CN106189961B - 一种鞋用耐低温eva粘合剂及其制备方法 - Google Patents

一种鞋用耐低温eva粘合剂及其制备方法 Download PDF

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CN106189961B
CN106189961B CN201610598538.6A CN201610598538A CN106189961B CN 106189961 B CN106189961 B CN 106189961B CN 201610598538 A CN201610598538 A CN 201610598538A CN 106189961 B CN106189961 B CN 106189961B
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马爱芬
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Huizhou Sikai Shoes Co., Ltd.
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    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08F222/06—Maleic anhydride
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract

本发明提供了一种鞋用耐低温EVA热熔胶及其制备方法，具体组成为：EVA 100重量份、乙烯‑辛烯共聚物25‑40份、马来酸酐5‑10重量份、二环戍二烯系石油树脂10‑15重量份、低分子量聚氨酯18‑22重量份、石蜡3‑5重量份、交联剂4‑10重量份、偶联剂1‑3重量份、抗氧剂2‑5重量份、紫外吸收剂0‑5重量份、石墨烯3‑7重量份。最终产品具有良好的耐低温性、柔韧性和粘接性，可以满足低温条件下长期的使用。

Description

一种鞋用耐低温EVA粘合剂及其制备方法
技术领域：
本发明涉及一种鞋用EVA粘合剂领域，具体涉及一种具有耐低温、柔韧性的鞋用EVA粘合剂领域。
背景技术：
EVA由于在分子链中引入醋酸乙烯单体，从而降低了高结晶度，提高了韧性、抗冲击性、填料相溶性和热密封性能，热熔胶是其一个重要的领域。EVA热熔胶是一种无溶剂、无水分的固体可熔性的聚合物，在常温下为固体，加热熔融到一定程度变为能流动且有一定粘性的液体粘合剂，其熔融后为浅棕色半透明体或本白色。
制鞋业属于劳动密集型产业，我国人口多、市场大、劳动力充足和成本低，每年生产100多亿双鞋，每双鞋基本都需要粘合剂进行部分结构的粘接，尤其皮鞋和旅游鞋，主要用于出口。俄罗斯等国家是主要的出口对象，但俄罗斯天气低，部分EVA粘接剂在低温下难以使用，低温下柔韧性降低很快，难以满足低温地区的需要，影响了特定区域的出口量。
发明内容：
发明目的：为了解决上述技术问题，本发明提供了一种鞋用耐低温EVA热熔胶其具有良好的耐低温性、柔韧性和粘接性，可以满足低温条件下长期的使用。同时。本发明还提供了一种鞋用耐低温EVA热熔胶的制备方法。
解决上述问题的技术方案为：
一种鞋用耐低温EVA粘合剂，其特征在于：EVA 100重量份、乙烯-辛烯共聚物25-40份、马来酸酐5-10重量份、二环戍二烯系石油树脂10-15重量份、低分子量聚氨酯18-22重量份、石蜡3-5重量份、交联剂4-10重量份、偶联剂1-3重量份、抗氧剂2-5重量份、紫外吸收剂0-5重量份、石墨烯3-7重量份。
所述EVA由两种EVA组成，其中第一EVA为VA含量在25-27％、熔融指数110-130，第二EVA为VA含量20-22％，熔融指数220-260。本发明采用了混合EVA，不同熔融指数影响热熔胶熔化后的流动性，一般热熔胶需要一定的流动性，满足热熔胶在被粘物表面的均匀分散；同时，热熔胶的粘合力通过VA含量可以调节，为了平衡流动性和粘合力，本发明选择了特定的熔融指数和VA含量。不在该范围的组合，其流动性和粘合力难以实现平衡，仅能满足一种一个性能。
作为优选的技术方案，第一EVA和第二EVA的重量比为5：2-5。
本发明还采用乙烯-辛烯共聚物，其増韧效果优异，但其一定程度上影响了体系的粘合力，故首先将EVA、乙烯-辛烯共聚物与马来酸酐进行混合，马来酸酐对EVA、乙烯-辛烯共聚物进行改性，通过改性大大提高了其粘合性，既满足了粘合性又提高了体系的柔韧性。
低分子量聚氨酯的加入提高了热熔胶的粘合性能和柔韧性，通过在后期交联反应中，其不参与交联，其作为一个柔性聚合物，贯穿于EVA的交联结构中，起到了应力分散作用，类似“水凝胶”领域的半互穿网络结构，可以有效的提高承重效果，并且聚氨酯具有良好的耐低温性。
作为优选技术方案，所述低分子量聚氨酯为低分子量聚醚型聚氨酯，聚醚型比聚酯型具有更好的柔韧性，作为更优选技术方案，低分子量为500-2000，在此分子量中可以使其在交联结构中更好的运动，不在该范围内，其应力分散效果会出现明显变差。
所述交联剂为过氧化二异丙苯。
本发明中使用了石墨烯，石墨烯为片状，力学性能优异，加入体系中可以使应力快速分散，提高了其承重能力。作为优选技术方案，所述石墨烯的最大尺寸处应大于10μm，大尺寸的石墨烯为一个大的受力面，受力更可以在更大范围内分散，应力传导速率更快。
所述偶联剂为含有丙烯酰氧基的偶联剂，偶联剂的使用起到了附着力促进剂，提高了不同界面之间的作用力，同时，使用丙烯酰氧基的偶联剂，丙烯酰氧具有较高的极性，可以提高其与EVA的作用力，粘着力较使用其他种类的偶联剂提高更为明显。
制备鞋用耐低温EVA粘合剂的方法，其特征在于：包括如下步骤：
(1)将EVA、乙烯-辛烯共聚物与马来酸酐进行混合，对EVA和乙烯-辛烯共聚物进行改性；
(2)剩余组分与马来酸酐改性后的EVA和乙烯-辛烯共聚物混合均匀，在120-175℃之间进行反应2小时，即得鞋用耐低温EVA粘合剂。
技术效果：
本发明通过EVA的复配平衡流动性和粘合力、通过乙烯-辛烯共聚物以及马来酸酐接枝改性改善韧性和粘合力；低分子量聚氨酯形成半互穿网络、使用大片石墨烯都可以有效的提高受力分散作用；含有丙烯酰氧基的偶联剂提高了粘合力。上述各组分均对产品对中粘合力、流动性、应力分散性，而其中诸多增加柔韧性的组分也提高了耐低温性、低温下应力分散性。为了平衡各种性能，本发明各组分用量选择也起到了至关重要的作用。
具体实施方式：
以下对本发明的原理和特征进行描述，所举实例只是用于解释本发明，并非用于限定本发明的范围。
实施例1：
鞋用耐低温EVA粘合剂的制备方法，主要步骤包括如下：
(1)将VA含量26％、熔融指数120的第一EVA 50重量份、VA含量22％、熔融指数240的第二EVA 50重量份、乙烯-辛烯共聚物30重量份与马来酸酐10重量份进行混合，对EVA和乙烯-辛烯共聚物进行改性；
(2)双环戊二烯石油树脂10重量份、分子量为1000的聚氨酯20重量份、石蜡4重量份、交联剂过氧化二异丙苯5重量份、偶联剂2重量份、抗氧剂3重量份、紫外吸收剂4重量份、最大尺寸处22微米石墨烯4重量份与马来酸酐改性后的EVA和乙烯-辛烯共聚物混合均匀，在120-175℃之间进行反应2小时，即得鞋用耐低温EVA粘合剂。
其他实施例和对比例见下表：
耐压测试为将粘合剂固化成直径1cm，高度1cm的圆柱，使用压力测试向下压缩
到70％后释放。

