, 1-15% of chain extender, 0.01-1.5% of catalyst, 0.2-1.5% of antioxidant and 0.1-1.0% of anti-ultraviolet absorber;

the component B is prepared from the following raw materials in percentage by weight:

35-80% of diisocyanate and 20-65% of polyol B;

the content of isocyanate groups in the component B is 18-25%.

2. The polyurethane elastomer for rapid prototyping low temperature resistant shoe material of claim 1, wherein: in the component A, the polyol A is one or more of polyester polyol or polytetrahydrofuran ether polyol with the functionality of 2 and the number average molecular weight of 1000-2000.

3. The polyurethane elastomer for rapid prototyping low temperature resistant shoe material of claim 1, wherein: in the component A, the chain extender is one or more of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, diethanolamine or triethanolamine.

4. The polyurethane elastomer for rapid prototyping low temperature resistant shoe material of claim 1, wherein: in the component A, the catalyst is one or more of an organic tin catalyst, an organic bismuth catalyst or an organic amine catalyst.

5. The polyurethane elastomer for rapid prototyping low temperature resistant shoe material of claim 1, wherein: in the component A, the antioxidant is one or more of an antioxidant 1070, an antioxidant 1010 or an antioxidant 1098.

6. The polyurethane elastomer for rapid prototyping low temperature resistant shoe material of claim 1, wherein: in the component A, the anti-ultraviolet absorbent is one or more of an anti-ultraviolet absorbent 328, an anti-ultraviolet absorbent 329 or an anti-ultraviolet absorbent UV-531.

7. The polyurethane elastomer for rapid prototyping low temperature resistant shoe material of claim 1, wherein: in the component B, the diisocyanate is one or more of diphenylmethane diisocyanate or carbodiimide modified diphenylmethane diisocyanate.

8. The polyurethane elastomer for rapid prototyping low temperature resistant shoe material of claim 1, wherein: in the component B, the polyol B is one or more of polyester polyol or polytetrahydrofuran ether polyol with the functionality of 2 and the number average molecular weight of 1000-2000.

9. A method for preparing the polyurethane elastomer for the rapid prototyping low temperature resistant shoe material of any one of claims 1-8, which is characterized in that: the method comprises the following steps:

(1) preparation of polymer a component:

uniformly mixing the polyol A, the antioxidant, the ultraviolet-resistant absorbent and the catalyst, performing vacuum dehydration, then adding the chain extender, and uniformly stirring to obtain a polymer A component;

(2) preparation of prepolymer B component:

after the polyol B is dehydrated in vacuum, adding diisocyanate, and after the reaction is finished, preparing a prepolymer B component;

(3) when the adhesive is used, the component A and the component B are mixed and stirred uniformly, poured into a mold and flowed uniformly, and after the adhesive reaches a solidifying point, the mold is pressed and opened, so that a target product can be obtained.

10. The method for preparing the polyurethane elastomer for the rapid prototyping low temperature resistant shoe material of claim 9, wherein: the method comprises the following steps:

(1) preparation of polymer a component:

uniformly mixing polyol A, an antioxidant, an anti-ultraviolet absorbent and a catalyst, dehydrating in vacuum at 100-120 ℃ until the moisture content is less than or equal to 0.05%, then cooling to 50-60 ℃, adding a chain extender with the moisture content of less than or equal to 0.05%, and uniformly stirring to obtain a polymer A component;

(2) preparation of prepolymer B component:

dehydrating the polyol B in vacuum until the moisture content is less than or equal to 0.05 percent, cooling to below 60 ℃, adding diisocyanate under stirring, heating to 75-85 ℃, and then preserving heat for reaction until the content of cyanate groups is 18-25 percent to prepare a prepolymer B component;

(3) when the curing agent is used, the component A and the component B are mixed and stirred uniformly according to the mass ratio of 100: 50-100, then the mixture is poured into a mold at the temperature of 50-80 ℃ and flows uniformly, the mold is pressed after the solidification point is reached, the mold is opened after 2-5 minutes, and the target product can be obtained without re-vulcanization.

Technical Field

The invention belongs to the technical field of polyurethane application, and particularly relates to a polyurethane elastomer for quickly forming a low-temperature-resistant shoe material and a preparation method thereof.

