WO2023125007A1 - 一种高阻隔性的热塑性弹性体及其制备方法与应用 - Google Patents

一种高阻隔性的热塑性弹性体及其制备方法与应用 Download PDF

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WO2023125007A1
WO2023125007A1 PCT/CN2022/139010 CN2022139010W WO2023125007A1 WO 2023125007 A1 WO2023125007 A1 WO 2023125007A1 CN 2022139010 W CN2022139010 W CN 2022139010W WO 2023125007 A1 WO2023125007 A1 WO 2023125007A1
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thermoplastic elastomer
parts
block copolymer
styrene
raw material
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PCT/CN2022/139010
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French (fr)
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石正兵
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广东太力科技集团股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Definitions

  • the invention belongs to the technical field of polymer materials, and in particular relates to a high-barrier thermoplastic elastomer and its preparation method and application.
  • Thermoplastic elastomer is a polymer material that can exhibit high elasticity like vulcanized rubber at room temperature, and is easy to process and shape like thermoplastic at high temperature. It has both vulcanized rubber and thermoplastic properties.
  • TPE has been widely used in many industries such as automobile, construction, household equipment, wire and cable. Under the background of increasingly scarce petroleum resources and increasingly serious environmental pollution, TPE has extremely important commercial value and environmental protection significance, and has become a research hotspot in the field of polymer materials.
  • the barrier property of the material is of great significance to its application in the sealing field.
  • the good barrier property of the material has greatly improved the function of the material, especially in some high-pressure or vacuum fields, such as for the preparation of automobile tires and sealing rings. , Vacuum suction cup, etc.
  • Barrier property is relative to permeability. Any object has a certain degree of permeability, and the only difference is the degree of permeability of different objects.
  • the most concerned about polymer materials are the barrier properties of related materials made of it to oxygen, carbon dioxide, nitrogen and other gases and the barrier properties to water vapor when packaging items.
  • the present invention hopes to propose a thermoplastic elastomer material with better barrier properties to overcome the deficiencies and defects of existing thermoplastic elastomers.
  • the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. Therefore, the present invention proposes a thermoplastic elastomer (TPE) with high barrier property and its preparation method and application. While maintaining good mechanical properties (high hardness), the thermoplastic elastomer also has quite excellent barrier properties, especially reflected in the gas barrier properties.
  • TPE thermoplastic elastomer
  • thermoplastic elastomer comprising the following raw material components: block copolymer, barrier material, compatibilizer, softener; the barrier material includes ethylene-vinyl alcohol copolymer (EVOH), polyethylene At least one of alcohol (PVA) and polyvinylidene chloride (PVDC).
  • EVOH ethylene-vinyl alcohol copolymer
  • PVA polyethylene At least one of alcohol
  • PVDC polyvinylidene chloride
  • the main components of air are non-polar gases such as nitrogen, oxygen, and nitrogen dioxide, so they are easily dissolved into thermoplastic elastomers with very weak polarity.
  • the invention effectively improves the thermoplastic elastomer by adding barrier materials such as EVOH, PVDC, and PVA.
  • barrier materials such as EVOH, PVDC, and PVA.
  • the polarity of the elastomer material thereby reducing the solubility of gas in the thermoplastic elastomer material and improving the barrier properties of the thermoplastic elastomer material.
  • the present invention adds a compatibilizer that can improve the compatibility of the two to improve the compatibility between the two.
  • the compatibility of the blend and improve the processing performance of the blend.
  • the block copolymer comprises hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene At least one of diene-styrene block copolymer (SBS), thermoplastic polyester elastomer (TPEE), polyethylene-olefin copolymer (TPO), ethylene-octene copolymer (POE).
  • SEBS hydrogenated styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SBS diene-styrene block copolymer
  • TPEE thermoplastic polyester elastomer
  • TPO polyethylene-olefin copolymer
  • POE ethylene-octene copolymer
  • the block copolymer comprises hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene- At least one of butadiene-styrene block copolymers (SBS).
