CN106957557B - 一种用于水性uv聚氨酯涂料的缔合型增稠剂及其制备方法 - Google Patents

一种用于水性uv聚氨酯涂料的缔合型增稠剂及其制备方法 Download PDF

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CN106957557B
CN106957557B CN201710188469.6A CN201710188469A CN106957557B CN 106957557 B CN106957557 B CN 106957557B CN 201710188469 A CN201710188469 A CN 201710188469A CN 106957557 B CN106957557 B CN 106957557B
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施丹
王�锋
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Abstract

本发明公开了一种用于水性UV聚氨酯涂料的缔合型增稠剂及其制备方法，包含以下组分：聚乙二醇，二异氰酸酯，烯醇封端剂，催化剂；其中聚乙二醇，二异氰酸酯，烯醇封端剂的摩尔比为1:1.1‑1.5:0.2‑1；催化剂占总物料的质量分数为0.05‑2％，本发明提供的用于水性UV聚氨酯涂料的缔合型增稠剂含有活性官能团，可参与UV涂料体系的紫外光固化交联反应，具有更好的稳定性。

Description

一种用于水性UV聚氨酯涂料的缔合型增稠剂及其制备方法
技术领域
本发明涉及新材料化学领域，尤其涉及一种用于水性UV聚氨酯涂料的缔合型增稠剂及其制备方法。
背景技术
水性UV涂料结合了水性涂料和光固化技术两者的优点，具有固化速度快、生产效率高、设备投资少、固化温度低、性能优异、对环境污染少等特点，近年来得到了广泛的应用。其中，水性UV聚氨酯涂料以其分子结构可设计性强、性能突出、与其他乳液体系相容性好等优点，成为应用量最大的水性UV涂料之一。
水性UV聚氨酯涂料以水作为稀释剂，避免了传统UV涂料使用大量活性稀释剂带来的毒害。水性UV聚氨酯涂料的黏度一般较低，在储存或施工时需要采用增稠剂来调节黏度，增稠剂是一类可以调节体系黏度与流变性能的重要助剂，传统的增稠剂如无机增稠剂和碱溶胀型增稠剂在水性涂料的应用中存在增稠以后对电解质比较敏感、黏度的稳定性不好等缺点，而水性聚氨酯缔合型增稠剂(HEUR)以其流平性好、剪切变稀作用、黏度稳定性强等特点，自20世纪80年代出现以来，十分受人们的欢迎，其应用也越来越广泛，但目前常用的水性聚氨酯缔合型增稠剂无法参与水性UV体系的交联反应，会影响到固化膜的性能稳定性。
发明内容
为了克服现有技术的不足，本发明的目的在于提供一种用于水性UV聚氨酯涂料的缔合型增稠剂及其制备方法，其能解决目前常用的水性UV聚氨酯缔合型增稠剂无法参与水性UV体系的交联反应，会影响到固化膜稳定性的问题。
本发明的目的采用以下技术方案实现：
一种用于水性UV聚氨酯涂料的缔合型增稠剂，包含以下组分：聚乙二醇，二异氰酸酯，烯醇封端剂，催化剂；其中聚乙二醇，二异氰酸酯，烯醇封端剂的摩尔比为1:1.1-1.5:0.2-1；催化剂占总物料的质量分数为0.05-2％。
本发明所述的一种用于水性UV聚氨酯涂料的缔合型增稠剂，其中，所述聚乙二醇分子量为3000-30000。
本发明所述的一种用于水性UV聚氨酯涂料的缔合型增稠剂，其中，所述二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环已基甲烷二异氰酸酯、萘1,5-二异氰酸酯中的一种。
本发明所述的一种用于水性UV聚氨酯涂料的缔合型增稠剂，其中，所述烯醇封端剂为十一烯醇、十八烯醇中的一种。
本发明所述的一种用于水性UV聚氨酯涂料的缔合型增稠剂，其中，所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的一种。
本发明还提供上述一种用于水性UV聚氨酯涂料的缔合型增稠剂的制备方法，包括如下步骤：
一种用于水性UV聚氨酯涂料的缔合型增稠剂的制备方法，包括如下步骤：
(1)将聚乙二醇进行脱水处理：将聚乙二醇加入到反应容器中，升温至100-120℃，真空干燥脱水1-3h；
(2)向步骤(1)反应容器通入惰性气体，在60-80℃，加入催化剂和二异氰酸酯，保温反应2-5h。
(3)将步骤(2)的反应液升温至90-100℃，加入烯醇封端剂，保温反应1-2h后，即得到增稠剂产品。
相比现有技术，本发明的有益效果在于：
1、本发明提供的用于一种水性UV聚氨酯涂料的缔合型增稠剂通过采用烯醇封端剂，引入不饱和的碳碳双键，具备了紫外光固化交联反应特性，可参与UV涂料体系的紫外光固化交联反应。
2、本发明提供的一种用于水性UV聚氨酯涂料的缔合型增稠剂具有优异的增稠效果，可以在较低用量时达到较好的增稠效果，当其用量为5％时，可使水性UV聚氨酯涂料在6rpm条件下的旋转黏度从360cps增加到6000cps以上，在6rpm和60rpm条件下的旋转黏度比值大于2.5。
具体实施方式
下面，结合具体实施方式，对本发明做进一步描述：一种用于水性UV聚氨酯涂料的缔合型增稠剂，包含以下组分：聚乙二醇，二异氰酸酯，烯醇封端剂，催化剂；其中聚乙二醇，二异氰酸酯，烯醇封端剂的摩尔比为1:1.5-1.1:0.2-1；催化剂占总物料的质量分数为0.05-2％。
所述聚乙二醇分子量为3000-30000。
所述二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环已基甲烷二异氰酸酯、萘1,5-二异氰酸酯中的一种；
所述烯醇封端剂为十一烯醇、十八烯醇中的一种；
所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的一种。
本发明还提供如上所述一种用于水性UV聚氨酯涂料的缔合型增稠剂的制备方法，包括如下步骤：
(1)将聚乙二醇进行脱水处理：将聚乙二醇加入到反应容器中，升温至100-120℃，真空干燥脱水1-3h；
(2)向步骤(1)反应容器通入惰性气体，在60-80℃，加入催化剂和二异氰酸酯，保温反应2-5h；
(3)将步骤(2)的反应液升温至90-100℃，加入烯醇封端剂，保温反应1-2h后，即得到增稠剂产品。
实施例1
(1)将10摩尔份聚乙二醇(分子量3000)加入到反应容器中，升温至100℃，真空干燥脱水2h。
(2)向反应容器通入氮气，并降温至60℃，加入催化剂二月桂酸二丁基锡(0.05wt％)和11摩尔份甲苯二异氰酸酯，保温反应3h。
(3)升温至90℃，加入2摩尔份十一烯醇封端剂，保温反应2h后，趁热倒入四氟模板中，放入真空烘箱，室温冷却后即得到增稠剂产品。
实施例2
(1)将10摩尔份聚乙二醇(分子量6000)加入到反应容器中，升温至110℃，真空干燥脱水3h。
(2)向反应容器通入氮气，并降温至70℃，加入催化剂二月桂酸二丁基锡(0.1wt％)和12摩尔份六亚甲基二异氰酸酯，保温反应4h。
(3)升温至90℃，加入4摩尔份十一烯醇封端剂，保温反应2h后，趁热倒入四氟模板中，放入真空烘箱，室温冷却后即得到增稠剂产品。
实施例3
(1)将10摩尔份聚乙二醇(分子量10000)加入到反应容器中，升温至120℃，真空干燥脱水1h。
(2)向反应容器通入氮气，并降温至80℃，加入催化剂辛酸亚锡(0.05wt％)和15摩尔份异佛尔酮二异氰酸酯，保温反应5h。
(3)升温至100℃，加入10摩尔份十八烯醇封端剂，保温反应1h后，趁热倒入四氟模板中，放入真空烘箱，室温冷却后即得到增稠剂产品。
实施例4
(1)将10摩尔份聚乙二醇(分子量30000)加入到反应容器中，升温至120℃，真空干燥脱水3h。
(2)向反应容器通入氮气，并降温至80℃，加入催化剂辛酸亚锡(0.2wt％)和13摩尔份二环已基甲烷二异氰酸酯，保温反应2h。
(3)升温至100℃，加入6摩尔份十八烯醇封端剂，保温反应2h后，趁热倒入四氟模板中，放入真空烘箱，室温冷却后即得到增稠剂产品。
增稠性测试：将实施例1-4得到的增稠剂产品按50％固含量溶于丙二醇-水混合溶液(丙二醇与水的体积比为1:2)，取20g加入到200g水性UV聚氨酯涂料(
Figure GDA0002450452930000061
UV2282)中，搅拌20min，静置20min后测试涂料的旋转黏度(NDJ-1型旋转黏度计，6rpm和60rpm)。
表1：不同剪切下的黏度和触变指数
Figure GDA0002450452930000062
由上表可知实施例1至4合成的用于水性UV聚氨酯涂料的缔合型增稠剂经测定，当其用量为涂料的5％时，可使水性UV聚氨酯涂料在6rpm条件下的旋转黏度从360cps增加到6000cps以上，在60rpm条件下的旋转黏度从356cps增加到2500cps以上说明具有良好的增稠效果；水性UV聚氨酯涂料在6rpm和60rpm条件下的旋转黏度比值(触变指数)大于2.5，说明具有了较好的剪切变稀效果。
对本领域的技术人员来说，可根据以上描述的技术方案以及构思，做出其它各种相应的改变以及形变，而所有的这些改变以及形变都应该属于本发明权利要求的保护范围之内。

