CN107857866A - 一种高固含量水性聚醚型聚氨酯树脂及其制备方法 - Google Patents

一种高固含量水性聚醚型聚氨酯树脂及其制备方法 Download PDF

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CN107857866A
CN107857866A CN201711164876.XA CN201711164876A CN107857866A CN 107857866 A CN107857866 A CN 107857866A CN 201711164876 A CN201711164876 A CN 201711164876A CN 107857866 A CN107857866 A CN 107857866A
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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

本发明提供一种高固含量水性聚醚型聚氨酯树脂，按重量份计，由以下原料组成：多元醇100～150份，多异氰酸酯20～40份，第一扩链剂4～8份，第二扩链剂3～5份，三乙胺3～6份，有机铋催化剂0.05～0.1份，水120～140份。按份数称取多元醇和多异氰酸酯，并在85～95℃下反应2～3h；再加入第一扩链剂、丙酮，并在75～85℃下反应1～3h；然后加入有机铋催化剂，在65～75℃下反应2～3h，降温至35～45℃后加入三乙胺并搅拌，加入水后继续搅拌，接着加入第二扩链剂，然后将反应物在30～60℃下反应2～3h，真空脱出丙酮即可获得所述高固含量水性聚醚型聚氨酯树脂。本发明的聚氨酯树脂的固含量可达60％以上，且具有极好的弹性、优秀的耐湿热性能、较高的剥离强度、优良的耐水性能，特别适合用于纺织涂层。

