CN103570915A - 一种高固含羟基型水性聚氨酯树脂的制备方法 - Google Patents

一种高固含羟基型水性聚氨酯树脂的制备方法 Download PDF

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CN103570915A
CN103570915A CN201310603259.0A CN201310603259A CN103570915A CN 103570915 A CN103570915 A CN 103570915A CN 201310603259 A CN201310603259 A CN 201310603259A CN 103570915 A CN103570915 A CN 103570915A
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闫福安
陈秋芬
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Abstract

本发明公开了一种柔感高固含羟基型水性聚氨酯树脂的制备方法。包括以下步骤：将聚酯二元醇、端羟基磺酸盐聚酯二醇、小分子二元醇、多元醇、亲水单体加入反应容器混合并脱水；60～65℃下缓慢加入二异氰酸酯，1h加完并再保温1h；加入催化剂，升温至65～70℃并保温反应，检测异氰酸酯含量达到小于或等于0.1wt％时停止加热；降温至40～50℃，用丙酮调节黏度，并用有机胺中和至7～8；在35～40℃高速搅拌下加入去离子水分散30min，减压脱除丙酮即得到乳白色泛蓝光的羟基型水性聚氨酯树脂。用其配制的双组分涂料外观好，柔软弹性好，具有优异耐刮擦耐磨损性能、耐化学品性能。

