CN112321803B - 一种低稳泡性水性环氧固化剂及其制备方法 - Google Patents

一种低稳泡性水性环氧固化剂及其制备方法 Download PDF

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CN112321803B
CN112321803B CN202011116615.2A CN202011116615A CN112321803B CN 112321803 B CN112321803 B CN 112321803B CN 202011116615 A CN202011116615 A CN 202011116615A CN 112321803 B CN112321803 B CN 112321803B
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周学军
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Abstract

本发明属于环氧树脂固化剂领域。一种低稳泡性水性环氧固化剂，由以下按质量份数计算的组分制备而成：环氧树脂30‑50份、多元胺10‑15份、异戊烯醇聚氧乙烯醚5‑10份、缩水甘油醚基烯丙基聚氧乙烯醚10‑20份、催化剂1‑5份、固化促进剂5‑10份、水45‑65份。本发明固化剂稳定性好、消泡速度快、抑泡时间长，与环氧树脂相容性好，在提高涂膜的固化速度和漆膜性能的同时，可有效降低涂膜的起泡量和稳泡时间。

Description

一种低稳泡性水性环氧固化剂及其制备方法
技术领域
本发明属于环氧树脂固化剂领域，具体涉及一种低稳泡性水性环氧固化剂及其制备方法。
背景技术
环氧树脂是指含两个或多个环氧基，以脂肪族、酯环族或芳香族作为主链的高分子预聚物，因其具有优异的机械性能和理化性能，被广泛应用于双组份环氧涂料中。固化剂作为环氧涂料的重要组成部分，其与环氧树脂形成的三维网状结构高聚物决定了涂料漆膜的综合性能。水性双组份环氧树脂涂料因同时具有亲水性和亲油性，其在成膜时气泡难以消散，限制了其应用。
水性双组份环氧树脂涂料与双组份溶剂型环氧预料相比，大幅度减少了挥发性有机物的排放。水性环氧固化剂多采用改性多元胺，如酰胺基胺类、聚酰胺类、聚酰胺加成物和环氧-多胺加成物等，其中环氧-多胺加成物适用于常温固化的水性环氧涂料，这类涂料的制备关键在于通过环氧树脂与多元胺开环反应，使多胺上的伯胺尽可能的转化完全，降低多胺的反应活性，从而提高固化剂与环氧树脂的相容性。然而，在如何提高此类水性环氧固化剂力学性能的同时降低其稳泡性的问题上未有令人满意的解决方案。
发明内容
本发明所要解决的技术问题是提供一种低稳泡性水性环氧固化剂，该固化剂稳定性好、消泡速度快、抑泡时间长，与环氧树脂相容性好，在提高涂膜的固化速度和漆膜性能的同时，可有效降低涂膜的起泡量和稳泡时间。
本发明的技术方案如下：
一种低稳泡性水性环氧固化剂，由以下按质量份数计算的组分制备而成：环氧树脂30-50份、多元胺10-15份、异戊烯醇聚氧乙烯醚5-10份、缩水甘油醚基烯丙基聚氧乙烯醚10-20份、催化剂1-5份、固化促进剂5-10份、水45-65份。
进一步的，所述环氧树脂的结构式为：
Figure BDA0002730446240000021
进一步的，所述多元胺为脂肪族多胺或芳香族多胺。
进一步的，所述脂肪族多胺为乙二胺、己二胺、三乙烯四胺、二乙氨基丙胺、四亚乙基五胺中的至少一种
进一步的，所述芳香族多胺为间苯二甲胺和/或异氟尔酮二胺。
进一步的，所述催化剂为三苯基膦。
进一步的，所述固化促进剂为2,4,6-三(二甲氨基甲基)苯酚。
一种所述的低稳泡性水性环氧固化剂的制备方法，包括以下步骤：将固化促进剂与多元胺混合，升温至50-60℃搅拌至固化促进剂完全溶解；加入异戊烯醇聚氧乙烯醚升温至85-95℃，滴加催化剂，滴加完毕后升温至110-120℃保温反应1-3h；降温至45-50℃，滴加环氧树脂和缩水甘油醚基烯丙基聚氧乙烯醚的混合溶液，滴加完毕后升温至85-95℃保温反应1-3h；降温至45-50℃，滴加水，速度为1300-1500r/min搅拌30-60min即可。
本发明具有如下有益效果：
选用的环氧树脂官能度高，可增加水性环氧固化剂结构中的亚氨基含量，亚氨基含量的增多可增进固化剂的亲水性能和固化性能，从而提高固化剂的稳定性和与树脂的相容性，降低涂膜的起泡量和稳泡时间，同时可提高固化膜的交联密度，提高漆膜的机械性能。选用的固化促进剂结构中含酚羟基，可提高固化剂的固化速度，在固化剂中引入苯环可提高漆膜的硬度和耐热性。选用的多元胺分子量小、黏度低，分子上含多个活泼氢原子和伯胺基团，可同时固化多个环氧基团，可提高固化剂的固化速度。选用的缩水甘油醚基烯丙基聚氧乙烯醚与环氧树脂相容性好，可增加基材的润湿性能，从而降低固化剂的稳泡性，有效减少固化膜的起泡量。
本发明通过多元胺与带有亲水链段的异戊烯醇聚氧乙烯醚反应，形成可与体系交联的大分子非离子型乳化剂，再以此和环氧树脂、缩水甘油醚基烯丙基聚氧乙烯醚反应制备水性环氧固化剂，提高了固化剂的稳定性和固化速度，同时可提高漆膜的理化性能。
具体实施方式
下面结合实施例对本发明进行详细的说明，实施例仅是本发明的优选实施方式，不是对本发明的限定。
实施例
下表为本发明低稳泡性水性环氧固化剂3个实施例的配方表(单位：份)：
Figure BDA0002730446240000031
其中，所述环氧树脂的结构式为：
Figure BDA0002730446240000032
一种所述的低稳泡性水性环氧固化剂的制备方法，包括以下步骤：将固化促进剂与多元胺混合，升温至50℃搅拌至固化促进剂完全溶解；加入异戊烯醇聚氧乙烯醚升温至90℃，滴加催化剂，滴加完毕后升温至110℃保温反应2h；降温至45℃，滴加环氧树脂和缩水甘油醚基烯丙基聚氧乙烯醚的混合溶液，滴加完毕后升温至90℃保温反应2h；降温至50℃，滴加水，速度为1300r/min搅拌30min即可。
对比例1
对比例1和实施例1的区别在于：将异戊烯醇聚氧乙烯醚替换为烯丙基聚氧乙烯醚。
对比例2
对比例2和实施例1的区别在于：所用固化促进剂为N,N-二甲基苄胺。
对比例3
对比例3和实施例1的区别在于：将缩水甘油醚基烯丙基聚氧乙烯醚替换为十二烷基缩水甘油醚。
检测本发明低稳泡性水性环氧固化剂3个实施例和3个对比例的各项性能，测试结果见下表：
Figure BDA0002730446240000041
可见，本发明固化剂稳泡性低、稳定性好、硬度高。
将本发明低稳泡性水性环氧固化剂3个实施例和3个对比例，与环氧树脂E-51按质量比1:4混合配，制成双组份环氧涂料。测试各组环氧涂料的性能，测试结果见下表：
Figure BDA0002730446240000042
Figure BDA0002730446240000051
可见，本发明固化剂可提高环氧涂料的固化速度，固化膜耐冲击性和耐盐雾性好。
本发明低稳泡性水性环氧固化剂稳定性好、消泡速度快、抑泡时间长，与环氧树脂相容性好，在提高涂膜的固化速度和漆膜性能的同时，可有效降低涂膜的起泡量和稳泡时间。

