CN107880236A - 一种高性能可uv固化超支化水性含氟聚氨酯树脂的制备方法 - Google Patents

一种高性能可uv固化超支化水性含氟聚氨酯树脂的制备方法 Download PDF

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CN107880236A
CN107880236A CN201711370296.6A CN201711370296A CN107880236A CN 107880236 A CN107880236 A CN 107880236A CN 201711370296 A CN201711370296 A CN 201711370296A CN 107880236 A CN107880236 A CN 107880236A
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姚伯龙
徐颖聪
王伟
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Jiangnan University
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Abstract

本发明的目的在于提供一种利用超支化含氟多元醇进行改性制备耐水、耐候、耐溶剂性可UV固化水性聚氨酯乳液及其制备方法。本发明的水性聚氨酯经超支化含氟多元醇进行改性得到的超支化水性含氟聚氨酯，分子结构中的碳氟链段在成膜过程中易于向涂膜表面迁移，富集于表面。这样既能在保证水性聚氨酯树脂优良的附着力、硬度、固化速率等的同时又赋予改性聚氨酯涂膜优良的耐水性、耐溶剂性和热稳定性。

Description

一种高性能可UV固化超支化水性含氟聚氨酯树脂的制备方法
技术领域
本发明高性能、可紫外光固化性聚氨酯材料的制备领域，具体涉及一种高性能具有紫外光固化性能的超支化水性含氟聚氨酯乳液的制备方法。
背景介绍
目前大量被使用的聚氨酯以溶剂型为主，但随着人们环保意识的增强和环保法规的确立，传统的溶剂型化学品的挥发性有机化合物(VOC)和有害空气污染物(HAP)的排放愈来愈受到严格限制。制备聚氨酯的水性化技术，以水代替有机溶剂，不仅提高了生产和施工的安全性，避免了有机溶剂的可燃性和毒性，而且能减少或消除聚氨酯固化过程中有机溶剂发带来的环境问题。同时，由于水性聚氨酯以水为介质，气味小、节能、操作加工方便等优点。但聚氨酯水性化后其耐水性、物理力学性能等都会有一定程度的下降，制约了水性聚氨酯材料的应用。超支化聚氨酯是一类具有高度支化结构的大分子，由于其含有大量的外部官能团和内部空腔结构，并且具有无链缠绕、非结晶性等特点，故其水分散体具有良好的稳定性、附着力、光泽度和抗溶剂性等独特的优点。通过引入超支化结构使体系交联是解决这些问题的有效途径，同时结合紫外光固化技术而制备的UV固化水性超支化聚氨酯是环境友好型聚氨酯新的发展方向。
近年来，关于氟改性聚氨酯的研究和报道很多，在传统聚氨酯链上引入氟基团，使其保持聚氨酯原有的优良特性，如优异的机械性能和两相微结构特征，良好的韧性、粘附性和拉伸性,很好的耐磨、耐疲劳、耐化学品腐蚀性等。另外，由于氟具有强的电负性，高的键能，很小的范德华半径和对碳链的屏蔽保护，使其具有良好的表面性能、整体性能。氟基团的引入，使聚氨酯材料具有优异的低表面能、耐热耐化学品性、耐水性、自清洁性以及良好的生物相容性和稳定性。
发明内容
本发明的目的在于提供一种利用超支化含氟多元醇进行改性制备耐水、耐候、耐溶剂性可UV固化水性聚氨酯乳液及其制备方法。本发明的水性聚氨酯经超支化含氟多元醇进行改性得到的超支化水性含氟聚氨酯，分子结构中的碳氟链段在成膜过程中易于向涂膜表面迁移，富集于表面。这样既能在保证水性聚氨酯树脂优良的附着力、硬度、固化速率等的同时又赋予改性聚氨酯涂膜优良的耐水性、耐溶剂性和热稳定性。
本发明的技术方案是：
(1)将聚酯二元醇和含氟丙烯酸酯分别升温至80-100℃，真空脱水处理30min，得到脱水后的聚酯二元醇和含氟丙烯酸酯；
(2)含氟多元醇的制备：将一定量的多元醇胺、含氟丙烯酸酯和溶剂A混合加入装有冷凝管、温度计和搅拌棒的100ml三口烧瓶中升温至80℃，反应6-7小时，胺基值滴定，当胺基值达到理论值时，减压旋蒸除去溶剂A得到含氟多元醇；
(3)超支化含氟多元醇的制备：将含氟多元醇、2-(溴甲基)-2-(羟甲基)-1,3-丙二醇和溶剂B、碳酸钾混合加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中，升温至80℃反应24h，加入一定量的四氢呋喃溶剂，将产物逐滴加到乙醚中并不断搅拌，静止沉淀，最后通过抽滤得到滤饼，滤饼溶于四氢呋喃后，再重复上述操作沉淀2次，最后在50℃干燥，直至样品质量不再变化，获得超支化含氟多元醇样品；
