CN111995719B - 一种高性能水性聚氨酯丙烯酸酯复合乳液及其制备方法 - Google Patents

一种高性能水性聚氨酯丙烯酸酯复合乳液及其制备方法 Download PDF

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CN111995719B
CN111995719B CN202010664351.8A CN202010664351A CN111995719B CN 111995719 B CN111995719 B CN 111995719B CN 202010664351 A CN202010664351 A CN 202010664351A CN 111995719 B CN111995719 B CN 111995719B
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李朝龙
吴声坤
潘长富
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Chongqing Institute Of Graphene
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Abstract

本发明提出了一种高性能水性聚氨酯丙烯酸酯复合乳液及其制备方法，先制备一种含有异氰酸酯基团和双键的功能性丙烯酸酯交联单体；再用功能性丙烯酸酯交联单体去改性制备高性能水性聚氨酯丙烯酸酯复合乳液。该复合乳液交联度高，分子量大，具有低模量、高回弹、高断裂伸长率等性能，特别适合制备薄壁材料。

Description

一种高性能水性聚氨酯丙烯酸酯复合乳液及其制备方法
技术领域
本发明属于水性聚氨酯薄壁材料应用领域，具体涉及一种高性能水性聚氨酯丙烯酸酯复合乳液及其制备方法和应用。
背景技术
高分子薄壁材料指的是由具有良好力学性能的高分子弹性体构成的薄膜，厚度在几个微米到几十个微米，特指可以构成完整制品的高分子弹性体薄膜材料。常见的这类制品有手术手套、避孕套、指套等。
水性聚氨酯材料通常作为涂料和粘合剂使用，其显著特征是其附着在其他材料之上使用。相对来说，其力学性能要求不高。以水性聚氨酯制作薄壁材料进而制备薄壁制品一直是水性聚氨酯研究者的梦想，但实践中并不成功，其原因是水性聚氨酯的力学性能很难达到薄壁材料对力学性能的要求。这里主要有三点：首先，薄壁材料不同于涂料和粘合剂，无基材的支撑，力学性能完全取决于水性聚氨酯本身；其次，水性聚氨酯材料本身受到合成工艺的限制，相对于溶剂型聚氨酯材料其相对分子质量较低，水性聚氨酯分散体材料的物理与化学性能存在先天不足；最后，薄壁制品如手术手套和避孕套等都需要低模量、高抗张性、高回弹性、低永久变形等性能，而这些性能都是水性聚氨酯材料的弱项。
目前，还没有相关水性聚氨酯丙烯酸酯复合乳液用于薄壁材料的相关研究和应用。本发明针对现有水性聚氨酯在薄壁材料领域应用的难点，提供了一种水性聚氨酯丙烯酸酯复合乳液，可以用于制备薄壁材料，如避孕套和手套等。
发明内容
本发明的目的是提供一种高性能水性聚氨酯丙烯酸酯复合乳液，其特征在于:先制备一种含有异氰酸酯基团和双键的功能性丙烯酸酯交联单体；用所述功能性丙烯酸酯交联单体去改性制备高性能水性聚氨酯丙烯酸酯复合乳液。
本发明公开制备上述高性能水性聚氨酯丙烯酸酯复合乳液的方法，其特征在于，包括以下步骤：
(1)特种功能性丙烯酸酯交联单体的制备
将异佛尔酮二异氰酸酯(IPDI)和带羟基的乙烯基单体加入反应器中，在惰性气体的保护下，催化反应制得双官能度的功能性丙烯酸酯交联单体。
(2)高性能水性聚氨酯丙烯酸酯复合乳液的制备
1)向反应器中加入二异氰酸酯、聚合物多元醇和亲水扩链剂，加热条件下进行反应；
2)再向步骤1)的混合物体系中加入带羟基的乙烯基单体进行封端反应；
3)封端反应结束后，对体系进行降温、中和。
4)加入可聚合表面活性单体、功能性丙烯酸酯交联单体的丙酮溶液，搅拌混合后，加水乳化,得到分散液；
5)将所述分散液升高后滴加水溶性引发剂的水溶液，反应完成后，降至室温，即制得高性能水性聚氨酯丙烯酸酯复合乳液。