  • SEBS hydrogenated styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SBS styrene- At least one of butadiene-styrene block copolymers
  • the mass percentage of styrene in the block copolymer is 10-60%.
  • the compatibilizer includes maleic anhydride grafted polypropylene (PP-g-MAH), maleic anhydride grafted linear low-density polyethylene (LLDPE-g-MAH), maleic anhydride grafted ethylene-octyl ethylene copolymer (POE ⁇ g ⁇ MAH), maleic anhydride grafted hydrogenated styrene ⁇ butadiene ⁇ styrene block copolymer (SEBS ⁇ g ⁇ MAH), maleic anhydride grafted polyethylene (PE ⁇ g ⁇ at least one of MAH).
  • PP-g-MAH maleic anhydride grafted polypropylene
  • LLDPE-g-MAH linear low-density polyethylene
  • POE ⁇ g ⁇ MAH maleic anhydride grafted ethylene-octyl ethylene copolymer
  • SEBS ⁇ g ⁇ MAH maleic anhydride grafted hydrogenated styrene ⁇ butadiene ⁇ styrene block copoly
  • the softener includes at least one of paraffin oil, naphthenic oil, and white mineral oil.
  • the raw material component of the thermoplastic elastomer further includes an antioxidant.
  • the antioxidant is selected from at least one of phenolic antioxidants, amine antioxidants, and phosphite antioxidants.
  • the antioxidant includes phenolic antioxidants and phosphite antioxidants.
  • the phenolic antioxidant includes ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (such as antioxidant 1076), tetrakis ( ⁇ -(3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate) pentaerythritol ester (such as antioxidant 1010); said amine antioxidant comprises octylated diphenylamine (such as antioxidant OD); said Phosphite antioxidants include tris(2,4-di-tert-butylphenyl)phosphite (such as Antioxidant 168).
  • thermoplastic elastomer includes the following raw material components in parts by weight: 20-70 parts of block copolymer, 1-20 parts of barrier material, 1-10 parts of compatibilizer, 30-80 parts of softener, anti- Oxygen agent 0.2-1 part.
  • thermoplastic elastomer comprises the following raw material components in parts by weight: 20-50 parts of block copolymer, 12-18 parts of barrier material, 5-10 parts of compatibilizer, 40-70 parts of softener, Antioxidant 0.2 ⁇ 1 part.
  • the present invention also provides a preparation method of the above-mentioned thermoplastic elastomer, which includes the following steps.
  • thermoplastic elastomer The various raw material components are mixed, extruded and granulated to obtain the thermoplastic elastomer.
  • a twin-screw extruder is used for the extrusion granulation.
  • the temperature of each zone of the twin-screw extruder is set at 180-220° C., and the extrusion speed is set at 80-300 r/min.
  • the present invention also provides the application of the above-mentioned thermoplastic elastomer in the field of sealing. Since the thermoplastic elastomer described in this application has high barrier properties and low permeability, it can be applied to the preparation of products with strict sealing requirements such as automobile tires, sealing rings, and vacuum suction cups.
  • the present invention improves the barrier performance of the thermoplastic elastomer material and ensures the high barrier performance of the thermoplastic elastomer material by using the high barrier performance, high strength, and easy processing properties of the barrier material by adding a barrier material to the thermoplastic elastomer. Strength of.
  • the present invention successfully improves the compatibility of the barrier material and the block copolymer material by adding a compatibilizer into the thermoplastic elastomer material.
  • the barrier performance of the prepared thermoplastic elastomer is significantly improved, and its oxygen transmission rate can be ⁇ 200cm 3 /(m 2 ⁇ 24h).
  • the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial channels, or can be obtained by existing known methods.
  • thermoplastic elastomer comprising the following raw material components by weight: 40 parts of hydrogenated styrene-butadiene-styrene block copolymer (Taiwan Rubber 6151), ethylene-vinyl alcohol copolymer (Japan Cola Li L171B) 6 parts, maleic anhydride graft hydrogenated styrene-butadiene-styrene block copolymer (American Kraton FG1901) 4 parts, white mineral oil 40 parts, antioxidant 1010 0.5 parts, antioxidant 168 0.5 servings.
