CN1138823C - 水分散型聚异氰酸酯交联剂 - Google Patents
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Abstract
本发明涉及一种交联剂，尤其是涉及一种水性双组份聚氨酯涂料用可水分散型聚氨酯交联剂及其制备方法。本发明是将平均异氰酸官能度为2.5-5的聚异氰酸酯，分子量为300-800的多乙二醇单烷基醚，其加入量为聚异氰酸酯重量的10-25%，在一定温度条件下进行化学反应而得，其中含有稀释剂，稀释剂占交联剂重量的10-50%。与水性羟基树脂组分配合的涂料有涂膜不易起泡、高光泽、表干时间快等特点。
Description
本发明水分散型聚异氰酸酯交联剂涉及一种交联剂，尤其是涉及一种用于水性双组份聚氨酯涂料的可水分散型聚氨酯交联剂及其制备方法。
传统涂料以溶剂型涂料为主，涂料中的挥发性有机化合物的排放对人体及环境都有害，随着环保意识的增强和环保法规的建立，传统溶剂型涂料愈来愈受到限制，因此，低污染环保型的水性涂料已成为涂料开发的方向；同时，水性涂料己在很多方面得到应用，但是，只有在其涂膜进行交联固化后，才能具备与溶剂型涂料相当的涂膜性能，如耐水性、耐溶剂性、耐化学品性、耐磨性等，故其交联剂交联特性的优劣直接影响涂料的质量，现有的交联剂如溶剂型双组份聚氨酯涂料中使用的聚异氰酸酯交联剂，不论是芳香族还是脂肪族和脂环族异氰酸酯都很难直接乳化或分散于水中，在水性双组份聚氨酯涂料中要对其进行化学改性，通过引入亲水性官能团来改善聚异氰酸酯的亲水性，以使其易于在水中乳化或分散，从而保持一定的稳定性。美国专利No.4,433,095制备了水分散型芳香族聚异氰酸酯交联剂，美国专利No.4,633,377制备了水分散型脂肪族脂环族聚异氰酸酯交联剂，其都是利用异氰酸官能团和多乙二醇单烷基醚或多乙二醇和多丙二醇共聚物的单烷基醚进行化学反应而保持其亲水性，以上的缺点一是亲水性差、在水中不稳定，常需使用较大量的有机溶剂，如醚类和醚酯类溶剂来稀释才能分散；另外，由于使用较高分子量的多乙二醇单烷基醚是固体，也导致改性的聚异氰酸酯为固体，造成使用上的困难。美国专利No.3,996,154和英国专利No.1,417,618和No.1,444,933使用较低分子量的多乙二醇单烷基醚主要用来改性芳香族聚异氰酸酯，但是，由于芳香族聚异氰酸酯官能团和水的反应很快，其放出的二氧化碳极易使涂膜起泡，用于水性双组分聚氨酯涂料是不适宜的，只能用于水性胶粘剂使用。美国专利No.5,200,489和No.5,252,696虽然使用了低分子量的多乙二醇单烷基醚来改性脂肪族和脂环族聚异氰酸酯，但由于其粘度较大，分散于水中较困难，与水性羟基树脂相容性差，造成涂膜光泽不高，及其它涂膜性能不佳。针对以上问题，本发明在充分考虑多乙二醇单烷基醚的分子量大小、加入量以及所得改性聚异氰酸酯的适宜分散粘度等影响因素，发明了一种适用于水性涂料的交联剂。
本发明的目的在于：提供一种适用于水性双组分涂料的水分散型聚异氰酸酯交联剂及其制备方法，该交联剂不但有好的水分散性，在双组分涂料中还有好的成膜性。
本发明的目的可通过下述技术方案实现：一种水分散型聚异氰酸酯交联剂，包括聚异氰酸酯、多乙二醇单烷基醚，特点是；聚异氰酸酯的平均异氰酸官能度为2.5-5；多乙二醇单烷基醚的分子量为300-800，其加入量为聚异氰酸酯重量的10-25％，其中，烷基可以是甲基、乙基、丙基、丁基或其异构体；有机稀释剂为芳香烃、酮、酯、醚或醚酯类有机溶剂，或以上溶剂不同比例之混合物，如甲苯、二甲苯、丙酮、丁酮、醋酸乙酯、醋酸丁酯、二丙二醇二甲醚醋酸酯、丙二醇甲醚醋酸酯等，稀释剂占交联剂重量的10-50％。使本发明具有粘度适宜，在水中分散效果好，与水性羟基树脂相容性好，提高涂膜性能的特性。
在上述技术方案基础上，本发明所述聚异氰酸酯包括：已二异氰酸酯、异佛尔酮二异氰酸酯、二环已基甲烷二异氰酸酯、四甲基苯二亚甲基二异氰酸酯的缩二脲、二聚体、三聚体、加成物中的一种或一种以上的混合物。
