CN107759741A - 无溶剂自交联改性水性聚氨酯树脂及其制备方法和应用 - Google Patents

无溶剂自交联改性水性聚氨酯树脂及其制备方法和应用 Download PDF

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CN107759741A
CN107759741A CN201711167796.XA CN201711167796A CN107759741A CN 107759741 A CN107759741 A CN 107759741A CN 201711167796 A CN201711167796 A CN 201711167796A CN 107759741 A CN107759741 A CN 107759741A
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刘巧
黄军波
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Heshan River Ben Polyfat Chemical Co Ltd
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Abstract

本发明公开了一种无溶剂自交联改性水性聚氨酯树脂，包括以下重量份的组分：20‑60份多异氰酸酯，100‑150份多元醇，10‑20份第一扩链剂，3‑5份第二扩链剂，0.05‑0.1份有机铋催化剂，50‑150份乙烯基单体，10‑15份三乙胺和400‑600份水。本发明的无溶剂自交联改性水性聚氨酯树脂能够用于各类涂料，其涂层具有高的剥离强度、优良的耐水性能等特点；合成过程中与传统的水性聚氨酯不同，在合成过程中无需任何溶剂，直接以乙烯基单体为溶剂，乳化后引发交联，简化了真空脱除溶剂的工艺，缩短了生产时间。

