CN107471509A - 一种热塑性弹性体的发泡方法及发泡材料 - Google Patents
一种热塑性弹性体的发泡方法及发泡材料 Download PDFInfo
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Abstract
本发明公开了一种热塑性弹性体的发泡方法及发泡材料,先通过辐照工艺实现热塑性弹性体的交联,之后将热塑性弹性体放入超临界反应釜中,通入气体,采用超临界间歇式升温法制得。本发明方法制备的发泡材料具有较高的强度、伸长率、耐老化性能、环保无毒、可回收、回弹性好、柔软、质轻、抗湿滑、易着色。本发明的制备方法安全无毒,达到真正意义上的环保,且简单、安全,易于实现连续化的工业生产。此发泡材料可用于瑜伽垫、儿童地垫、鞋中底。
Description
技术领域
本发明涉及一种聚合物发泡材料,特别是涉及一种热塑性弹性体的发泡方法及发泡材料。
背景技术
瑜伽垫、儿童地垫或鞋材发泡中底材料一般要求具有良好的防滑性、柔软性和回弹性,可以在活动过程中保护运动者和婴幼儿防止碰伤,同时增加舒适感。因此瑜伽垫或儿童地垫或鞋材发泡中底的重要组成部分就是聚合物发泡材料。而聚合物发泡材料基本是采用传统的化学发泡方法制备,传统的化学发泡聚合物材料存在着化学残留、甲酰胺、气味(如氨气)等环境问题,如中国台湾地区环保部门10月25日将甲酰胺列为第一、二类毒性化学物质管制,规定从2012年1月1日起,禁止在14岁以下儿童玩具(含玩具组件)及儿童用品、塑胶地垫中使用甲酰胺;法国、比利时对含有甲酰胺的适用于婴儿和儿童的泡沫拼图垫子颁布了禁令;欧盟REACH法规也将甲酰胺列为高度关注物质。而超临界二氧化碳(CO2)或氮气(N2)替代有机发泡剂则是目前最新、最环保和最安全的聚合物发泡技术,完全消除了氟氯烃、烷烃、石油醚等有机溶剂以及发泡剂偶氮二甲酰胺带来的环境危害和安全问题,属于低碳绿色环境友好发泡材料。
乙烯-辛烯共聚物(POE)与SEBS都是热塑性弹性体。POE具有较高的强度、伸长率、耐老化性能。目前,POE主要作为增韧改性剂用于聚合物改性和发泡领域,如专利CN0292802A、CN104861280A等提及的。在以POE为主制备发泡制品的研究较少,但在专利CN1020770A中以及文献中报道以POE为主制备发泡材料的制备中,这些研究也都是以化学发泡剂来制备的。SEBS具有与传统橡胶相同的弹性、回复性、强韧性与耐候性,及热塑性塑料一样容易加工成型的特性且可以再回收使用等优点。而且它与其它的塑料原料具有极佳的兼容性,SEBS因具有热可塑的特性,故发泡后的成型品亦可再进行二次定型以制得形状复杂的成品,且发泡成品可再回收利用。目前已经有许多人利用化学发泡法制备含有SEBS的发泡材料,如专利CN102888067A和CN103087383A分别公开了SEBS与PP、EVA共混发泡材料的制备方法及LDPE/EVA/SEBS复合发泡材料的制备方法,他们都是使用化学发泡剂进行发泡。且SEBS都与其他聚合物共混进行发泡,专利CN103819885A中公开了一种PLA与SEBS共混物超临界发泡材料的制备方法,其配方中虽然含有SEBS,但其含量只有5%-20%,是作为聚合物改性剂加入的。
发明内容
本发明针对目前市面上的瑜伽垫、儿童地垫和鞋中底气味问题开发了一种完全无毒、环保、高性能的瑜伽垫及儿童地垫用发泡材料。
为实现上述目的,本发明是通过以下技术方案实现的。
一种热塑性弹性体的发泡方法,其特征在于:先通过辐照工艺实现热塑性弹性体的交联,之后将热塑性弹性体放入超临界反应釜中,通入气体,采用超临界间歇式升温法制得。
所述热塑性弹性体为POE或SEBS。
所述的辐照工艺为电子束辐射器辐照,剂量为40-90KGy。
所述超临界反应釜中通入的气体为N2或CO2或N2、CO2混合物。
所述超临界间歇式升温法的工艺为:超临界反应釜温度为15-50℃,饱和时间为2-24h,饱和压力为12-60MPa,之后饱和材料在100-150℃烘箱中进行发泡,得到发泡材料。
本发明还涉及采用上述方法制备的发泡材料。
本发明还涉及上述发泡材料在环保瑜伽垫、儿童地垫、鞋中底中的应用。
本发明还涉及基于上述应用制备的环保瑜伽垫、儿童地垫、鞋中底,所述环保瑜伽垫、儿童地垫、鞋中底由发泡颗粒经蒸汽热压成型得到;或者先经发泡制成发泡板,再经切片、印花制得工艺制成品。
