CN114656615A - 一种水性阳离子型聚氨酯固化剂 - Google Patents
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Abstract
本发明涉及一种水性阳离子型聚氨酯固化剂，以重量计的原料配方组成如下：50～60份异氰酸酯单体、10～20份二元醇醚溶剂、0.1～0.3份催化剂、14～22份二羟基的季铵盐化合物、20～30份水溶性非质子溶剂、0.05～0.5份阻聚剂。本发明的优点为：(1)以季铵盐阳离子为水性化基团，所述的固化剂水溶性好；(2)使用的二元醇醚溶剂、水溶性非质子溶剂为水溶性溶剂，同时有助于聚氨酯双组份木器漆的成膜；(3)所述固化剂能够有效提高水性聚氨酯木器漆的硬度和耐水性能，应用前景广泛。
Description
技术领域
本发明涉及一种水性固化剂，尤其涉及到一种水性阳离子型聚氨酯固化剂，属于水性合成技术领域。
技术背景
出于对环境保护与成本效益的综合考虑，促使越来越多的化学工作者致力于开发既能减少VOC排放，又不影响树脂性能的新型涂料。因此，涂料的水性化成为了一种重要手段。水性聚氨酯是以水代替有机溶剂作为分散介质的新型聚氨酯体系，其以水为溶剂，无污染，安全可靠，粘度低，易于施工，机械性能优良，相容性好，易于改性。水性聚氨酯可广泛应用于胶粘剂、涂料、油墨、织物涂层与整理剂等领域。
水性聚氨酯可以以单组份和双组份形式使用。双组分水性聚氨酯主要由水性聚氨酯多元醇组分和多异氰酸酯固化剂构成，固化剂组分的选择对于聚氨酯的性能有重要影响。用于双组分水性聚氨酯的固化剂分为两类：未改性的多异氰酸酯和亲水改性的多异氰酸酯。与未改性的多异氰酸酯相比，亲水改性的多异氰酸酯与水性聚氨酯多元醇组分相容性好，易均匀混合，具有良好的固化效率。但是，在双组份水性聚氨酯混合中，由于异氰酸根可与水发生副反应，而且该反应比较剧烈，在双组份聚氨酯混合成膜过程中这个副反应的反应程度直接影响最终材料或胶膜的性能。
中国专利CN201110060585.2公开了一种水性聚氨酯固化剂和与该水性聚氨酯固化剂搭配使用的水性聚氨酯分散体，该水性聚氨酯的原料配方，按质量百分比计，由70～73％的异佛尔酮二异氰酸酯、8～9％的聚乙二醇单丁醚、0.1～0.5％的2、4、6-三(二甲氨基甲基)苯酚和18～21％的丙酮组成。该发明的水性聚氨酯分散体和水性聚氨酯固化剂可实现水性聚氨酯涂料的高性能，其漆膜的各项性能指标与油性类相当；同时使用IPDI二异氰酸脂提高了成漆漆膜的硬度，又由于使用水作为稀释溶剂，大大降低了有害溶剂的释放同时通过控制反应的进行，减少有害游离的单体二异氰酸脂的含量，使产品做到了低毒或无毒，是环境友好型产品。但该发明仍然含有非活性有机溶剂丙酮，未真正做到完全无溶剂。
发明内容
本发明旨在提供一种水性阳离子型聚氨酯固化剂。
本发明所述的的一种水性阳离子型聚氨酯固化剂，采用季铵盐阳离子改性，具有易水性化的特点，以TDI为例，其分子结构式如下所示：
为克服现有技术的缺点和不足，所述的一种水性阳离子型聚氨酯固化剂，以重量计的原料配方组成如下：50～60份异氰酸酯单体、10～20份二元醇醚溶剂、0.1～0.3份催化剂、14～22份二羟基的季铵盐化合物、20～30份水溶性非质子溶剂、0.05～0.5份阻聚剂。
本发明采取以下技术方案，所述的水性阳离子型聚氨酯固化剂，其制备方法包括以下步骤：
将异氰酸酯单体、二元醇醚溶剂加入到反应装置中，开启搅拌、通氮气并加热至70～90℃反应2～4h后，然后加入总重50％～70％的催化剂，保温继续反应，每小时测量体系-NCO百分含量，当体系达到目标-NCO百分含量为20％～10％后，即得异氰酸酯三聚体；70～90℃条件下向上述异氰酸酯三聚体中加入二羟基的季铵盐化合物、水溶性非质子溶剂、总重30％～50％的催化剂，保温搅拌反应至-NCO百分含量为13％～7％，立即降温至20℃，并加入阻聚剂，即得固含为55％～75％的水性阳离子型聚氨酯固化剂。