  • the preparation method of the thermoplastic elastomer in this embodiment includes the following steps.
  • thermoplastic elastomer comprising the following raw material components in parts by weight: 60 parts of hydrogenated styrene-butadiene-styrene block copolymer (Taiwan Rubber 6151), polyvinyl alcohol (Japan Kuraray PVA224) 10 parts, 4 parts of maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer (U.S. Kraton FG1901), 40 parts of white mineral oil, 0.5 part of antioxidant 1010, and 168 parts of antioxidant 0.5 servings.
  • the preparation method of the thermoplastic elastomer in this embodiment includes the following steps.
  • thermoplastic elastomer comprising the following raw material components in parts by weight: 60 parts of hydrogenated styrene-butadiene-styrene block copolymer (Taiwan Rubber 6151), polyvinyl alcohol (Japan Kuraray PVA224) 15 parts, 8 parts of maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer (U.S. Kraton FG1901), 60 parts of naphthenic oil, 0.5 part of antioxidant 1010, 168 parts of antioxidant 0.5 servings.
  • the preparation method of the thermoplastic elastomer in this embodiment includes the following steps.
  • thermoplastic elastomer comprising the following raw material components by weight: 40 parts of hydrogenated styrene-butadiene-styrene block copolymer (Taiwan Rubber 6151), ethylene-vinyl alcohol copolymer (Japan Cola Li L171B) 16 parts, maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer (U.S. Kraton FG1901) 8 parts, 40 parts of white mineral oil, 0.5 parts of antioxidant 1010, anti-oxidant Oxygen 168 0.5 servings.
  • the preparation method of the thermoplastic elastomer in this embodiment includes the following steps.
  • This comparative example provides a kind of thermoplastic elastomer, comprises the raw material component of following parts by weight: 60 parts of hydrogenated styrene-butadiene-styrene block copolymers (Taiwan Rubber 6151), maleic anhydride grafted hydrogenated styrene- Butadiene-styrene block copolymer (American Kraton FG1901) 5 parts, naphthenic oil 60 parts, antioxidant 1010 0.5 parts, antioxidant 168 0.5 parts.
  • 60 parts of hydrogenated styrene-butadiene-styrene block copolymers (Taiwan Rubber 6151), maleic anhydride grafted hydrogenated styrene- Butadiene-styrene block copolymer (American Kraton FG1901) 5 parts, naphthenic oil 60 parts, antioxidant 1010 0.5 parts, antioxidant 168 0.5 parts.
  • thermoplastic elastomer in this comparative example includes the following steps.
  • thermoplastic elastomers in this comparative example do not contain barrier materials.
  • This comparative example provides a kind of thermoplastic elastomer, comprises the raw material component of following weight portion: hydrogenated styrene-butadiene-styrene block copolymer (Taiwan Rubber 6151) 40 parts, mica 16 parts, maleic anhydride graft 8 parts of hydrogenated styrene-butadiene-styrene block copolymer (Kraton FG1901 of the United States), 40 parts of white mineral oil, 0.5 part of antioxidant 1010, and 0.5 part of antioxidant 168.
  • thermoplastic elastomer in this comparative example includes the following steps.
  • the raw material component of the thermoplastic elastomer in this comparative example uses mica instead of ethylene-vinyl alcohol copolymer.
  • thermoplastic elastomer in embodiment 1-4 Carry out performance test, test standard and test result to the thermoplastic elastomer in embodiment 1-4, comparative example 1-2.
  • thermoplastic elastomer prepared in Example 1-4 has higher oxygen permeability, which proves that The barrier material used in the present invention can indeed improve the barrier performance of the material.
  • Example 1 which has less barrier material addition, has insufficient oxygen transmission rate and hardness; Adjustment further improves the barrier properties of thermoplastic elastomers significantly, and its oxygen transmission rate can be as low as 197.4cm 3 /(m 2 ⁇ 24h).

