CN116284800A - 一种水性环氧树脂固化剂及水性环氧涂料的制备方法 - Google Patents
一种水性环氧树脂固化剂及水性环氧涂料的制备方法 Download PDFInfo
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Abstract
本发明提供一种水性环氧树脂固化剂及水性环氧涂料的制备方法,其特征在于,水性环氧树脂固化剂的制备流程如下:先将多乙烯多胺和溶剂置于85℃的恒温水浴中混合均匀;然后向混合溶液中加入聚硅氧烷环氧树脂,搅拌3‑5小时获得聚硅氧烷环氧树脂与胺的加合物;接着将加合物的温度降至65℃,并将环氧树脂以及聚乙二醇二缩水甘油醚与1‑甲氧基‑2‑丙醇的混合物缓慢加入加合物中;最后,将上述溶液倒入去离子水并保持1小时,获得水性环氧树脂固化剂;将水性环氧树脂固化剂、乳化型水性环氧树脂、颜料浆和其他添加剂混合均匀并脱除气泡得到水性环氧涂料,引入的聚硅氧烷使得水性环氧涂料具有较好的冲击韧性和耐热性。
Description
技术领域
本发明涉及环氧树脂技术领域,具体涉及一种水性环氧树脂固化剂及水性环氧涂料的制备方法。
背景技术
环氧树脂因其良好的附着力、较低的固化收缩率、优异的耐化学性和防腐特性在许多行业中得到广泛应用,尤其是水性环氧树脂,它可以减少挥发性有机化合物的排放,满足绿色发展的需要,已经发展成为粘合剂的主要发展趋势。在工业市场上,水性环氧涂料已逐渐取代传统的溶剂型环氧涂料。然而,水性环氧涂料的性能不如溶剂型涂料,如脆性、耐热性和耐腐蚀性较差等。此外,水性环氧固化剂对固化环氧体系的性能起着至关重要的作用。因此,对其进行改性是优化环氧固化体系性能的有效方法之一。
发明专利CN112745482 A公开了一种使环氧树脂接枝羧基的水性环氧树脂固化剂及其制备方法,功能基团的引入提高了环氧树脂的耐光照性能,延长了使用寿命,但是水性环氧树脂的脆性、较差的耐热性、较差的耐冲击性等性能没有得到提升。
发明内容
针对现有技术中存在的问题,本发明提供了一种水性环氧树脂固化剂及水性环氧涂料的制备方法,本发明制备了聚硅氧烷改性的环氧树脂固化剂,然后用该固化剂与水性环氧树脂固化,得到具有高韧性、高耐热性和高抗冲击韧性的环氧树脂涂料。
本发明的目的在于提供一种水性环氧树脂固化剂及水性环氧涂料的制备方法,
其特征在于,水性环氧树脂固化剂制备流程如下:
(1)将多乙烯多胺和1-甲氧基-2-丙醇加入到容器中,并置于85℃的恒温水浴中混合均匀得到混合溶液1。
(2)向混合溶液1中加入聚硅氧烷环氧树脂,搅拌3-5小时使其发生化学反应,获得聚硅氧烷环氧树脂与胺的加合物。
(3)将聚硅氧烷环氧树脂与胺的加合物的温度降至65℃,在4-6小时内,将环氧树脂以及聚乙二醇二缩水甘油醚与1-甲氧基-2-丙醇的混合物缓慢通过恒压分配漏斗加入65℃聚硅氧烷环氧树脂与胺的加合物得到混合溶液2。
(4)最后,将混合溶液2倒入去离子水中并保持1小时,获得水性环氧树脂固化剂。
优选的,所述多乙烯多胺为乙二胺、二乙烯三胺、三乙烯四胺和四乙烯五胺中的一种或几种。
优选的,所述聚硅氧烷环氧树脂的结构式为:
其中R为-CH2-CH2-、-CH2-CH2-CH2-、-CH2-O-CH2-中的一种连接基团。
优选的,所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂中的一种。
优选的,所述聚乙二醇二缩水甘油醚与1-甲氧基-2-丙醇的重量比为1:1-1:1.5。
