CN115521437A - 一种水溶性紫外光固化超支化聚氨酯丙烯酸树脂的制备方法 - Google Patents
一种水溶性紫外光固化超支化聚氨酯丙烯酸树脂的制备方法 Download PDFInfo
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- CN115521437A CN115521437A CN202211216494.8A CN202211216494A CN115521437A CN 115521437 A CN115521437 A CN 115521437A CN 202211216494 A CN202211216494 A CN 202211216494A CN 115521437 A CN115521437 A CN 115521437A
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- diisocyanate
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Abstract
本发明属水溶性聚氨酯技术领域，具体公开了一种水溶性紫外光固化超支化聚氨酯丙烯酸树脂的制备方法。具体制备过程如下：（1）将二异氰酸酯、聚醚二元醇、二羟甲基丙酸、烷基二元醇进行化学反应合成异氰酸酯基封端的齐聚物；（2）再依次与（甲基）丙烯酸羟基烷基酯、端羟基超支化聚酯反应，得到紫外光固化超支化聚氨酯；（3）加入活性稀释剂，经胺中和、乳化和去离子水稀释后，即可得到固含量为40‑60%的水溶性紫外光固化超支化聚氨酯丙烯酸树脂。本发明工艺简单，易产业化，产品具有VOC含量低、不含有机溶剂、水可稀释、稳定性优异等优点，可望在水溶性涂料等领域得到广泛应用。
Description
技术领域
本发明涉及水溶性聚氨酯技术领域，具体涉及一种水溶性紫外光固化超支化聚氨酯丙烯酸树脂的制备方法。
背景技术
水溶性聚氨酯是水可分散的新型聚氨酯体系，也称水分散聚氨酯、水系聚氨酯或水基聚氨酯。水溶性聚氨酯以水为溶剂，具有环保无污染、施工安全可靠、机械性能优良、相容性好、易于改性、与其它水溶性树脂相容性优异等优点。水溶性聚氨酯涂料是以水溶性聚氨酯树脂为基料、辅于其它助剂制得的一类环保涂料，广泛用于表面涂覆、涂装等领域，因交联密度不高，所得涂层的铅笔硬度、附着力等机械性能不高，而通过交联改性的水溶性聚氨酯涂料可提高交联密度，因此具有良好的贮存稳定性、高机械性能、高耐水性、优异的耐溶剂性及耐老化性能，因此可用于先进涂层材料领域。交联改性的手段(丙烯酸、环氧等)决定了水溶性聚氨酯的固化形式(热固化、光固化)，最后影响产品的固化效率及其应用领域，与热交联固化相比，紫外光固化具有固化时间短、效率高、膜性能均匀等优异特点，已经成为水溶性聚氨酯涂料的一个重要发展方向。
超支化聚合物具有椭球形的拓扑结构，展现出优异的流变性能、低粘度、高活性等优点，近年来，已经成为高分子材料领域研究的热点。将传统线性聚氨酯设计为超支化拓扑结构的聚氨，不仅具有传统聚氨酯的优异性能，又具有高度支化的拓扑结构的优异性质，如末端大量活性基团，使其改性更加容易，交联密度高、机械性能优异，使其具有极其广润的应用前景。紫外光固化技术具有固化速度快、无污染，固化产品光泽度高等优点，在涂料领域已经得到广泛应用。
现有超支化聚氨酯的合成大多直接用二官能度的异氰酸酯与三羟基化合物为主要原料来制备，表面上看，一步法可以完成，方法和工艺过程简单，但三羟基化合物的三个羟基的活性相近，合成过程中容易凝胶，难于合成性能稳定的超支化聚氨酯，加大了后续水溶性改性和紫外光固化改性的难度和产业化。为解决这一难题，开发工艺简单、无挥发、无污染、低成本、能产业化及规模化应用的紫外光固化水溶性聚氨酯的合成技术是解决目前该领域存在问题的根本途径。