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

本发明属于高分子材料技术领域，公开了一种高阻隔性的热塑性弹性体及其制备方法与应用。该热塑性弹性体包括以下原料组分：嵌段共聚物、阻隔性材料、相容剂、软化剂；所述阻隔性材料包括乙烯‑乙烯醇共聚物、聚乙烯醇、聚偏二氯乙烯中的至少一种。该热塑性弹性体在保持良好力学性能的同时，还具有相当优异的阻隔性能，尤其体现在对于气体的隔绝性能上。

Description

一种高阻隔性的热塑性弹性体及其制备方法与应用 技术领域
本发明属于高分子材料技术领域，特别涉及一种高阻隔性的热塑性弹性体及其制备方法与应用。
 背景技术
热塑性弹性体(Thermoplastic elastomer，TPE)是一种在常温下可显示像硫化橡胶一样的高弹性，而高温下又像热塑性塑料一样易于加工成型，兼具硫化橡胶和热塑性塑料特性的聚合物材料。目前，TPE已被广泛应用于汽车、建筑、家用设备、电线电缆众多行业。在当今石油资源日益匮乏、环境污染日益严重的背景下，TPE具有极其重要的商业价值和环保意义，已成为高分子材料领域的一个研究热点。
而材料的阻隔性对其在密封领域的应用具有重要的意义，材料良好的阻隔性能为材料的功能带来巨大的提升，尤其是在一些高压或者真空领域，如用于制备汽车轮胎、密封圈、真空吸盘等。阻隔性是相对于渗透性而言的。任何物体都有一定的渗透性，差别仅是不同物体的渗透性高低。通常在高分子聚合物材料上最为关注的是由它制得的相关材料在包装物品时对氧气、二氧化碳、氮气等气体的阻隔性以及对水蒸气的阻隔性。
目前，在针对于高阻隔性能材料方面，大多是有关塑料类薄膜制品，涉及到热塑性弹性体类的较少，更进一步的，涉及到提升TPE等相关制品阻隔性能的文献资料更是少之又少。在当前TPE领域不多的阻隔性能相关研究开发中，主流的做法是在TPE材料中添加宽/厚比高的片层材料，如蒙脱土、云母、滑石粉、石墨等材料，通过延长气体的扩散路径来提高材料的阻隔性。然而，常用片状的无机填充物往往较难分散，且与材料相容性极差，并不能很好地达到提升阻隔性能的要求。
因此，本发明希望提出一种具备更好阻隔性能的热塑性弹性体材料，以克服现有热塑性弹性体的不足和缺陷。
 技术解决方案
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种高阻隔性的热塑性弹性体(TPE)及其制备方法与应用。该热塑性弹性体在保持良好力学性能(硬度高)的同时，还具有相当优异的阻隔性能，尤其体现在对于气体的隔绝性能上。
本发明提供了一种热塑性弹性体，包括以下原料组分：嵌段共聚物、阻隔性材料、相容剂、软化剂；所述阻隔性材料包括乙烯‑乙烯醇共聚物(EVOH)、聚乙烯醇(PVA)、聚偏二氯乙烯(PVDC)中的至少一种。
空气的主要成分为氮气、氧气、二氧化氮等非极性气体，因而容易溶解到极性很弱的热塑性弹性体中，本发明通过加入EVOH、PVDC、PVA等阻隔性材料，有效提升了热塑性弹性体材料的极性，从而降低气体在热塑性弹性体材料中的溶解度并提升热塑性弹性体材料的阻隔性能。此外，由于阻隔材料与嵌段共聚物的相容性还有所不足，故而为实现两者更好的相容性能，本发明通过添加可提高二者相容性的相容剂，以提高共混物的相容性，并改善共混物的加工性能。
优选地，所述嵌段共聚物包括氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(SEBS)、苯乙烯‑异戊二烯‑苯乙烯嵌段共聚物(SIS)、苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(SBS)、热塑性聚酯弹性体(TPEE)、聚乙烯‑烯烃共聚物(TPO)、乙烯‑辛烯共聚物(POE)中的至少一种。
