CN109096468A - 一种无溶剂水性聚氨酯树脂及其制备方法 - Google Patents

一种无溶剂水性聚氨酯树脂及其制备方法 Download PDF

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CN109096468A
CN109096468A CN201811054377.XA CN201811054377A CN109096468A CN 109096468 A CN109096468 A CN 109096468A CN 201811054377 A CN201811054377 A CN 201811054377A CN 109096468 A CN109096468 A CN 109096468A
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polyurethane resin
waterborne polyurethane
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dihydric alcohol
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李延科
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Luoyang Sheng Jiaxin Materials Co Ltd
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Abstract

本发明公开了一种无溶剂水性聚氨酯树脂及其制备方法，无溶剂水性聚氨酯树脂的原料由以下重量份数组成：聚酯或聚醚二元醇80～150份，2,2‑二羟甲基异戊酸（2,2‑二羟甲基‑3甲基丁酸）1～25份，亲水羧基二元醇0～10份，小分子二元醇0～15份，非离子二元醇0～10份，二异氰酸酯40～150份，成盐剂1～20份，二胺扩链剂0～30份，去离子水500～700份。该树脂制备过程无有机溶剂，树脂的预聚体粘度小，分散体的稳定性高。

Description

一种无溶剂水性聚氨酯树脂及其制备方法
技术领域
本发明涉及水性聚氨酯树脂，特别涉及无溶剂水性聚氨酯的制备。
背景技术
随着国家环保政策日趋严厉及人们环保安全意识的增强，对于水性聚氨酯工业来说，无论是在产品的生产过程，还是在使用阶段，都要求尽量不使用溶剂及产品的VOC尽量为零。在传统的水性聚氨酯生产过程中，需要添加NMP、丁酮和丙酮等溶剂作为降粘稀释剂，这些溶剂不仅在生产环节污染环境，而且在应用环节中如果不蒸出，要么污染环境要么对基材有影响，如果蒸出这些溶剂会极大增加成本。因此，无溶剂制备水性聚氨酯的研究越来越受到重视。专利文献CN102585154A公开了一种无溶剂制备水性聚氨酯的方法，该方法属于细乳液聚合法，由于是在微乳化阶段添加聚醚二元醇和小分子二元醇，存在原料反应不完全、有大量残余小分子单体及乳液稳定性差等缺点。专利文献CN107936221A公开了一种无溶剂型水性聚氨酯的制备方法，这种方法的主要特点是用二羟甲基丁酸（DMBA）作为亲水羧基二元醇。虽然添加DMBA的预聚体粘度比二羟甲基丙酸DMPA的要小，但在使用结晶性较强聚酯二元醇、大量添加小分子二元醇扩链剂或使用分子量较大的二元醇等情况下，预聚体的粘度依然较高。专利文献107522839A公开了一种无溶剂具备阴离子和非离子特性的水性聚氨酯树脂制备方法。该方法虽然结合了阴离子亲水二元醇和非离子亲水二元醇的优点，能很大程度降低预聚体的粘度，但是因为受现有阴离子亲水二元醇结构的限制，只在部分预聚体系有较好降粘效果。
发明内容
针对现有技术的缺点，本发明要解决的第一个技术问题是提供一种一种无溶剂水性聚氨酯树脂，该树脂的预聚体粘度小，分散体的稳定性高。
本发明要解决的第二个技术问题是提供一种该无溶剂水性聚氨酯树脂的制备方法。
本发明的技术思路是：通过在预聚体合成时加入特殊羧基二元醇得到较低粘度的预聚体，避免添加溶剂降粘带来的缺陷。由于特殊羧基二元醇的结构特性，在预聚时能降低不同结构类型预聚体的粘度，因此可用于不同水性聚氨酯的合成，有很大的普适性。另外，本发明所述的特殊羧基二元醇也可与其它阴离子扩链剂和非离子亲水二元醇混合使用，所得水性聚氨酯树脂性能亦很优异。
为解决第一个技术问题，本发明提供一种无溶剂水性聚氨酯树脂，其原料由以下重量份数组成：
