CN106957409B - 一种水性环氧树脂固化剂 - Google Patents
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Abstract
本发明涉及一种水性环氧树脂固化剂,属涂料化工领域。该固化剂采用芳香族对位取代的二胺作为主要胺类化合物,其成分及质量比如下:对苯二胺类化合物20~30 wt%、环氧树脂10%~15 wt%、环氧活性稀释剂AGE 5~10 wt%、二乙醇胺2~3 wt%、乙酸10~15 wt%、去离子水40~50 wt%。所述水性环氧固化剂首先将二乙醇胺与环氧树脂开环制得改性环氧树脂,而后将改性环氧树脂与对苯二胺类化合物加成,中和之后滴加去离子水分散制得。本发明操作简单,反应温度低、反应过程易控制,所得的固化剂无VOCs的排放、粘度低,固化时间短。
Description
技术领域
本发明涉及一种强效水性环氧树脂固化剂,属涂料化工领域。
背景技术
环氧树脂类涂料具有优良的物理性能、机械性能、电绝缘性能,它对各种材料具有极好的粘接性能,同时其施工工艺简单灵活,所以环氧树脂类涂料在涂料领域中应用非常广泛。溶剂型环氧涂料含有大量挥发性有机物(Volatile Organic Compounds, VOCs),VOCs是造成光化学烟雾的主要原因,它会引发慢性呼吸道疾病、损伤中枢神经、刺激黏膜、致癌致畸等,所以控制VOCs的排放量势在必行。因此,国家出台了一系列政策法规来限制VOCs的排放,环氧涂料水性化是目前涂料发展的一大趋势。
固化剂是影响水性环氧涂料性能的关键因素之一。传统的溶剂型固化剂难以与水性环氧涂料混溶,所以针对水性环氧体系必须用水性环氧固化剂才能解决此问题。普通的脂肪族胺类固化剂对人体刺激较大,同时易于与空气中CO2反应生成盐,或吸收潮气泛白,因此实际使用水性环氧固化剂多为多胺与环氧树脂加成产物。但目前改性胺固化剂仍存在多种缺陷,专利CN103788343A公开了一种零VOCs水性环氧固化剂的制备方法,该法采用聚醚胺(易挥发、有毒)作为环氧树脂改性剂进而接枝在胺类化合物上,该固化剂稳定性好、粘度适中、固化物无色透明,但是耐侯性差、易变黄,其柔韧性、附着力也欠佳。
发明内容
本发明所要解决的技术问题是克服现有技术中的缺陷,提供一种以水作为溶剂,无VOCs排放的强效水性环氧树脂固化剂的制备方法。
本发明采用的技术方案是:
一种水性环氧树脂固化剂其组成及质量分数如下:环氧树脂10%~15 wt %、环氧活性稀释剂AGE 5~10 wt %、对苯二胺类化合物20~30 wt%、二乙醇胺2~3 wt %、乙酸10~15 wt%、去离子水40~50 wt %。
所述水性环氧固化剂首先将二乙醇胺与环氧树脂开环制得改性环氧树脂,而后将改性环氧树脂与对苯二胺类化合物加成,中和之后滴加去离子水分散制得。
所述水性环氧固化剂以芳香族对位取代的二胺作为主要胺类化合物,如对苯二胺、N-苯基对苯二胺、N,N-二甲基对苯二胺、N-异丙基-N’-苯基-对苯二胺、N-乙基对苯二胺、N,N-二乙基对苯二胺。更优选为对苯二胺。
所述水性环氧树脂固化剂结构式如(I)所示:
其中,R1、R2、R3、R4至少包含一个H和一个(II)
所述的水性环氧树脂固化剂,制备方法包括以下步骤:
步骤一:改性环氧树脂制备
(1)稀释:将环氧树脂与活性稀释剂AGE按上述的质量比稀释至均一透明;
(2)改性:将温度控制在80~85℃,搅拌状态下滴加二乙醇胺,控制二乙醇胺与环氧树脂摩尔比0.3~0.5,恒温反应1~2 h得到改性环氧树脂。
步骤二:固化剂制备
(1)溶解:按上述质量比例将胺类化合物与丙二醇甲醚加入到有保护气、冷凝管、搅拌装置的烧瓶中,在100~150℃下溶解呈暗红色均一透明液体;
(2)反应:缓慢滴加步骤一中改性环氧树脂,降温至90℃反应3~5 h;
(3)蒸馏:加入乙酸,恒温反应30 min,减压蒸馏出丙二醇甲醚以及多余的乙酸中和剂;