更优选地，所述嵌段共聚物包括氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(SEBS)、苯乙烯‑异戊二烯‑苯乙烯嵌段共聚物(SIS)、苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(SBS)中的至少一种。
进一步优选地，所述嵌段共聚物中苯乙烯所占质量百分数为10‑60％。
优选地，所述相容剂包括马来酸酐接枝聚丙烯(PP‑g‑MAH)、马来酸酐接枝线性低密度聚乙烯(LLDPE‑g‑MAH)、马来酸酐接枝乙烯‑辛烯共聚物(POE‑g‑MAH)、马来酸酐接枝氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(SEBS‑g‑MAH)、马来酸酐接枝聚乙烯(PE‑g‑MAH)中的至少一种。
优选地，所述软化剂包括石蜡油、环烷油、白矿油中的至少一种。
优选地，所述热塑性弹性体的原料组分还包括有抗氧剂。
更优选地，所述抗氧剂选自酚类抗氧剂、胺类抗氧剂、亚磷酸酯类抗氧剂的至少一种。
进一步优选地，所述抗氧剂包括酚类抗氧剂和亚磷酸酯类抗氧剂。
其中，所述酚类抗氧剂包括β-(3，5-二叔丁基‑4‑羟基苯基)丙酸正十八碳醇酯(如抗氧剂1076)、四(β‑(3，5‑二叔丁基‑4‑羟基苯基)丙酸)季戊四醇酯(如抗氧剂1010) ；所述胺类抗氧剂包括辛基化二苯胺(如抗老剂OD)；所述亚磷酸酯类抗氧化剂包括三(2，4‑二叔丁基苯基)亚磷酸酯(如抗氧剂168)。
优选地，所述热塑性弹性体包括以下重量份的原料组分：嵌段共聚物20‑70份、阻隔性材料1‑20份、相容剂1‑10份、软化剂30‑80份、抗氧剂0.2‑1份。
更优选地，所述热塑性弹性体包括以下重量份的原料组分：嵌段共聚物20‑50份、阻隔性材料12‑18份、相容剂5‑10份、软化剂40‑70份、抗氧剂0.2‑1份。
本发明还提供了上述热塑性弹性体的制备方法，包括以下步骤。
将各原料组分混合，经挤出造粒，制得所述热塑性弹性体。
优选地，采用双螺杆挤出机进行所述挤出造粒。
更优选地，所述双螺杆挤出机的各区温度设为180‑220℃，挤出速度设为80‑300r/min。
本发明还提供了上述热塑性弹性体在密封领域的应用。由于本申请所述热塑性弹性体具备高阻隔性和低渗透性，因而可应用于制备如汽车轮胎、密封圈、真空吸盘等对密封性要求较严苛的产品。
 有益效果
相对于现有技术，本发明的有益效果如下。
 (1)本发明通过在热塑性弹性体中加入阻隔材料，利用阻隔材料所具有的对气体的高阻隔性能、高强度、易加工等性能，从而提高了热塑性弹性体材料的阻隔性能并保证了材料的强度。
(2)本发明通过在热塑性弹性体材料中加入相容剂，成功提高了阻隔材料与嵌段共聚物材料的相容性。
(3)本发明通过调整配方组分，使得所制得热塑性弹性体的阻隔性能得到了显著提升，其氧气透过率可≤200cm 3/(m 2·24h)。
本发明的最佳实施方式
具体实施方式为了让本领域技术人员更加清楚明白本发明所述技术方案，现列举以下实施例进行说明。需要指出的是，以下实施例仅为本发明的优选实施例，对本发明要求的保护范围不构成限制作用，任何未违背本发明的精神实质和原理下所做出的修改、替代、组合，均包含在本发明的保护范围内。
以下实施例中所用的原料、试剂或装置如无特殊说明，均可从常规商业途径得到，或者可以通过现有已知方法得到。
实施例1。
本实施例提供一种热塑性弹性体，包括以下重量份的原料组分：氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(台橡6151)40份、乙烯‑乙烯醇共聚物(日本可乐丽L171B)6份、马来酸酐接枝氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(美国科腾FG1901)4份、白矿油40份、抗氧剂1010  0.5份、抗氧剂168  0.5份。
本实施例中热塑性弹性体的制备方法，包括以下步骤。
(1)按重量份数称取各原料组分，加入到高速混合机中一起进行混合，使其分散均匀，得到共混物。
