CN109081898A - 含氟水基聚氨酯的制备方法 - Google Patents

含氟水基聚氨酯的制备方法 Download PDF

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CN109081898A
CN109081898A CN201810213793.3A CN201810213793A CN109081898A CN 109081898 A CN109081898 A CN 109081898A CN 201810213793 A CN201810213793 A CN 201810213793A CN 109081898 A CN109081898 A CN 109081898A
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fluorine
based polyurethane
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water
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李成祥
文嘉婷
黄军江
江河
陈龙勋
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ZHEJIANG DYMATIC BOSHIDA POLYMER MATERIAL CO Ltd
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Abstract

本发明涉及新材料技术领域，特别是公开了一种含氟水基聚氨酯的制备方法，首先针对含氟二元醇单体缺乏的技术问题，制备含氟侧基的二元醇，然后根据水基聚氨酯的制备技术原理，以含氟侧基的二元醇作为共聚单体，制备含氟水基聚氨酯，不仅解决了现有共混复配型含氟材料与聚氨酯配伍性差、易迁移析出、质量不均匀的技术问题，而且很好解决了传统溶剂型聚氨酯涂层材料的有机溶剂污染问题，将其应用于纺织涂层、合成革等的制造，可满足各类高端客户对纺织、合成革等涂层的疏水防污要求和生态环保要求。

