CN108047921A - 一种水性聚氨酯涂料及其制备方法 - Google Patents

一种水性聚氨酯涂料及其制备方法 Download PDF

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CN108047921A
CN108047921A CN201711376633.2A CN201711376633A CN108047921A CN 108047921 A CN108047921 A CN 108047921A CN 201711376633 A CN201711376633 A CN 201711376633A CN 108047921 A CN108047921 A CN 108047921A
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aqueous polyurethane
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许学梅
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Jiangmen Jianpai coating Co., Ltd
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Abstract

本发明涉及一种水性聚氨酯涂料及其制备方法，属于水性涂料技术领域。本发明通过制备得到的水性聚氨酯涂料中，通过引入含氰基的改性剂，与多元醇和异氰酸酯之间形成了共穿网络，提高了在高温条件下水性聚氨酯涂层的耐老化性能，避免了涂层变色的问题。

Description

一种水性聚氨酯涂料及其制备方法
技术领域
本发明涉及一种水性聚氨酯涂料及其制备方法，属于水性涂料技术领域。
背景技术
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，也称水分散聚氨酯、水系聚氨酯或水基聚氨酯。水性聚氨酯以水为溶剂，无污染、安全可靠、机械性能优良、相容性好、易于改性等优点。聚氨酯树脂的水性化已逐步取代溶剂型，成为聚氨酯工业发展的重要方向。水性聚氨酯可广泛应用于涂料、胶粘剂、织物涂层与整理剂、皮革涂饰剂、纸张表面处理剂和纤维表面处理剂。
水性聚氨酯涂料有许多优异的性能，例如：①涂膜耐磨与粘附力强；②涂膜防腐性能优异，耐油、耐酸碱盐，耐工业废气；③施工温度范围广，0℃-室温-加热固化；④涂膜软硬可调；⑤具有优良的电性能，可作漆包线；⑥与多种树脂混用性好； ⑦装饰与保护性能好。如环氧树脂保护性好但装饰性差，硝基漆等装饰性好但保护差，所以，聚氨酯涂料可用于高级木器、钢琴、大型客机的外涂饰；⑧耐高低温性好，从-40℃到300℃都可有相应的品种。
但是，水性聚氨酯涂料在高温环境下，由于其涂膜的温度在≥150℃下长期烘烤容易发生黄变现象，限制了其在高温环境中的应用。
发明内容
本发明所要解决的技术问题在于：水性聚氨酯涂料长期在高温条件下会出现涂层变色的问题。本发明采用了带氰基的硅氧烷化合物改性剂对水性聚氨酯涂料进行接枝，提高了涂层的耐高温性能。
为解决上述问题，采用了如下技术手段：
一种水性聚氨酯涂料的制备方法，包括如下步骤：
第1步，将聚醚多元醇、聚酯多元醇、第一扩链剂、式（I）所示的改性剂按照重量比混合，升温之后，再加入多异氰酸酯，进行反应；
（I）；
其中，R1、R2、R3分别独立地选自含有1～10个碳原子的直链或带支链的烷基，更优选的是R1、R2和R3都是乙基或者异丙基；
第2步，在第1步的反应物中加入第二扩链剂，继续进行反应；
第3步，在第2步的反应物中加入有机溶剂，并降温，再加入水、水性分散剂、pH调节剂，分散均匀后，得到水性聚氨酯涂料。
