WO2009140825A1

WO2009140825A1 - A thermoplastic elastomer composition, its process and the product obtained by the process

Info

Publication number: WO2009140825A1
Application number: PCT/CN2008/071062
Authority: WO
Inventors: 黄丽慧; 杨荣嵢
Original assignee: 杨浩宇
Priority date: 2008-05-23
Filing date: 2008-05-23
Publication date: 2009-11-26

Abstract

A thermoplastic elastomer composition, its process and the product obtained by the process are provided. The composition includes (a) 50-90 parts by weight of a syndiotactic 1,2-polybutadiene, (b) 10-50 parts by weight of an unsaturated rubber, (c) a crosslinking agent and optionally (d) auxiliaries, in which the total amount of components (a) and (b) is 100 parts by weight. And the components (a), (b), (c) and optionally (d) are mixed and vulcanized to form the crosslinking between the components (a) and (b).

Description

Thermoplastic elastomer composition, preparation method thereof and system made therefrom

The present invention relates to a thermoplastic elastomer composition comprising syndiotactic 1,2-polybutadiene, to a method of preparing the thermoplastic elastomer composition, and an article produced by the preparation method and the thermoplastic elastomer composition the use of.

Background technique

Thermoplastic elastomer (TPE) is a material that combines the dual properties of rubber and thermoplastics. Its functional and physical properties are similar to those of conventional thermoset rubber, but can be processed as fast, efficiently and economically as thermoplastics. Due to the greatly simplified processing, thermoplastic elastomers are becoming more widely used.

Syndiotactic 1,2-polybutadiene (RB) is a typical thermoplastic elastomer which is mainly obtained by 1,2-polymerization of butadiene. The syndiotactic 1,2-polybutadiene can crystallize and its crystallinity increases as the degree of regularity increases. When the degree of regularity reaches 99%, the tensile strength of the syndiotactic 1,2-polybutadiene can reach 30 ~ 50MPa, which is basically equivalent to crystalline polypropylene, and the melting point is as high as 150, which leads to easy thermal degradation during processing. Therefore, the syndiotactic 1,2-polybutadiene having too high crystallinity is relatively difficult to apply.

Japan Synthetic Rubber Co., Ltd. (JSR) developed a practically practical syndiotactic 1,2-polybutadiene in 1974, which utilizes a small amount of random polymeric chains between regular molecular chains to control crystallinity, successfully The crystallinity is controlled below 35%, and the melting point is controlled below 90 °C, thereby reducing the possibility of thermal degradation of the syndiotactic 1,2-polybutadiene during processing.

Syndiotactic 1,2-polybutadiene has many unique advantages. First, compared to conventional vulcanized rubber, the main chain of syndiotactic 1,2-polybutadiene is saturated, so it has good weather resistance and light resistance. Secondly, compared with other commonly used thermoplastic elastomers, its side chain has Double bond, which can be crosslinked by peroxide or sulfur, so the elasticity is closer to the traditional vulcanized rubber, and it is easier to blend with other unsaturated rubber, and the syndiotactic 1,2-polybutadiene has excellent impact resistance. , its products will not be sticky. Therefore, it is widely used in various fields such as shoes, film materials, foamed products, medical supplies, sports equipment and the like. In recent years, the application of syndiotactic 1,2-polybutadiene in the manufacture of soles has received attention. It is reported that almost 80% of the Italian soles currently use syndiotactic 1,2-polybutadiene, the main The advantage is that blending a small amount of syndiotactic 1,2-polybutadiene can result in a sole with a shiny or matt finish without the need for a spray coating process, while also having a rubber sole-like texture.

However, since the syndiotactic 1,2-polybutadiene is easily thermally degraded and the dimensional stability of the foamed article is poor, the syndiotactic 1,2-polybutadiene is currently only used as an additive or an auxiliary material to improve the main gum. The performance of the material is only 5 to 30% by weight of the total amount of the compound.