Description

一种高固含量水性聚醚型聚氨酯树脂及其制备方法
技术领域
本发明涉及高分子聚合物领域，具体涉及一种高固含量水性聚醚型聚氨酯树脂及其制备方法。
背景技术
水性聚氨酯树脂是以水为分散介质，采用自乳化或外加乳化剂的方法，但目前国内的水性聚醚聚氨酯的固含量普遍在50％以下，造成后期加工烘烤成本过高，厚涂膜干燥困难且耐湿热性差。而常规的聚酯水性聚氨酯又有耐水解差的问题。因此，现在的高分子领域迫切地需要一种高固含量的水性聚醚型聚氨酯树脂。
发明内容
本发明的目的在于克服现有技术的缺陷，提供一种高固含量水性聚醚型聚氨酯树脂及其制备方法。
为了实现以上目的及其它相关目的，本发明是通过包括以下的技术方案实现的：
一种高固含量水性聚醚型聚氨酯树脂，按重量份计，由以下原料组成：
进一步地，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、聚硅氧烷多元醇和聚酯醚多元醇中的一种或多种。
进一步优选地，所述的多元醇为二元醇。
进一步更优选地，所述多元醇选自己内酯二元醇、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、端羟基聚丁二烯和聚硅氧烷二元醇中的一种或多种。
本发明中对于多元醇的聚醚需要选择合适的分子量和特殊的起始剂来满足容易的相转化。
进一步地，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多种。
进一步地，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0.6～0.8，这有利于实现相转化；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高于0.8不利于实现相转化，达到高固含量的难度大大增加。
进一步地，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多种。
进一步优选地，所述第一扩链剂选择两种或以上，可以达到树脂产品粒径的合理分布，降低成品的粘度。
进一步地，所述第二扩链剂选自乙二胺、异佛尔酮二胺、己二胺、二乙烯三胺中的一种或多种。
进一步地，所述第二扩链剂可以调整整体树脂的最终分子量，从而可以达到最终的要求性能。
进一步地，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中的一种或多种。
一种高固含量水性聚醚型聚氨酯树脂的制备方法，包括以下步骤：
按份数称取多元醇和多异氰酸酯，并在85～95℃下反应2～3h；再加入第一扩链剂、丙酮，并在75～85℃下反应1～3h；然后加入有机铋催化剂，在65～75℃下反应2～3h，降温至35～45℃后加入三乙胺并搅拌，加入水后继续搅拌，接着加入第二扩链剂，然后将反应物在30～60℃下反应2～3h，真空脱出丙酮即可获得所述高固含量水性聚醚型聚氨酯树脂。
本发明中丙酮的作用为调整反应溶液的粘度，其添加量可根据反应需要酌情添加，比如10～100份，优选20～80份，更优选30～60份。
本发明中所述三乙胺可以起到中和的作用。
一种高固含量水性聚醚型聚氨酯树脂的用途，将所述高固含量水性聚醚型聚氨酯树脂经增稠、润湿、消泡处理后，直接进行涂布。
所述增稠、润湿、消泡处理步骤均采用本领域公知的常规技术手段来实现。
本发明的高固含量水性聚醚型聚氨酯树脂能够用于纺织涂层，其涂层具有较高的剥离强度、优良的耐水性能、极好的弹性和优秀的耐湿热性能。
本发明的高固含量水性聚醚型聚氨酯树脂在合成过程中利用不同亲水剂组合达到高固低粘，利用现有设备，成功制备出60％及以上固含量的聚醚型聚氨酯树脂。
本发明的高固含量水性聚醚型聚氨酯树脂特别适合用于纺织涂层。
本发明的有益效果：
(1)本发明的高固含量水性聚醚型聚氨酯树脂具有较高的固含量，可达60％以上；
(2)本发明的高固含量水性聚醚型聚氨酯树脂具有极好的弹性、优秀的耐湿热性能、较高的剥离强度、优良的耐水性能，特别适合用于纺织涂层；
(3)本发明的制备方法操作简单，对设备要求低，可以直接使用现有的设备进行大规模生产，成本低廉。
具体实施方式
为了更好的解释本发明，现结合以下具体实施例做进一步说明，但是本发明不限于具体实施例。
实施例1
一种高固含量水性聚醚型聚氨酯树脂，按重量份计，由以下原料组成：
按份数称取聚硅氧烷多元醇和异佛尔酮二异氰酸酯，并在85～95℃下反应2～3h；再加入二羟甲基丙酸、二羟甲基丁酸、丙酮，并在75～85℃下反应1～3h；然后加入有机铋1610，在65～75℃下反应2～3h，降温至35～45℃后加入三乙胺并搅拌，加入水后继续搅拌，接着加入异佛尔酮二胺，然后将反应物在30～60℃下反应2～3h，真空脱出丙酮即可获得所述高固含量水性聚醚型聚氨酯树脂。
将所述高固含量水性聚醚型聚氨酯树脂经增稠、润湿、消泡处理后，直接涂布于纺织涂层。
本实施例的高固含量水性聚醚型聚氨酯树脂具有60％以上的固含量，特别适合用于纺织涂层，其具有较高的剥离强度、优良的耐水性能、极好的弹性和优秀的耐湿热性能。
实施例2
一种高固含量水性聚醚型聚氨酯树脂，按重量份计，由以下原料组成：
按份数称取端羟基聚丁二烯和萘-1,5-二异氰酸酯，并在90℃下反应2～3h；再加入二羟甲基丁酸、二羟甲基辛酸、丙酮，并在80℃下反应2h；然后加入有机铋2010，在70℃下反应2～3h，降温至40℃后加入三乙胺并搅拌，加入水后继续搅拌，接着加入己二胺，然后将反应物在50℃下反应2～3h，真空脱出丙酮即可获得所述高固含量水性聚醚型聚氨酯树脂。
将所述高固含量水性聚醚型聚氨酯树脂经增稠、润湿、消泡处理后，直接涂布于纺织涂层。
本实施例的高固含量水性聚醚型聚氨酯树脂具有60％以上的固含量，特别适合用于纺织涂层，其具有较高的剥离强度、优良的耐水性能、极好的弹性和优秀的耐湿热性能。
实施例3
一种高固含量水性聚醚型聚氨酯树脂，按重量份计，由以下原料组成：
按份数称取聚环氧丙烷多元醇和甲基环己基二异氰酸酯，并在95℃下反应3h；再加入二羟甲基戊酸、二羟甲基丁酸、丙酮，并在85℃下反应3h；然后加入有机铋2810，在75℃下反应3h，降温至45℃后加入三乙胺并搅拌，加入水后继续搅拌，接着加入二乙烯三胺，然后将反应物在60℃下反应3h，真空脱出丙酮即可获得所述高固含量水性聚醚型聚氨酯树脂。
将所述高固含量水性聚醚型聚氨酯树脂经增稠、润湿、消泡处理后，直接涂布于纺织涂层。
本实施例的高固含量水性聚醚型聚氨酯树脂具有65％的固含量，特别适合用于纺织涂层，其具有较高的剥离强度、优良的耐水性能、极好的弹性和优秀的耐湿热性能。
实施例4
一种高固含量水性聚醚型聚氨酯树脂，按重量份计，由以下原料组成：
按份数称取聚环氧乙烷二元醇和四甲基苯二亚甲基二异氰酸酯，并在85℃下反应2h；再加入二羟甲基辛酸、二羟甲基丙酸、丙酮，并在75℃下反应1h；然后加入有机铋2808，在65℃下反应2h，降温至35～℃后加入三乙胺并搅拌，加入水后继续搅拌，接着加入乙二胺，然后将反应物在30℃下反应2h，真空脱出丙酮即可获得所述高固含量水性聚醚型聚氨酯树脂。
将所述高固含量水性聚醚型聚氨酯树脂经增稠、润湿、消泡处理后，直接涂布于纺织涂层。
本实施例的高固含量水性聚醚型聚氨酯树脂具有70％的固含量，特别适合用于纺织涂层，其具有较高的剥离强度、优良的耐水性能、极好的弹性和优秀的耐湿热性能。
以上所述仅为本发明的具体实施例，并非因此限制本发明的专利范围，凡是利用本发明作的等效变换，或直接或间接运用在其它相关的技术领域，均同理包括在本发明的专利保护范围之中。