Description

无溶剂自交联改性水性聚氨酯树脂及其制备方法和应用
技术领域
本发明涉及高分子聚合物领域，具体涉及一种无溶剂自交联改性水性聚氨酯树脂及其制备方法和其在涂料中的应用。
背景技术
水性聚氨酯树脂是以水为分散介质，以有机溶剂为溶剂，采用自乳化或外加乳化剂的方法合成的。目前，水性聚氨酯树脂在加工过程中需要大量有机溶剂，而有机溶剂对环境和操作人员造成健康危害。随着人们环保意识的提高，开发对环境友好的水性聚氨酯树脂是一种趋势，因此水性聚氨酯树脂的绿色合成方法逐渐成为研究的热点。
水性聚氨酯树脂由于具有各项优异的性能，其广泛应用于皮革涂饰、涂料、黏合剂等领域。但目前，水性聚氨酯树脂在耐水耐溶剂等方面达不到溶剂型产品的性能，这在一定程度上限制了其的进一步应用。
因此，有必要研发一种具有优异的耐水、耐溶剂的水性聚氨酯树脂，且该水性聚氨酯树脂不需要使用大量有机溶剂。
发明内容
本发明的目的在于克服现有技术的缺陷，提供一种改性水性聚氨酯树脂，用于克服现有技术中需要使用大量有机溶剂，以及耐水性差的缺陷，简化了真空脱除溶剂的工艺，缩短了生产时间。
本发明是通过以下技术方案实现的：一种无溶剂自交联改性水性聚氨酯树脂，包括以下重量份的组分：
优选的，无溶剂自交联改性水性聚氨酯树脂，包括以下重量份的组分：
优选的，所述多异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯、多亚甲基多苯基异氰酸酯、四甲基苯二亚甲基二异氰酸酯、甲基环己基二异氰酸酯和二环己基甲烷二异氰酸酯中的一种或几种。
优选的，所述多元醇选自聚己内酯多元醇、聚碳酸酯多元醇、聚四氢呋喃醚多元醇、聚环氧乙烷多元醇、聚环氧丙烷多元醇、端羟基聚丁二烯和聚硅氧烷多元醇和聚酯醚多元醇中的一种或几种。
优选的，所述的多元醇为二元醇。
更优选的，所述多元醇选自聚己内酯二元醇、聚碳酸酯二元醇、聚四氢呋喃醚二元醇、聚环氧乙烷二元醇、聚环氧丙烷二元醇和端羟基聚丁二烯和聚硅氧烷二元醇中的一种或几种。
优选的，所述多异氰酸酯中的多异氰酸酯基团与所述多元醇中的羟基基团的摩尔数之比为0.97-0.98：1。
优选的，所述第一扩链剂选自二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸和二羟甲基辛酸中的一种或几种。
优选的，所述第二扩链剂选自乙二醇、一缩二乙二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、新戊二醇、二甘醇、甘油、山梨醇、三羟甲基丙烷和二羟甲基环己烷中的一种或几种。
优选的，所述有机铋催化剂选自Coscat83、有机铋1610、有机铋2010、有机铋2810、有机铋2808中的一种或几种。
优选的，所述乙烯基单体选自甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸乙酯、羟丙酯、羟乙酯、丙烯酸、AAEM、DAAM、NMA和GMA中的一种或几种。
本发明还提供了无溶剂自交联改性水性聚氨酯树脂的制备方法，包括以下步骤：
1)将多元醇和多异氰酸酯在85-95℃下反应2-3h；
2)加入第一扩链剂和第二扩链剂在75-85℃下反应1-3h；
3)加入有机铋催化剂在65-75℃下反应2-3h；
4)加入乙烯基单体，降温至35～45℃加入三乙胺中和；
5)加入水，在85～95℃下继续反应2～3h，即获得无溶剂自交联改性水性聚氨酯树脂。
优选的，可以在加入第一扩链剂和第二扩链剂的同时加入乙烯基单体。
乙烯基单体的作用为调整反应溶液的粘度，乙烯基单体的添加量可根据反应需要酌情添加。
本发明还公开了一种如上述所述的无溶剂自交联改性水性聚氨酯树脂在涂料中的应用。
应用的方法为：将无溶剂自交联改性水性聚氨酯树脂增稠、润湿、消泡处理后，用于直接涂布。
上述所述的增稠、润湿、消泡处理步骤可以采用现有技术中常用的方式进行。
本发明的有益技术效果是：(1)本发明的无溶剂自交联改性水性聚氨酯树脂能够用于各类涂料，其涂层具有高的剥离强度、优良的耐水性能等特点；(2)本发明的无溶剂自交联改性水性聚氨酯树脂，其合成过程中与传统的水性聚氨酯不同，在合成过程中无需任何溶剂，直接以乙烯基单体为溶剂，乳化后引发交联，简化了真空脱除溶剂的工艺，缩短了生产时间。
具体实施方式
实施例1
一种无溶剂自交联改性水性聚氨酯树脂，包括以下重量份的组分：
一种无溶剂自交联改性水性聚氨酯树脂的制备方法，包括以下步骤：
1)将多元醇(聚己内酯多元醇)和多异氰酸酯(甲苯二异氰酸酯)在85℃下反应3h；
2)加入第一扩链剂(二羟甲基丙酸)和第二扩链剂(乙二醇)在75℃下反应3h；
3)加入有机铋催化剂(Coscat83)在65℃下反应2h；
4)加入乙烯基单体(甲基丙烯酸甲酯)，降温至45℃加入三乙胺中和；
5)加入水，在95℃下继续反应2h，即获得无溶剂自交联改性水性聚氨酯树脂。
实施例2
一种无溶剂自交联改性水性聚氨酯树脂，包括以下重量份的组分：
一种无溶剂自交联改性水性聚氨酯树脂的制备方法，包括以下步骤：
1)将多元醇(聚碳酸酯多元醇)和多异氰酸酯(二苯基甲烷二异氰酸酯)在90℃下反应3h；
2)加入第一扩链剂(二羟甲基丁酸)和第二扩链剂(一缩二乙二醇)在85℃下反应2h；
3)加入有机铋催化剂(有机铋1610)在70℃下反应3h；
4)加入乙烯基单体(丙烯酸丁酯)，降温至35℃加入三乙胺中和；
5)加入水，在855℃下继续反应3h，即获得无溶剂自交联改性水性聚氨酯树脂。
实施例3
一种无溶剂自交联改性水性聚氨酯树脂，包括以下重量份的组分：
无溶剂自交联改性水性聚氨酯树脂的制备方法与实施例2的无溶剂自交联改性水性聚氨酯树脂的制备方法相同。
实施例4
一种无溶剂自交联改性水性聚氨酯树脂，包括以下重量份的组分：
无溶剂自交联改性水性聚氨酯树脂的制备方法与实施例2的无溶剂自交联改性水性聚氨酯树脂的制备方法相同。
实施例5
一种无溶剂自交联改性水性聚氨酯树脂，包括以下重量份的组分：
无溶剂自交联改性水性聚氨酯树脂的制备方法与实施例2的无溶剂自交联改性水性聚氨酯树脂的制备方法相同。
实施例1-5制备的无溶剂自交联改性水性聚氨酯树脂的涂层具有优异的剥离强度和耐水性能，在合成过程中无需任何有机溶剂，是一种绿色的合成方法，避免了对操作人员的人体和环境造成一定的危害。

