CN107778438A - 水性聚氨酯缔合型增稠剂及其制备方法 - Google Patents

水性聚氨酯缔合型增稠剂及其制备方法 Download PDF

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CN107778438A
CN107778438A CN201711061241.7A CN201711061241A CN107778438A CN 107778438 A CN107778438 A CN 107778438A CN 201711061241 A CN201711061241 A CN 201711061241A CN 107778438 A CN107778438 A CN 107778438A
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张善志
徐群策
徐卡特
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WENZHOU GUOSHIBANG POLYMER MATERIALS CO Ltd
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Abstract

本发明涉及一种水性聚氨酯缔合型增稠剂及其制备方法，包括聚乙二醇、二异氰酸酯、溶剂、中和剂、催化剂和抗氧化剂；主要是在聚乙二醇与二异氰酸酯的混合反应物加入双羟基羧酸亲水扩链剂、极性非质子化强溶剂、长链烷基醇和一乙醇胺；聚乙二醇的分子量为400‑800，其物质的量为二异氰酸酯的50%；双羟基羧酸亲水扩链剂的物质的量为二异氰酸酯的33.3%；极性非质子化强溶剂物质的量为聚乙二醇、二异氰酸酯、双羟基羧酸亲水扩链剂组成聚合物的40%‑50%；长链烷基醇的碳原子数为12以上，其物质的量为二异氰酸酯的16.7%；一乙醇胺物质的量为二异氰酸酯的3%‑5%。具有亲水性好，增稠效果好，产品性能稳定，制备工艺简单等优点。

