CN110204822B - 一种eva发泡材料及其制备方法 - Google Patents

一种eva发泡材料及其制备方法 Download PDF

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CN110204822B
CN110204822B CN201910456201.5A CN201910456201A CN110204822B CN 110204822 B CN110204822 B CN 110204822B CN 201910456201 A CN201910456201 A CN 201910456201A CN 110204822 B CN110204822 B CN 110204822B
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eva
foaming
ethylene
vinyl acetate
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李明春
辛梅华
陈登鑫
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Fujian Wanjiaxin Light Industry Development Co ltd
Huaqiao University
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Abstract

本发明公开一种EVA发泡材料，包括以下原料：乙烯‑醋酸乙烯酯共聚物、热塑性聚氨酯、烯烃嵌段共聚物、交联剂、发泡剂及填充剂。本发明还公开了一种EVA发泡材料的制备方法，将乙烯‑醋酸乙烯酯共聚物、热塑性聚氨酯及烯烃嵌段共聚物经机械共混，再与交联剂、发泡剂及填充剂混炼，最后通过模压发泡得到上述EVA发泡材料。通过本制备方法所制得的EVA发泡材料相比于传统的EVA发泡材料具有硬度小、密度低、热收缩小、压缩永久变形小、物性优良等优点。

Description

一种EVA发泡材料及其制备方法
技术领域
本发明涉及发泡材料技术领域，具体涉及的是一种EVA发泡材料及其制备方法。
背景技术
EVA(乙烯-醋酸乙烯酯共聚物)是由乙烯和醋酸乙烯共聚而制得，其中，醋酸乙烯含量一般为5％～40％，与聚乙烯(PE)相比，EVA由于在分子链中引入醋酸乙烯单体，从而提高了聚合物的支化度，提高了柔韧性、抗冲击性、填料相容性和热密封性，产品在较宽的温度范围内具有良好的柔软性、耐冲击强度、耐环境、应力开裂性和良好的光学性能、耐低温及无毒的特性。因此被广泛的应用于各个领域。
EVA发泡材料是指以EVA为原料并加入发泡剂、交联剂等助剂后经模压发泡或注塑发泡所制得的发泡类材料。EVA发泡材料是一种发泡物性优良的发泡材料，其具有质轻、密度低、能吸收载荷等许多优点，因此在各行各业得到广泛的应用，尤其在发泡制鞋工业，被应用于中高档旅游鞋、登山鞋、拖鞋、凉鞋的鞋底和内饰材料中。但EVA发泡材料客观的存在回弹不足、热收缩大和压缩永久变形大等缺陷，从而限制它在鞋材制造业中的应用范围。因此，如何改善EVA发泡材料的缺陷成为本技术领域人员需要解决的技术问题。
发明内容
本发明的目的在于提供一种EVA发泡材料，相比于传统的EVA发泡材料，具有硬度小、密度低、高回弹、热收缩小、压缩永久变形小以及物性优良等优点，由该EVA发泡材料加工得到的鞋材更加舒适轻便。
本发明的目的还在于提供上述EVA发泡材料的制备方法。
为了达成上述目的，本发明的解决方案是：
一种EVA发泡材料，以重量份计，包括以下原料：乙烯-醋酸乙烯酯共聚物70～90份、热塑性聚氨酯1～20份以及烯烃嵌段共聚物1～20份，其中所述乙烯-醋酸乙烯酯共聚物、热塑性聚氨酯与烯烃嵌段共聚物三者的重量份数之和为100份，还包括交联剂、发泡剂及填充剂，所述交联剂的含量为所述乙烯-醋酸乙烯酯共聚物、热塑性聚氨酯与烯烃嵌段共聚物三者总重量的0.2％～0.9％，所述发泡剂的含量为所述乙烯-醋酸乙烯酯共聚物、热塑性聚氨酯与烯烃嵌段共聚物三者总重量的1％～5％，所述填充剂的含量为所述乙烯-醋酸乙烯酯共聚物、热塑性聚氨酯与烯烃嵌段共聚物三者总重量的1％～5％。
所述交联剂为过氧化二异丙苯、偶氮二甲酸二异丙酯、偶氮二异丁腈和对甲苯磺酰肼中的一种或者两种，所述发泡剂为偶氮二甲酰胺、膨胀微球或者OBSH发泡剂，所述填充剂为氧化锌、硬脂酸和硬脂酸锌中的一种或者多种。
一种EVA发泡材料的制备方法，包括以下步骤：
步骤1、按重量份称取乙烯-醋酸乙烯酯共聚物70～90份、热塑性聚氨酯1～20份以及烯烃嵌段共聚物1～20份，所述乙烯-醋酸乙烯酯共聚物、热塑性聚氨酯与烯烃嵌段共聚物三者的重量份数之和为100份；
步骤2、将步骤1称取的乙烯-醋酸乙烯酯共聚物、热塑性聚氨酯以及烯烃嵌段共聚物进行机械共混，得到共聚物混合物；
步骤3、向步骤2得到的共聚物混合物中加入交联剂、发泡剂及填充剂进行混炼，加入的所述交联剂的含量为所述共聚物混合物总重量的0.2％～0.9％，所述发泡剂的含量为所述共聚物混合物总重量的1％～5％，所述填充剂的含量为所述所述共聚物混合物总重量的1％～5％；