进一步，步骤(1)中，异佛尔酮二异氰酸酯(IPDI)和带羟基的乙烯基单体摩尔比为1:2；
进一步，催化剂为羧酸铋；
进一步，催化反应是在60℃～70℃下反应4～5h，然后降温并加入丙酮降低粘度。
进一步，步骤2的原料的配比为：
Figure BDA0002579785000000021
进一步，带羟基的乙烯基单体包括甲基丙烯酸羟乙酯、丙烯酸羟乙酯、甲基丙烯酸羟丙酯；
进一步，二异氰酸酯为异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯，优选异佛尔酮二异氰酸酯；
进一步，聚合物多元醇包括聚醚二元醇、聚酯二元醇、聚丁二烯二元醇中的一种或几种；
进一步，亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸；
进一步，带羟基的乙烯基单体为甲基丙烯酸羟乙酯、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯的一种或2种混合物；
进一步，可聚合表面活性单体为烯丙氧基癸基聚氧乙烯醚(10)硫酸氨或十二烷基二甲基乙基甲基丙烯酸酯；
进一步，功能性丙烯酸酯交联单体丙酮溶液的浓度为50～70％；
进一步，水溶性引发剂为过硫酸铵或过硫酸钾，水溶性引发剂的水溶液的浓度为：0.5-1％。
进一步，步骤1)中，反应温度恒定为75～85℃，反应时间为2-3小时；
进一步，步骤2)中，封端反应的体系温度保持为60～75℃，反应2h；
进一步，步骤3)中，封端反应结束后，降温到40-50℃，再加入三乙胺中和剂后，进行中和反应0.5小时。
进一步，步骤4)中，可聚合表面活性单体和功能性丙烯酸酯交联单体丙酮溶液混合后，搅拌5-10分钟，然后加去离子水进行高速乳化0.5～1h,得到分散液；
进一步，步骤5)中，体系升高温度，在恒温72～80℃下，匀速滴加水溶性引发剂的水溶液反应2-3小时后，降至室温。
本发明取得的有益效果如下：通过先制备一种含有异氰酸酯基团和双键的功能性丙烯酸酯交联单体，再用功能性丙烯酸酯交联单体去改性制备高性能水性聚氨酯丙烯酸酯复合乳液。该方法与传统水性聚氨酯丙烯酸酯复合乳液相比，没有单体残留，合成方法工艺简单，可以制备高交联度和高分子量的水性聚氨酯丙烯酸酯复合乳液，该乳液制得的薄膜具有低模量、高回弹、高断裂伸长率，特别适合用于制备薄壁材料。
具体实施方式
下面结合实施例对本发明作进一步说明，但不应该理解为本发明上述主题范围仅限于下述实施例。在不脱离本发明上述技术思想的情况下，根据本领域普通技术知识和惯用手段，做出各种替换和变更，均应包括在本发明的保护范围内。
实施例1
1、特种功能性丙烯酸酯交联单体的制备
准确称量异佛尔酮二异氰酸酯(IPDI)222.3g和甲基丙烯酸羟乙酯260.28g加入装有搅拌装置的三口烧瓶中，通氮气，在催化剂羧酸铋作用下，在60℃～70℃下反应4～5h，然后降温并加入丙酮206.82g稀释降低粘度，即得到70％质量分数的双官能度的功能性丙烯酸酯交联单体A-1。
2、高性能水性聚氨酯丙烯酸酯复合乳液的制备
1)向干燥的三口烧瓶中加入20g异佛尔酮二异氰酸酯、50g的聚四氢呋喃醚2000、6g亲水扩链剂二羟甲基丙酸，反应温度恒定为75～85℃，反应时间为2-3小时；
2)再向体系中加入2g甲基丙烯酸羟乙酯单体进行封端，体系温度保持为60～75℃，反应2h；
3)封端反应结束后降温到40-50℃，再加入4g三乙胺中和剂，进行中和反应0.5小时。
4)加入0.05g可聚合表面活性单体烯丙氧基癸基聚氧乙烯醚(10)硫酸氨KL-100、10g功能性丙烯酸酯交联单体丙酮溶液A-1，搅拌混合5-10分钟，然后加去离子水进行高速乳化0.5～1h,得到分散液；
5)最后升高温度，在恒温72～80℃下，匀速滴加20g含有0.5％过硫酸钾水溶液，反应2-3小时后，降至室温，即制得高交联度高分子量的水性聚氨酯丙烯酸酯复合乳液PUA-1。
实施例2
1、特种功能性丙烯酸酯交联单体的制备
准确称量异佛尔酮二异氰酸酯(IPDI)222.3g和丙烯酸羟乙酯232.24g加入装有搅拌装置的三口烧瓶中，通氮气，在催化剂羧酸铋作用下，在60℃～70℃下反应4～5h，然后降温并加入丙酮194.8g稀释降低粘度，即得到70％质量分数的双官能度的功能性丙烯酸酯交联单体A-2。