Background

At present, the materials of the shoe uppers and the shoe soles commonly used in the market comprise high polymer materials such as leather, rubber, polyvinyl chloride, polyurethane and the like. Leather and rubber products have heavy smell, single appearance color and general wear resistance; the polyvinyl chloride products are often added with a large amount of o-benzene plasticizers, so that the precipitation risk is caused, the environmental protection is poor, and the products are forbidden in developed countries such as Europe and America at the present stage; compared with the former materials, the polyurethane elastomer is a high-molecular polymer material between rubber and plastic, has higher tensile strength and elongation, good mechanical property, wear resistance and resilience, and is more and more widely applied in the field of shoe materials in recent years. Among them, the polyurethane elastomers are most widely used in the field of shoe materials as two types of products: thermoplastic polyurethane elastomers (TPU) and cast polyurethane elastomers (CPU). But the TPU product has the defects of poor wear resistance, poor tear resistance, easy yellowing, secondary processing and the like when the hardness is medium or low, and is not suitable for being made into sole and vamp products; the CPU product has the advantages of comprehensive performance of rubber and TPU, excellent mechanical property, wear resistance, superior flex resistance, energy conservation and environmental protection, is used for manufacturing shoe material products, and has good economic benefit and social benefit.

However, the present CPU used for producing vamp and sole products has the following problems: the production process is complex, the mold opening speed is low, the production efficiency is low, the hardness range is narrow, the low temperature resistance is poor, the requirement on high efficiency in the existing shoe material production process cannot be met, and the hardness range is narrow.

CN201910350176.2 discloses a preparation method and application of a polyurethane elastomer sole material, the hardness range of the product is only 57-65A, and the requirements of different hardness indexes of the existing shoe material accessories cannot be met; the low temperature resistance is poor, and the use requirements of the shoe material in low-temperature and severe cold environments cannot be met.

CN201811108410.2 discloses a method for manufacturing polyurethane soles and a polyurethane raw material used in the method, wherein a mixture of a defoamed CPU polyurethane prepolymer and a curing agent is poured into a mold cavity to finally obtain a product. The polyurethane can be reacted and cured at a lower temperature, secondary vulcanization is not needed, the physical property requirement of the sole can be met only by standing for 6-8 hours at normal temperature after demolding, the hardness range is 62-75A, the low-temperature resistance is poor, and the use requirement of the shoe material in a low-temperature and severe cold environment cannot be met.

The technical problems limit further application of the CPU product in the related manufacturing fields of shoe materials and the like.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the prepared product has the advantages of high mold opening speed, high production efficiency, excellent low temperature resistance, wide hardness adjustable range and the like, and the prepared vamp and sole products have excellent comprehensive performance, can be used for producing high-performance soles and vamp products in large scale in industry, and have great application in the preparation field of related products such as shoe material production and manufacturing; the invention also provides a preparation method of the compound, which is scientific, reasonable, simple and easy to implement and is easy for industrial production.

The invention is realized by adopting the following technical scheme:

the polyurethane elastomer for the rapid forming low temperature resistant shoe material is prepared from a polymer A component and a prepolymer B component, wherein:

the component A is prepared from the following raw materials in percentage by weight:

82-96% of polyol A, 1-15% of chain extender, 0.01-1.5% of catalyst, 0.2-1.5% of antioxidant and 0.1-1.0% of anti-ultraviolet absorber;

the component B is prepared from the following raw materials in percentage by weight:

35-80% of diisocyanate and 20-65% of polyol B;

the content of the isocyanate group (NCO) in the component B is 18-25%.

Wherein:

in the component A, the polyol A is one or more of polyester polyol or polytetrahydrofuran ether polyol with the functionality of 2 and the number average molecular weight of 1000-2000, the polyester polyol is preferably polyester polyol of a polyester adipate series, and the polyester polyol is prepared from adipic acid and one or more of ethylene glycol, diethylene glycol, methyl propylene glycol, butanediol, hexanediol and neopentyl glycol, and the polyol A is prepared from the following components: polytetramethylene glycol adipate diol, polyadipate adipate diol, poly (methyl propylene glycol adipate) diol, poly (neopentyl glycol adipate) diol, and the like.

In the component A, the chain extender is one or more of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, diethanolamine or triethanolamine.

In the component A, the catalyst is one or more of an organic tin catalyst, an organic bismuth catalyst or an organic amine catalyst. The organic tin catalyst is preferably dibutyltin dilaurate or stannous octoate; the organic bismuth catalyst is preferably selected from bismuth isooctanoate, bismuth laurate and bismuth naphthenate; the organic amine catalyst is preferably triethylene diamine or triethylamine.

In the component A, the antioxidant is one or more of an antioxidant 1070 (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester), an antioxidant 1010 (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester) or an antioxidant 1098(N, N' -1, 6-hexamethylene-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide), and the antioxidant 1070 is preferably used in an amount of 0.5 percent.