步骤4、将经过步骤3混炼的混合物进行模压发泡，得到所述EVA发泡材料。
步骤2中，采用双螺杆水下造粒机进行所述机械共混。
步骤2中，所述机械共混的温度为120～205℃。
步骤3中，采用开炼机组进行所述混炼。
步骤3中，所述混炼的温度为80～100℃，所述混炼的时间为6～8min。
步骤4中，所述模压发泡的温度为170～190℃，所述模压发泡的时间为6～10min。
采用上述技术方案后，本发明一种EVA发泡材料，原料热塑性聚氨酯(TPU)具有超轻密度、高回弹性、耐磨性、低温性能好、环保性等优点，且其结构可与乙烯-醋酸乙烯酯共聚物(EVA)形成氢键基团，提高两者的相容性，烯烃嵌段共聚物(OBC)相比于EVA发泡材料在较宽的温度范围内具有收缩明显小、压缩永久形变小的优势，同硬度下具有更好的回弹，疲劳后恢复好，密度更小，触感极佳，在较宽的温度范围内性能保持稳定，且OBC的乙烯主链与EVA主链结构相似，两者具有一定的相容性，从而使得该EVA发泡材料与传统的EVA发泡材料相比，具有硬度小、密度低、热收缩小、压缩永久变形小以及物性优良等优点，由该EVA发泡材料加工得到的鞋材更加舒适轻便。
具体实施方式
为了进一步解释本发明的技术方案，下面通过具体实施例来对本发明进行详细阐述。
一、EVA发泡材料的制备
实施例1
一种EVA发泡材料的制备方法，包括以下步骤：
步骤1、按表1所示的重量份称取乙烯-醋酸乙烯酯共聚物85份、热塑性聚氨酯10份以及烯烃嵌段共聚物5份；
步骤2、采用双螺杆水下造粒机将步骤1称取的乙烯-醋酸乙烯酯共聚物、热塑性聚氨酯以及烯烃嵌段共聚物在120～205℃下进行机械共混，得到共聚物混合物；
步骤3、向步骤2得到的共聚物混合物中按重量份加入过氧化二异丙苯0.6份、偶氮二甲酰胺2.0份、氧化锌1.0份、硬脂酸0.4份和硬脂酸锌0.65份，采用开炼机组在80℃下进行混炼6min；
步骤4、将经过步骤3混炼的混合物进行在180℃下模压发泡10min，得到该EVA发泡材料。
上述制备方法中，乙烯-醋酸乙烯酯共聚物(EVA)选用扬子石化-巴斯夫有限公司生产的EVA5110和亚洲聚合股份有限公司生产的EVA33121的混合物，二者比例为1：1；热塑性聚氨酯(TPU)选用德国拜耳公司生产的TPU390；烯烃嵌段共聚物(OBC)选用陶氏化学公司生产的INFUSE9107。
实施例2
一种EVA发泡材料的制备方法，包括以下步骤：
步骤1、按表1所示的重量份称取乙烯-醋酸乙烯酯共聚物80份、热塑性聚氨酯10份以及烯烃嵌段共聚物10份；
步骤2、采用双螺杆水下造粒机将步骤1称取的乙烯-醋酸乙烯酯共聚物、热塑性聚氨酯以及烯烃嵌段共聚物在120～205℃下进行机械共混，得到共聚物混合物；
步骤3、向步骤2得到的共聚物混合物中按重量份加入偶氮二甲酸二异丙酯0.2份、过氧化二异丙苯0.4份、偶氮二甲酰胺2.0份、氧化锌1.0份、硬脂酸0.4份和硬脂酸锌0.65份，采用开炼机组在80℃下进行混炼6min；
步骤4、将经过步骤3混炼的混合物进行在180℃下模压发泡10min，得到该EVA发泡材料。
上述制备方法中，乙烯-醋酸乙烯酯共聚物(EVA)选用扬子石化-巴斯夫有限公司生产的EVA5110和亚洲聚合股份有限公司生产的EVA33121的混合物，二者比例为1：1；热塑性聚氨酯(TPU)选用德国拜耳公司生产的TPU390；烯烃嵌段共聚物(OBC)选用陶氏化学公司生产的INFUSE9107。
对比例
一种EVA发泡材料的制备方法，包括以下步骤：
步骤1、按表1所示的重量份称取乙烯-醋酸乙烯酯共聚物100份；
步骤2、向步骤1称取的乙烯-醋酸乙烯酯共聚物中按重量份加入过氧化二异丙苯0.6份、偶氮二甲酰胺2.0份、氧化锌1.0份、硬脂酸0.4份和硬脂酸锌0.65份，采用开炼机组在80℃下进行混炼6min；
步骤3、将经过步骤2混炼的混合物进行在180℃下模压发泡10min，得到该EVA发泡材料。
上述制备方法中，乙烯-醋酸乙烯酯共聚物(EVA)选用扬子石化-巴斯夫有限公司生产的EVA5110和亚洲聚合股份有限公司生产的EVA33121的混合物，二者比例为1：1。
表1各EVA发泡材料的原料组成
Figure BDA0002076660010000061
二、性能测试
对各实施例和对比例得到的EVA发泡材料进行物理性能测试，对比两者性能，结果表2所示，检测条件为：室温23±3℃、湿度60±5％。
表2各EVA发泡材料的性能测试结果
测试项目 实施例1 实施例2 对比例
硬度(Shore C) 56 55 59
回弹(％) 45 47 44
密度(g/cm<sup>3</sup>) 0.168 0.154 0.178
压缩永久变形(％) 31 29 35
热收缩(％) 2.51 2.15 3.17
拉伸强度(MPa) 1.6 1.4 1.9
断裂伸长率(％) 587 609 401
由表2中所示数据可知，通过本发明制备得到的EVA发泡材料相比于传统的EVA发泡材料，在回弹基本不改变的情况下具有硬度小、密度低、热收缩小、压缩永久变形小、物性(包括拉伸强度和断裂伸长率)优良等优点。
上述实施例并非限定本发明的产品形态和式样，任何所属技术领域的普通技术人员对其所做的适当变化或修饰，皆应视为不脱离本发明的专利范畴。