Summary of the invention

It is an object of the present invention to overcome the above limitations for the use of syndiotactic 1,2-polybutadiene to provide a thermoplastic elastomer composition in which the amount of syndiotactic 1,2-polybutadiene exceeds 50% by weight of the total size. A thermoplastic elastomer composition having high slip resistance, good texture, good elasticity, small amount of compression deformation, good abrasion resistance, no special odor, environmental protection, and the like is obtained.

According to an aspect of the present invention, there is provided a thermoplastic elastomer composition comprising a) 50 to 90 parts by weight of syndiotactic 1,2-polybutadiene, b) 10 to 50 parts by weight of an unsaturated rubber, c a crosslinking agent and optionally d) an auxiliary wherein the total amount of components a) and b) is 100 parts by weight, and wherein said components a), b), c) and optionally d) The vulcanization is blended to form a crosslink between the components a) and b).

Component a) in the thermoplastic elastomer composition is preferably 50 to 80 parts by weight of syndiotactic 1,2-polybutadiene, more preferably 50 to 70 parts by weight of syndiotactic 1,2-polybutylene. The component b) in the thermoplastic elastomer composition is preferably 20 to 50 parts by weight of an unsaturated rubber, more preferably 30 to 50 parts by weight of an unsaturated rubber, wherein the total of the components a) and b) The amount is 100 parts by weight.

In one embodiment of the invention, the syndiotactic 1,2-polybutadiene has a crystallinity of less than 35%, preferably less than 30%, more preferably less than 25%.

The unsaturated rubber may be any rubber or elastomer material having an unsaturated bond, such as polybutadiene rubber, natural rubber, isoprene rubber, styrene butadiene rubber, hydrogenated styrene butadiene rubber, butadiene-styrene-butyl A diene copolymer (SBS), a nitrile rubber, a chloroprene rubber, or the like, or a mixture thereof.

The crosslinking agent may be any suitable crosslinking agent such as peroxide, sulfur, metal oxide, phenolic resin, anthraquinone, maleimide or the like or a mixture thereof, preferably using peroxidation. As a crosslinking agent.

The crosslinking agent is used in an amount of 0.1 to 3.5 parts by weight, preferably 0.15 to 3.0 parts by weight, more preferably 0.20 to 2.5 parts by weight, most preferably 0.20 to 2.0 parts by weight, based on 100 parts by weight of the total of components a) and b) Part.

In one embodiment of the invention, the thermoplastic elastomer composition further comprises an adjuvant. The auxiliaries are various types of auxiliaries commonly used in rubber compounding systems, such as vulcanization accelerators, plasticizers, fillers, antioxidants, foaming agents, flame retardants, colorants, reinforcing agents, and the like, or mixtures thereof.

The crosslinking agent may be any suitable crosslinking agent, such as a peroxide crosslinking agent, sulfur, metal oxide, phenolic resin, anthraquinone derivative, maleimide, or the like, or a mixture thereof, preferably used. The oxide acts as a crosslinking agent.

In an embodiment of the present invention, any suitable vulcanization accelerator may also be used, such as a thiazole accelerator, a thiuram accelerator, a sulfenamide accelerator, a quinone accelerator, a dithiocarbamate. Promoters, thiourea accelerators and aldehyde amine accelerators, specifically, for example, DM, NOBS. CZ, NS, TMTD, PZ, EZ, DPG, DOTG, NA-22, TMTU, accelerator H and the like.

Any suitable filler may be used in the present invention, including but not limited to: carbon black, white carbon black, calcium carbonate, magnesium carbonate, dolomite powder, barium sulfate, lithopone, gypsum powder, aluminum silicate, titanium dioxide, clay, mica. Powder, wollastonite powder, talc powder, diatomaceous earth powder, attapulgite, sepiolite powder, zeolite powder, vermiculite powder, light carbonic acid, rayon, etc.

The foaming agent which can be used in the present invention mainly includes, but is not limited to, an organic foaming agent such as an azo compound, a sulfonyl hydrazide compound, a nitroso compound or a mixture thereof, preferably, for example, azobisnonanoate, azobisindole Diisopropyl acid, hydrazine, Ν'-dinitroso pentadecyltetramine, hydrazine, Ν'-dinitroso-p-phthalamide, p-phenylene sulfonyl hydrazide, phenylsulfonyl hydrazide, etc. .