在上述技术方案基础上，本发明水分散型聚异氰酸酯交联剂制备工艺如下：聚异氰酸酯与多乙二醇单烷基醚两组分在30-100℃条件下进行化学反应至异氰酸含量不再发生变化，在反应中可加入少许催化剂，如二丁基锡等，待反应完全，再加入稀释剂调合成粘度适宜的交联剂。
在上述技术方案基础上，本发明水分散型聚异氰酸酯交联剂制备工艺如下：聚异氰酸酯、多乙二醇单烷基醚和稀释剂混合后，要在30-100℃条件下进行化学反应至异氰酸含量不再发生变化为止。
本发明的优越性在于；粘度适宜，与水相容性好，本发明产品与水性羟基树脂组分配合成的涂料具有涂膜不易起泡、高光泽、表干时间快，易在短时间内复涂的特点。
下面通过实例详述。
实施例：在反应釜中第一步分别加入：100份重量的聚异氰酸酯，本实施例中选用IPDI三聚体25份重量分子量为650的多乙二醇单丁醚和少量二月桂酸二丁基锡催化剂。第二步将反应釜中各组份搅拌均匀，升温至60℃，在此温度条件下反应约4小时，加入75份重量的丙二醇甲醚醋酸酯稀释后出料即成水分散型聚异氰酸酯交联剂。
应用例：在固含量为35％、羟基含量1.5％的水性羟基聚氨酯分散液中，按NCO∶OH＝1.5∶1的比例加入上述实施例中制备的水分散型聚异氰酸酯交联剂，手动搅拌均匀，加入水稀释至涂刷适宜的粘度，按中华人民共和国家标准制板和进行涂膜性能测试，结果如下：
涂膜外观： 平整光滑
光泽(60°)： 98 GB1743-79
耐水： 120小时无变化 GB/T1733-93
铅笔硬度： 2H GB/T6739-1966
耐磨(750g/500r)： 10mg GB1768-79
表干时间 10min. GB6753.2-86
Claims (4)
1，一种水分散型聚异氰酸酯交联剂，包括聚异氰酸酯、多乙二醇单烷基醚，其特征在于：聚异氰酸酯的平均异氰酸官能度为2.5-5；多乙二醇单烷基醚的分子量为300-800，其加入量为聚异氰酸酯重量的10-25％，其中，烷基可以是甲基、乙基、丙基、丁基或其异构体；有机稀释剂，包括了芳香烃、酮、酯、醚、醚酯类有机溶剂，稀释剂占交联剂重量的10-50％。
2，根据权利要求1所述的水分散型聚异氰酸酯交联剂，其特征在于：所述聚异氰酸酯为己二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、四甲基苯二亚甲基二异氰酸酯的缩二脲、二聚体、三聚体、加成物中的一种或一种以上的混合物。
3，根据权利要求1或2所述的水分散型聚异氰酸酯交联剂的制备工艺，其特征在于：将聚异氰酸酯与多乙二醇单烷基醚两组分在30-100℃条件下进行化学反应至异氰酸含量不再发生变化，然后，再加入稀释剂。
4，根据权利要求1或2所述的水分散型聚异氰酸酯交联剂的制备工艺，其特征在于：聚异氰酸酯、多乙二醇单烷基醚和稀释剂混合后，在30-100℃条件下进行化学反应至异氰酸含量不再发生变化为止。
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| CN101619128B (zh) * | 2009-07-31 | 2011-12-21 | 中国科学院广州化学研究所 | 酰胺封端非离子型水性异氰酸酯及其制备方法与应用 |
| CN106967229A (zh) * | 2017-03-30 | 2017-07-21 | 广元瑞峰新材料有限公司 | 一种异氰酸酯交联促进剂的制备方法 |
| CN109467671B (zh) * | 2017-09-08 | 2020-12-18 | 乐陵思盛聚合物材料有限公司 | 水性聚异氰酸酯固化剂的制备 |
| CN108587112A (zh) * | 2018-04-13 | 2018-09-28 | 上海浩登材料股份有限公司 | 一种水性芳香族聚异氰酸酯交联剂及其制备方法 |
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