Description

含氟水基聚氨酯的制备方法
技术领域
本发明涉及新材料技术领域，特别涉及一种含氟水基聚氨酯的制备方法。
背景技术
目前，水性聚氨酯 (WPU) 具有VOC含量低、机械性能好、附着力高、装饰性优良、透湿透气性好等优点，同时，通过控制原料、软硬段结构、分子量、交联等参数，可以得到性能不同的水性聚氨酯，广泛用于皮革、合成革的制造。随着人们对于高性能、高品质、高环保的生态合成革的需求持续上升，对聚氨酯合成革的安全性、疏水防污性（自洁）等功能提出了更高的要求。
目前报道的具有疏水防污的聚合物物质主要是含氟聚合物。氟元素的电负性极大，原子半径小，极化性很低，其原子最外层的电子排布为2s22p5，如此独特的结构决定了含氟物质的很多特殊的物理化学性质。由于其原子半径小，形成的化学键短，键能大，因此有机氟化合物结构稳定，耐候性，耐热稳定性好。有机氟化合物分子间作用力小，界面分子作用力低，因此具有极低的表面能和优异的防水防油性能。
含氟聚合物表面能低，疏水、防污能力强。将含氟组分引入到聚氨酯体系中，所得含氟聚氨酯既保留了聚氨酯的弹性、力学性能、耐磨性、耐腐蚀性，又同时兼具有含氟材料所具备的独特性能，包括低的表面能、高耐候性、耐热、耐化学品性以及疏水、防污等特性。因而，含氟聚氨酯的应用前景可观，在涂料、家装、航天、交通等领域均有广泛应用，已成为业界研究的热点，但仍存在两个关键技术瓶颈。
其一是市场上含氟二元醇稀少，故大多相关研究是将含氟的疏水防污组分以物理共混或表面处理的形式引入纺织、合成革涂层中，这会存在含氟组分易迁移、与树脂基材相容性差、分布不均匀，质量不稳定等技术缺陷，从而影响涂层的疏水防污性能；另外，单独用作涂层表面处理时因界面张力差异太大，润湿流平性差，附着不牢，也影响其使用性能；
其二是市场上氟碳树脂多为油性树脂，水性氟碳树脂较少。溶剂型聚氨酯被广泛应用在涂料、纺织、合成革、皮革加工制造、造纸行业和胶粘剂等各个领域，但溶剂型聚氨酯容易造成环境污染，易造成火灾，且对人体造成危害。随着人们环保意识的提高，世界各国对涂层材料中挥发性有机物及有毒溶剂的要求越来越高，含量限制越来越严苛，甚至很多有机溶剂被禁止使用。因此，开发水基聚氨酯，以水作为溶剂，替代原有的有机溶剂，是行业发展的必然趋势。
发明内容
为了克服现有技术的不足，本发明提供了一种含氟水基聚氨酯的制备方法，首先针对含氟二元醇单体缺乏的技术问题，制备含氟侧基的双官能团二元醇，然后再根据水基聚氨酯的制备技术原理，制备含氟水基聚氨酯，不仅解决了现有共混复配型含氟材料与聚氨酯配伍性差、易迁移析出、分布不均匀的问题，而且良好地解决了传统溶剂型聚氨酯涂层材料存在的有机溶剂污染问题，将其应用于纺织涂层、合成革等的制造，可满足各类高端客户对纺织、合成革等涂层的疏水防污要求。
为了实现上述目的，本发明采用的技术方案是：一种含氟水基聚氨酯的制备方法，包括以下步骤：
（1）含氟二元醇的制备
将二羟甲基羧酸与一元氟醇按摩尔比1.2:1加入带有氮气保护和搅拌装置的反应瓶中，以甲苯作为溶剂和带水剂，重量分数计0.1%浓硫酸作为催化剂，控温100-120℃反应3h后，将产物倒入水中，去除硫酸和未反应的二羟甲基羧酸，滤液经减压脱出溶剂获得带有含氟侧基的二元醇；
（2）含氟水基聚氨酯的制备
在反应釜中投入真空脱水后的聚醚二元醇或聚酯二元醇60-100份，二异氰酸酯15-25份、含氟二元醇5-10份，抗氧剂0.16-0.3份、催化剂0.01-0.02于70-85℃进行反应2-3h，再加入亲水扩链剂3-6份，继续反应2h后测定-NCO%含量达理论值，加入三乙胺中和，然后在高剪切下加入去离子水乳化，获得含氟水基聚氨酯，其中所用原料均以重量份数计。
与现有技术相比，本发明具有以下明显优点：
（1）制备了具有双官能团的含氟二元醇，为疏水防污聚氨酯的开发提供了关键材料；
（2）以化学键的形式将疏水防污组分引入聚氨酯大分子侧链，增加了其与聚氨酯的相容性，解决了现有共混复配型长余辉发光材料与聚氨酯配伍性差、易迁移析出、分布不均匀等问题，具有稳定持久的疏水防污特性。
（3）所制得的含氟聚氨酯为水基聚氨酯，安全环保，使用过程无三废排放，所制备的终端产品如纺织品、合成革等生态等级高。
作为优选，所述二羟甲基羧酸为二羟甲基丙酸、二羟甲基丁酸或酒石酸中的一种或多种的混合。
作为优选，所述一元氟醇为六氟异丙醇、八氟戊醇或全氟辛醇中的一种或多种的混合。
作为优选，所述聚醚二元醇或聚酯二元醇为相对分子质量在2000-4000的聚己二酸乙二醇酯、聚己内酯二醇、聚丙二醇、聚碳酸酯二醇、聚乙二醇、聚四氢呋喃二醇中的一种或多种的混合。
作为优选，所述二异氰酸酯为异佛尔酮二异氰酸酯、2,4-甲苯二异氰酸酯、六亚甲基二异氰酸酯或4,4’-二环己基甲烷二异氰酸酯中的一种或多种的混合。
作为优选，所述亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸中的一种或两种的混合。
具体实施方式
下面通过实施例对本发明进行具体描述，有必要在此指出的是以下实施例只是用于对本发明进行进一步的说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容做出一些非本质的改进和调整，仍属于本发明的保护范围。
实施例1：
（1）含氟二元醇的制备
将二羟甲基丙酸与八氟戊醇按摩尔比1.2:1加入带有氮气保护和搅拌装置的反应瓶中，以甲苯作为溶剂和带水剂，重量分数0.1%浓硫酸作为催化剂，控温110℃反应3h后，将产物倒入水中，去除硫酸和未反应的二羟甲基丙酸，滤液经减压脱出溶剂获得带有含氟侧基的二元醇；
（2）含氟水基聚氨酯的制备
在反应釜中投入真空脱水后的分子量为2000聚丙二醇60份，异佛尔酮二异氰酸酯7.5份，六亚甲基二异氰酸酯7.5份、步骤（1）所制备的含氟二元醇5.0份，受阻酚类抗氧剂0.16份、有机铋催化剂0.01份于70-85℃进行反应2-3h，再加入亲水扩链剂二羟甲基丁酸3份，继续反应2h后测定-NCO%含量，合格后加入三乙胺中和，然后在高剪切下加入去离子水乳化，获得含氟水基聚氨酯，其中所用原料均以重量份数计。经检测，通过上述所述的方法制备的含氟聚氨酯乳液的表面张力为18.6mN/m，胶膜表面张力为25.37mN/m，油、水接触角分别为123.2°/133.7°，胶膜24h吸水率为4.7%，表现出含氟聚氨酯良好的疏水防油特性。
实施例2：
（1）含氟二元醇的制备
将二羟甲基丁酸与六氟异丙醇摩尔比1.2:1加入带有氮气保护和搅拌装置的反应瓶中，以甲苯作为溶剂和带水剂，重量分数0.1%浓硫酸作为催化剂，控温100-120℃反应3h后，将产物倒入水中，去除硫酸和未反应的二羟甲基丁酸，滤液经减压脱出溶剂获得带有含氟侧基的二元醇；
（2）含氟水基聚氨酯的制备
在反应釜中投入真空脱水后的分子量4000的聚丙二醇50份，分子量2000的聚四氢呋喃二醇50份，异佛尔酮二异氰酸酯20份，4,4’-二苯甲烷二异氰酸酯5份、步骤（1）所制备的含氟二元醇10份，受阻酚类抗氧剂0.3份、有机铋催化剂0.02份于70℃进行反应3h，再加入亲水扩链剂二羟甲基丙酸6份，继续反应2h后测定-NCO%含量，合格后加入三乙胺中和，然后在高剪切下加入去离子水乳化，获得含氟水基聚氨酯，其中所用原料均以重量份数计。经检测，通过专利所述的方法制备的含氟聚氨酯乳液的表面张力为20.4mN/m，胶膜表面张力为24.6mN/m，油、水接触角分别为120.4°/129.3°，胶膜24h吸水率为5.2%，表现出良好的疏水防油特性。
实施例3：
（1）含氟二元醇的制备
将酒石酸与全氟辛醇按摩尔比1.2:1加入带有氮气保护和搅拌装置的反应瓶中，以甲苯作为溶剂和带水剂，重量分数0.1%浓硫酸作为催化剂，控温100-120℃反应3h后，将产物倒入水中，去除硫酸和未反应的酒石酸，滤液经减压脱出溶剂获得带有含氟侧基的二元醇；
（2）含氟水基聚氨酯的制备
在反应釜中投入真空脱水后的分子量2000的聚丙二醇50份，聚碳酸酯二醇30份，4,4’-二环己基甲烷二异氰酸酯20份、步骤（1）所制备的含氟二元醇7.5份，受阻酚类抗氧剂0.2份、有机铋催化剂0.015于80℃进行反应3h，再加入亲水扩链剂二羟甲基丙酸4份，继续反应2h后测定-NCO%含量，合格后加入三乙胺中和，然后在高剪切下加入去离子水乳化，获得含氟水基聚氨酯，其中所用原料均以重量份数计。经检测，通过专利所述的方法制备的含氟聚氨酯乳液的表面张力为18.2mN/m，胶膜表面张力为22.6mN/m，油/水接触角分别为122°/140.2°，胶膜24h吸水率为4.2%，表现出优异的疏水防油特性。
根据上述表格可知，采用本发明技术制备的含氟水基聚氨酯具有较低的表面张力、胶膜表面张力、胶膜24h吸水率和较大的油/水接触角，油接触角处于120-130°范围，水接触角随氟碳链的延长可达到140°以上，与普通的聚氨酯相比（油/水接触角θ分别为84°/87°），其疏水防油性得到明显提升。
本发明不局限于上述具体实施方式，本领域一般技术人员根据本发明公开的内容，可以采用其他多种具体实施方式实施本发明的，或者凡是采用本发明的设计结构和思路，做简单变化或更改的，都落入本发明的保护范围。