In one embodiment of the present invention, the thermoplastic elastomer composition may further comprise an elastomer other than the unsaturated rubber, such as silicone rubber, fluororubber, polyurethane, ethylene-vinyl acetate copolymer, acrylic rubber, chlorine. The ether rubber or the like or a mixture thereof is preferably a silicone rubber, a fluororubber, and an ethylene-vinyl acetate copolymer. The other elastomer is used in an amount of from 0.5 to 10% by weight, preferably from 1 to 5% by weight, more preferably from 1.5 to 3.5% by weight, based on 100 parts by total of the components a) and b).

According to another aspect of the present invention, there is provided a process for preparing the thermoplastic elastomer composition The method comprises the step of dynamically vulcanizing and kneading the components a), b), c) and optionally d).

In one embodiment of the invention, the dynamic vulcanization process comprises a one-stage dynamic vulcanization process; in another embodiment of the invention, the dynamic vulcanization process comprises a two-stage dynamic vulcanization process.

In one embodiment of the present invention, the dynamic vulcanization is a dynamic vulcanization process comprising: adding an auxiliary agent other than a crosslinking agent, a vulcanization accelerator, and a foaming agent, and the component The compound consisting of a) and b) is put into the mixer, and the mixing time is about 5 to 15 minutes, during which the mixing temperature is not more than about 150 ° C; then the crosslinking agent, vulcanization accelerator and optional hair are added. The foaming agent is then mixed for about 1 to 10 minutes and discharged, and the discharge temperature does not exceed about 120 °C.

In another embodiment of the present invention, the dynamic vulcanization compounding is a two-stage dynamic vulcanization mixing process, comprising: adding an auxiliary agent other than a crosslinking agent, a vulcanization accelerator, and a foaming agent, and the group The rubber consisting of a) and b) is put into the mixer, and the first discharge is carried out after about 5 to 15 minutes of mixing, while the mixing temperature is kept below about 110 °C; the first mixed material obtained will be obtained. Put it into the mixer again, mix for about 1 to 10 minutes, and control the temperature not higher than about 110 °C, then put in the cross-linking agent, vulcanization accelerator and optional foaming agent, and continue mixing for about 1 to 10 minutes. After the second discharge, the temperature of the second discharge does not exceed about 120 °C.

In one embodiment of the present invention, the thermoplastic elastomer molding compound is obtained by further subjecting the rubber compound discharged from the dynamic vulcanization mixing process to an granulation process through an extrusion process and a granulation process and sufficiently stirring again.

In one embodiment of the invention, the molding compound is molded by an injection molding process, wherein the process conditions of the injection molding process are as follows:

Injection speed: 24 - 36 bar

Injection pressure: 75 ~ 105 bar

Injection port temperature: 80 - 95 ° C

Screw speed: 90 RPM

Mold temperature: 165 ° C ~ 175 ° C.

In another embodiment of the invention, the molding compound is molded by an extrusion molding process.

In still another embodiment of the present invention, when the thermoplastic elastomer composition comprises hair In the case of a foaming agent, the method further comprises, during the injection molding process or the extrusion molding process, foaming the thermoplastic elastomer molding compound in a mold, for example, at about

It is carried out in a mold at 165 to 180 ° C, preferably at about 170 to 175 ° C for about 5 to 15 minutes, preferably about 8 to 12 minutes, more preferably about 10 minutes.

According to still another aspect of the present invention, there is also provided an article prepared by using the thermoplastic elastomer composition according to the present invention. The article may be an integrally formed, molded or otherwise formed article, including article of footwear such as a sole, a film article, a foamed article, a medical article, a sports device, and the like.

According to still another aspect of the present invention, there is also provided the use of the thermoplastic elastomer composition according to the present invention for the manufacture of an article of footwear such as a shoe sole, a film article, a foamed article, a medical article, a sports article or the like.