发明内容
为了解决现有技术中存在的不足，本发明提供了一种水溶性紫外光固化超支化聚氨酯丙烯酸树脂的制备方法。
本发明以如下技术方案解决上述技术问题：
一种水溶性紫外光固化超支化聚氨酯丙烯酸树脂的制备方法，具体过程如下：
(1)将二异氰酸酯、聚醚二元醇、二羟甲基丙酸、烷基二元醇和催化剂加到反应瓶中，在40-80℃的条件下搅拌反应1-3小时，得到两端为异氰酸酯基的齐聚物；
(2)向反应瓶中加入含约0.1wt％阻聚剂对羟基苯甲醚的(甲基)丙烯酸羟基烷基酯，在50-90℃的条件下搅拌反应1-3小时，得到一端为异氰酸酯基、一端为丙烯酸酯基的齐聚物；
(3)向反应瓶中加入端羟基超支化聚酯，在50-90℃的条件下搅拌反应2-4小时至异氰酸酯基反应完全，即得到紫外光固化超支化聚氨酯，相应的化学反应式如下：
紫外光固化超支化聚氨酯的反应式
(4)降温至30-50℃，向其中加入活性稀释剂，然后加入胺类中和剂中和至pH值为6.8～7.5，再加入乳化剂，最后逐步加入去离子水，在搅拌速率为500-1000rpm的条件下乳化0.5-2小时，即得到固含量为40-60％的水溶性紫外光固化超支化聚氨酯丙烯酸树脂；
所述(甲基)丙烯酸羟基烷基酯为丙烯酸羟基烷基酯和/或甲基丙烯酸羟基烷基酯。
进一步的，所述的催化剂为二月桂酸二丁基锡、二(十二烷基硫)二丁基锡、二醋酸二丁基锡、辛酸亚锡中的一种或多种，用量为二异氰酸酯总质量的0.05％-0.5％，优选为0.05％-0.2％。
进一步的，所述的二异氰酸酯、聚醚二元醇、二羟甲基丙酸、烷基二元醇、(甲基)丙烯酸羟基烷基酯、端羟基超支化聚酯的摩尔比为(1.0～2.0)：(0.1-0.5)：(0.5-1.2)：(0.1-0.5)：(0.01-0.6)：(0.01-0.6)。
进一步的，所述的二异氰酸酯为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、1,6-己二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、二环己基甲烷二异氰酸酯(HMDI)、赖氨酸二异氰酸酯(LDI)、苯二亚甲基二异氰酸酯(XDI)中的一种或多种。
进一步的，所述的聚醚二元醇为市售的聚四氢呋喃、聚丙二醇、聚乙二醇中的一种或多种，它们的数均分子量在400-20000g/mol。
进一步的，所述的烷基二元醇为市售的烷基碳原子为2-6个的二元醇中的一种或多种，优选为丁二醇、丙二醇、一缩二乙二醇中的一种或多种。
更进一步的，所述的(甲基)丙烯酸羟基烷基酯为丙烯酸羟基乙基酯(HEA)、丙烯酸羟基丙基酯(HPA)、甲基丙烯酸羟基乙基酯(HEMA)、甲基丙烯酸羟基丙基酯(HPMA)、丙烯酸-4-羟基丁基酯(HBA)、甲基丙烯酸-2-羟基丁基酯(HBMA)中的一种或多种。
进一步的，所述端羟基超支化聚酯为武汉超支化树脂科技有限公司的HyPerH101、HyPer H102、HyPer H103、HyPer H104、HyPer H201、HyPer H202、HyPer H203和HyPerH204中的一种或多种，端羟基超支化聚酯的数均分子量为500～5400g/mol，羟值为490～670mgKOH/g。它们的性质如表1所示。
表1端羟基超支化聚酯的性质
| 产品名称 | 羟值，mgKOH/g | 数均分子量，g/mol |
| HyPer H101 | 670 | 500 |