In the component A, the anti-ultraviolet absorbent is one or more of an anti-ultraviolet absorbent 328(2- (2' -hydroxyphenyl 3',5' -dipentylphenyl) benzotriazole), an anti-ultraviolet absorbent 329(2- (2-hydroxy-5-tert-octylphenyl) benzotriazole) or an anti-ultraviolet absorbent UV-531 (2-hydroxy-4-n-octyloxybenzophenone), preferably the anti-ultraviolet absorbent 328, and the using amount is preferably 0.3%.

In the component B, the diisocyanate is one or more of diphenylmethane diisocyanate (MDI-50, MDI-100) or carbodiimide modified diphenylmethane diisocyanate (liquefied MDI).

In the component B, the polyol is one or more of polyester polyol or polytetrahydrofuran ether polyol with the functionality of 2 and the number average molecular weight of 1000-2000, and the polyester polyol is preferably polyester polyol of a polyadipic acid series, such as: one or more of polytetramethylene glycol adipate diol, polyhexamethylene glycol adipate diol, poly (methyl propylene glycol adipate) diol and poly (neopentyl glycol adipate) diol.

The preparation method of the polyurethane elastomer for the rapid forming low temperature resistant shoe material comprises the following steps:

(1) preparation of polymer a component:

uniformly mixing the polyol A, the antioxidant, the ultraviolet-resistant absorbent and the catalyst, performing vacuum dehydration, then adding the chain extender, and uniformly stirring to obtain a polymer A component;

(2) preparation of prepolymer B component:

after the polyol B is dehydrated in vacuum, adding diisocyanate, and after the reaction is finished, preparing a prepolymer B component;

(3) when the adhesive is used, the component A and the component B are mixed and stirred uniformly, poured into a mold and flowed uniformly, and after the adhesive reaches a solidifying point, the mold is pressed and opened, so that a target product can be obtained.

Preferably, the preparation method of the polyurethane elastomer for the rapid prototyping low-temperature resistant shoe material comprises the following steps:

(1) preparation of polymer a component:

uniformly mixing polyol A, an antioxidant, an anti-ultraviolet absorbent and a catalyst, dehydrating for 1-2 hours at 100-120 ℃ and under the vacuum degree of 0.1MPa, dehydrating in vacuum until the moisture content is less than or equal to 0.05 percent, then cooling to 50-60 ℃, adding a chain extender with the moisture content of less than or equal to 0.05 percent, and uniformly stirring to obtain a polymer A component;

(2) preparation of prepolymer B component:

dehydrating the polyol B in vacuum until the moisture content is less than or equal to 0.05 percent, cooling to below 60 ℃, adding diisocyanate under stirring, heating to 75-85 ℃, and then preserving heat for reaction until the content of cyanate groups is 18-25 percent to prepare a prepolymer B component;

(3) when the curing agent is used, the component A and the component B are mixed and stirred uniformly according to the mass ratio of 100: 50-100, then the mixture is poured into a mold at the temperature of 50-80 ℃ and flows uniformly, the mold is pressed after the solidification point is reached, the mold is opened after 2-5 minutes, and the target product can be obtained without re-vulcanization.

In the prior art, the low temperature resistance of polyurethane is improved by using polytetrahydrofuran ether, but the polyether polyurethane has poor mechanical property and is difficult to meet the requirement of high performance of shoe materials. According to the invention, the polytetrahydrofuran ether polyol and the low-temperature-resistant polyester polyol are cooperatively used, and the low-temperature-resistant polyester polyol has low temperature resistance on the basis of ensuring high performance, wherein the low-temperature-resistant polyester polyol is obtained by reacting long-chain small molecular alcohols (such as butanediol and hexanediol) with adipic acid, so that the ester group density and polarity of the polyester polyol are reduced, and in addition, the introduction of side methyl long-chain small molecular alcohols (such as methyl propanediol and neopentyl glycol) further destroys the crystallinity of polyurethane and improves the low-temperature resistance of the polyurethane. Meanwhile, proper crosslinking degree (such as triethanolamine and liquefied MDI) is introduced into the system, so that the polyurethane forms a net structure, the mold opening speed of the product is greatly improved, and the production efficiency is improved.

Compared with the prior art, the invention has the following beneficial effects:

1. the polyurethane elastomer for quickly forming the low-temperature-resistant shoe material has the advantages of low operation temperature, small viscosity, easiness in mixing, convenience in machine and manual operation, capability of opening a die for 2-5 minutes in a pressing die, high production efficiency and suitability for industrial production of accessories such as shoe uppers, soles and the like.