(4)NCO半封端聚酯型预聚物的合成：将一定量的催化剂、二异氰酸酯和丙酮加入装有冷凝管、氮气管、搅拌棒和温度计的250ml四口烧瓶中将温度升至45-50℃滴加一定量的聚酯二元醇，反应3-4小时当NCO达到理论值时结束，得到初聚体。再将初聚体温度控制在78-80℃，加入扩链剂反应2-3小时当NCO达到理论值后降温到60-65℃加入活性封端剂、阻聚剂、丙酮保温反应3小时，NCO达到理论值，反应停止，得到异氰酸酯封端聚酯型预聚物；
(5)超支化含氟水性聚氨酯乳液的制备：将一定量的催化剂、异氰酸酯封端聚酯型预聚物加入装有冷凝管、氮气管、搅拌棒和温度计的250ml四口烧瓶中将温度升至75-80℃，在氮气氛围下加入一定含量的超支化含氟多元醇。反应3-4小时，当-NCO红外吸收峰完全消失时终止反应。将反应温度降至20-25℃，加入一定量的三乙胺，高速剪切30min，再加入去离子水，高速剪切乳化30min，减压旋蒸除去溶剂，即得超支化含氟水性聚氨酯乳液。
步骤(2)中所述多元醇胺为二乙醇胺、三(羟甲基)氨基甲烷中的至少一种；
步骤(1)和(2)中所述含氟丙烯酸酯为甲基丙烯酸三氟乙酯、甲基丙烯酸六氟丁酯、丙烯酸六氟丁酯、甲基丙烯酸八氟戊酯、丙烯酸十二氟庚酯、甲基丙烯酸十二氟庚酯、甲基丙烯酸十三氟辛酯中的至少一种；
步骤(2)中所述溶剂A为丙酮、丁酮的至少一种；
步骤(2)中所述溶剂B为N，N-二甲基甲酰胺、N-甲基吡咯烷酮中的至少一种；
步骤(4)中所述聚酯二元醇为聚碳酸酯二元醇、聚己内酯二元醇、己二酸聚酯二元醇中的至少一种；
步骤(4)和(5)中所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的至少一种；
步骤(4)中所述扩链剂为二羟甲基丙酸(DMPA)、二羟甲基丁酸(DMBA)中的至少一种；
步骤(4)中所述活性封端剂为丙烯酸羟乙酯(HEA)、甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟丙酯(HPA)、甲基丙烯酸羟丙酯(HPMA)、季戊四醇三丙烯酸酯(PETA)中的至少一种；
步骤(4)中所述阻聚剂为对苯二酚、对甲氧基苯酚中的至少一种；
本发明的有益效果是：通过以上反应，合成得到一种高性能可UV固化超支化水性含氟聚氨酯树脂涂料用树脂。该树脂可用于提高涂料的耐水性、耐溶剂性、防污性、耐热性、耐疲劳性，且具有优异的机械性能，低吸水性，低表面能，可广泛用于塑料、薄膜、门窗等具有耐水、防污要求的表面。
具体实施方式
实施例1
含氟多元醇的制备：将12.11g三(羟甲基)氨基甲烷、16.80g甲基丙烯酸三氟乙酯和30ml丙酮混合加入装有冷凝管、温度计和搅拌棒的100ml三口烧瓶中升温至80℃，反应7小时，胺基值滴定胺基值达到理论值时，减压旋蒸除去丙酮得到含氟多元醇；
超支化含氟多元醇的制备：将14.46g含氟多元醇、29.86g 2-(溴甲基)-2-(羟甲基)-1,3-丙二醇和150g N，N-二甲基甲酰胺(DMF)、22.80g碳酸钾混合加入装有冷凝管、氮气导管、搅拌棒和温度计的250ml四口烧瓶中，升温至80℃反应24h，加入一定量的四氢呋喃溶剂，将产物逐滴加到乙醚中并不断搅拌，静止沉淀，最后通过抽滤，滤饼溶于四氢呋喃后，再沉淀2次，进行两次干燥获得超支化含氟多元醇样品；
NCO半封端聚酯型预聚物的合成：将0.05g二月桂酸二丁基锡、8.89g异佛尔酮二异氰酸酯和15ml丙酮加入装有冷凝管、氮气管、搅拌棒和温度计的250ml四口烧瓶中将温度升至48℃滴加12g日本旭化成的聚碳酸酯二醇，反应3小时当NCO达到理论值时，升高温度到80℃，加入1.34g 2,2-二羟甲基丙酸(DMPA)反应3小时当NCO达到理论值后降温到65℃加入0.65g甲基丙烯酸羟乙酯(HEMA)、0.01g对甲氧基苯酚、5ml丙酮保温反应3小时，NCO达到理论值，反应停止，得到异氰酸酯封端聚酯型预聚物；
超支化含氟水性聚氨酯乳液的制备：将0.05g的二月桂酸二丁基锡、第三步异氰酸酯封端聚酯型预聚物加入装有冷凝管、氮气管、搅拌棒和温度计的250ml四口烧瓶中将温度升至78℃，在氮气氛围下加入8.86g超支化含氟多元醇。反应4小时，当-NCO红外吸收峰完全消失时终止反应。将反应温度降至25℃，加入1.15g的三乙胺，转速800rpm高速剪切30min，再加入60g去离子水，转速1200rpm高速剪切乳化30min，减压旋蒸除去溶剂，即得超支化含氟水性聚氨酯乳液。