The invention also has the following advantages: 1. The thermoplastic elastomer composition of the invention has loose processing conditions, and the formula adjustment range is expanded, thereby facilitating the expansion of the application range; 2. advantageously overcoming the syndiotactic 1,2-polybutyl The dimensional instability of the olefinic material after foaming is obtained, and a dimensionally stable foamed product is obtained; 3. The syndiotactic 1,2-polybutadiene can be used for food packaging and manufacturing medical equipment (US FDA certification), so the human body Excellent acceptability, better odor than EVA or rubber products, and easy to be favored by consumers; 4. In terms of environmental protection, the thermoplastic elastomer composition according to the present invention does not generate hydrogen chloride when incinerated. Harmful gases such as nitrogen compounds do not leave harmful heavy metals in the incineration residue, so they are relatively environmentally friendly when used.

detailed description

Further advantages and features of the present invention are further described below in accordance with specific embodiments.

Implementation 1

The formulation of the thermoplastic elastomer composition according to Embodiment 1 of the present invention is as shown in Table 1 below: Table 1: No. Raw material name Use Formulation ratio (parts by weight)

01 Syndiotactic 1,2-polybutadiene (RB) component a) 50.000 ~ 70.000

02 Isoprene rubber (IR) component b) 20.000 ~ 30.000

03 Hydrogenated styrene butadiene rubber (SBR) component b) 10.000 ~ 20.000 04 Silicone rubber elastomer 3.000 ~ 5.000

05 Metal Wax ( PP1602 ) Processing Aid 2.000 ~ 5.000

06 Zinc Oxide (ZnO) Vulcanization Activator 0.500 ~ 5.000

07 Stearic acid (ST) vulcanization activator 0.500 ~ 1.500

08 TPN-65 Antioxidant 0.500 ~ 1.500

09 nanometer calcium carbonate, magnesium carbonate, filler 2.500 ~ 10.000

Carbon black, white carbon black, aluminum silicate,

Talc, rayon, etc.

10 DCP-40BTD crosslinker 0.100 ~ 1.000

11 ET-102 Crosslinking Aid 0.140 ~ 2.000

12 AK-M foaming agent 3.600 ~ 5.000

13 BK-66 Flow Aid 1.000 ~ 4.000

Among them, the processing aid metal wax (PP1602) can improve the dispersibility of the material during kneading and the fluidity during molding.

The formulation of this embodiment is characterized by: 1) It can effectively improve the tensile strength of the material, and is suitable for products with high tensile and tear requirements, such as sports or medical protection products; 2) appropriately reducing the elasticity of the material, with a certain reduction The shock effect is suitable for the manufacture of shock absorbing products; and 3) has good wear and slip resistance.

Implementation 2

The formulation of the thermoplastic elastomer composition according to Embodiment 2 of the present invention is as shown in Table 2 below: Table 2: No. Raw material name Use Formulation ratio (parts by weight)

01 Syndiotactic 1,2-polybutadiene (RB) component a) 50.000 ~ 90.000

02 Isoprene rubber (IR) component b) 5.000 ~ 25.000

03 Hydrogenated styrene butadiene rubber (SBR) component b) 5.000 ~ 25.000

04 Light Carbonic Acid Reinforcing Agent 5.000 ~ 10.000

05 nanometer calcium carbonate, magnesium carbonate, carbon filler 5.000 ~ 15.000

Black, white carbon black, aluminum silicate, slippery

Stone powder, rayon, etc. 06 Stearic acid vulcanization activator 0.300 ~ 1.000

07 Silicone Rubber Elastomer 1.500 ~ 3.500

08 PEG 4000 Active Agent 1.000 ~ 4.000

09 ZnO zinc oxide 1.000 ~ 3.800

10 BK-66 Flow Aid 1.000 ~ 3.200

11 AO-60 Antioxidant 0.100 ~ 0.500

12 DCP-40BTD crosslinker 0.190

13 ET 102 Antioxidant 0.140

14 AK-M foaming agent 1.000 ~ 2.000

15 AC-9 foaming agent 1.300 ~ 1.900

16 Qunqing (EVA 5202) Colorant 0.010 ~ 0.050

The formulation of this embodiment is characterized by: 1) having good tensile strength and high fluidity, suitable for products with complicated mold structure; and 2) rubbery soft hand feeling elastic, good slip resistance, Can be used in injection molding pads, sandals, slippers and other products.