| HyPer H102 | 600 | 1100 |
| HyPer H103 | 560 | 2400 |
| HyPer H104 | 520 | 5200 |
| HyPer H201 | 550 | 600 |
| HyPer H202 | 520 | 1200 |
| HyPer H203 | 500 | 2600 |
| HyPer H204 | 490 | 5400 |
进一步的，所述的活性稀释剂为三官能度及以上的(甲基)丙烯酸酯中的一种或多种，用量为最终水溶性紫外光固化超支化聚氨酯丙烯酸树脂总质量的5％-20％。
更进一步的，所述活性稀释剂为三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯中的一种或多种。
进一步的，所述乳化剂为琥珀酸二异辛酯磺酸钠、十二烷基聚氧乙烯醚硫酸钠、十二烷基磺酸钠、十六烷基磺酸钠和十二烷基苯磺酸钠中的一种或多种，用量为最终水溶性紫外光固化超支化聚氨酯丙烯酸树脂总质量的0.5％-2％。
进一步的，所述胺类中和剂为三乙醇胺、二乙醇胺、甲基二乙醇胺、N,N-二甲基乙醇胺、三乙胺、氨水中的一种或多种。
本发明制备的水溶性紫外光固化超支化聚氨酯丙烯酸树脂与现有技术的产品相比具有以下优点：
(1)先合成异氰酸酯的齐聚物，再用端羟基超支化聚酯进行改性，整个过程不涉及多官能团之间的反应，没有凝胶过程产生，反应条件容易控制，产品质量稳定，容易产业化；
(2)端羟基超支化聚酯具有椭球的拓扑结构，制备的超支化聚氨酯粘度低、粒径小、固含量高，反应过程中不使用有机溶剂，不仅降低了VOC含量和有机溶剂的污染，还减少了除去有机溶剂的繁琐过程，降低了生产成本；
(3)超支化的拓扑结构可有效提高涂料的流平性能，可在不加有机溶剂条件下制备薄涂涂料；
(4)体系中，多官能度活性稀释剂可与超支化聚氨酯表面的(甲基)丙烯酸酯基团在紫外光固化过程中进行交联，进一步提高交联密度、硬度和附着力；
(5)此工艺简单，乳化的转速较低，有利于工业化应用。
附图说明
图1为实施例5制备的水溶性紫外光固化超支化聚氨酯丙烯酸树脂的粒径分布图。
具体实施方式
下面结合实施例对本发明的具体实施方式作进一步说明。在此需要说明的是，对于这些实施方式的说明用于帮助理解本发明，但并不构成对本发明的限定。此外，下面所描述的本发明各个实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互组合。
以下所有实施例中：
所用的端羟基超支化聚酯均采购自武汉超支化树脂科技有限公司，具体性质见发明内容中的表1。
所用聚醚多元醇、二异氰酸酯等其它原材料均为市售产品。
实施例1
将甲苯二异氰酸酯(0.1mol，17.4g)、分子量为400g/mol的聚乙二醇(0.03mol，12.0g)、二羟甲基丙酸(0.05mol，6.7g)、丁二醇(0.01mol，0.9g)和0.02g二月桂酸二丁基锡加到反应瓶中，在40℃的条件下搅拌反应3小时；然后向反应瓶中加入含约0.1wt％阻聚剂对羟基苯甲醚的丙烯酸羟乙酯(0.01mol，1.16g)，在50℃的条件下搅拌反应3小时；再向反应瓶中加入0.01mol(5.0g)端羟基超支化聚酯HyPer H101，在50℃的条件下搅拌反应约4小时至异氰酸酯基反应完全，即得到紫外光固化超支化聚氨酯；降温至30℃，向其中加入5.0g活性稀释剂三羟甲基丙烷三丙烯酸酯，接着加入三乙醇胺中和至pH值为6.8，再加入0.5g乳化剂琥珀酸二异辛酯磺酸钠，逐步加入50.0g去离子水，加完后在搅拌速率为500rpm的条件下乳化2小时，即得到固含量约50％的水溶性紫外光固化超支化聚氨酯丙烯酸树脂100g。