(4)稀释:搅拌状态下缓慢滴加去离子水,稀释至固含量为50%,室温分散30 min即得到强效水性环氧固化剂。
与现有技术相比,本发明具有以下优点:
本发明操作简单,反应温度低、反应过程易控制,该固化剂以水作为溶剂,无VOCs排放,粘度低(18℃,< 200 mPa·s),固化时间短(表干时间< 30 min,实干时间< 3 h),柔韧性好(≤1级),附着力好(≤1级)。
具体实施方式
下面结合具体实施例对本发明进一步详细说明。
实施例1:
一种水性环氧树脂固化剂,制备工艺如下:
步骤一:改性环氧树脂制备
(1)将100 g环氧树脂E-44与80 g环氧活性稀释剂AGE稀释30 min至均一透明;
(2)将温度控制在80~85℃,滴加二乙醇胺14 g,反应1~1.5 h;
步骤二:固化剂制备
(1)取对苯二胺100 g与20 g丙二醇甲醚在有保护气、冷凝管、搅拌装置的烧瓶中,在100℃溶解呈暗红色至均一透明液体;
(2)缓慢滴加步骤一中改性环氧树脂115 g,90℃反应3~5 h;
(3)加入冰醋酸75 g,恒温反应30 min,减压蒸馏出丙二醇甲醚以及多余的有机酸中和剂;
(4)搅拌状态下缓慢滴加215 g去离子水,室温分散30 min即得到零VOCs强效水性环氧树脂固化剂。
该水性环氧树脂固化剂外观为深红色液体;固含量50%;活泼氢当量(mol/100g):0.546;粘度(18℃):≤200 mPa•s;离心稳定性(3000r/min,30min):不分层。
实施例2:
一种水性环氧树脂固化剂制备工艺如下:
步骤一:改性环氧树脂制备
(1)将100 g环氧树脂E-51与100 g环氧活性稀释剂AGE稀释至均一透明;
(2)将温度控制在80~90℃,滴加二乙醇胺16 g,反应1~1.5 h;
步骤二:固化剂制备
(1)取N-苯基对苯二胺150 g与30 g丙二醇甲醚在有保护气、冷凝管、搅拌装置的烧瓶中,在150℃溶解呈暗红色至均一透明液体;
(2)缓慢滴加步骤一中改性环氧树脂100 g,8 0℃反应3~5 h;
(3)加入冰醋酸50 g,恒温反应30 min,减压蒸馏出丙二醇甲醚以及多余的有机酸中和剂;
(4)搅拌状态下缓慢滴加250 g去离子水,室温分散30 min即得到零VOCs强效水性环氧树脂固化剂。
该水性环氧树脂固化剂外观为深红色液体;固含量50%;活泼氢当量(mol/100g):0.546;粘度(18℃):≤200 mPa•s;离心稳定性(3000r/min,30min):不分层。
Claims (1)
1.一种水性环氧树脂固化剂,其特征在于:所述水性环氧树脂固化剂结构式如(I)所示:
其中,R1、R2、R3、R4至少包含一个H和一个(II)
所述的水性环氧树脂固化剂,其原料及质量比如下:
环氧树脂10%~15wt%、环氧活性稀释剂AGE 5~10wt%、对苯二胺类化合物20~30wt%、二乙醇胺2~3wt%、乙酸10~15wt%、去离子水40~50wt%;
所述的水性环氧树脂固化剂,其制备方法包括如下步骤:
步骤一:改性环氧树脂制备
将环氧树脂与活性稀释剂AGE按上述的质量比稀释至均一透明;将温度升至85℃,搅拌状态下滴加二乙醇胺,控制二乙醇胺与环氧树脂摩尔比0.3~0.5,恒温反应1~2h得到改性环氧树脂;
步骤二:固化剂制备
(1)溶解:按上述质量比例将胺类化合物与丙二醇甲醚加入到有保护气、冷凝管、搅拌装置的烧瓶中,在100~150℃下溶解呈暗红色均一透明液体;
(2)反应:缓慢滴加步骤一中改性环氧树脂,降温至90℃反应3~5h;
(3)蒸馏:加入乙酸,恒温反应30min,减压蒸馏出丙二醇甲醚以及多余的乙酸中和剂;
(4)稀释:搅拌状态下缓慢滴加去离子水,稀释至固含量为50%,室温分散30min即得到水性环氧固化剂;
所述的对苯二胺类化合物为对苯二胺。
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