Claims (3)

1.一种低稳泡性水性环氧固化剂，其特征在于，由以下按质量份数计算的组分制备而成：环氧树脂30-50份、多元胺10-15份、异戊烯醇聚氧乙烯醚5-10份、缩水甘油醚基烯丙基聚氧乙烯醚10-20份、催化剂1-5份、固化促进剂5-10份、水45-65份；其中，所述多元胺为脂肪族多胺或芳香族多胺，所述脂肪族多胺为乙二胺、己二胺、三乙烯四胺、二乙氨基丙胺、四亚乙基五胺中的至少一种，所述芳香族多胺为间苯二甲胺和/或异氟尔酮二胺，所述固化促进剂为2,4,6-三（二甲氨基甲基）苯酚，所述环氧树脂的结构式为：
Figure DEST_PATH_IMAGE001
。
2.根据权利要求1所述的低稳泡性水性环氧固化剂，其特征在于，所述催化剂为三苯基膦。
3.一种权利要求1-2任一项所述的低稳泡性水性环氧固化剂的制备方法，其特征在于，包括以下步骤：将固化促进剂与多元胺混合，升温至50-60℃搅拌至固化促进剂完全溶解；加入异戊烯醇聚氧乙烯醚升温至85-95℃，滴加催化剂，滴加完毕后升温至110-120℃保温反应1-3h；降温至45-50℃，滴加环氧树脂和缩水甘油醚基烯丙基聚氧乙烯醚的混合溶液，滴加完毕后升温至85-95℃保温反应1-3h；降温至45-50℃，滴加水，速度为1300-1500r/min搅拌30-60min即可。
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