实施例2
将二苯基甲烷二异氰酸酯(0.2mol，50.0g)、分子量为1000g/mol的聚四氢呋喃(0.05mol，50.0g)、二羟甲基丙酸(0.12mol，16.08g)、乙二醇(0.02mol，1.24g)和0.025g二(十二烷基硫)二丁基锡加到反应瓶中，在60℃的条件下搅拌反应2小时；接着向反应瓶中加入含约0.1wt％阻聚剂对羟基苯甲醚的丙烯酸羟基丙酯(0.01mol，1.30g)，在70℃的条件下搅拌反应2小时；再向反应瓶中加入0.01mol(24.0g)端羟基超支化聚酯HyPer H103，在70℃的条件下搅拌反应约3小时至异氰酸酯基反应完全，即得到紫外光固化超支化聚氨酯；降温至40℃，向其中加入48.0g活性稀释剂季戊四醇三丙烯酸酯，接着加入甲基二乙醇胺中和至pH值为7.0，再加入10.0g乳化剂十二烷基磺酸钠，逐步加入300.0g去离子水，加完后在搅拌速率为700rpm的条件下乳化1小时，即得到固含量约40％的水溶性紫外光固化超支化聚氨酯丙烯酸树脂500g。
实施例3
将异佛尔酮二异氰酸酯(0.18mol，40.0g)、分子量为6000g/mol的聚乙二醇(0.01mol，60.0g)、二羟甲基丙酸(0.06mol，8.04g)、丙二醇(0.05mol，3.8g)和0.025g二醋酸二丁基锡加到反应瓶中，在80℃的条件下搅拌反应1小时；接着向反应瓶中加入含约0.1wt％阻聚剂对羟基苯甲醚的甲基丙烯酸羟基乙基酯(0.06mol，7.80g)，在90℃的条件下搅拌反应1小时；再向反应瓶中加入0.06mol(66.0g)端羟基超支化聚酯HyPer H102，在90℃的条件下搅拌反应约2小时至异氰酸酯基反应完全，即得到紫外光固化超支化聚氨酯；降温至50℃，向其中加入100.0g活性稀释剂季戊四醇三丙烯酸酯，接着加入N,N-二甲基乙醇胺中和至pH值为7.5，再加入8.0g乳化剂十六烷基磺酸钠，逐步加入200.0g去离子水，加完后在搅拌速率为1000rpm的条件下乳化0.5小时，即得到固含量约60％的水溶性紫外光固化超支化聚氨酯丙烯酸树脂500g。
实施例4
将1,6-己二异氰酸酯(0.15mol，25.2g)、分子量为20000g/mol的聚丙二醇(0.01mol，200.0g)、二羟甲基丙酸(0.1mol，13.4g)、一缩二乙二醇(0.02mol，2.12g)和0.025g辛酸亚锡加到反应瓶中，在60℃的条件下搅拌反应1.5小时；接着向反应瓶中加入含约0.1wt％阻聚剂对羟基苯甲醚的甲基丙烯酸羟基丙基酯(0.02mol，2.88g)，在80℃的条件下搅拌反应1.5小时；再向反应瓶中加入0.02mol(24.0g)端羟基超支化聚酯HyPer H202，在90℃的条件下搅拌反应约2小时至异氰酸酯基反应完全，即得到紫外光固化超支化聚氨酯；降温至50℃，向其中加入45.0g活性稀释剂季戊四醇三丙烯酸酯，接着加入三乙胺中和至pH值为7.2，再加入13.0g乳化剂十二烷基苯磺酸钠，逐步渐加入320.0g去离子水，加完后在搅拌速率为800rpm的条件下乳化1.0小时，即得到固含量约50％的水溶性紫外光固化超支化聚氨酯丙烯酸树脂650g。
实施例5