所述的异氰酸酯单体为芳香族异氰酸酯、脂肪族异氰酸酯、脂环族异氰酸酯，进一步地，优选为TDI、MDI、NDI、TODI、HDI、TMDI、XDI、IPDI、HMDI、HTDI中至少一种。
所述的二元醇醚溶剂为二乙二醇二甲醚、二丙二醇二甲醚、二乙二醇二丁醚、二乙二醇二丁醚、聚乙二醇单丁醚(分子量200～800)中的至少一种。
所述的催化剂为二月桂酸二丁基锡、辛酸亚锡、环烷酸锡、环烷酸铅或环烷酸钴、马来酸二丁基锡、二乙酸二丁基锡、三乙胺、K-1000、苯甲基缩水甘油醚中的至少一种。
所述的二羟基的季铵盐化合物为2,3-二羟基丙基三甲基铵氯化物、2,3-二羟基丙基三乙醇铵氯化物、2,3-二羟基丙基三乙基铵氯化物、3,4-二羟基丁基基三甲基铵氯化物、3,4-二羟基丁基基三乙基铵氯化物、3,4-二羟基丁基基三乙醇铵氯化物中的至少一种。
所述的水溶性非质子溶剂为N-甲基吡咯烷酮、N-乙烯基吡咯烷酮、N-乙基吡咯烷酮中的至少一种。
所述的阻聚剂为苯甲酰氯、磷酸氢盐、磷酸中的至少一种。
本发明的制备原理为：首先在催化剂作用下制备出异氰酸酯三聚体，然后两个异氰酸酯三聚体与二羟基的季铵盐化合物反应，生成所述的阳离子型聚氨酯固化剂；所述的相对于现有技术，本发明的优点为：(1)首次公开了水性阳离子型聚氨酯固化剂，以季铵盐阳离子为水性化基团，所述的固化剂水溶性好；(2)使用的二元醇醚溶剂、水溶性非质子溶剂为水溶性溶剂，同时与异氰酸酯单体相溶性好，同时有助于聚氨酯双组份木器漆的成膜；(3)所述固化剂含有4个异氰酸酯基团，有效提高水性聚氨酯木器漆的硬度和耐水性能，应用前景广泛。
具体实施方式
下面结合实施例对本发明的一种水性阳离子型聚氨酯固化剂做进一步的描述。可以理解的是，此处所描述的具体实施例仅仅用于解释相关发明，而非对该发明的限定。
实施例1
一种水性阳离子型聚氨酯固化剂，以重量计的原料配方组成如下：60份IPDI、20份二乙二醇二甲醚、0.1份二乙酸二丁基锡、22份2,3-二羟基丙基三乙基铵氯化物、30份N-甲基吡咯烷酮、0.05份苯甲酰氯。
本实施例中所述的水性阳离子型聚氨酯固化剂，其制备方法包括以下步骤：
将IPDI、二乙二醇二甲醚加入到反应装置中，开启搅拌、通氮气并加热至70℃反应4h后，然后加入总重50％的二乙酸二丁基锡，保温继续反应，每小时测量体系-NCO百分含量，当体系达到目标-NCO百分含量为10％后，即得异氰酸酯三聚体；70℃条件下向上述异氰酸酯三聚体中加入2,3-二羟基丙基三乙基铵氯化物、N-甲基吡咯烷酮、总重50％的二乙酸二丁基锡，保温搅拌反应至-NCO百分含量为7％，立即降温至20℃，并加入苯甲酰氯，即得固含为60.5％的水性阳离子型聚氨酯固化剂。
实施例2
一种水性阳离子型聚氨酯固化剂，以重量计的原料配方组成如下：50份TDI、10份二丙二醇二甲醚、0.3份二月桂酸二丁基锡、14份3,4-二羟基丁基基三乙基铵氯化物、20份水溶性非质子溶剂、0.5份阻聚剂。
本实施例中所述的水性阳离子型聚氨酯固化剂，其制备方法包括以下步骤：
将TDI、二丙二醇二甲醚加入到反应装置中，开启搅拌、通氮气并加热至90℃反应2h后，然后加入总重70％的二月桂酸二丁基锡，保温继续反应，每小时测量体系-NCO百分含量，当体系达到目标-NCO百分含量为20％％后，即得异氰酸酯三聚体；90℃条件下向上述异氰酸酯三聚体中加入3,4-二羟基丁基基三乙基铵氯化物、N-乙烯基吡咯烷酮、总重30％的二月桂酸二丁基锡，保温搅拌反应至-NCO百分含量为13％，立即降温至20℃，并加入磷酸氢钠，即得固含为68.4％的水性阳离子型聚氨酯固化剂。
实施例3
一种水性阳离子型聚氨酯固化剂，以重量计的原料配方组成如下：54份MDI、16份聚乙二醇单丁醚、0.18份马来酸二丁基锡、20份2,3-二羟基丙基三乙基铵氯化物、25份N-甲基吡咯烷酮、0.12份苯甲酰氯。