Claims (10)

1.一种高固含量水性聚醚型聚氨酯树脂，其特征在于，按重量份计，由以下原料组成：
2.根据权利要求1所述的高固含量水性聚醚型聚氨酯树脂，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、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多种。
3.根据权利要求1所述的高固含量水性聚醚型聚氨酯树脂，其特征在于，所述的多元醇为二元醇。
4.根据权利要求1所述的高固含量水性聚醚型聚氨酯树脂，其特征在于，所述多元醇选自己内酯二元醇、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、端羟基聚丁二烯和聚硅氧烷二元醇中的一种或多种。
5.根据权利要求1所述的高固含量水性聚醚型聚氨酯树脂，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多种。
6.根据权利要求1所述的高固含量水性聚醚型聚氨酯树脂，其特征在于，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0.6～0.8。
7.根据权利要求1所述的高固含量水性聚醚型聚氨酯树脂，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多种；所述第二扩链剂选自乙二胺、异佛尔酮二胺、己二胺、二乙烯三胺中的一种或多种。
8.根据权利要求1所述的高固含量水性聚醚型聚氨酯树脂，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中的一种或多种。
9.一种根据权利要求1-8中任一项所述的高固含量水性聚醚型聚氨酯树脂的制备方法，其特征在于，包括以下步骤：
按份数称取多元醇和多异氰酸酯，并在85～95℃下反应2～3h；再加入第一扩链剂、丙酮，并在75～85℃下反应1～3h；然后加入有机铋催化剂，在65～75℃下反应2～3h，降温至35～45℃后加入三乙胺并搅拌，加入水后继续搅拌，接着加入第二扩链剂，然后将反应物在30～60℃下反应2～3h，真空脱出丙酮即可获得所述高固含量水性聚醚型聚氨酯树脂。
10.一种根据权利要求1-8中任一项所述的高固含量水性聚醚型聚氨酯树脂的用途，其特征在于，将所述高固含量水性聚醚型聚氨酯树脂经增稠、润湿、消泡处理后，直接进行涂布。
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Publication number Priority date Publication date Assignee Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110105535A (zh) * 2019-05-21 2019-08-09 华侨大学 一种硅烷偶联剂接枝改性水性聚氨酯的制备方法

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