所述的第1步中，聚醚多元醇、聚酯多元醇、第一扩链剂、改性剂、多异氰酸酯之间的重量比是30～35：40～50：8～12：8～12：6～9，反应过程中的温度范围是70～75℃，反应时间控制在35～55min。
所述的第1步中，第一扩链剂选自二羟甲基丙酸、二羟基甲基丁酸或酒石酸。
所述的第1步中，聚醚多元醇是聚丙二醇和聚四氢呋喃二醇按照重量比2：1.8～3.5的混合；聚酯多元醇是分子量2000的聚乙二醇丁二醇己二酸共聚酯二醇和分子量2000的聚乙二醇己二酸酯二醇按质量比1.5～1.8：1的混合；异氰酸酯为甲苯二异氰酸酯(TDI)和六亚甲基二异氰酸酯按照重量比1：1.5～2.0的混合。
所述的第2步中，第二扩链剂选自乙二胺和1,2-丙二胺按照重量比3：1～1.2的混合；反应温度是80～85℃，反应时间控制在15～25min；第二扩链剂的用量是第一扩链剂重量的1.2～1.6倍。
所述的第3步中，所述的有机溶剂选自丙酮、异丙醇中的任意一种或者两者的混合，所述的pH调节剂是三乙胺，降温是指将温度降至30～35℃；有机溶剂、水、水性分散剂、pH调节剂的加入量分别是聚醚多元醇的重量的1.4～2.0倍、2.5～3.2倍、0.05～0.2倍、0.05～0.3倍；所述的水性分散剂选自含有12～18烷基苯磺酸盐。
由上述方法直接制备得到的水性聚氨酯涂料。
有益效果
本发明通过制备得到的水性聚氨酯涂料中，通过引入含氰基的改性剂，与多元醇和异氰酸酯之间形成了共穿网络，提高了在高温条件下水性聚氨酯涂层的耐老化性能，避免了涂层变色的问题。
具体实施方式
实施例1
水性聚氨酯涂料的制备方法，包括如下步骤：
第1步，将聚醚多元醇、聚酯多元醇、二羟甲基丙酸、改性剂(2-氰乙基)三异丙氧基硅烷按照重量比混合，升温之后，再加入多异氰酸酯，进行反应；聚醚多元醇、聚酯多元醇、第一扩链剂、改性剂、多异氰酸酯之间的重量比是30：40：8：8：6，反应过程中的温度范围是70℃，反应时间控制在35min；聚醚多元醇是聚丙二醇和聚四氢呋喃二醇按照重量比2：1.8的混合；聚酯多元醇是分子量2000的聚乙二醇丁二醇己二酸共聚酯二醇和分子量2000的聚乙二醇己二酸酯二醇按质量比1.5：1的混合；异氰酸酯为甲苯二异氰酸酯(TDI)和六亚甲基二异氰酸酯按照重量比1：1.5的混合；
第2步，在第1步的反应物中加入第二扩链剂，继续进行反应；第二扩链剂选自乙二胺和1,2-丙二胺按照重量比3： 1.2的混合；反应温度是85℃，反应时间控制在25min；第二扩链剂的用量是第一扩链剂重量的1.6倍；
第3步，在第2步的反应物中加入丙酮、异丙醇按照重量比2：1的混合溶剂，并降温至35℃，再加入水、十八烷基苯磺酸钠、三乙胺；有机溶剂、水、十八烷基苯磺酸钠、三乙胺的加入量分别是聚醚多元醇的重量的2.0倍、3.2倍、0.2倍、0.3倍；分散均匀后，得到水性聚氨酯涂料。
实施例2
水性聚氨酯涂料的制备方法，包括如下步骤：
第1步，将聚醚多元醇、聚酯多元醇、二羟甲基丙酸、改性剂(2-氰乙基)三异丙氧基硅烷按照重量比混合，升温之后，再加入多异氰酸酯，进行反应；聚醚多元醇、聚酯多元醇、第一扩链剂、改性剂、多异氰酸酯之间的重量比是35： 50： 12： 12： 9，反应过程中的温度范围是75℃，反应时间控制在55min；聚醚多元醇是聚丙二醇和聚四氢呋喃二醇按照重量比2：3.5的混合；聚酯多元醇是分子量2000的聚乙二醇丁二醇己二酸共聚酯二醇和分子量2000的聚乙二醇己二酸酯二醇按质量比1.8：1的混合；异氰酸酯为甲苯二异氰酸酯(TDI)和六亚甲基二异氰酸酯按照重量比1： 2.0的混合；
第2步，在第1步的反应物中加入第二扩链剂，继续进行反应；第二扩链剂选自乙二胺和1,2-丙二胺按照重量比3： 1.2的混合；反应温度是85℃，反应时间控制在25min；第二扩链剂的用量是第一扩链剂重量的1.6倍；