 (2)将共混物投入至双螺杆挤出机的加料斗中，经熔融挤出、造粒，得到热塑性弹性体；双螺杆挤出机各区温度为180‑220℃，挤出速度为200r/min。
实施例2。
本实施例提供一种热塑性弹性体，包括以下重量份的原料组分：氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(台橡6151)60份、聚乙烯醇(日本可乐丽PVA224)10份、马来酸酐接枝氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(美国科腾FG1901)4份、白矿油40份、抗氧剂1010 0 .5份、抗氧剂168  0.5份。
本实施例中热塑性弹性体的制备方法，包括以下步骤。
 (1)按重量份数称取各原料组分，加入到高速混合机中一起进行混合，使其分散均匀，得到共混物。
(2)将共混物投入至双螺杆挤出机的加料斗中，经熔融挤出、造粒，得到热塑性弹性体；双螺杆挤出机各区温度为180‑220℃，挤出速度为200r/min。
实施例3。
本实施例提供一种热塑性弹性体，包括以下重量份的原料组分：氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(台橡6151)60份、聚乙烯醇(日本可乐丽PVA224)15份、马来酸酐接枝氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(美国科腾FG1901)8份、环烷油60份、抗氧剂1010 0 .5份、抗氧剂168  0 .5份。
本实施例中热塑性弹性体的制备方法，包括以下步骤。
 (1)按重量份数称取各原料组分，加入到高速混合机中一起进行混合，使其分散均匀，得到共混物。
(2)将共混物投入至双螺杆挤出机的加料斗中，经熔融挤出、造粒，得到热塑性弹性体；双螺杆挤出机各区温度为180‑220℃，挤出速度为200r/min。
实施例4。
本实施例提供一种热塑性弹性体，包括以下重量份的原料组分：氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(台橡6151)40份、乙烯‑乙烯醇共聚物(日本可乐丽L171B)16份、马来酸酐接枝氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(美国科腾FG1901)8份、白矿油40份、抗氧剂1010  0 .5份、抗氧剂168  0 .5份。
本实施例中热塑性弹性体的制备方法，包括以下步骤。
 (1)按重量份数称取各原料组分，加入到高速混合机中一起进行混合，使其分散均匀，得到共混物。
 (2)将共混物投入至双螺杆挤出机的加料斗中，经熔融挤出、造粒，得到热塑性弹性体；双螺杆挤出机各区温度为180‑220℃，挤出速度为200r/min。
对比例1。
本对比例提供一种热塑性弹性体，包括以下重量份的原料组分：氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(台橡6151)60份、马来酸酐接枝氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(美国科腾FG1901)5份、环烷油60份、抗氧剂1010  0 .5份、抗氧剂168  0 .5份。
本对比例中热塑性弹性体的制备方法，包括以下步骤。
 (1)按重量份数称取各原料组分，加入到高速混合机中一起进行混合，使其分散均匀，得到共混物。
 (2)将共混物投入至双螺杆挤出机的加料斗中，经熔融挤出、造粒，得到热塑性弹性体；双螺杆挤出机各区温度为180‑220℃，挤出速度为200r/min。
与实施例相比 ，本对比例中热塑性弹性体的原料组分不包含阻隔材料。
对比例2。