Description

水性聚氨酯缔合型增稠剂及其制备方法
技术领域
本发明属于高分子材料领域，尤其涉及一种水性聚氨酯缔合型增稠剂。
背景技术
水性聚氨酯缔合型增稠剂一般由疏水基、亲水链和交联剂组成。疏水基通常是油基、十八烷基、十二烷苯基、壬酚基等，其起缔合作用，是决定增稠效果的的主要因素。亲水链通常是聚醚醇等物质，能提供化学稳定性和粘度稳定性。交联剂指的是二异氰酸酯或多异氰酸酯，通常使用的是六亚甲基二异氰酸酯HDI、异佛尔酮二异氰酸酯IPDI、4,4'-二环己基甲烷二异氰酸酯H12MDI 等。其增稠机理是通过分子疏水端与乳胶粒子、表面活性剂、颜料等疏水结构缔合，形成立体网状结构，当其浓度高于临界胶束浓度时，形成胶束；而亲水链与水分子氢键起作用，从而达到增稠结果。如专利CN201210426530.3 “含疏水侧基的线型水性聚氨酯增稠剂的制备方法”，描述一种由40%-60%聚乙二醇、10%-30%二异氰酸酯和10%-30%封端剂在催化剂作用下反应形成半封端结构，然后使用小分子扩链剂增大分子量，形成最终的水性聚氨酯增稠剂。其缺点在于反应过程中粘度较大，最后形成的预聚体需要进行干燥，干燥后按20：80加水搅拌形成20%固含量的增稠剂，产品稳定性较差，影响了增稠性能。
发明内容
本发明的目的是针对现有技术存在的缺点，提供一种产品性能稳定、增稠效果好，反应过程粘度低，制备工艺简单的水性聚氨酯缔合型增稠剂及其制备方法。
本发明水性聚氨酯缔合型增稠剂组成方案，包括聚乙二醇、二异氰酸酯、溶剂、中和剂、催化剂和抗氧化剂；主要是在聚乙二醇与二异氰酸酯的混合反应物加入双羟基羧酸亲水扩链剂、极性非质子化强溶剂、长链烷基醇和一乙醇胺；聚乙二醇的分子量为400-800，其物质的量为二异氰酸酯的50%；双羟基羧酸亲水扩链剂的物质的量为二异氰酸酯的33.3%；极性非质子化强溶剂物质的量为聚乙二醇、二异氰酸酯、双羟基羧酸亲水扩链剂组成聚合物的40%-50%；长链烷基醇的碳原子数为12以上，其物质的量为二异氰酸酯的16.7%；一乙醇胺物质的量为二异氰酸酯的3%-5%。
最好是，双羟基羧酸亲水扩链剂为2，2-二羟基丙酸或2，2-二羟基丁酸，或两者的混合物。
最好是，二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯的一种或多种的混合物。
最好是，极性非质子化强溶剂为N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基甲酰胺中的一种或两种。
最好是，抗氧化剂为四【β-（3，5-二叔丁基-4-羟基苯基）丙酸】季戊四醇酯。
本发明水性聚氨酯缔合型增稠剂的制备方法，其特征是：
1）投料聚乙二醇900-1200份入2000L备料釜，升温至1150C，抽真空脱水0.5小时，打开回流冷凝阀，通入氮气保护；
2）降温至800C，中速搅拌下，投料抗氧化剂0.2-0.5份，搅拌均匀后，按顺序投料150-200份极性非质子化强溶剂、250-350份二异氰酸酯、1-2份催化剂，保温反应1.0-1.5小时至设定异氰酸根值；
3）投料65-75份双羟基羧酸亲水扩链剂，保温反应2小时至设定异氰酸根值；
4）投料150-200份极性非质子化强溶剂、120-140份长链烷基醇，保温反应1.5-2.0小时至异氰酸根达到设定含量；
5）关闭热水阀，打开冷却水阀，将物料降温至500C以下时，投料50-100份醋酸乙酯溶剂、40-50份三乙胺中和剂、3-5份一乙醇胺，并充分搅拌30分钟；
6）慢速搅拌下，投料450-550份水进行稀释，并搅拌均匀；
7）检测合格后，过滤包装。
本发明与现有技术相比的有益效果是：本发明采用亲水性双羟基羧酸作为扩链剂，并且在疏水基团反应前进行扩链，形成端基为异氰酸根的分子，然后与长链烷基醇反应，形成最后的两端疏水、中间亲水的长分子链，该分子链的中间部分为亲水性部分，包括聚乙二醇和双羟基羧酸盐，分子链两端为通过异氰酸酯根连接的长链烷基醇疏水基团，经双羟基羧酸盐强化后的聚乙二醇中间分子链具有很强的亲水性，在极性非质子化强溶剂的作用下，与水和亲水性基团具有很好的缔合效果，制备工艺过程中混合物粘度低，其亲水性好，增稠效果好，产品性能稳定，制备工艺简单。
具体实施方式