其优点在于所选材料为纯的POE或纯的SEBS,二者都是热塑性弹性体,通过辐射交联-超临界发泡的方式制备发泡材料,且所制备的SEBS发泡材料无甲酰胺残留,可以达到真正意义上的环保。
本发明方法制备的发泡材料具有较高的强度、伸长率、耐老化性能、环保无毒、可回收、回弹性好、柔软、质轻、抗湿滑、易着色。本发明的制备方法安全无毒,达到真正意义上的环保,且简单、安全,易于实现连续化的工业生产。
附图说明
图1本发明制备方法中,实施例4的扫描电镜图;
图2本发明制备方法中,实施例4发泡颗粒的照片。
具体实施方式:
实施例1
配方:POE 100份
工艺:将纯的POE粒料放入电子束辐射器中进行辐射交联,辐射剂量为70KGy,之后将将辐射交联POE放入25℃超临界反应釜中,通入氮气,使釜内压力达到28Mpa,饱和24h后泄压,将饱和有氮气的SEBS颗粒放入120℃烘箱中进行发泡,5min后得到POE超临界发泡颗粒,密度为0.125g/cm3。后经蒸汽热压成型得到密度为0.15g/cm3的发泡颗粒板。回弹性为61%。
实施例2
配方:POE 100份
工艺:将密炼机温度设置为130℃,放入POE,混炼均匀后,混炼0.5min后出料,下片,之后将混炼料放入模具中于170℃平板硫化机中进行模压成型,之后取出POE片材,
将纯的POE片材放入电子束辐射器中进行辐射交联,辐射剂量为60KGy,之后将将辐射交联POE放入50℃超临界反应釜中,通入二氧化碳,使釜内压力达到20MPa,饱和8h后泄压,将饱和有二氧化碳的POE片材放入120℃烘箱中进行发泡,5min后得到POE超临界发泡板材,密度为0.137g/cm3。再经切割裁成厚度为6mm的片材。回弹性为59%。
实施例3
配方:SEBS 100份
工艺:将SEBS板放入电子束辐射器中进行辐射交联,辐射剂量为65KGy,之后将辐射交联的SEBS板放入30℃超临界反应釜中,通入23MPa氮气和2MPa二氧化碳混合气体,使釜内压力达到25MPa,饱和10h后泄压。将饱和有氮气和二氧化碳混合气的SEBS板放入140℃烘箱中进行发泡,5min后得到SEBS超临界发泡板,密度为0.147g/cm3。后经裁片制得厚度为8mm的片材。回弹性为60%。
实施例4
配方:SEBS 100份
工艺:将纯的SEBS粒料放入电子束辐射器中进行辐射交联,辐射剂量为70kgy,之后将将辐射交联SEBS放入20℃超临界反应釜中,通入氮气,使釜内压力达到30Mpa,饱和16h后泄压,将饱和有氮气的SEBS颗粒放入130℃烘箱中进行发泡,5min后得到SEBS超临界发泡颗粒,密度为0.102g/cm3,后经蒸汽热压成型得到密度为0.15g/cm3的发泡颗粒板。回弹性为61%。
以上所述仅为本发明的实施例,并不限制本发明,凡采用等同替换或等效变换的方式所获得的技术方案,均落在本发明的保护范围内。
Claims (8)
1.一种热塑性弹性体的发泡方法,其特征在于:先通过辐照工艺实现热塑性弹性体的交联,之后将热塑性弹性体放入超临界反应釜中,通入气体,采用超临界间歇式升温法制得。
2.根据权利要求1所述的一种热塑性弹性体的发泡方法,其特征在于:所述热塑性弹性体为POE或SEBS。
3.根据权利要求1所述的一种热塑性弹性体的发泡方法,其特征在于:所述的辐照工艺为电子束辐射器辐照,剂量为40-90KGy。
4.根据权利要求1所述的一种热塑性弹性体的发泡方法,其特征在于:所述超临界反应釜中通入的气体为N2或CO2或N2、CO2混合物。
5.根据权利要求1所述的一种热塑性弹性体的发泡方法,其特征在于:所述超临界间歇式升温法的工艺为:超临界反应釜温度为15-50℃,饱和时间为2-24h,饱和压力为12-60MPa,之后饱和材料在100-150℃烘箱中进行发泡,得到发泡材料。
6.采用如权利要求1-5任一所述方法制备的发泡材料。
7.权利要求6所述发泡材料在环保瑜伽垫、儿童地垫或鞋中底中的应用。
8.基于权利要求7所述应用制备的环保瑜伽垫、儿童地垫或鞋中底,其特征在于:所述瑜伽垫、儿童地垫或鞋中底由发泡颗粒经蒸汽热压成型得到;或者先经发泡制成发泡板,再经切片、印花制得工艺制成品。
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CN110734621A (zh) * | 2019-11-27 | 2020-01-31 | 特塑(大连)高分子材料有限公司 | 一种塑料弹性体地板材料及其制备方法 |
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