聚酯或聚醚二元醇80～150份， 2,2-二羟甲基异戊酸（2,2-二羟甲基-3甲基丁酸）1～25份，亲水羧基二元醇0～10份，小分子二元醇0～15份，非离子二元醇0～10份，二异氰酸酯40～150份，成盐剂1～20份，二胺扩链剂0～30份，去离子水500～700份。2,2-二羟甲基异戊酸（2,2-二羟甲基-3甲基丁酸）优选用量为10～25份。
所述的聚酯二元醇可为聚己二酸酯二醇、聚己内酯二醇、聚碳酸酯二醇等中的至少一种，优选数均分子量为1000～4000。
所述的聚醚二元醇可为聚氧化丙烯二醇，聚四氢呋喃二醇等中的至少一种，优选数均分子量为400～4000。
所述的亲水羧基二元醇为2,2-二羟甲基丙酸（DMPA）、2,2-二羟甲基丁酸（DMBA）等中的至少一种。
所述的小分子二元醇是指乙二醇、丙二醇、丁二醇、新戊二醇、己二醇、乙基丁基丙二醇或环己烷二甲醇等及其混合物。
所述的非离子二元醇是分子量500～1500的聚合物非离子二元醇，含有两个伯羟基官能团和一条由乙氧基封端的长侧链。
所述的二异氰酸酯是指异佛尔酮二异氰酸酯（IPDI）、六亚甲基二异氰酸酯（HDI）或二环已基甲烷二异氰酸酯（HMDI）等及其混合物。
所述二胺扩链剂是指异氟尔酮二胺（IPDA）、环己二甲胺或乙二胺等及其混合物。
为解决第二个技术问题，本发明的技术方案是：一种制备无溶剂水性聚氨酯树脂的方法，包括以下步骤：
（1）预聚
将聚酯多元醇、2,2-二羟甲基异戊酸（2,2-二羟甲基-3甲基丁酸）、亲水羧基二元醇、小分子二元醇、非离子二元醇及二异氰酸酯加入到反应器中，在温度70~90℃，搅拌反应4~5小时。
（2）成盐
体系降温至35~45℃，加入成盐剂成盐10~20分钟。所述成盐剂是本领域常用品种。
（3）分散和扩链反应
加入去离子水、二胺扩链剂分散扩链30~40分钟，得到水性聚氨酯树脂分散液。分散方式和搅拌速度是本领域常规使用的。
本发明的有益效果主要体现在以下几个方面：
1.本发明通过引入特殊羧基二元醇，极大地降低了预聚体粘度，从而达到不添加溶剂的目的。
2.本发明通过将2,2-二羟甲基异戊酸（2,2-二羟甲基-3甲基丁酸）与其它阴离子和非离子亲水二元醇组合，既能最大限度降低预聚体系粘度，又能提高水性聚氨酯分散体的稳定性，同其它无溶剂方法相比，稳定性超过半年以上。这种组合几乎可用于各种无溶剂水性聚氨酯配方设计中，有很高的普适性。
3.本发明方法在预聚、成盐过程均不添加有机溶剂，实现无有机溶剂制备过程。
具体实施方式
下面结合实施例对本发明作进一步的描述。
实施例1
（1）预聚
依次将真空脱水后的120份聚己二酸丁二醇酯二元醇（MW, 2000）、16份2,2-二羟甲基-3甲基丁酸、8份乙二醇及115份异氟尔酮二异氰酸酯（IPDI）加入到反应器中，70~90℃搅拌反应5小时得到低粘度预聚体；
（2）成盐
体系降温至40℃，加入10份三乙胺成盐15分钟；
（3）分散和扩链
高速搅拌下加入550份去离子水，随即加入10份乙二胺和110份水的混合溶液进行扩链，再高速搅拌30分钟，扩链反应结束，减压蒸馏出溶剂，得到稳定水性聚氨酯分散液。
实施例2
（1）预聚
依次将110份聚己二酸己二醇酯二元醇（MW, 2000）、20份2,2-二羟甲基-3甲基丁酸、8份非离子聚醚二元醇（瑞典PERSTORP公司生产的N120产品）、6份乙二醇及120份异氟尔酮二异氰酸酯（IPDI）加入到反应器中，在搅拌下，70~90℃反应5小时得到低粘度预聚体；
（2）成盐
体系降温至40℃，加入10份三乙胺成盐15分钟；
（3）分散和扩链
高速搅拌下加入550份去离子水，随即加入10份IPDA、5份乙二胺和110份水的混合溶液进行扩链，再高速搅拌30分钟，扩链反应结束，减压蒸馏出溶剂，得到稳定水性聚氨酯分散液。
实施例3
（1）预聚
依次将100份聚氧化丙醚二元醇（MW, 2000）、10份2,2-二羟甲基-3甲基丁酸、7份DMPA、6份1，4-丁二醇及115份异氟尔酮二异氰酸酯（IPDI）加入到反应器中，70~90℃搅拌反应5小时得到低粘度预聚体；
（2）成盐
体系降温至40℃，加入10份三乙胺成盐15分钟；
（3）分散和扩链
高速搅拌下加入550份去离子水，随即加入16份IPDA、4份乙二胺和110份水的混合溶液进行扩链，再高速搅拌30分钟，扩链反应结束，减压蒸馏出溶剂，得到稳定水性聚氨酯分散液。
实施例4
（1）预聚
依次将80份聚己二酸新戊二醇二元醇（MW, 2000）、25份2,2-二羟甲基-3甲基丁酸、6份乙二醇及120份异氟尔酮二异氰酸酯（IPDI）加入到反应器中， 70~90℃搅拌反应5小时得到低粘度预聚体；
（2）成盐
体系降温至40℃，加入16份三乙胺成盐15分钟；
（3）分散和扩链
高速搅拌下加入550份去离子水，随即加入12份二胺和110份水的混合溶液进行扩链，再高速搅拌30分钟，扩链反应结束，减压蒸馏出溶剂，得到稳定水性聚氨酯分散液。