将二环己基甲烷二异氰酸酯(0.15mol，39.3g)、苯二亚甲基二异氰酸酯(0.03mol，5.64g)、分子量为2000g/mol的聚乙二醇(0.01mol，20.0g)、分子量为1000g/mol的聚乙二醇(0.02mol，20.0g)、二羟甲基丙酸(0.12mol，16.08g)、一缩二乙二醇(0.01mol，1.06g)、丁二醇(0.01mol，0.9g)和0.045g二醋酸二丁基锡加到反应瓶中，在65℃的条件下搅拌反应1.5小时；接着向反应瓶中加入含约0.1wt％阻聚剂对羟基苯甲醚的甲基丙烯酸-2-羟基丁基酯(0.005mol，0.79g)、丙烯酸-4-羟基丁基酯(0.005mol，0.72g)，在75℃的条件下搅拌反应2小时；再向反应瓶中加入0.005mol(3.0g)端羟基超支化聚酯HyPer H201、0.005mol(27.0g)端羟基超支化聚酯HyPer H204，在80℃的条件下搅拌反应约3.5小时至异氰酸酯基反应完全，即得到紫外光固化超支化聚氨酯；降温至40℃，向其中加入10.0g活性稀释剂季戊四醇三丙烯酸酯、15.0g三羟甲基丙烷三丙烯酸酯，接着加入氨水中和至pH值为7.0，再加入2.0g乳化剂十六烷基磺酸钠、3.0g十二烷基聚氧乙烯醚硫酸钠，逐步加入130.0g去离子水，加完后在搅拌速率为700rpm的条件下乳化1.5小时，即得到固含量约55％的水溶性紫外光固化超支化聚氨酯丙烯酸树脂300g。
实施例6
将二环己基甲烷二异氰酸酯(0.15mol，39.3g)、赖氨酸二异氰酸酯(0.03mol，6.36g)、分子量为2000g/mol的聚乙二醇(0.01mol，20.0g)、分子量为1000g/mol的聚四氢呋喃(0.02mol，20.0g)、二羟甲基丙酸(0.12mol，16.08g)、一缩二乙二醇(0.01mol，1.06g)、丁二醇(0.01mol，0.9g)和0.045g二醋酸二丁基锡加到反应瓶中，在65℃的条件下搅拌反应1.5小时；接着向反应瓶中加入含约0.1wt％阻聚剂对羟基苯甲醚的甲基丙烯酸-2-羟基丁基酯(0.01mol，1.58g)，在75℃的条件下搅拌反应2小时；再向反应瓶中加入0.005mol(26.0g)端羟基超支化聚酯HyPer H104、0.005mol(27.0g)端羟基超支化聚酯HyPer H204，在80℃的条件下搅拌反应约3.5小时至异氰酸酯基反应完全，即得到紫外光固化超支化聚氨酯；降温至40℃，向其中加入20.0g活性稀释剂三羟甲基丙烷三丙烯酸酯，接着加入氨水中和至pH值为7.0，再加入3.0g乳化剂十二烷基磺酸钠、3.0g十二烷基聚氧乙烯醚硫酸钠，逐步加入120.0g去离子水，加完后在搅拌速率为700rpm的条件下乳化1.5小时，即得到固含量约60％的水溶性紫外光固化超支化聚氨酯丙烯酸树脂300g。
水溶性紫外光固化超支化聚氨酯丙烯酸树脂的粒径用马尔文粒度仪进行测试，其离心稳定性等级的测试参照文献《张道洪,周继亮,刘娜.水溶性双酚A型环氧树脂乳液的制备,粘接,2008,2,30》进行，结果如表2所示。将实施例1～
实施例6所制备产品中分别添加其质量的1.0wt％的光引发剂1173，然后在800W的汞灯照射3分钟左右，分别按照国家标准GB/T26704-2011、GB/T9754-2007、GB/T9286-2021、GB/T24148.9-2014测试紫外光固化膜的铅笔硬度、光泽度、附着力和体积收缩率。
表2水溶性紫外光固化超支化聚氨酯丙烯酸树脂的性质和性能
从表2可以看出，本发明所制备的水溶性紫外光固化超支化聚氨酯丙烯酸树脂具有优异的稳定性，高硬度、强附着力、高光泽度和低体积收缩率，而且从实施例5所制备水溶性紫外光固化超支化聚氨酯丙烯酸树脂的粒径分布图(图1)可以看出，粒径比较均匀，分布较窄。
Claims (10)
1.一种水溶性紫外光固化超支化聚氨酯丙烯酸树脂的制备方法，其具体过程如下：
