CN109265815B - 一种改性eva发泡材料及其制备方法 - Google Patents

一种改性eva发泡材料及其制备方法 Download PDF

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CN109265815B
CN109265815B CN201811154011.XA CN201811154011A CN109265815B CN 109265815 B CN109265815 B CN 109265815B CN 201811154011 A CN201811154011 A CN 201811154011A CN 109265815 B CN109265815 B CN 109265815B
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丁华雄
陈渠鍫
曹峥
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Sansd Jiangsu Environmental Protection Technology Co ltd
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Abstract

本发明公开了一种改性EVA发泡材料及其制备方法，包括改性EVA材料100份、发泡剂3‑6份、氧化锌1‑3份、硬脂酸1‑2份、交联剂0.5‑1.0份、填料30‑100份；所述改性EVA材料为EVA、SEBS、PA‑11共混改性的三元复合发泡材料体系。与现有技术相比，发泡材料成品邵氏A硬度降低到28以下，明显优于传统材料的30以上，不仅柔软，而且回弹性好，拉伸强度较高，断裂伸长率高。

Description

一种改性EVA发泡材料及其制备方法
技术领域
本发明涉及发泡材料领域，尤其涉及一种改性EVA发泡材料及其制备方法。
背景技术
发泡材料是指在物质内部气化产生气泡使之成为多孔物质的发泡的物质，具有重量轻、比强度高、绝缘性能优异、缓冲能力显著以及吸附能力强的优势，已经被广泛的应用在了汽车工业、建筑工业、包装工业、农业、水处理和空气过滤等领域；如制造泡沫塑料、泡沫橡胶、泡沫树脂等。
应用于儿童爬行垫和家装材料的聚烯烃(主要是聚乙烯或EVA)泡沫地垫的主要特性是兼有一定的柔性和刚性，也就是弹性和塑性的结合。但总的来说，回弹性不够，脚踩上去舒适度不够。一般聚乙烯或EVA泡沫地垫的邵氏A硬度大于30°，正常情况是38°左右。
而目前更多需求对于泡沫地垫的弹性要求更高，要求泡沫地垫做得更有弹性，更柔软，脚感舒适，不易疲劳。而且要求脚面和泡沫地垫之间以及泡沫地垫与地面之间不容易滑动，也就是有一定的止滑作用，防止老人小孩摔倒。
但是目前大部分的泡沫地垫其弹性提高后，拉伸强度就会有一定的下降，如何做到二者的平衡，值得研究。
发明内容
发明目的：为了解决现有技术中所存在的问题，本发明提出了一种改性EVA发泡材料及其制备方法，制备而成的高弹性发泡材料的邵氏硬度降低到28以下，整体提升发泡材料的弹性和柔韧，同时拉伸强度也较高，综合力学性能佳。
技术方案：为达以上目的，本发明采取以下技术方案：一种改性EVA发泡材料，包括如下以重量计算的制备原料：改性EVA材料100份、发泡剂3-6份、氧化锌1-3份、硬脂酸1-2份、交联剂0.5-1.0份、填料30-100份；所述改性EVA材料为EVA、SEBS、PA-11共混改性的三元复合发泡材料体系。
EVA与SEBS进行共混后制备发泡材料对于材料的柔软性和弹性来说有了很大的提高，硬度有一定的下降，但是拉伸强度也有一定的下降，增加了PA-11之后有效对其拉伸强度有了一定的提升，从而进一步改善发泡材料的力学性能。
更为优选的，所述改性EVA材料中EVA、SEBS、PA-11共混配比为EVA50％-70％、SEBS10％-20％、余量的PA-11。
更为优选的，采用超临界二氧化碳间歇式高压反应釜发泡法进行改性EVA材料的制备，具体包括如下步骤：
(1)将EVA、SEBS、PA-11按共混配比干燥后经双螺杆挤出机共混造粒得三元复合材料；
(2)将三元复合材料置于高压反应釜中，连续4次通入二氧化碳并排出；继续通入二氧化碳调节压力为15MPa,调节温度为300℃，维持压力不变保持20min后调节温度为150℃，排出部分二氧化碳压力调节为10MPa，维持压力不变保持40min后调节温度为80℃，维持压力为10MPa不变保持20min后升温至220℃，并通入二氧化碳至饱和压力，保温1h后排出二氧化碳，取出三元复合材料，冷却定型得改性EVA材料。