Claims (6)

1.一种EVA发泡材料的制备方法，其特征在于：包括以下步骤：
步骤1、按重量份称取乙烯-醋酸乙烯酯共聚物70~90份、热塑性聚氨酯1~20份以及烯烃嵌段共聚物1~20份，所述乙烯-醋酸乙烯酯共聚物、热塑性聚氨酯与烯烃嵌段共聚物三者的重量份数之和为100份；
步骤2、采用双螺杆水下造粒机对步骤1称取的乙烯-醋酸乙烯酯共聚物、热塑性聚氨酯以及烯烃嵌段共聚物进行机械共混，得到共聚物混合物；
步骤3、向步骤2得到的共聚物混合物中加入交联剂、发泡剂及填充剂进行混炼，加入的所述交联剂的含量为所述共聚物混合物总重量的0.2%~0.9%，所述发泡剂的含量为所述共聚物混合物总重量的1%~5%，所述填充剂的含量为所述共聚物混合物总重量的1%~5%，所述填充剂为氧化锌、硬脂酸和硬脂酸锌中的一种或者多种；
步骤4、将经过步骤3混炼的混合物进行模压发泡，得到所述EVA发泡材料。
2.根据权利要求1所述的一种EVA发泡材料的制备方法，其特征在于：所述交联剂为过氧化二异丙苯、偶氮二甲酸二异丙酯、偶氮二异丁腈和对甲苯磺酰肼中的一种或者两种，所述发泡剂为偶氮二甲酰胺、膨胀微球或者OBSH发泡剂。
3.根据权利要求1所述的一种EVA发泡材料的制备方法，其特征在于：步骤2中，所述机械共混的温度为120~205℃。
4.根据权利要求1所述的一种EVA发泡材料的制备方法，其特征在于：步骤3中，采用开炼机组进行所述混炼。
5.根据权利要求1所述的一种EVA发泡材料的制备方法，其特征在于：步骤3中，所述混炼的温度为80~100℃，所述混炼的时间为6~8min。
6.根据权利要求1所述的一种EVA发泡材料的制备方法，其特征在于：步骤4中，所述模压发泡的温度为170~190℃，所述模压发泡的时间为6~10min。
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