一种利用所述水性环氧树脂固化剂制备得到的水性环氧涂料,其特征在于,制备流程如下:
(a)首先,将乳化型水性环氧树脂、颜料浆和其他添加剂混合均匀。
(b)然后加入所述水性环氧树脂固化剂混合均匀后脱除气泡得到水性环氧涂料。
(c)使用高压枪将水性环氧涂料喷涂到用砂纸打磨并用乙醇擦拭过的马口铁和钢板上,涂层厚度控制在60-65mm。
(d)最后将喷涂的涂层在80℃下干燥2.5 h,并在室温下保持一天用于性能测试。
(e)将水性环氧涂料倒入PTFE模具中,并在80℃下干燥2.5小时,以获得厚度约为0.5 mm的薄膜,用于性能测试。
优选的,所述乳化型水性环氧树脂为双酚A型环氧树脂或酚醛型环氧树脂中的一种。
优选的,所述其他添加剂包括成膜助剂、水性消泡剂、润湿剂、防闪光剂、增稠剂。
优选的,所述颜料浆的制备流程如下:首先,将去离子水和溶剂放入容器中预分散5分钟;然后依次混入水性消泡剂、分散剂和各种填料进行高速分散;最后,加入锆珠,并在密封的涂料混合器中振荡,直到细度低于15 微米。
优选的,所述溶剂为1-甲氧基-2-丙醇,所述填料为云母粉、硫酸钡、二氧化钛、三磷酸铝、磷酸锌、滑石粉、炭黑、热解二氧化硅中的一种或几种。
本发明的有益效果是:聚硅氧烷是环氧树脂固化体系的理想改性剂,具有高键能和链段旋转自由度、优异的耐热性、柔韧性、电绝缘性、耐候性和疏水性,与环氧树脂有效互补。聚硅氧烷与环氧树脂通过化学键连接是一种有效的改性方法,通过基于基团之间的化学反应合成接枝或嵌段改性共聚物来增强相容性,可以显著地提高环氧树脂的韧性和耐热性。此外,环氧树脂固化剂中引入的聚硅氧烷和环氧树脂结构具有增韧、柔性调节和耐热性能,可以显著提高水性环氧涂料的延伸强度、耐热性和冲击韧性。
首先,多乙烯多胺与聚硅氧烷环氧树脂在溶剂中发生化学反应,多乙烯多胺的活泼氢使得聚硅氧烷环氧树脂中的末端环氧基团开环,获得聚硅氧烷环氧树脂与胺的加合物,此时的一次改性固化剂的主链上引入了聚硅氧烷,显著提高了固化剂的柔韧性、耐热性、疏水性等性能。然后,在活性稀释剂与溶剂的作用下,聚硅氧烷环氧树脂与胺的加合物与环氧树脂发生开环反应得到水性环氧固化剂,小分子环氧树脂的引入可以提高水性环氧固化剂与水性环氧树脂的润湿性。最后,聚硅氧烷改性的水性环氧固化剂与水性环氧树脂按一定比例混合,与溶剂及其他填料共混,制备得到水性环氧涂料,将水性环氧涂料制成涂层和薄膜以测试涂料的性能。
具体实施方式
实施例1
一种水性环氧树脂固化剂及水性环氧涂料的制备方法,其特征在于,水性环氧树脂固化剂制备流程如下:
(1)将19g三乙烯四胺和30g 1-甲氧基-2-丙醇加入到容器中,并置于85℃的恒温水浴中混合均匀得到混合溶液1。
(2)向混合溶液1中加入10g聚硅氧烷环氧树脂,搅拌3-5小时使其发生化学反应,获得聚硅氧烷环氧树脂与胺的加合物。
(3)将聚硅氧烷环氧树脂与胺的加合物的温度降至65℃,在4小时内,将17.8g双酚A型环氧树脂以及20g聚乙二醇二缩水甘油醚与30g 1-甲氧基-2-丙醇的混合物缓慢通过恒压分配漏斗加入65℃聚硅氧烷环氧树脂与胺的加合物得到混合溶液2。
(4)最后,将混合溶液2倒入去离子水中并保持1小时,获得水性环氧树脂固化剂。
所述聚硅氧烷环氧树脂的结构式为:
一种利用所述水性环氧树脂固化剂制备得到的水性环氧涂料,其特征在于,制备流程如下:
(a)首先,将44.17g双酚A型环氧树脂、52.28g颜料浆、1.6g二丙二醇丁基醚、0.25g水性消泡剂、0.45g润湿剂、0.4g防闪光剂、0.4g增稠剂混合均匀。