更为优选的，所述EVA的VA含量为10％-20％。
更为优选的，所述SEBS的熔融指数MI值范围为3.0-5.0g/10min。
更为优选的，所述发泡剂为4,4’-氧代双苯磺酰肼。
更为优选的，所述交联剂为二叔丁过氧基二异丙苯。
更为优选的，所述填料为滑石粉、碳酸钙中的至少一种。
本发明还公开了上述改性EVA发泡材料的制备方法，包括如下步骤：将所需原料按需备好，置于密闭式炼胶机内进行混料塑炼处理，置于密炼机进行混料处理，经开炼、出片、硫化发泡、冷却成型、切割、冲裁、印刷，得到所需改性EVA发泡材料。
有益效果：本发明提供的一种改性EVA发泡材料及其制备方法，与现有技术相比具备以下优点：
(1)发泡材料成品邵氏A硬度降低到28以下，明显优于传统材料的30以上。
(2)发泡材料成品不仅柔软，而且回弹性好，拉伸强度较高，断裂伸长率高。
(3)制备材料不含甲醛、增塑剂、氯化物等有害物质，安全环保性能高。
具体实施方式
实施例1-7以及对比例1-2中的改性EVA材料的制备方法如下：
(1)将EVA、SEBS、PA-11按共混配比干燥后经双螺杆挤出机共混造粒得三元复合材料；
(2)将三元复合材料置于高压反应釜中，连续4次通入二氧化碳并排出；继续通入二氧化碳调节压力为15MPa,调节温度为300℃，维持压力不变保持20min后调节温度为150℃，排出部分二氧化碳压力调节为10MPa，维持压力不变保持40min后调节温度为80℃，维持压力为10MPa不变保持20min后升温至220℃，并通入二氧化碳至饱和压力，保温1h后排出二氧化碳，取出三元复合材料，冷却定型得改性EVA材料。
实施例1：
一种改性EVA发泡材料，包括如下以重量计算的制备原料：改性EVA 4kg(EVA50％、SEBS 20％、PA-11 30％)，4,4’-氧代双苯磺酰肼(OBSH)200g，氧化锌80g，硬脂酸60g、二叔丁基过氧异丙基苯(BIBP)40g，，滑石粉2.4kg。其中EVA的VA含量为12％，生产厂家为美国杜邦，SEBS的熔融指数MI值范围为4.0g/10min，生产厂家为美国科腾；PA-11生产厂家为日本旭化成。
其制备方法如下：将所需原料按需备好，置于密闭式炼胶机内进行混料塑炼处理，置于密炼机进行混料处理，经开炼、出片、硫化发泡、冷却成型、切割、冲裁、印刷，得到所需改性EVA发泡材料。
实施例2-实施例7：
除去改性EVA中三种成分的配比不同，其他制备原料的种类用量均与实施例1相同；且制备方法也与实施例1相同，实施例2-7中三种成分配比具体如表1所示，分别考察了EVA质量百分比依次为50％、60％、70％，SEBS质量百分比依次为20％、10％等情况制备成发泡材料。
对比例1：
除去改性EVA中仅仅使用EVA和SEBS进行二元共混，具体配比见表1，其他制备原料的种类用量均与实施例1相同；且制备方法也与实施例1相同。
对比例2：
除去改性EVA中仅仅使用EVA和PA-11进行二元共混，具体配比见表1，其他制备原料的种类用量均与实施例1相同；且制备方法也与实施例1相同。
对比例3：
未使用改性EVA，采用普通的EVA材料进行制备，其他制备原料的种类用量均与实施例1相同；制备方法与实施例1相同。
成品测试测试方法：
邵氏A硬度的测定方法：
根据GB/T530-1999《橡胶袖珍硬度计压入硬度试验方法》，国际标准ISO7619:1986进行测试，硬度计型号为：LX-A邵氏硬度计。
断裂伸长率以及拉伸强度的测定方法：
根据GB/T6344-2008《软质泡沫聚合材料拉伸强度和断裂伸长率的测定》使用仪器电子万能试验机型号：日本岛津AGS-X5KN。试样尺寸为140mm×12mm×10mm，横截面为矩形；拉伸速度为500mm/min±50mm/min；测定温度23℃±2℃，相对湿度50％±5％。
表1：不同配比的改性EVA材料制备的改性EVA发泡材料对比
Figure BDA0001818510340000041
从表1中可以看出，本发明实施例1-7改性EVA材料制备的改性EVA发泡材料其成品的硬度均低于28，且断裂伸长率较高，拉伸强度较未添加PA-11的对比例1来说也有了明显的提升，而硬度比未添加SEBS的对比例2以及未使用改性EVA材料的对比例3来说有大幅度的降低，综合性能更佳，此外实施例7中60％的EVA、15％的SEBS的比例制备的发泡材料其显现的综合力学性能更佳。
本发明一种改性EVA发泡材料成品邵氏A硬度降低到28以下，明显优于传统材料的30以上，不仅柔软，而且回弹性好，拉伸强度较高，断裂伸长率高。
应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以作出若干改进，这些改进也应视为本发明的保护范围。