本发明水性聚氨酯缔合型增稠剂组成方案，包括聚乙二醇、二异氰酸酯、、溶剂、中和剂、催化剂和抗氧化剂；在聚乙二醇与二异氰酸酯的混合反应物加入双羟基羧酸亲水扩链剂、极性非质子化强溶剂、长链烷基醇和一乙醇胺，乙醇胺作为反应终止剂；聚乙二醇采用分子量为400-800，其物质的量为二异氰酸酯的50%，即两个异氰酸酯与一个聚乙二醇反应，这样形成端异氰酸根的分子链，这时R值为2.0，即异氰酸根：羟基=2.0；双羟基羧酸亲水扩链剂物质的量为二异氰酸酯的33.3%；极性非质子化强溶剂物质的量为聚乙二醇、二异氰酸酯、双羟基羧酸亲水扩链剂组成聚合物的40%-50%；长链烷基醇的碳原子数为12以上，其物质的量为二异氰酸酯的16.7%；一乙醇胺物质的量为二异氰酸酯的3%-5%。以上所述物质的量单位为mol。
聚乙二醇和亲水性扩链剂两种反应物叠加达成亲水基团，亲水基团与水亲和越好，增稠效果就越明显；长链烷基醇形成疏水基团，疏水基团越排斥亲水性的环境，缔合效果越佳。
长链烷基醇与分子反应进行封端（这里所述的“分子”是指前面物质反应所组成的中间体的分子），形成最终的大分子。使分子链中间的强亲水性缔合点比一般增稠剂分子更多，亲水性更强，增稠效果更为明显。通常的水性聚氨酯缔合型增稠剂的反应，是先封端，相当于将二异氰酸酯进行半封端，然后将一个小分子扩链剂连接另一半的基团，这样形成的分子链间亲水性基团至少少了一半。而本方案是利用封端前二异氰酸根可以重复反应的特点，两次叠加亲水性缔合点，甚至可以多次叠加，最后进行封端反应。
采用一乙醇胺，对可能未反应的异氰酸根进行终止反应，以增强产品的品质稳定性。
双羟基羧酸亲水扩链剂为2，2-二羟基丙酸或2，2-二羟基丁酸，或两者的混合物。双羟基羧酸使异氰酸根的羟基=1.5，R值为1.5，形成中间有两个双羟基羧酸、两端是异氰酸根的分子链，整条分子链中通过羧酸盐形成的亲水性缔合点为2个，其它为聚乙二醇。
二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯的一种或多种的混合物。
极性非质子化强溶剂为N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基甲酰胺中的一种或两种。其除了用于溶解双羟基羧酸形成透明溶液，保证反应均匀性之外，还有助于亲水基团形成缔合作用。
抗氧化剂为四【β-（3，5-二叔丁基-4-羟基苯基）丙酸】季戊四醇酯，可以有效防止芳香族二异氰酸酯在反应时氧化，形成无色透明液体。该抗氧化剂无需进行后处理，留在产品中不影响最终使用效果。
本发明水性聚氨酯缔合型增稠剂的制备方法一：
1）投料分子量600的聚乙二醇953.5份入2000L备料釜，升温至1150C，抽真空脱水0.5小时，打开回流冷凝阀，通入氮气保护；
2）降温至800C，中速搅拌下，投料抗氧化剂0.2份，搅拌均匀后，按顺序投料200份N-甲基吡咯烷酮、252.3份六亚甲基二异氰酸酯、1份催化剂，保温反应1.0-1.5小时至设定异氰酸根值；
3）投料67份二羟基丙酸，保温反应2小时至设定异氰酸根值；
4）投料200份N,N-二甲基乙酰胺、135.2份长链烷基醇，保温反应1.5-2.0小时至异氰酸根达到设定含量；
5）关闭热水阀，打开冷却水阀，将物料降温至500C以下时，投料100份醋酸乙酯为溶剂、45份三乙胺为中和剂、3份一乙醇胺，并充分搅拌30分钟；
6）慢速搅拌下，投料453.5份水进行稀释，并搅拌均匀；
7）检测合格后，过滤包装。
本发明水性聚氨酯缔合型增稠剂的制备方法二：
1）投料分子量600的聚乙二醇953.5份入2000L备料釜，升温至1150C，抽真空脱水0.5小时，打开回流冷凝阀，通入氮气保护；
2）降温至800C，中速搅拌下，投料抗氧化剂0.2份，搅拌均匀后，按顺序投料200份N-甲基吡咯烷酮、333.4份异佛尔酮二异氰酸酯、1份催化剂，保温反应1-1.5小时至设定异氰酸根值；
3）投料75份二羟基丁酸，保温反应2小时至设定异氰酸根值；
4）投料200份N,N-二甲基乙酰胺、135.2份长链烷基醇，保温反应1.5-2.0小时至异氰酸根达到设定含量；
5）关闭热水阀，打开冷却水阀，将物料降温至500C以下时，投料100份醋酸乙酯溶剂、45份三乙胺中和剂、3份一乙醇胺，并充分搅拌30分钟；
6）慢速搅拌下，投料542.4份水进行稀释，并搅拌均匀；
7）检测合格后，过滤包装。
本发明所述的“份”为一个单位质量，一般采用1Kg为一个单位质量；本发明中各种物质成分的比例为相对较佳值，本发明制备方法中的各种时间设定是相对较佳时间；各物质的投放量可根据反应釜容量或批量大小按比例增减。