（1）将二异氰酸酯、聚醚二元醇、二羟甲基丙酸、烷基二元醇和催化剂加到反应瓶中，在40-80℃的条件下搅拌反应1-3小时，得到两端为异氰酸酯基的齐聚物；
（2）向反应瓶中加入含0.1wt%阻聚剂对羟基苯甲醚的（甲基）丙烯酸羟基烷基酯，在50-90℃的条件下搅拌反应1-3小时，得到一端为异氰酸酯基、一端为丙烯酸酯基的齐聚物；
（3）向反应瓶中加入端羟基超支化聚酯，在50-90℃的条件下搅拌反应2-4小时至异氰酸酯基反应完全，即得到紫外光固化超支化聚氨酯；
（4）降温至30-50℃，向其中加入活性稀释剂，然后加入胺类中和剂中和至pH值为6.8～7.5，再加入乳化剂，最后逐步加入去离子水，在搅拌速率为500-1000rpm的条件下乳化0.5-2小时，即得到固含量为40-60%的水溶性紫外光固化超支化聚氨酯丙烯酸树脂；
所述（甲基）丙烯酸羟基烷基酯为丙烯酸羟基烷基酯和/或甲基丙烯酸羟基烷基酯。
2.根据权利要求1所述的制备方法，其特征在于：所述的二异氰酸酯、聚醚二元醇、二羟甲基丙酸、烷基二元醇、（甲基）丙烯酸羟基烷基酯、端羟基超支化聚酯的摩尔比为（1.0～2.0）：（0.1-0.5）：（0.5-1.2）：（0.1-0.5）：（0.01-0.6）：（0.01-0.6）。
3.根据权利要求1所述的制备方法，其特征在于：所述的二异氰酸酯为甲苯二异氰酸酯（TDI）、二苯基甲烷二异氰酸酯（MDI）、1,6-己二异氰酸酯（HDI）、异佛尔酮二异氰酸酯（IPDI）、二环己基甲烷二异氰酸酯（HMDI）、赖氨酸二异氰酸酯（LDI）、苯二亚甲基二异氰酸酯（XDI）中的一种或多种。
4.根据权利要求1所述的制备方法，其特征在于：所述的聚醚二元醇为聚四氢呋喃、聚丙二醇、聚乙二醇中的一种或多种，它们的数均分子量在400-20000g/mol；所述的烷基二元醇为烷基碳原子为2-6个的二元醇的一种或多种。
5.根据权利要求1所述的制备方法，其特征在于：所述的催化剂为二月桂酸二丁基锡、二(十二烷基硫)二丁基锡、二醋酸二丁基锡、辛酸亚锡中的一种或多种，用量为二异氰酸酯总质量的0.05%-0.5%。
6.根据权利要求1所述的制备方法，其特征在于：所述的（甲基）丙烯酸羟基烷基酯为丙烯酸羟基乙基酯（HEA）、丙烯酸羟基丙基酯（HPA）、甲基丙烯酸羟基乙基酯（HEMA）、甲基丙烯酸羟基丙基酯（HPMA）、丙烯酸-4-羟基丁基酯（HBA）、甲基丙烯酸-2-羟基丁基酯（HBMA）中的一种或多种。
7.根据权利要求1所述的制备方法，其特征在于：所述端羟基超支化聚酯为武汉超支化树脂科技有限公司的HyPer H101、HyPer H102、HyPer H103、HyPer H104、HyPer H201、HyPer H202、HyPer H203和HyPer H204中的一种或多种，端羟基超支化聚酯的数均分子量为500～5400 g/mol，羟值为490～670mgKOH/g。
8.根据权利要求1所述的制备方法，其特征在于：所述述的活性稀释剂为三官能度及以上的（甲基）丙烯酸酯中的一种或多种，用量为最终水溶性紫外光固化超支化聚氨酯丙烯酸树脂总质量的5%-20%。
9.根据权利要求1所述的制备方法，其特征在于：所述乳化剂为琥珀酸二异辛酯磺酸钠、十二烷基聚氧乙烯醚硫酸钠、十二烷基磺酸钠、十六烷基磺酸钠和十二烷基苯磺酸钠中的一种或多种，用量为最终水溶性紫外光固化超支化聚氨酯丙烯酸树脂总质量的0.5%-2%。
10.根据权利要求1所述的制备方法，其特征在于：所述胺类中和剂为三乙醇胺、二乙醇胺、甲基二乙醇胺、N,N-二甲基乙醇胺、三乙胺、氨水中的一种或多种。
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