(b)然后加入所述水性环氧树脂固化剂混合均匀后脱除气泡得到水性环氧涂料。
(c)使用高压枪将水性环氧涂料喷涂到用砂纸打磨并用乙醇擦拭过的马口铁和钢板上,涂层厚度控制在60-65 mm。
(d)最后将喷涂的涂层在80℃下干燥2.5 h,并在室温下保持一天用于性能测试。
(e)将水性环氧涂料倒入PTFE模具中,并在80℃下干燥2.5小时,以获得厚度约为0.5 mm的薄膜,用于性能测试。
所述颜料浆的制备流程如下:首先,将28.8g去离子水和2g 1-甲氧基-2-丙醇放入容器中预分散5分钟;然后依次混入0.2g水性消泡剂、3g分散剂、2g云母粉、16g硫酸钡、23g二氧化钛、7g三磷酸铝、7g磷酸锌、10g滑石粉、0.2g炭黑、0.8g热解二氧化硅进行高速分散;最后,加入锆珠,并在密封的涂料混合器中振荡,直到细度低于15 微米。
实施例2
一种水性环氧树脂固化剂及水性环氧涂料的制备方法,其特征在于,水性环氧树脂固化剂制备流程如下:
(1)将19g三乙烯四胺和30g 1-甲氧基-2-丙醇加入到容器中,并置于85℃的恒温水浴中混合均匀得到混合溶液1。
(2)向混合溶液1中加入25g聚硅氧烷环氧树脂,搅拌3-5小时使其发生化学反应,获得聚硅氧烷环氧树脂与胺的加合物。
(3)将聚硅氧烷环氧树脂与胺的加合物的温度降至65℃,在4小时内,将15.1g双酚A型环氧树脂以及17.3g聚乙二醇二缩水甘油醚与25g 1-甲氧基-2-丙醇的混合物缓慢通过恒压分配漏斗加入65℃聚硅氧烷环氧树脂与胺的加合物得到混合溶液2。
(4)最后,将混合溶液2倒入去离子水中并保持1小时,获得水性环氧树脂固化剂。
所述聚硅氧烷环氧树脂的结构式为:
一种利用所述水性环氧树脂固化剂制备得到的水性环氧涂料,其特征在于,制备流程如下:
(a)首先,将44.17g双酚A型环氧树脂、52.28g颜料浆、1.6g二丙二醇丁基醚、0.25g水性消泡剂、0.45g润湿剂、0.4g防闪光剂、0.4g增稠剂混合均匀。
(b)然后加入所述水性环氧树脂固化剂混合均匀后脱除气泡得到水性环氧涂料。
(c)使用高压枪将水性环氧涂料喷涂到用砂纸打磨并用乙醇擦拭过的马口铁和钢板上,涂层厚度控制在60-65 mm。
(d)最后将喷涂的涂层在80℃下干燥2.5 h,并在室温下保持一天用于性能测试。
(e)将水性环氧涂料倒入PTFE模具中,并在80℃下干燥2.5小时,以获得厚度约为0.5 mm的薄膜,用于性能测试。
所述颜料浆的制备流程如下:首先,将28.8g去离子水和2g 1-甲氧基-2-丙醇放入容器中预分散5分钟;然后依次混入0.2g水性消泡剂、3g分散剂、2g云母粉、16g硫酸钡、23g二氧化钛、7g三磷酸铝、7g磷酸锌、10g滑石粉、0.2g炭黑、0.8g热解二氧化硅进行高速分散;最后,加入锆珠,并在密封的涂料混合器中振荡,直到细度低于15 微米。
制备了未改性固化剂水性环氧涂料作为对照组。
性能测试:为了表征涂料的性能,通过测试涂层和薄膜的性能来反应。
根据ASTM D3363使用了BGD 506/1铅笔硬度计评估涂层的硬度。参考标准GB/T9754,使用BGD 516/3光泽度仪测量涂层的光泽度。根据GB/T 1732,用BGD 302漆膜冲击器对漆膜的抗冲击性能进行了评估。参考标准GB/T 1731,使用薄膜弹性测试仪BGD 560测量薄膜的柔韧性。涂层的耐水性根据GB/T 1733-1993进行测量,用胶带将涂层黏附于纤维纸上,将去离子水覆盖在纤维纸涂层的顶部,放置10天,记录吸水前后的质量,纤维纸上涂层的吸水率通过以下方程计算:
表1. 实施例的硬度、光泽度、抗冲击性、柔韧性和吸水率
通过TGA测试薄膜的热稳定性以反应涂料的热稳定性,温度以10℃/min的恒定速
度从25℃上升到750℃,利用氧气用作燃烧气体,氮气用作保护和冷却气体,选取
(物质重量为50%时的温度)、(物质重量降低最快时的温度)和(物质在700℃
时的残余质量百分比)作为指标来表征热稳定性。
通过对比对照组与实施例的数据可以看出,聚硅氧烷改性固化剂制备得到的水性环氧树脂的光泽度提高、吸水率降低且热稳定性更好,并且保持优异的抗冲击性和柔韧性,且在一定范围内随着聚硅氧烷含量的增大,水性环氧涂料的性能提升更为显著。
Claims (10)
1.一种水性环氧树脂固化剂的制备方法,其特征在于,制备流程如下:
(1)将多乙烯多胺和1-甲氧基-2-丙醇加入到容器中,并置于85℃的恒温水浴中混合均匀得到混合溶液1;
(2)向混合溶液1中加入聚硅氧烷环氧树脂,搅拌3-5小时使其发生化学反应,获得聚硅氧烷环氧树脂与胺的加合物;
(3)将聚硅氧烷环氧树脂与胺的加合物的温度降至65℃,在4-6小时内,将环氧树脂以及聚乙二醇二缩水甘油醚与1-甲氧基-2-丙醇的混合物缓慢通过恒压分配漏斗加入65℃聚硅氧烷环氧树脂与胺的加合物得到混合溶液2;
(4)最后,将混合溶液2倒入去离子水中并保持1小时,获得水性环氧树脂固化剂。
2.根据权利要求1所述的一种水性环氧树脂固化剂的制备方法,其特征在于,所述多乙烯多胺为乙二胺、二乙烯三胺、三乙烯四胺和四乙烯五胺中的一种或几种。
4.根据权利要求1所述的一种水性环氧树脂固化剂的制备方法,其特征在于,所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂中的一种。
5.根据权利要求1所述的一种水性环氧树脂固化剂的制备方法,其特征在于,所述聚乙二醇二缩水甘油醚与1-甲氧基-2-丙醇的重量比为1:1-1:1.5。
6.一种利用权利要求1所述的水性环氧树脂固化剂制备得到的水性环氧涂料,其特征在于,制备流程如下:
(a)首先,将乳化型水性环氧树脂、颜料浆和其他添加剂混合均匀;
(b)然后加入所述水性环氧树脂固化剂混合均匀后脱除气泡得到水性环氧涂料;
(c)使用高压枪将水性环氧涂料喷涂到用砂纸打磨并用乙醇擦拭过的马口铁和钢板上,涂层厚度控制在60-65 mm;
(d)最后将喷涂的涂层在80℃下干燥2.5 h,并在室温下保持一天用于性能测试;
(e)将水性环氧涂料倒入PTFE模具中,并在80℃下干燥2.5小时,以获得厚度约为0.5mm的薄膜,用于性能测试。
7.根据权利要求6所述的一种水性环氧涂料,其特征在于,所述乳化型水性环氧树脂为双酚A型环氧树脂或酚醛型环氧树脂中的一种。
8.根据权利要求6所述的一种水性环氧涂料,其特征在于,所述其他添加剂包括成膜助剂、水性消泡剂、润湿剂、防闪光剂、增稠剂。
9.根据权利要求6所述的一种水性环氧涂料,其特征在于,所述颜料浆的制备流程如下:首先,将去离子水和溶剂放入容器中预分散5分钟;然后依次混入水性消泡剂、分散剂和各种填料进行高速分散;最后,加入锆珠,并在密封的涂料混合器中振荡,直到细度低于15微米。
10.根据权利要求9所述的一种水性环氧涂料,其特征在于,所述溶剂为1-甲氧基-2-丙醇,所述填料为云母粉、硫酸钡、二氧化钛、三磷酸铝、磷酸锌、滑石粉、炭黑、热解二氧化硅中的一种或几种。
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