本对比例提供一种热塑性弹性体，包括以下重量份的原料组分：氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(台橡6151)40份、云母16份、马来酸酐接枝氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物(美国科腾FG1901)8份、白矿油40份、抗氧剂1010 0.5份、抗氧剂168 0.5份。
本对比例中热塑性弹性体的制备方法，包括以下步骤。
 (1)按重量份数称取各原料组分，加入到高速混合机中一起进行混合，使其分散均匀，得到共混物；。
(2)将共混物投入至双螺杆挤出机的加料斗中，经熔融挤出、造粒，得到热塑性弹性体；双螺杆挤出机各区温度为180‑220℃，挤出速度为200r/min。
与实施例4相比 ，本对比例中热塑性弹性体的原料组分采用云母替代了乙烯‑乙烯醇共聚物。
产品效果测试。
对实施例1‑4、对比例1‑2中的热塑性弹性体进行性能测试，测试标准和测试结果。
如表1所示。
表1性能测试结果。
Figure 395001dest_path_image001
。
由表1可知：相比于未添加阻隔材料的对比例1以及添加有片层材料的对比例2，实施例1‑4所制得的热塑性弹性体具备更高的氧气透过性，证明了本发明所采用的阻隔材料确实能提升材料的阻隔性能。而从实施例1‑4的内部比较可以看出，阻隔材料添加量较少的实施例1，其氧气透过率和硬度有所不足；而实施例4中通过对组分间的用量比例进行调整，进一步使热塑性弹性体的阻隔性能得到显著提升，其氧气透过率可低至197 .4cm 3/(m 2·24h)。
上面对本申请实施例作了详细说明，但是本申请不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本申请宗旨的前提下作出各种变化。此外，在不冲突的情况下，本申请的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种热塑性弹性体，其特征在于，包括以下原料组分：嵌段共聚物、阻隔性材料、相容剂、软化剂；所述阻隔性材料包括乙烯‑乙烯醇共聚物、聚乙烯醇、聚偏二氯乙烯中的至少一种。
  2. 根据权利要求1所述的热塑性弹性体，其特征在于，所述嵌段共聚物包括氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物、苯乙烯‑异戊二烯‑苯乙烯嵌段共聚物、苯乙烯‑丁二烯‑苯乙烯嵌段共聚物、热塑性聚酯弹性体、聚乙烯‑烯烃共聚物、乙烯‑辛烯共聚物中的至少一种。
  3. 根据权利要求1所述的热塑性弹性体，其特征在于，所述相容剂包括马来酸酐接枝聚丙烯、马来酸酐接枝线性低密度聚乙烯、马来酸酐接枝乙烯‑辛烯共聚物、马来酸酐接枝氢化苯乙烯‑丁二烯‑苯乙烯嵌段共聚物、马来酸酐接枝聚乙烯中的至少一种。
  4. 根据权利要求1所述的热塑性弹性体，其特征在于，所述软化剂包括石蜡油、环烷油、白矿油中的至少一种。
  5. 根据权利要求1所述的热塑性弹性体，其特征在于，所述热塑性弹性体的原料组分还包括有抗氧剂。
  6. 根据权利要求5所述的热塑性弹性体，其特征在于，所述热塑性弹性体包括以下重量份的原料组分：嵌段共聚物20‑70份、阻隔性材料1‑20份、相容剂1‑10份、软化剂30‑80份、抗氧剂0.2‑1份。
  7. 根据权利要求6所述的热塑性弹性体，其特征在于，所述热塑性弹性体包括以下重量份的原料组分：嵌段共聚物20‑50份、阻隔性材料12‑18份、相容剂5‑10份、软化剂40‑70份、抗氧剂0.2‑1份。
  8. 权利要求1‑7中任一项所述的热塑性弹性体的制备方法，其特征在于，包括以下步骤：将各原料组分混合，经挤出造粒，制得所述热塑性弹性体。
  9. 根据权利要求8所述的制备方法，其特征在于，采用双螺杆挤出机进行所述挤出造粒。
  10. 权利要求1‑7中任一项所述的热塑性弹性体在密封领域的应用。
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