Description

一种高固含羟基型水性聚氨酯树脂的制备方法
技术领域
本发明属于高分子材料领域，具体涉及一种柔感高固含羟基型水性聚氨酯树脂的制备方法。
背景技术
随着水性聚氨酯制备技术水平的提高和对性能要求的提高，简单的单组份水性聚氨酯已经无法完全满足市场的需求，双组份水性聚氨酯可以弥补单组份水性聚氨酯性能方面的不足。双组份水性聚氨酯是由含有-OH基团的羟基型水性聚氨酯树脂和含-NCO基团的水性多异氰酸酯组成，在室温下可以自交联固化、成膜，性能优异。
羟基型水性聚氨酯树脂以水为分散介质，不含有有机溶剂，具有无毒、不易燃烧、不污染环境、不易损伤被涂饰表面、易操作等优点，理化性能可与溶剂型聚氨酯涂料相媲美。特别是在塑料涂料和汽车工业涂料方面有很广泛的应用。目前市面上出现的羟基型水性聚氨酯树脂多为线性结构，而且相对分子质量低，固含不高，对固化剂的分散性不强，不利于施工，增加了涂膜干燥的时间。同时配制出来的双组份水性聚氨酯涂料弹性差、手感不好，不适用于弹性涂料。
发明内容
本发明目的在于提供一种性能优异的柔感高固含羟基型水性聚氨酯树脂的制备方法，用其与水性多异氰酸酯固化剂制备的双组份水性聚氨酯涂料手感柔软光滑，固含量高，耐溶剂性强。
为达到上述目的，采用的技术方案如下：
一种高固含羟基型水性聚氨酯树脂的制备方法，包括以下步骤：
1）将聚酯二元醇、端羟基磺酸盐聚酯二醇、小分子二元醇、多元醇、亲水单体加入反应容器混合并脱水；
2）60～65℃下缓慢加入二异氰酸酯，1h加完并再保温1h；
3）加入催化剂，升温至65～70℃并保温反应，检测异氰酸酯含量达到小于或等于0.1wt％时停止加热；
4）降温至40～50℃，用丙酮调节黏度，并用有机胺中和至7～8；
5）在35～40℃高速搅拌下加入去离子水分散30min，减压脱除丙酮即得到乳白色泛蓝光的羟基型水性聚氨酯树脂；
其中，上述原料按重量份数计为：
Figure BDA0000421341360000021
按上述方案，所述的聚酯二元醇为聚己二酸丁二醇酯二醇、聚己二酸新戊二醇酯二醇、聚己内酯二醇或聚碳酸酯二醇。
按上述方案，所述的端羟基磺酸盐聚酯二醇为北京佰源化工有限公司生产，型号为BY3301、BY3305、BY3306的任意一种。
按上述方案，所述的小分子二元醇为辛二醇、己二醇或丁二醇。
按上述方案，所述的亲水单体为二羟甲基丙酸或二羟甲基丁酸。
按上述方案，所述的多元醇为蓖麻油、分子量500的聚己内酯三元醇、分子量1000的聚环氧丙烷三元醇中的任意一种。
按上述方案，所述的二异氰酸酯为甲苯二异氰酸酯或异佛尔酮二异氰酸酯。
按上述方案，所述的催化剂为二月桂酸二丁基锡或辛酸亚锡。
按上述方案，所述的有机胺（中和剂）为三乙胺或二甲基乙醇胺。
本发明使用的多元醇为蓖麻油、聚己内酯三元醇或聚环氧丙烷三元醇，通过与二异氰酸酯反应，所制备的水性聚氨酯树脂具有分支结构。其中蓖麻油组分中较长的、非极性脂肪酸链使涂膜具有良好的疏水作用，同时赋予涂层良好的柔软性和耐曲挠性以及耐寒性。同时，聚己内酯三元醇以及聚环氧丙烷三元醇也可以用作三羟基扩链剂，作为蓖麻油的替代品，它们可以增加涂膜的柔韧性、韧性，改善低温特性，反应性，提高交联密度。总的来说使用它们来替代市面上常用的三羟甲基丙烷（TMP），使羟基在大分子链上的分布更加均匀，制成的羟基型水性聚氨酯树脂与固化剂混合使用时活性更高，涂膜弹性更好，耐化学品性更加优异。
除了常规聚酯二元醇，本发明使用的一部分不同分子量的端羟基的磺酸盐型聚酯二元醇，因为在软段上含有磺酸钠基亲水基团，预聚的时候就嵌在聚氨酯树脂大分子链上，可避免使用大量溶剂。同时在水中分散进行相反转的时候，粘度适中，制备出的羟基型水性聚氨酯树脂粘度小、固含高。同时，由于采用端羟基的磺酸盐聚酯，可以减少亲水单体二羟甲基丙酸的用量，因此制备柔感羟基型水性聚氨酯树脂时可以不用添加对环境有污染的N-甲基吡咯烷酮(NMP)，从而使制备工艺更加环保。
本发明的有益效果为：
用其配制的双组分涂料具有良好的综合性能，涂膜外观好，柔和且柔软，弹性好，具有优异机械性如耐刮擦耐磨损性能、耐化学品性能。
具体实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
高固含羟基型水性聚氨酯树脂的制备方法，按照以下步骤：
1）将聚酯二元醇、端羟基磺酸盐聚酯二醇、小分子二元醇、多元醇、亲水单体加入反应容器混合并脱水；
2）60～65℃下缓慢加入二异氰酸酯，1h加完并再保温1h；
3）加入催化剂，升温至65～70℃并保温反应，检测异氰酸酯含量达到小于或等于0.1wt％时停止加热；
4）降温至40～50℃，用丙酮调节黏度，并用有机胺中和至7～8；
5）在35～40℃高速搅拌下加入去离子水分散30min，减压脱除丙酮即得到乳白色泛蓝光的羟基型水性聚氨酯树脂；
其中，上述原料按重量份数计为：
Figure BDA0000421341360000031
实施例1
1）将聚己二酸丁二醇酯二醇（分子量1000）、端羟基的磺酸盐聚酯（北京佰源化工有限公司生产BY3301）、辛二醇、聚己内酯三元醇（分子量为500）、2,2-二羟甲基丙酸加入反应容器混合，并在0.05MPa，107℃抽真空1h去除水分；
2）撤除真空，通入氮气保护，在65℃下缓慢滴加异佛尔酮二异氰酸酯，1h滴加完并再保温1h；