Claims (7)

1.一种改性EVA发泡材料，其特征在于包括如下以重量计算的制备原料：改性EVA材料100份、发泡剂3-6份、氧化锌1-3份、硬脂酸1-2份、交联剂0 .5-1 .0份、填料30-100份；所述改性EVA材料为EVA、SEBS、PA-11共混改性的三元复合发泡材料体系；所述改性EVA材料中EVA、
SEBS、PA-11共混配比为EVA 50%-70%、SEBS 10%-20%、余量的PA-11；
采用超临界二氧化碳间歇式高压反应釜发泡法进行改性EVA材料的制备，具体包括如下步骤：
(1)将EVA、SEBS、PA-11按共混配比干燥后经双螺杆挤出机共混造粒得三元复合材料；
(2)将三元复合材料置于高压反应釜中，连续4次通入二氧化碳并排出；继续通入二氧化碳调节压力为15MPa ,调节温度为300℃，维持压力不变保持20min后调节温度为150℃，排出部分二氧化碳压力调节为10MPa，维持压力不变保持40min后调节温度为80℃，维持压力为10MPa不变保持20min后升温至220℃，并通入二氧化碳至饱和压力，保温1h后排出二氧化碳，取出三元复合材料，冷却定型得改性EVA材料。
2.根据权利要求1所述的改性EVA发泡材料，其特征在于：所述EVA的VA含量为10％-20％。
3.根据权利要求1所述的改性EVA发泡材料，其特征在于：所述SEBS的熔融指数MI值范围为3.0-5.0g/10min。
4.根据权利要求1所述的改性EVA发泡材料，其特征在于：所述发泡剂为4 ,4’-氧代双苯磺酰肼。
5.根据权利要求1所述的改性EVA发泡材料，其特征在于：所述交联剂为二叔丁过氧基二异丙苯。
6.根据权利要求1所述的改性EVA发泡材料，其特征在于：所述填料为滑石粉、碳酸钙中至少一种。
7.如权利要求1所述的改性EVA发泡材料的制备方法，其特征在于包括如下步骤：将所需原料按需备好，置于密闭式炼胶机内进行混料塑炼处理，置于密炼机进行混料处理，经开炼、出片、硫化发泡、冷却成型、切割、冲裁、印刷，得到所需改性EVA发泡材料。
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