2. The polyurethane elastomer for the rapid forming low temperature resistant shoe material does not need post-vulcanization, the tensile strength is more than or equal to 25MPa, and the elongation at break is more than 450%; the trouser tear strength is not less than 15KN/m, the low temperature resistance is excellent, and the comprehensive performance is excellent.

3. The polyurethane elastomer for the rapid forming low temperature resistant shoe material has the hardness which can be adjusted within the range of 60-95A, and meets different hardness requirements of shoe materials.

Detailed Description

The present invention is further described with reference to the following examples, which are not intended to limit the practice of the invention.

PTMG 1000: a polytetrahydrofuran ether polyol having a number average molecular weight of 1000;

PTMG 2000: a polytetrahydrofuran ether polyol having a number average molecular weight of 2000;

PE-2515: poly adipic acid polyester diol, number average molecular weight 1500, prepared from adipic acid, ethylene glycol, diethylene glycol, Shandong-Nonwei polyurethane GmbH;

PE-2410: a poly (adipic acid polyester diol) having a number average molecular weight of 1000, prepared from adipic acid, ethylene glycol, and butanediol, available from Shandong-Nowei polyurethane corporation;

PE-5020: a poly (adipic acid polyester diol) having a number average molecular weight of 2000, prepared from adipic acid and methyl propylene glycol, available from Shandong-Nowei polyurethane corporation;

PE-4020: a poly (adipic acid polyester diol) having a number average molecular weight of 2000, prepared from adipic acid and butanediol, available from Shandong-Nowei polyurethane corporation;

PE-6020: the polyester diol adipate has a number average molecular weight of 2000, is prepared from adipic acid and hexanediol, and is available from Shandong-Nonwei polyurethane GmbH.

PE-7020; a poly (adipic acid polyester diol) having a number average molecular weight of 2000, prepared from adipic acid and neopentyl glycol, available from Shandong-Nowei polyurethane GmbH;

MDI-100: 4, 4' -diphenylmethane diisocyanate;

MDI-50: mixtures of 2,4 '-diphenylmethane diisocyanate and 4, 4' -diphenylmethane diisocyanate

MM 103C: carbodiimide modified MDI-100.

The raw materials used in the examples were all commercially available materials except those described above.

The contents of the materials in the examples are in terms of mass percent unless otherwise specified.

Example 1

The polyurethane elastomer for the rapid forming low temperature resistant shoe material and the preparation method thereof are as follows:

(1) preparation of polymer a component:

uniformly mixing PE-251594%, bismuth isooctanoate 0.3%, antioxidant 10760.4% and ultraviolet absorbent 3280.3%, dehydrating at 110 ℃ and under the vacuum degree of 0.1MPa until the moisture content is less than or equal to 0.05%, then cooling to 55 ℃, adding chain extender diethanolamine 5 with the moisture content of less than or equal to 0.05%, and uniformly stirring to obtain a polymer A component;

(2) preparation of prepolymer B component:

vacuum dehydrating PE-602029% until the water content is less than or equal to 0.05%, cooling to 55 ℃, adding diisocyanate MM103C 57% and MDI-10014% while stirring, heating to 80 ℃, keeping the temperature, reacting for 3 hours until the content of cyanate groups is 20%, and preparing a prepolymer B component;

(3) when the elastomer is used, the component A and the component B are mixed and stirred uniformly according to the mass ratio of 100:50, then the mixture is poured into a mold at 80 ℃ and flows uniformly, the mold is pressed after the mixture reaches the solidifying point, the mold is opened after 5 minutes, and the elastomer with the hardness of 60A can be obtained without re-vulcanization.

Example 2

The polyurethane elastomer for the rapid forming low temperature resistant shoe material and the preparation method thereof are as follows:

(1) preparation of polymer a component:

uniformly mixing PTMG 100096%, bismuth laurate 0.3%, antioxidant 10980.4% and ultraviolet absorbent 3280.3%, dehydrating at 110 ℃ and under the vacuum degree of 0.1MPa until the moisture content is less than or equal to 0.05%, then cooling to 50 ℃, adding chain extender diethanolamine 3 with the moisture content of less than or equal to 0.05%, and uniformly stirring to obtain a polymer A component;

(2) preparation of prepolymer B component:

vacuum dehydrating PE-502029% until the water content is less than or equal to 0.05%, cooling to 50 ℃, adding diisocyanate MM103C 36% and MDI-10035% while stirring, heating to 80 ℃, keeping the temperature, reacting for 3 hours until the content of cyanate groups is 21%, and preparing a prepolymer B component;

(3) when the elastomer is used, the component A and the component B are mixed and stirred uniformly according to the mass ratio of 100:60, then the mixture is poured into a mold at 80 ℃ and flows uniformly, the mold is pressed after the mixture reaches the solidifying point, the mold is opened after 5 minutes, and the elastomer with the hardness of 65A can be obtained without re-vulcanization.