Claims (6)

1.一种水性聚氨酯缔合型增稠剂，包括聚乙二醇、二异氰酸酯、、溶剂、中和剂、催化剂和抗氧化剂；其特征是在聚乙二醇与二异氰酸酯的混合反应物加入双羟基羧酸亲水扩链剂、极性非质子化强溶剂、长链烷基醇和一乙醇胺；聚乙二醇采用分子量为400-800，其物质的量为二异氰酸酯的50%；双羟基羧酸亲水扩链剂物质的量为二异氰酸酯的33.3%；极性非质子化强溶剂物质的量为聚乙二醇、二异氰酸酯、双羟基羧酸亲水扩链剂组成聚合物的40%-50%；长链烷基醇的碳原子数为12以上，其物质的量为二异氰酸酯的16.7%；一乙醇胺物质的量为二异氰酸酯的3%-5%。
2.根据权利要求1所述的水性聚氨酯缔合型增稠剂，其特征是双羟基羧酸亲水扩链剂为2，2-二羟基丙酸或2，2-二羟基丁酸，或两者的混合物。
3.根据权利要求1所述的水性聚氨酯缔合型增稠剂，其特征是二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯的一种或多种的混合物。
4.根据权利要求1所述的水性聚氨酯缔合型增稠剂，其特征是极性非质子化强溶剂为N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基甲酰胺中的一种或两种。
5.根据权利要求1所述的水性聚氨酯缔合型增稠剂，其特征是抗氧化剂为四【β-（3，5-二叔丁基-4-羟基苯基）丙酸】季戊四醇酯。
6.根据权利要求1或2或3或4或5所述的水性聚氨酯缔合型增稠剂的制备方法，其特征是：
1）投料聚乙二醇900-1200份入2000L备料釜，升温至1150C，抽真空脱水0.5小时，打开回流冷凝阀，通入氮气保护；
2）降温至800C，中速搅拌下，投料抗氧化剂0.2-0.5份，搅拌均匀后，按顺序投料150-200份极性非质子化强溶剂、250-350份二异氰酸酯、1-2份催化剂，保温反应1.0-1.5小时至设定异氰酸根值；
3）投料65-75份双羟基羧酸亲水扩链剂，保温反应2小时至设定异氰酸根值；
4）投料150-200份极性非质子化强溶剂、120-140份长链烷基醇，保温反应1.5-2.0小时至异氰酸根达到设定含量；
5）关闭热水阀，打开冷却水阀，将物料降温至500C以下时，投料50-100份醋酸乙酯溶剂、40-50份三乙胺中和剂、3-5份一乙醇胺，并充分搅拌30分钟；
6）慢速搅拌下，投料450-550份水进行稀释，并搅拌均匀；
7）检测合格后，过滤包装。
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CN109705649A (zh) * 2018-12-11 2019-05-03 万华化学（宁波）有限公司 含有非离子聚氨酯化合物的协同混合物溶液及含有其的金属底材水性涂料
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CN115401364A (zh) * 2021-10-21 2022-11-29 上海华庆焊材技术股份有限公司 一种高活性水洗助焊剂及其制备工艺

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109705649A (zh) * 2018-12-11 2019-05-03 万华化学（宁波）有限公司 含有非离子聚氨酯化合物的协同混合物溶液及含有其的金属底材水性涂料
CN111648142A (zh) * 2020-06-28 2020-09-11 北京中纺化工股份有限公司 聚氨酯类复合活性印花糊料及其制备方法
CN112831010A (zh) * 2021-02-07 2021-05-25 湖北达雅生物科技股份有限公司 具有离子化多臂的星型结构聚氨酯增稠剂及其制备方法
CN115401364A (zh) * 2021-10-21 2022-11-29 上海华庆焊材技术股份有限公司 一种高活性水洗助焊剂及其制备工艺
CN115401364B (zh) * 2021-10-21 2023-12-22 上海华庆焊材技术股份有限公司 一种高活性水洗助焊剂及其制备工艺

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