Implementation 3

The formulation of the thermoplastic elastomer composition according to Embodiment 3 of the present invention is shown in Table 3 below: Table 3: No. Original Material Name Use Formulation Ratio (parts by weight)

01 Syndiotactic 1,2-polybutadiene (RB) component a) 50.000 ~ 70.000

02 Isoprene rubber (IR) component b) 10.000 ~ 15.000

03 Butadiene rubber (BR) Component b) 20.000 ~ 40.000

04 nanometer calcium carbonate, magnesium carbonate, carbon filler 5.000 ~ 15.000

Black, white carbon black, aluminum silicate, slippery

Stone powder, rayon, etc.

05 Zinc Oxide (ZnO) Vulcanization Activator 2.000 ~ 5.000

06 Stearic acid vulcanization activator 1.000 ~ 3.000

07 BK-66 vulcanization accelerator 1.500 ~ 4.500 08 TPN-65 Antioxidant 1.000 ~ 1.500

09 Metal Wax ( PP1602 ) Processing Aid 2.000 ~ 4.000

10 DCP-40BTD crosslinker 0.100 ~ 1.000

11 ET-102 crosslinker 0.150 ~ 1.000

12 AK-M foaming agent 1.500 ~ 3.500

The formulation of this embodiment is characterized by: excellent wear resistance, close to the wear of general vulcanized rubber; lighter weight, suitable for the manufacture of outsole and midsole for footwear.

Preparation of Formulation Compositions of Embodiments 1-3

The dynamic vulcanization process of the formulation of Embodiment 1 is:

The mixing is carried out using an internal mixer, a two-stage dynamic vulcanization mixing process is employed, and the kneaded material can be formed into a molding compound by extrusion granulation, and then optionally foamed. The details are shown in Table 4 below.

Foaming condition

Time

170 ° C 600 seconds

Mold specification

180xl20xl0mm

Physical properties

(Shaw C): 55±3

Pull force (KG/CM ² ): 29 or more

Elongation (%): 300 or more

Strength (KG/CM ² ): 13 or more

Specific gravity (G/CM ³ ): 0.22±0.03

The dynamic vulcanization process of the formulation of Embodiment 2:

The mixing is carried out using an internal mixer, a dynamic vulcanization mixing process is employed, and the kneaded material can be formed into a molding compound by extrusion granulation, and then optionally foamed, as shown in Table 5 below.

table 5:

Dynamic vulcanization process of the formulation of Embodiment 3:

The mixing is carried out using an internal mixer, a two-stage dynamic vulcanization mixing process is employed, and the kneaded material can be formed into a molding compound by extrusion granulation, and then optionally foamed, as shown in Table 6 below.

Extrusion granulation of thermoplastic elastomer molding compound

The kneading rubber obtained in Embodiments 1 to 3 can be melt-extruded and matched by an extruder. The granulator granulates the kneaded rubber, pours it into a mixing tank and stirs it, and thoroughly mixes it to obtain a thermoplastic elastomer molding compound according to the present invention.

Injection molding of thermoplastic elastomer molding compound

Injection molding process conditions:

Injection speed: 24 - 36 bar

Injection pressure: 75 ~ 105 bar

Injection port temperature: 80 - 95 ° C

Screw speed: 90 RPM (rpm)

Mold temperature: 165 ° C - 175 ° C

Time: Adjust according to the actual process settings of various products.

Physical properties of the formulated compositions of Embodiments 1 to 3 after molding

Three formulations were selected from the formulations of Embodiments 1-3, and after the corresponding kneading, extrusion, granulation, and molding processes described above, samples of the thermoplastic elastomer compositions of Examples 1 to 3 were obtained, respectively. Tests are performed to obtain their respective physical properties.