Claims (6)

1.一种含氟水基聚氨酯的制备方法，其特征在于：
包括以下步骤：
（1）含氟二元醇的制备
将二羟甲基羧酸与一元氟醇按摩尔比1.2:1加入带有氮气保护和搅拌装置的反应瓶中，以甲苯作为溶剂和带水剂，重量分数计0.1%浓硫酸作为催化剂，控温100-120℃反应3h后，将产物倒入水中，去除硫酸和未反应的二羟甲基羧酸，滤液经减压脱出溶剂获得带有含氟侧基的二元醇；
（2）含氟水基聚氨酯的制备
在反应釜中投入真空脱水后的聚醚二元醇或聚酯二元醇60-100份，二异氰酸酯15-25份、含氟二元醇5-10份，抗氧剂0.16-0.3份、催化剂0.01-0.02于70-85℃进行反应2-3h，再加入亲水扩链剂3-6份，继续反应2h后测定-NCO%含量达理论值，加入三乙胺中和，然后在高剪切下加入去离子水乳化，获得含氟水基聚氨酯，其中所用原料均以重量份数计。
2.根据权利要求1所述的含氟水基聚氨酯的制备方法，其特征在于：所述二羟甲基羧酸为二羟甲基丙酸、二羟甲基丁酸或酒石酸中的一种或多种的混合。
3.根据权利要求1或2所述的含氟水基聚氨酯的制备方法，其特征在于：所述一元氟醇为六氟异丙醇、八氟戊醇或全氟辛醇中的一种或多种的混合。
4.根据权利要求3所述的含氟水基聚氨酯的制备方法，其特征在于：所述聚醚二元醇或聚酯二元醇为相对分子质量在2000-4000的聚己二酸乙二醇酯、聚己内酯二醇、聚丙二醇、聚碳酸酯二醇、聚乙二醇、聚四氢呋喃二醇中的一种或多种的混合。
5.根据权利要求1或2或4所述的含氟水基聚氨酯的制备方法，其特征在于：所述二异氰酸酯为异佛尔酮二异氰酸酯、2,4-甲苯二异氰酸酯、六亚甲基二异氰酸酯或4,4’-二环己基甲烷二异氰酸酯中的一种或多种的混合。
6.根据权利要求1或2或4所述的含氟水基聚氨酯的制备方法，其特征在于：所述亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸中的一种或两种的混合。
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CN109912776A (zh) * 2019-03-12 2019-06-21 上海应用技术大学 一种uv固化水性含氟树脂及其制备方法
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