第3步，在第2步的反应物中加入丙酮、异丙醇按照重量比2：1的混合溶剂，并降温至35℃，再加入水、十八烷基苯磺酸钠、三乙胺；有机溶剂、水、十八烷基苯磺酸钠、三乙胺的加入量分别是聚醚多元醇的重量的2.0倍、3.2倍、0.2倍、0.3倍；分散均匀后，得到水性聚氨酯涂料。
实施例3
水性聚氨酯涂料的制备方法，包括如下步骤：
第1步，将聚醚多元醇、聚酯多元醇、二羟甲基丙酸、改性剂(2-氰乙基)三乙氧基硅烷按照重量比混合，升温之后，再加入多异氰酸酯，进行反应；聚醚多元醇、聚酯多元醇、第一扩链剂、改性剂、多异氰酸酯之间的重量比是32：45：10：11：8，反应过程中的温度范围是72℃，反应时间控制在45min；聚醚多元醇是聚丙二醇和聚四氢呋喃二醇按照重量比2：2.2的混合；聚酯多元醇是分子量2000的聚乙二醇丁二醇己二酸共聚酯二醇和分子量2000的聚乙二醇己二酸酯二醇按质量比1.6：1的混合；异氰酸酯为甲苯二异氰酸酯(TDI)和六亚甲基二异氰酸酯按照重量比1：1.7的混合；
第2步，在第1步的反应物中加入第二扩链剂，继续进行反应；第二扩链剂选自乙二胺和1,2-丙二胺按照重量比3：1.1的混合；反应温度是83℃，反应时间控制在20min；第二扩链剂的用量是第一扩链剂重量的1.3倍；
第3步，在第2步的反应物中加入丙酮、异丙醇按照重量比2：1的混合溶剂，并降温至33℃，再加入水、十八烷基苯磺酸钠、三乙胺；有机溶剂、水、十八烷基苯磺酸钠、三乙胺的加入量分别是聚醚多元醇的重量的1.6倍、2.7倍、0.1倍、0.2倍；分散均匀后，得到水性聚氨酯涂料。
对照例1
与实施例3的区别是：未加入改性剂。
水性聚氨酯涂料的制备方法，包括如下步骤：
第1步，将聚醚多元醇、聚酯多元醇、二羟甲基丙酸按照重量比混合，升温之后，再加入多异氰酸酯，进行反应；聚醚多元醇、聚酯多元醇、第一扩链剂、多异氰酸酯之间的重量比是32：45：10：8，反应过程中的温度范围是72℃，反应时间控制在45min；聚醚多元醇是聚丙二醇和聚四氢呋喃二醇按照重量比2：2.2的混合；聚酯多元醇是分子量2000的聚乙二醇丁二醇己二酸共聚酯二醇和分子量2000的聚乙二醇己二酸酯二醇按质量比1.6：1的混合；异氰酸酯为甲苯二异氰酸酯(TDI)和六亚甲基二异氰酸酯按照重量比1：1.7的混合；
第2步，在第1步的反应物中加入第二扩链剂，继续进行反应；第二扩链剂选自乙二胺和1,2-丙二胺按照重量比3：1.1的混合；反应温度是83℃，反应时间控制在20min；第二扩链剂的用量是第一扩链剂重量的1.3倍；
第3步，在第2步的反应物中加入丙酮、异丙醇按照重量比2：1的混合溶剂，并降温至33℃，再加入水、十八烷基苯磺酸钠、三乙胺；有机溶剂、水、十八烷基苯磺酸钠、三乙胺的加入量分别是聚醚多元醇的重量的1.6倍、2.7倍、0.1倍、0.2倍；分散均匀后，得到水性聚氨酯涂料。
性能表征
将薄钢板（50mm×120mm×0.5mm）采用1000目细砂纸进行打磨处理；
将实施例配制涂料与水性聚氨酯固化剂按照重量比5：1混合后，在适度为湿度为80%条件下使用ANNEST IWATA NEW-71空气喷枪喷涂于薄钢板，流平2分钟后，在220℃烘箱烘烤20min，干膜厚度为25-40μm得到的涂膜，再经过养护7天后，进行测序，性能检测下表所示。色差值的检测方法是采用色差仪（6835/BYK Gardner）在23℃、50%RH条件下测试。
从表中可以看出，本发明制备得到的水性聚氨酯涂料具有较好的与基材之间的附着力，通过实施例3与对照例1相比可以看出，通过改性剂对水性聚氨酯涂料进行改性之后，利用引入含氰基的改性剂，与多元醇和异氰酸酯之间形成了共穿网络，提高了在高温条件下水性聚氨酯涂层的耐老化性能，高温试验后的色差较小，避免了涂层变色的问题。