3）加入辛酸亚锡，升温至70℃并保温反应，检测异氰酸酯含量达到小于或等于0.1wt％时停止加热；
4）降温至50℃，用丙酮调节黏度，并用二甲基乙醇胺中和至7～8；
5）在45℃高速搅拌下加入去离子水分散30min，减压脱除丙酮即得到乳白色泛蓝光的羟基型水性聚氨酯树脂。
其中所用各种原料的用量为（按重量份数计）
Figure BDA0000421341360000041
经检测：本实施例所得产品白色不透明泛蓝光乳液，固含42.8%，PH值7～8，羟值为0.53%；将本实施例合成出来的羟基型水性聚氨酯树脂作为双组份水性聚氨酯的羟基组分与水性多异氰酸酯固化剂（拜耳305）nNCO:nOH=1.2:1(即异氰酸酯基与羟基的摩尔比）复配配制双组份水性聚氨酯清漆，涂于洁净玻璃板上进行性能检测。结果见表1。
表1
Figure BDA0000421341360000042
Figure BDA0000421341360000051
实施例2
1）将聚己二酸新戊二醇酯二醇（分子量1000）、端羟基的磺酸盐聚酯（北京佰源化工有限公司生产BY3305）、己二醇、蓖麻油、2,2-二羟甲基丙酸加入反应容器混合，并在0.05MPa，107℃抽真空1h去除水分；
2）撤除真空，通入氮气保护，在60℃下缓慢滴加甲苯二异氰酸酯，1h滴加完并再保温1h；
3）加入二月桂酸二丁基锡，升温至65℃并保温反应，检测异氰酸酯含量达到小于或等于0.1wt％时停止加热；
4）降温至40℃，用丙酮调节黏度，并用三乙胺中和至7～8；
5）在35℃高速搅拌下加入去离子水分散30min，减压脱除丙酮即得到乳白色泛蓝光的羟基型水性聚氨酯树脂。
实施例2中所用各种原料的用量为（按重量份数计）
Figure BDA0000421341360000052
经检测：本实施例所得产品白色不透明泛蓝光乳液，固含45.0%，PH值7～8，羟值为1.97%；
将实施例2合成出来的羟基型水性聚氨酯树脂作为双组份水性聚氨酯的羟基组分与水性多异氰酸酯固化剂（拜耳305）nNCO:nOH=1.2:1(即异氰酸酯基与羟基的摩尔比）复配配制双组份水性聚氨酯清漆，涂于洁净玻璃板上进行性能检测。测试结果见表2.
表2
Figure BDA0000421341360000061
实施例3
1）将聚己内酯二醇（分子量1000）、端羟基的磺酸盐聚酯（北京佰源化工有限公司生产BY3306）、丁二醇、聚环氧丙烷三元醇（分子量为1000）、2,2-二羟甲基丁酸加入反应容器混合，并在0.05MPa，107℃抽真空1h去除水分；
2）撤除真空，通入氮气保护，在65℃下缓慢滴加甲苯二异氰酸酯，1h滴加完并再保温1h；
3）加入二月桂酸二丁基锡，升温至70℃并保温反应，检测异氰酸酯含量达到小于或等于0.1wt％时停止加热；
4）降温至50℃，用丙酮调节黏度，并用三乙胺中和至7～8；
5）在45℃高速搅拌下加入去离子水分散30min，减压脱除丙酮即得到乳白色泛蓝光的羟基型水性聚氨酯树脂。
实施例3中所用各种原料的质量分数
经检测：本实施例所得产品白色不透明泛蓝光乳液，固含43.8.0%，PH值7～8，羟值为0.73%；将实施例3合成出来的羟基型水性聚氨酯树脂作为双组份水性聚氨酯的羟基组分与水性多异氰酸酯固化剂（拜耳305）nNCO:nOH=1.2:1(即异氰酸酯基与羟基的摩尔比）复配配制双组份水性聚氨酯清漆，涂于洁净玻璃板上进行性能检测。性能检测见表3。
表3
Figure BDA0000421341360000071
实施例4
重复实施例1的制备工艺步骤，改变原料及用量为（按重量份数计）：
Figure BDA0000421341360000072
经检测：本实施例所得产品白色不透明泛蓝光乳液，固含46.7%，PH值7～8，羟值为2.03%；将实施例4合成出来的羟基型水性聚氨酯树脂作为双组份水性聚氨酯的羟基组分与水性多异氰酸酯固化剂（拜耳305）nNCO:nOH=1.2:1(即异氰酸酯基与羟基的摩尔比）复配配制双组份水性聚氨酯清漆，涂于洁净玻璃板上进行性能检测。性能检测见表4。
表4
Figure BDA0000421341360000081
实施例5
重复实施例2的制备工艺步骤，改变原料的用量为（按重量份数计）：
Figure BDA0000421341360000082
经检测：本实施例所得产品白色不透明泛蓝光乳液，固含43.8.0%，PH值7～8，羟值为2.89%；将实施例5合成出来的羟基型水性聚氨酯树脂作为双组份水性聚氨酯的羟基组分与水性多异氰酸酯固化剂（拜耳305）nNCO:nOH=1.2:1(即异氰酸酯基与羟基的摩尔比）复配配制双组份水性聚氨酯清漆，涂于洁净玻璃板上进行性能检测。性能检测见表5。
表5
Figure BDA0000421341360000083
实施例6
重复实施例3的制备工艺步骤，改变原料的用量为（按重量份数计）：
Figure BDA0000421341360000091
经检测：本实施例所得产品白色不透明泛蓝光乳液，固含43.8.0%，PH值7～8，羟值为0.73%；将实施例6合成出来的羟基型水性聚氨酯树脂作为双组份水性聚氨酯的羟基组分与水性多异氰酸酯固化剂（拜耳305）nNCO:nOH=1.2:1(即异氰酸酯基与羟基的摩尔比）复配配制双组份水性聚氨酯清漆，涂于洁净玻璃板上进行性能检测。性能检测见表6。
表6