2、高性能水性聚氨酯丙烯酸酯复合乳液的制备
1)向干燥的三口烧瓶中加入18g异佛尔酮二异氰酸酯、42g的聚己内酯二元醇2000、5g亲水扩链剂二羟甲基丙酸，反应温度恒定为75～85℃，反应时间为2-3小时；
2)再向体系中加入2g丙烯酸羟乙酯单体进行封端，体系温度保持为60～75℃，反应2h；
3)封端反应结束后降温到40-50℃，再加入3.5g三乙胺中和剂，进行中和反应0.5小时。
4)加入0.04g可聚合表面活性单体烯丙氧基癸基聚氧乙烯醚(10)硫酸氨KL-100、9g功能性丙烯酸酯交联单体丙酮溶液A-2，搅拌混合5-10分钟，然后加去离子水进行高速乳化0.5～1h,得到分散液；
5)最后升高温度，在恒温72～80℃下，匀速滴加15g含有0.5％过硫酸钾水溶液，反应2-3小时后，降至室温，即制得高交联度高分子量的水性聚氨酯丙烯酸酯复合乳液PUA-2。
实施例3
1、特种功能性丙烯酸酯交联单体的制备
准确称量异佛尔酮二异氰酸酯(IPDI)222.3g和甲基丙烯酸羟丙酯288.34g加入装有搅拌装置的三口烧瓶中，通氮气，在催化剂羧酸铋作用下，在60℃～70℃下反应4～5h，然后降温并加入丙酮218.8g稀释降低粘度，即得到70％质量分数的双官能度的功能性丙烯酸酯交联单体A-3。
2、高性能水性聚氨酯丙烯酸酯复合乳液的制备
1)向干燥的三口烧瓶中加入18g异佛尔酮二异氰酸酯、30g的端羟基聚丁二烯二元醇、6g亲水扩链剂二羟甲基丙酸，反应温度恒定为75～85℃，反应时间为2-3小时；
2)再向体系中加入2g甲基丙烯酸羟丙酯单体进行封端，体系温度保持为60～75℃，反应2h；
3)封端反应结束后降温到40-50℃，再加入4g三乙胺中和剂，进行中和反应0.5小时。
4)加入0.05g可聚合表面活性单体十二烷基二甲基乙基甲基丙烯酸酯、8g功能性丙烯酸酯交联单体丙酮溶液A-3，搅拌混合5-10分钟，然后加去离子水进行高速乳化0.5～1h,得到分散液；
5)最后升高温度，在恒温72～80℃下，匀速滴加10g含有0.5％过硫酸钾水溶液，反应2-3小时后，降至室温，即制得高交联度高分子量的水性聚氨酯丙烯酸酯复合乳液PUA-3。
实施例4
1、特种功能性丙烯酸酯交联单体的制备
准确称量异佛尔酮二异氰酸酯(IPDI)222.3g和丙烯酸羟丙酯260.28g加入装有搅拌装置的三口烧瓶中，通氮气，在催化剂羧酸铋作用下，在60℃～70℃下反应4～5h，然后降温并加入丙酮206.8g稀释降低粘度，即得到70％质量分数的双官能度的功能性丙烯酸酯交联单体A-4。
2、高性能水性聚氨酯丙烯酸酯复合乳液的制备
1)向干燥的三口烧瓶中加入18g异佛尔酮二异氰酸酯、30g的端羟基聚丁二烯二元醇、4.5g亲水扩链剂二羟甲基丙酸，反应温度恒定为75～85℃，反应时间为2-3小时；
2)再向体系中加入1.2g丙烯酸羟丙酯单体进行封端，体系温度保持为60～75℃，反应2h；
3)封端反应结束后降温到40-50℃，再加入3g三乙胺中和剂，进行中和反应0.5小时。
4)加入0.02g可聚合表面活性单体十二烷基二甲基乙基甲基丙烯酸酯、7g功能性丙烯酸酯交联单体丙酮溶液A-4，搅拌混合5-10分钟，然后加去离子水进行高速乳化0.5～1h,得到分散液；
5)最后升高温度，在恒温72～80℃下，匀速滴加6g含有0.5％过硫酸钾水溶液，反应2-3小时后，降至室温，即制得高交联度高分子量的水性聚氨酯丙烯酸酯复合乳液PUA-4。
将实施例1-4水性聚氨酯丙烯酸酯复合乳液成膜，然后测试各项性能，性能数据如下表所示。
实施例 实施例1 实施例2 实施例3 实施例4
薄膜厚度μm 25 25 25 25
100％模量/MPa 0.82 0.91 0.75 0.98
拉伸强度/MPa 32.5 41.8 28.8 35.2
断裂伸长率/％ 650 632 608 592
拉伸永久形变(1min)/％ 1.2 0.8 1 1.5
从表中性能数据可以看出，本发明方法制备出的高性能水性聚氨酯丙烯酸酯复合乳液具有低模量、高强度、高断裂伸长率和高回弹性等性能，特别适合用于制备薄壁材料，完全满足薄壁材料所需性能。