The formulations of Examples 1 ~ 3 are shown in Table 7 below:

Table 7

Raw materials Example 1 Example 2 Example 3 Producer

(parts by weight) (parts by weight) (parts by weight)

Syndiode 1,2-polybutadiene 70.00 70.00 70.00 JSR

RB-830

Isoprene rubber strand IR-2200 20.00 10.00 10.00 JSR hydrogenated styrene butadiene rubber 10.00 20.00 Taiwan

HSBR-1305

Butadiene rubber BR-150L 20.00 UBE Silicone Rubber HT9514 5.00 2.00 Dow

Corning Metal Wax PP1602 4.00 4.00 Taiwan Zinc Oxide ZnO 1.50 1.50 2.00 Taiwan Stearic acid ST 0.60 0.60 1.00 Taiwan nano-calcium carbonate, 10.00 10.00 10.00 Taiwanese light carbonic acid 5.000 Taiwan

ΤΡΝ-65 0.50 1.00 Taiwan

DCP-40BTD 0.22 0.19 0.22 Taiwan

ET-102 0.20 0.14 0.20 Taiwan

ΑΚ-Μ 3.60 1.00 1.50 Taiwan

ΒΚ-66 1.00 1.00 1.00 Taiwan

PEG 4000 2.00 Taiwanese

AO-60 0.20 Taiwan The physical properties measured by the thermoplastic elastomer compositions of Examples 1 to 3 are shown in Table 8 below:

Note: ASTM: American Materials Association Test Standard

DIN: German technical standards

As can be seen from the above Table 8, as the composition of the composition is adjusted, the physical properties of the thermoplastic elastomer composition according to the present invention after dynamic vulcanization can be varied within a wide range, and thus can be applied to various applications. However, while the physical properties are largely changed, the elongation at break of the thermoplastic elastomer composition according to the present invention does not change much, that is, it suppresses the retention of excellent elasticity.

From the data in Table 8 above, it is apparent that the physical properties of the thermoplastic elastomer composition of the present invention are very close to those of conventional vulcanized rubber, but are far easier to process than conventional vulcanized rubber. At the same time, the physical properties, particularly the strength properties, of the thermoplastic elastomer composition of the present invention are far superior to those of conventional thermoplastic elastomers such as ethylene-vinyl acetate copolymer (EVA).

Table 9 below lists the general properties of the foamed articles obtained by the above foaming process and the foamed articles of ethylene-vinyl acetate copolymer (EVA) and natural rubber foamed articles of the thermoplastic elastomer compositions of Examples 1 to 3. Comparison: Table 9:

It can be seen from Table 9 that the foamed article according to the present invention is superior to conventional EVA, natural rubber foamed articles and the like in terms of performance, manufacturing process and environmental protection.

In summary, the processing conditions of the present invention are loose, and the formulation adjustment range is obviously expanded, which is advantageous for expanding the application range, and the product of the invention has high slip resistance, good texture, good elasticity, small compressive deformation, and abrasion resistance. Good, no special smell, environmental protection and so on. The auxiliary agent comparison table used in the invention

Auxiliary chemical structure or composition of blowing agent AC-9 II II ²

〇0 blowing agent AK-M II II ²

0 交联剂 Crosslinker ET102 C12H15M3O3

CH3 CH3

. , 1 1 , „—■. Crosslinker DCP-40BTD >― C- O -O - C ― ^

1 1

CH3 CH3 Antioxidant AO-50 Antioxidant TNP-65 Antioxidant AO-60 C73H10SO12 Zinc Oxide ZnO ZnO Stearic acid ST CH ₃ (CH ₂ ) ₁₆ COOH Polyethylene glycol PEG4000 Light carbonic acid CaC0 ₃ CaC0 ₃ (grinding method) Heavy carbonic acid CaC0 ₃ CaC0 ₃ (precipitation method) Ultrafine talc powder BH325 3mg〇■ 4Si02-H ₂ 0 Talc powder RB500D 3mg〇■ 4Si02-H ₂ 0 Processing aid AFLUK-12 Mixture of ester and surfactant Mixed active emulsifier of BK-66 higher fatty acid ester

R R

1 1 1 Silicone rubber HT9514 - Si - o - Si - o - Si ϋ

'■ 1 1 1

RRR

— LI—

Z90l.0/800ZN3/X3d

Claims

Rights request

A thermoplastic elastomer composition comprising a) 50 to 90 parts by weight of syndiotactic 1,2-polybutadiene, b) 10 to 50 parts by weight of an unsaturated rubber, c) a crosslinking agent, and Selected d) an auxiliary wherein the total amount of components a) and b) is 100 parts by weight, and wherein said components a), b), c) and optionally d) are blended and vulcanized, thereby Crosslinking is formed between the components a) and b).