Claims (7)

1.一种水性聚氨酯涂料的制备方法，其特征在于，包括如下步骤：
第1步，将聚醚多元醇、聚酯多元醇、第一扩链剂、式（I）所示的改性剂按照重量比混合，升温之后，再加入多异氰酸酯，进行反应；
（I）；
其中，R1、R2、R3分别独立地选自含有1～10个碳原子的直链或带支链的烷基，更优选的是R1、R2和R3都是乙基或者异丙基；
第2步，在第1步的反应物中加入第二扩链剂，继续进行反应；
第3步，在第2步的反应物中加入有机溶剂，并降温，再加入水、水性分散剂、pH调节剂，分散均匀后，得到水性聚氨酯涂料。
2.根据权利要求1所述的水性聚氨酯涂料的制备方法，其特征在于，所述的第1步中，聚醚多元醇、聚酯多元醇、第一扩链剂、改性剂、多异氰酸酯之间的重量比是30～35：40～50：8～12：8～12：6～9，反应过程中的温度范围是70～75℃，反应时间控制在35～55min。
3.根据权利要求1所述的水性聚氨酯涂料的制备方法，其特征在于，所述的第1步中，第一扩链剂选自二羟甲基丙酸、二羟基甲基丁酸或酒石酸。
4.根据权利要求1所述的水性聚氨酯涂料的制备方法，其特征在于，所述的第1步中，聚醚多元醇是聚丙二醇和聚四氢呋喃二醇按照重量比2：1.8～3.5的混合；聚酯多元醇是分子量2000的聚乙二醇丁二醇己二酸共聚酯二醇和分子量2000的聚乙二醇己二酸酯二醇按质量比1.5～1.8：1的混合；异氰酸酯为甲苯二异氰酸酯(TDI)和六亚甲基二异氰酸酯按照重量比1：1.5～2.0的混合。
5.根据权利要求1所述的水性聚氨酯涂料的制备方法，其特征在于，所述的第2步中，第二扩链剂选自乙二胺和1,2-丙二胺按照重量比3：1～1.2的混合；反应温度是80～85℃，反应时间控制在15～25min；第二扩链剂的用量是第一扩链剂重量的1.2～1.6倍。
6.根据权利要求1所述的水性聚氨酯涂料的制备方法，其特征在于，所述的第3步中，所述的有机溶剂选自丙酮、异丙醇中的任意一种或者两者的混合，所述的pH调节剂是三乙胺，降温是指将温度降至30～35℃；有机溶剂、水、水性分散剂、pH调节剂的加入量分别是聚醚多元醇的重量的1.4～2.0倍、2.5～3.2倍、0.05～0.2倍、0.05～0.3倍；所述的水性分散剂选自含有12～18烷基苯磺酸盐。
7.权利要求1～6任一项所述的制备方法所直接得到的水性聚氨酯涂料。
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