Claims (10)

1.一种无溶剂水性聚氨酯树脂，其原料由以下重量份数组成：聚酯或聚醚二元醇80～150份，2,2-二羟甲基异戊酸（2,2-二羟甲基-3甲基丁酸）1～25份，亲水羧基二元醇0～10份，小分子二元醇0～15份，非离子二元醇0～10份，二异氰酸酯40～150份，成盐剂1～20份，二胺扩链剂0～30份，去离子水500～700份。
2.根据权利要求1所述的无溶剂水性聚氨酯树脂，2,2-二羟甲基异戊酸（2,2-二羟甲基-3甲基丁酸）的用量为10～25份。
3.根据权利要求1所述的无溶剂水性聚氨酯树脂，所述的聚酯二元醇是指聚己二酸酯二醇、聚己内酯二醇、聚碳酸酯二醇中的至少一种，数均分子量为1000～4000。
4.根据权利要求1所述的无溶剂水性聚氨酯树脂，所述的聚醚二元醇是指聚氧化丙烯二醇，聚四氢呋喃二醇中的至少一种，数均分子量为400～4000。
5.根据权利要求1所述的无溶剂水性聚氨酯树脂，所述的亲水羧基二元醇是指2,2-二羟甲基丙酸（DMPA）、2,2-二羟甲基丁酸（DMBA）中的至少一种。
6.根据权利要求1所述的无溶剂水性聚氨酯树脂，所述的小分子二元醇是指乙二醇、丙二醇、丁二醇、新戊二醇、己二醇、乙基丁基丙二醇或环己烷二甲醇及其混合物。
7.根据权利要求1所述的无溶剂水性聚氨酯树脂，所述的非离子二元醇是指分子量500～1500的聚合物非离子二元醇，含有两个伯羟基官能团和一条由乙氧基封端的长侧链。
8.根据权利要求1所述的无溶剂水性聚氨酯树脂，所述的二异氰酸酯是指异佛尔酮二异氰酸酯（IPDI）、六亚甲基二异氰酸酯（HDI）或二环已基甲烷二异氰酸酯（HMDI）及其混合物。
9.根据权利要求1所述的无溶剂水性聚氨酯树脂，所述二胺扩链剂是指异氟尔酮二胺（IPDA）、环己二甲胺或乙二胺及其混合物。
10.一种制备权利要求1~9之一所述的无溶剂水性聚氨酯树脂的方法，包括以下步骤：
（1）预聚
将聚酯多元醇、2,2-二羟甲基异戊酸（2,2-二羟甲基-3甲基丁酸）、亲水羧基二元醇、小分子二元醇、非离子二元醇及二异氰酸酯加入到反应器中，在温度70~90℃，搅拌反应4~5小时；
（2）成盐
体系降温至35~45℃，加入成盐剂成盐10~20分钟；
（3）分散和扩链反应
加入去离子水、二胺扩链剂分散扩链30~40分钟，得到水性聚氨酯树脂分散液。
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