Claims (9)

1.一种高性能水性聚氨酯丙烯酸酯复合乳液的制备方法，其特征在于:先制备一种含有异氰酸酯基团和双键的功能性丙烯酸酯交联单体；用所述功能性丙烯酸酯交联单体去改性制备高性能水性聚氨酯丙烯酸酯复合乳液；包括以下步骤：
（1）所述功能性丙烯酸酯交联单体的制备
将异佛尔酮二异氰酸酯（IPDI）和带羟基的乙烯基单体加入反应器中，在惰性气体的保护下，催化反应制得双官能度的功能性丙烯酸酯交联单体；
（2）高性能水性聚氨酯丙烯酸酯复合乳液的制备
1）向反应器中加入二异氰酸酯、聚合物多元醇和亲水扩链剂，加热条件下进行反应；
2）再向步骤1）的混合物体系中加入带羟基的乙烯基单体进行封端反应；
3）封端反应结束后，对体系进行降温、中和；封端反应结束后，降温到40-50℃，再加入三乙胺中和剂后，进行中和反应0.5小时；
4）加入可聚合表面活性单体、功能性丙烯酸酯交联单体的丙酮溶液，搅拌混合后，加水乳化，得到分散液；
5）将所述分散液升高温度后滴加水溶性引发剂的水溶液，反应完成后，降至室温，即制得高性能水性聚氨酯丙烯酸酯复合乳液。
2.根据权利要求1所述的制备方法，其特征在于，步骤（2）的原料的配比为：步骤（1）中，异佛尔酮二异氰酸酯（IPDI）和带羟基的乙烯基单体摩尔比为1:2；
催化剂为羧酸铋类；
催化反应是在60℃~70℃下反应4~5h，然后降温并加入丙酮降低粘度。
3.根据权利要求1所述的制备方法，其特征在于，步骤（2）的原料的配比为：
二异氰酸酯 10-20份
聚合物多元醇 30-50份
亲水扩链剂 3-6份
带羟基的乙烯基单体 1.5-4份
三乙胺 1.5-4份
可聚合表面活性单体 0.02-0.05份
功能性丙烯酸酯交联单体丙酮溶液 1-10份
水溶性引发剂的水溶液 20份。
4.根据权利要求1所述的制备方法，其特征在于：
二异氰酸酯为异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯；
聚合物多元醇包括聚醚二元醇、聚酯二元醇、聚丁二烯二元醇中的一种或几种；
亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸；
带羟基的乙烯基单体为甲基丙烯酸羟乙酯、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯的一种或2种混合物；
可聚合表面活性单体为烯丙氧基癸基聚氧乙烯醚（10）硫酸氨或十二烷基二甲基乙基甲基丙烯酸酯；
水溶性引发剂为过硫酸铵或过硫酸钾。
5.根据权利要求1所述的制备方法，其特征在于：
步骤1）中，反应温度恒定为75～85℃，反应时间为2-3小时。
6.根据权利要求2所述的制备方法，其特征在于：步骤2）中，封端反应的体系温度保持为60～75℃，反应2h。
7.根据权利要求6所述的制备方法，其特征在于：步骤4）中，可聚合表面活性单体和功能性丙烯酸酯交联单体丙酮溶液混合后，搅拌5-10分钟，然后加去离子水进行高速乳化0.5~1h,得到分散液。
8.根据权利要求6所述的制备方法，其特征在于：步骤5）中，体系升高温度，在恒温72～80℃下，匀速滴加水溶性引发剂的水溶液反应2-3小时后，降至室温。
9.一种高性能水性聚氨酯丙烯酸酯复合乳液，其特征在于：采用权利要求1～8任意一项所述的方法制备。
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