Example 3

The polyurethane elastomer for the rapid forming low temperature resistant shoe material and the preparation method thereof are as follows:

(1) preparation of polymer a component:

uniformly mixing PE-241094%, triethylene diamine 0.3%, antioxidant 10980.3% and ultraviolet absorbent 3280.4%, dehydrating at 120 ℃ and under the vacuum degree of 0.1MPa until the moisture content is less than or equal to 0.05%, then cooling to 60 ℃, adding chain extender diethanolamine 3 with the moisture content of less than or equal to 0.05%, and uniformly stirring to obtain a polymer A component;

(2) preparation of prepolymer B component:

vacuum dehydrating PE-402022% until the water content is less than or equal to 0.05%, cooling to 50 ℃, adding diisocyanate MM103C 47% and MDI-5031% while stirring, heating to 80 ℃, keeping the temperature, reacting for 3 hours until the content of cyanate groups is 23%, and preparing a prepolymer B component;

(3) when the elastomer is used, the component A and the component B are mixed and stirred uniformly according to the mass ratio of 100:65, then the mixture is poured into a mold at 80 ℃ and flows uniformly, the mold is pressed after the mixture reaches the solidifying point, the mold is opened after 5 minutes, and the elastomer with the hardness of 70A can be obtained without re-vulcanization.

Example 4

The polyurethane elastomer for the rapid forming low temperature resistant shoe material and the preparation method thereof are as follows:

(1) preparation of polymer a component:

uniformly mixing PE-251585%, triethylene diamine 0.4%, antioxidant 10980.2% and ultraviolet absorbent 3280.4%, dehydrating at 100 ℃ and a vacuum degree of 0.1MPa until the moisture content is less than or equal to 0.05%, then cooling to 50 ℃, adding chain extender 1 with the moisture content of less than or equal to 0.05% and 4-butanediol 14%, and uniformly stirring to obtain a polymer A component;

(2) preparation of prepolymer B component:

vacuum dehydrating PTMG 200022% until the water content is less than or equal to 0.05%, cooling to 50 ℃, adding diisocyanate MM103C 47% and MDI-5031% under stirring, heating to 80 ℃, keeping the temperature, reacting for 3 hours until the content of cyanate groups is 23%, and preparing a prepolymer B component;

(3) when the elastomer is used, the component A and the component B are mixed and stirred uniformly according to the mass ratio of 100:80, then the mixture is poured into a mold at 80 ℃ and flows uniformly, the mold is pressed after the mixture reaches the solidifying point, the mold is opened after 4 minutes, and the elastomer with the hardness of 80A can be obtained without vulcanizing again.

Example 5

The polyurethane elastomer for the rapid forming low temperature resistant shoe material and the preparation method thereof are as follows:

(1) preparation of polymer a component:

uniformly mixing PTMG 100090%, bismuth isooctanoate 0.3%, antioxidant 10760.4% and ultraviolet absorbent 3290.3%, dehydrating at 110 ℃ and under the vacuum degree of 0.1MPa until the moisture content is less than or equal to 0.05%, then cooling to 55 ℃, adding chain extender glycol 9 with the moisture content of less than or equal to 0.05%, and uniformly stirring to obtain a polymer A component;

(2) preparation of prepolymer B component:

vacuum dehydrating PE-702029% until the water content is less than or equal to 0.05%, cooling to 55 ℃, adding diisocyanate MM103C 36% and MDI-10035% while stirring, heating to 80 ℃, keeping the temperature, reacting for 3 hours until the content of cyanate groups is 21%, and preparing a prepolymer B component;

(3) when the elastomer is used, the component A and the component B are mixed and stirred uniformly according to the mass ratio of 100:100, then the mixture is poured into a mold at 80 ℃ and flows uniformly, the mold is pressed after the mixture reaches the solidifying point, the mold is opened after 3 minutes, and the elastomer with the hardness of 90A can be obtained without re-vulcanization.

The elastomers prepared in examples 1-5 were subjected to performance testing with the test data given in the following table:

note: the performance parameters are measured data after the test piece is placed for 24 hours at normal temperature after the mold is opened. The hardness is tested according to GB/T531.1-2008 vulcanized rubber or thermoplastic rubber press-in hardness test method; the tensile strength and the elongation at break are tested according to GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber; the right angle, pant-type tear was tested according to GBT529-2008 determination of tear Strength of vulcanized rubber or thermoplastic rubber.

Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.