Claims (10)

1.一种无溶剂自交联改性水性聚氨酯树脂，其特征在于，包括以下重量份的组分：
2.根据权利要求1所述的无溶剂自交联改性水性聚氨酯树脂，其特征在于，包括以下重量份的组分：
3.根据权利要求1或2所述的无溶剂自交联改性水性聚氨酯树脂，其特征在于，所述多异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯、多亚甲基多苯基异氰酸酯、四甲基苯二亚甲基二异氰酸酯、甲基环己基二异氰酸酯和二环己基甲烷二异氰酸酯中的一种或几种。
4.根据权利要求1或2所述的无溶剂自交联改性水性聚氨酯树脂，其特征在于，所述多元醇选自聚己内酯多元醇、聚碳酸酯多元醇、聚四氢呋喃醚多元醇、聚环氧乙烷多元醇、聚环氧丙烷多元醇和端羟基聚丁二烯、聚硅氧烷多元醇和聚酯醚多元醇中的一种或几种；所述多异氰酸酯中的多异氰酸酯基团与所述多元醇中的羟基基团的摩尔数之比为0.97-0.98:1。
5.根据权利要求1或2所述的无溶剂自交联改性水性聚氨酯树脂，其特征在于，所述第一扩链剂选自二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸和二羟甲基辛酸中的一种或几种。
6.根据权利要求1或2所述的无溶剂自交联改性水性聚氨酯树脂，其特征在于，所述第二扩链剂选自乙二醇、一缩二乙二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、新戊二醇、二甘醇、甘油、山梨醇、三羟甲基丙烷和二羟甲基环己烷中的一种或几种。
7.根据权利要求1或2所述的无溶剂自交联改性水性聚氨酯树脂，其特征在于，所述有机铋催化剂选自Coscat83、有机铋1610、有机铋2010、有机铋2810、有机铋2808中的一种或几种。
8.根据权利要求1或2所述的无溶剂自交联改性水性聚氨酯树脂，其特征在于，所述乙烯基单体选自甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸乙酯、羟丙酯、羟乙酯、丙烯酸、AAEM、DAAM、NMA和GMA中的一种或几种。
9.权利要求1-8中任一项所述的无溶剂自交联改性水性聚氨酯树脂的制备方法，其特征在于，包括以下步骤：
1)将多元醇和多异氰酸酯在85-95℃下反应2-3h；
2)加入第一扩链剂和第二扩链剂在75-85℃下反应1-3h；
3)加入有机铋催化剂在65-75℃下反应2-3h；
4)加入乙烯基单体，降温至35-45℃加入三乙胺中和；
5)加入水，在85-95℃下继续反应2-3h，即获得无溶剂自交联改性水性聚氨酯树脂。
10.权利要求1-8中任一项所述的无溶剂自交联改性水性聚氨酯树脂在涂料中的应用。
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