Claims (4)

1.一种鞋用耐低温EVA粘合剂，其特征在于：EVA 100重量份、乙烯-辛烯共聚物25-40份、马来酸酐5-10重量份、二环戊二烯系石油树脂10-15重量份、低分子量聚氨酯18-22重量份、石蜡3-5重量份、交联剂4-10重量份、偶联剂1-3重量份、抗氧剂2-5重量份、紫外吸收剂0-5重量份、石墨烯3-7重量份；
所述EVA由两种EVA组成，其中第一EVA为VA含量在25-27%、熔融指数110-130 g/10min，第二EVA为VA含量20-22%，熔融指数220-260 g/10min；
第一EVA和第二EVA的重量比为5：2-5；
所述低分子量聚氨酯为低分子量聚醚型聚氨酯，低分子量为500-1000；
所述石墨烯的最大尺寸处大于10μm；
首先将EVA、乙烯-辛烯共聚物与马来酸酐进行混合，马来酸酐对EVA、乙烯-辛烯共聚物进行改性。
2.如权利要求1所述的鞋用耐低温EVA粘合剂，其特征在于：所述交联剂为过氧化二异丙苯。
3.如权利要求1所述的鞋用耐低温EVA粘合剂，其特征在于：所述偶联剂为含有丙烯酰氧基的偶联剂。
4.制备权利要求1-3任一所述鞋用耐低温EVA粘合剂的方法，其特征在于：包括如下步骤：
（1）将EVA、乙烯-辛烯共聚物与马来酸酐进行混合，对EVA和乙烯-辛烯共聚物进行改性；
（2）剩余组分与马来酸酐改性后的EVA和乙烯-辛烯共聚物混合均匀，在120-175℃之间进行反应2小时，即得鞋用耐低温EVA粘合剂。
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CN109280530A (zh) * 2018-09-11 2019-01-29 平湖展鹏热熔胶膜有限公司 热熔胶功能材料及其制备方法、热熔胶流延裸膜制备方法
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