本实施例中所述的水性阳离子型聚氨酯固化剂，其制备方法包括以下步骤：
将MDI、聚乙二醇单丁醚加入到反应装置中，开启搅拌、通氮气并加热至80℃反应2.5h后，然后加入总重60％的马来酸二丁基锡，保温继续反应，每小时测量体系-NCO百分含量，当体系达到目标-NCO百分含量为13％后，即得异氰酸酯三聚体；80℃条件下向上述异氰酸酯三聚体中加入2,3-二羟基丙基三乙基铵氯化物、N-甲基吡咯烷酮、总重40％的马来酸二丁基锡，保温搅拌反应至-NCO百分含量为9％，立即降温至20℃，并加入苯甲酰氯，即得固含为64.4％的水性阳离子型聚氨酯固化剂。
将实施例1、2、3中水性阳离子型聚氨酯固化剂、市售水性固化剂与市售聚氨酯木器漆按照相同比例，在使用前2h充分分散均匀，同时与不添加固化剂聚氨酯作对比，喷涂于木器表面后，附着力按照GB/T1720-1988的规定，硬度按照GB/T6739-2006色漆和清铅笔法测定漆膜硬度，耐冲击性按照GB/T1732-2007的规定进行检测，耐水性按照GB/T1733-93的规定进行检测，性能参数如下表：
Claims (8)
1.一种水性阳离子型聚氨酯固化剂，其特征在于，它以季铵盐阳离子为水性化基团，以TDI为例，其分子结构式如下所示：
所述的水性阳离子型聚氨酯固化剂，以重量计的原料配方组成如下：50～60份异氰酸酯单体、10～20份二元醇醚溶剂、0.1～0.3份催化剂、14～22份二羟基的季铵盐化合物、20～30份水溶性非质子溶剂、0.05～0.5份阻聚剂。
2.根据权利要求1所述的一种水性阳离子型聚氨酯固化剂，其特征在于，所述的水性阳离子型聚氨酯固化剂，其制备方法包括以下步骤：
将异氰酸酯单体、二元醇醚溶剂加入到反应装置中，开启搅拌、通氮气并加热至70～90℃反应2～4h后，然后加入总重50％～70％的催化剂，保温继续反应，每小时测量体系-NCO百分含量，当体系达到目标-NCO百分含量为20％～10％后，即得异氰酸酯三聚体；70～90℃条件下向上述异氰酸酯三聚体中加入二羟基的季铵盐化合物、水溶性非质子溶剂、剩余的催化剂，保温搅拌反应至-NCO百分含量为13％～7％，立即降温至20℃，并加入阻聚剂，即得固含为55％～75％的水性阳离子型聚氨酯固化剂。
3.根据权利要求1所述的一种水性阳离子型聚氨酯固化剂，其特征在于，所述的异氰酸酯单体为芳香族异氰酸酯、脂肪族异氰酸酯、脂环族异氰酸酯，进一步地，优选为TDI、MDI、NDI、TODI、HDI、TMDI、XDI、IPDI、HMDI、HTDI中至少一种。
4.根据权利要求1所述的一种水性阳离子型聚氨酯固化剂，其特征在于，所述的二元醇醚溶剂为二乙二醇二甲醚、二丙二醇二甲醚、二乙二醇二丁醚、二乙二醇二丁醚、聚乙二醇单丁醚(分子量200～800)中的至少一种。
5.根据权利要求1所述的一种水性阳离子型聚氨酯固化剂，其特征在于，所述的催化剂为二月桂酸二丁基锡、辛酸亚锡、环烷酸锡、环烷酸铅、环烷酸钴、马来酸二丁基锡、二乙酸二丁基锡、三乙胺、K-1000、苯甲基缩水甘油醚中的至少一种。
6.根据权利要求1所述的一种水性阳离子型聚氨酯固化剂，其特征在于，所述的二羟基的季铵盐化合物为2,3-二羟基丙基三甲基铵氯化物、2,3-二羟基丙基三乙醇铵氯化物、2,3-二羟基丙基三乙基铵氯化物、3,4-二羟基丁基基三甲基铵氯化物、3,4-二羟基丁基基三乙基铵氯化物、3,4-二羟基丁基基三乙醇铵氯化物中的至少一种。
7.根据权利要求1所述的一种水性阳离子型聚氨酯固化剂，其特征在于，所述的水溶性非质子溶剂为N-甲基吡咯烷酮、N-乙烯基吡咯烷酮、N-乙基吡咯烷酮中的至少一种。
8.根据权利要求1所述的一种水性阳离子型聚氨酯固化剂，其特征在于，所述的阻聚剂为苯甲酰氯、磷酸氢钠、磷酸中的至少一种。
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