Claims (4)

1.一种用于水性UV聚氨酯涂料的缔合型增稠剂，其特征在于，包含以下组分：聚乙二醇，二异氰酸酯，烯醇封端剂，催化剂；其中聚乙二醇，二异氰酸酯，烯醇封端剂的摩尔比为1:1.1-1.5:0.2-1；催化剂占总物料的质量分数为0.05-2％；所述烯醇封端剂为十一烯醇、十八烯醇中的一种；
一种用于水性UV聚氨酯涂料的缔合型增稠剂的制备方法，包括如下步骤：
(1)将聚乙二醇进行脱水处理：将聚乙二醇加入到反应容器中，升温至100-120℃，真空干燥脱水1-3h；
(2)向步骤(1)所述反应容器中通入惰性气体，在60-80℃，加入催化剂和二异氰酸酯，保温反应2-5h；
(3)将步骤(2)的反应液升温至90-100℃，加入烯醇封端剂，保温反应1-2h后，即得到增稠剂产品。
2.根据权利要求1所述的一种用于水性UV聚氨酯涂料的缔合型增稠剂，其特征在于，所述聚乙二醇分子量为3000-30000。
3.根据权利要求1所述的一种用于水性UV聚氨酯涂料的缔合型增稠剂，其特征在于，所述二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环已基甲烷二异氰酸酯、萘1,5-二异氰酸酯中的一种。
4.根据权利要求1所述的一种用于水性UV聚氨酯涂料的缔合型增稠剂，其特征在于，所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的一种。
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