Claims (9)

1.一种高固含羟基型水性聚氨酯树脂的制备方法，其特征在于包括以下步骤：
1）将聚酯二元醇、端羟基磺酸盐聚酯二醇、小分子二元醇、多元醇、亲水单体加入反应容器混合并脱水；
2）60～65℃下缓慢加入二异氰酸酯，1h加完并再保温1h；
3）加入催化剂，升温至65～70℃并保温反应，检测异氰酸酯含量达到小于或等于0.1wt％时停止加热；
4）降温至40～50℃，用丙酮调节黏度，并用有机胺中和至7～8；
5）在35～40℃高速搅拌下加入去离子水分散30min，减压脱除丙酮即得到乳白色泛蓝光的羟基型水性聚氨酯树脂；
其中，上述原料按重量份数计为：
Figure FDA0000421341350000011
2.如权利要求1所述的高固含羟基型水性聚氨酯树脂的制备方法，其特征在于所述的聚酯二元醇为聚己二酸丁二醇酯二醇、聚己二酸新戊二醇酯二醇、聚己内酯二醇或聚碳酸酯二醇。
3.如权利要求1所述的高固含羟基型水性聚氨酯树脂的制备方法，其特征在于所述的端羟基磺酸盐聚酯二醇为北京佰源化工有限公司生产，型号为BY3301、BY3305、BY3306的任意一种。
4.如权利要求1所述的高固含羟基型水性聚氨酯树脂的制备方法，其特征在于所述的亲水单体为二羟甲基丙酸或二羟甲基丁酸。
5.如权利要求1所述的高固含羟基型水性聚氨酯树脂的制备方法，其特征在于所述的多元醇为蓖麻油、分子量500的聚己内酯三元醇、分子量1000的聚环氧丙烷三元醇中的任意一种。
6.如权利要求1所述的高固含羟基型水性聚氨酯树脂的制备方法，其特征在于所述的二异氰酸酯为甲苯二异氰酸酯或异佛尔酮二异氰酸酯。
7.如权利要求1所述的高固含羟基型水性聚氨酯树脂的制备方法，其特征在于所述的催化剂为二月桂酸二丁基锡或辛酸亚锡。
8.如权利要求1所述的高固含羟基型水性聚氨酯树脂的制备方法，其特征在于所述的有机胺为三乙胺或二甲基乙醇胺。
9.如权利要求1所述的高固含羟基型水性聚氨酯树脂的制备方法，其特征在于所述的小分子二元醇为辛二醇、己二醇或丁二醇。
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