The thermoplastic elastomer composition according to claim 1, wherein the thermoplastic elastomer composition comprises a) 50 to 70 parts by weight of syndiotactic 1,2-polybutadiene, and b) 30 to 50 parts by weight. An unsaturated rubber, c) a crosslinking agent and optionally d) an auxiliary agent, wherein the total amount of components a) and b) is 100 parts by weight, and wherein said components a), b), c) and Optional d) is vulcanized by blending to form a crosslink between said components a) and b).

The thermoplastic elastomer composition according to claim 1 or 2, wherein the syndiotactic 1,2-polybutadiene has a crystallinity of less than 35%.

The thermoplastic elastomer composition according to claim 1 or 2, wherein the unsaturated rubber is selected from the group consisting of polybutadiene rubber, natural rubber, isoprene rubber, styrene butadiene rubber, hydrogenated styrene butadiene rubber, and butadiene. - styrene-butadiene copolymer, ethylene propylene rubber, nitrile rubber, neoprene rubber and mixtures thereof.

The thermoplastic elastomer composition according to claim 1 or 2, wherein the crosslinking agent is selected from the group consisting of peroxides, sulfur, metal oxides, phenol resins, anthraquinones, maleimides, and mixtures thereof.

The thermoplastic elastomer composition according to claim 1 or 2, wherein the auxiliary agent is selected from the group consisting of a vulcanization accelerator, a plasticizer, a filler, an antioxidant, a foaming agent, a flame retardant, a colorant, and a reinforcing agent. Agents and mixtures thereof.

A method of preparing a thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the method comprises the components a), b), c) and optionally d) - Dynamic vulcanization and mixing.

8. The method of claim 7, wherein the dynamic vulcanization process comprises a one-stage dynamic vulcanization process or a two-stage dynamic vulcanization process.

9. The method of claim 8 wherein said one-stage dynamic vulcanization process comprises The following steps: adding an auxiliary agent other than the crosslinking agent, the vulcanization accelerator and the foaming agent, and the compound consisting of the components a) and b) to the mixer, mixing for 5 to 15 minutes, and mixing The refining temperature does not exceed 150 ° C; then the cross-linking agent, vulcanization accelerator and optional blowing agent are added, and the mixing is continued for 1 to 10 minutes, and the discharge temperature is not more than 120 ° C.

10. The method according to claim 8, wherein the two-stage dynamic vulcanization mixing process comprises the steps of: adding an auxiliary agent other than a crosslinking agent, a vulcanization accelerator, and a foaming agent, and the component a) The compound consisting of b) and b) is put into the mixer, and the first discharge is carried out after 5 to 15 minutes of mixing, while the mixing temperature is kept below 110 °C; the first mixed material obtained is again put into the mixer. , mixing for 1 to 10 minutes, during which the controlled temperature is not higher than 110 ° C, then introducing a crosslinking agent, a vulcanization accelerator and an optional blowing agent, and kneading for a second time, after 1 to 10 minutes, the second discharge is performed. The temperature of the second discharge does not exceed 120 °C

The method according to claim 10, further comprising extruding and granulating the kneaded material and thoroughly mixing it again to form a thermoplastic elastomer molding compound.

The method according to claim 11, further comprising molding the thermoplastic elastomer molding by an injection molding process or an extrusion molding process.

13. The method according to claim 12, wherein when said thermoplastic elastomer composition comprises a blowing agent, said method further comprises: said thermoplastic elastomer during said injection molding process or said extrusion molding process The molding compound is foamed in a mold.

14. An article made using the thermoplastic elastomer composition of claim 1.

15. The article of claim 15 selected from the group consisting of an article of footwear including a sole, a film article, a foamed article, a medical article, and a sports equipment.