Claims (2)

1.一种高性能可UV固化超支化水性含氟聚氨酯树脂的制备方法，其特征步骤为：
(1)将聚酯二元醇和含氟丙烯酸酯分别升温至80-100℃，真空脱水处理30min，得到脱水后的聚酯二元醇和含氟丙烯酸酯；
(2)含氟多元醇的制备：将一定量的多元醇胺、含氟丙烯酸酯和溶剂A混合加入装有冷凝管、温度计和搅拌棒的100ml三口烧瓶中升温至80℃，反应6-7小时，胺基值滴定，当胺基值达到理论值时，减压旋蒸除去溶剂A得到含氟多元醇；
(3)超支化含氟多元醇的制备：将含氟多元醇、2-(溴甲基)-2-(羟甲基)-1,3-丙二醇和溶剂B、碳酸钾混合加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中，升温至80℃反应24h，加入一定量的四氢呋喃溶剂，将产物逐滴加到乙醚中并不断搅拌，静止沉淀，最后通过抽滤得到滤饼，滤饼溶于四氢呋喃后，再重复上述操作沉淀2次，最后在50℃干燥，直至样品质量不再变化，获得超支化含氟多元醇样品；
(4)NCO半封端聚酯型预聚物的合成：将一定量的催化剂、二异氰酸酯和丙酮加入装有冷凝管、氮气管、搅拌棒和温度计的250ml四口烧瓶中将温度升至45-50℃滴加一定量的聚酯二元醇，反应3-4小时当NCO达到理论值时结束，得到初聚体。再将初聚体温度控制在78-80℃，加入扩链剂反应2-3小时当NCO达到理论值后降温到60-65℃加入活性封端剂、阻聚剂、丙酮保温反应3小时，NCO达到理论值，反应停止，得到异氰酸酯封端聚酯型预聚物；
(5)超支化含氟水性聚氨酯乳液的制备：将一定量的催化剂、异氰酸酯封端聚酯型预聚物加入装有冷凝管、氮气管、搅拌棒和温度计的250ml四口烧瓶中将温度升至75-80℃，在氮气氛围下加入一定含量的超支化含氟多元醇。反应3-4小时，当-NCO红外吸收峰完全消失时终止反应。将反应温度降至20-25℃，加入一定量的三乙胺，高速剪切30min，再加入去离子水，高速剪切乳化30min，减压旋蒸除去溶剂，即得超支化含氟水性聚氨酯乳液。
2.如权利要求1所述的一种高性能可UV固化超支化水性含氟聚氨酯树脂的制备方法，其特征在于：
步骤(2)中所述多元醇胺为二乙醇胺、三(羟甲基)氨基甲烷中的至少一种；
步骤(1)和(2)中所述含氟丙烯酸酯为甲基丙烯酸三氟乙酯、甲基丙烯酸六氟丁酯、丙烯酸六氟丁酯、甲基丙烯酸八氟戊酯、丙烯酸十二氟庚酯、甲基丙烯酸十二氟庚酯、甲基丙烯酸十三氟辛酯中的至少一种；
步骤(2)中所述溶剂A为丙酮、丁酮的至少一种；
步骤(2)中所述溶剂B为N，N-二甲基甲酰胺、N-甲基吡咯烷酮中的至少一种；
步骤(4)中所述聚酯二元醇为聚碳酸酯二元醇、聚己内酯二元醇、己二酸聚酯二元醇中的至少一种；
步骤(4)和(5)中所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的至少一种；
步骤(4)中所述扩链剂为二羟甲基丙酸(DMPA)、二羟甲基丁酸(DMBA)中的至少一种；
步骤(4)中所述活性封端剂为丙烯酸羟乙酯(HEA)、甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟丙酯(HPA)、甲基丙烯酸羟丙酯(HPMA)、季戊四醇三丙烯酸酯(PETA)中的至少一种；
步骤(4)中所述阻聚剂为对苯二酚、对甲氧基苯酚中的至少一种。
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