CN108003320B - 一种高耐水性侧链含氟-硅uv固化水性聚氨酯树脂的制备方法 - Google Patents
一种高耐水性侧链含氟-硅uv固化水性聚氨酯树脂的制备方法 Download PDFInfo
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Abstract
本发明涉及一种高耐水性侧链含氟‑硅UV固化水性聚氨酯树脂的制备方法。本发明的目的在于提供一种利用高分子有机氟和有机硅进行改性制备高耐水、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有机氟和有机硅改性得到侧链含有机氟硅的水性聚氨酯，该聚合物成膜后，聚合物侧链的有机氟和有机硅链段更倾向于表面聚集取向，而聚氨酯链段朝向内层。这样既能在保证聚酯型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、耐溶剂性和耐候性。
Description
技术领域
本发明属于高分子材料技术领域，具体涉及一种高耐水性侧链含氟-硅UV固化水性聚氨酯树脂的制备方法。
背景介绍
紫外光固化水性树脂继承和发展了传统UV固化技术和水性涂料技术的许多优点，如低成本、低粘度、良好的涂布适应性、设备简单、无毒性、无刺激性、不燃性等。由于UV固化水性树脂的优点突出，近年来得到较快的发展，其产品已被众多领域应用。
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。
有机硅是一类以重复单元Si-O键为主链，且有机基团直接连接在Si原子上的聚合物。它是半有机、半无机结构的高分子化合物，兼具有机和无机化合物的特性，具有良好的耐低温、耐候性、疏水性、生理惰性以及电绝缘等许多优异的性能。将其用于水性聚氨酯的改性，能有效的提高涂膜的耐水性、耐候型、耐溶剂性和滑爽性。通过在聚酯型水性聚氨酯树脂主链中引入Si-O键得到有机硅改性水性聚氨酯，以提高涂层的耐水性、耐溶剂性、耐候性和抗污性。
含氟聚氨酯以其独有的性能，受到广泛关注。氟原子半径小、电负性强、碳氟键键能高，因此赋予了聚氨酯材料极好的耐紫外线和核辐射性、优良耐磨性，低表面能和高耐候性等性能。与含氟主链型聚氨酯相比，侧链含氟型聚氨酯在自身表面张力的驱动下成膜时，分布于侧链的含氟链段更易于向表面迁移和富集，形成对聚氨酯表面进行有效保护。通常由侧链含氟聚醚多元醇制备的含氟聚氨酯材料，可实现只在表面结构中含氟，体相可少氟或无氟，在不降低材料的力学性能、粘结性和防护性的同时，可实现低氟含量、低成本、高耐水性。
发明内容
本发明的目的在于提供一种利用高分子有机氟和有机硅进行改性制备高耐水、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有机氟和有机硅改性得到侧链含有机氟硅的水性聚氨酯，该聚合物成膜后，聚合物侧链的有机氟和有机硅链段更倾向于表面聚集取向，而聚氨酯链段朝向内层。这样既能在保证聚酯型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、耐溶剂性和耐候性。
本发明的技术方案是：
一种高耐水性侧链含氟-硅UV固化水性聚氨酯树脂的制备方法，包括如下步骤：
(1)侧链含氟硅预聚体的制备：将计量含氟丙烯酸酯、有机硅丙烯酸酯、甲基丙烯酸羟乙酯、N，N-二甲基甲酰胺和引发剂加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中，通入氮气保护，升温至75-80℃反应7-8小时，得到侧链含氟硅预聚体；
(2)NCO半封端聚氨酯预聚物的制备：将计量HDI三聚体(HDT)、催化剂和丙酮加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中，升温至50-55℃滴加一定量的聚酯二元醇，反应3-4h，采用二正丁胺法滴定体系中游离的-NCO含量，当-NCO达到理论值时，升温至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NCO半封端聚氨酯预聚物；
(3)侧链含氟硅水性聚氨酯乳液的制备：将计量侧链含氟硅预聚体、NCO半封端聚氨酯预聚物、催化剂、丙酮加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中，升温至60℃反应4h，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，剪切乳化30min，减压旋蒸除去溶剂，即得侧链含氟水性聚氨酯乳液。
步骤(1)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(1)中所述有机硅丙烯酸酯为3-(三甲氧基甲硅烷基)丙基-2-甲基-2-丙烯酸酯、三异丙基硅烷基甲基丙烯酸酯中的至少一种；
步骤(1)中所述引发剂为偶氮二异丁腈、过氧化二苯甲酰中的至少一种；
步骤(2)和(3)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(2)中所述阻聚剂为对苯二酚、对甲氧基苯酚中的至少一种；
步骤(2)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(2)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(3)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。
本发明的有益效果是：通过以上反应，合成得到高耐水性侧链含氟-硅可UV固化水性聚氨酯树脂涂料用树脂。该树脂可用于提高涂料的耐水性、耐候性、防污性、耐热性，可广泛用于塑料、薄膜、门窗等具有耐水、耐候、防污要求的表面。
具体实施方式
实施例1
侧链含氟硅预聚体的制备：将1.5g甲基丙烯酸十二氟庚酯、2g 3-(三甲氧基甲硅烷基)丙基-2-甲基-2-丙烯酸酯、6.5g甲基丙烯酸羟乙酯、20ml N，N-二甲基甲酰胺和0.25g偶氮二异丁腈加入装有冷凝管、氮气导管、搅拌棒的100ml的三口烧瓶中，通入氮气保护，升温至80℃反应8小时，得到侧链含氟硅预聚体；
NCO半封端聚氨酯预聚物的制备：将10.08g HDI三聚体(HDT)、0.05g二月桂酸二丁基锡和15ml丙酮加入装有冷凝管、氮气导管、搅拌棒100ml三口烧瓶中，升温至55℃滴加12g日本旭化成的聚碳酸酯二醇，反应4h，采用二正丁胺法滴定体系中游离的-NCO含量，当-NCO达到理论值时，升温至80℃，加入1.34g二羟甲基丙酸(DMPA)反应3小时当NCO达到理论值后降温到60℃加入1.30g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NCO半封端聚氨酯预聚物；
侧链含氟硅水性聚氨酯乳液的制备：将第一步合成的侧链含氟硅预聚体、第二步合成的NCO半封端聚氨酯预聚物、0.05g二月桂酸二丁基锡、10ml丙酮加入装有冷凝管、氮气导管、搅拌棒和温度计250ml四口烧瓶中，升温至60℃反应4h，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，再加入去55g离子水，转速1200rpm剪切乳化30min，减压旋蒸除去溶剂，即得侧链含氟硅水性聚氨酯乳液。
Claims (2)
1.一种高耐水性侧链含氟-硅UV固化水性聚氨酯树脂的制备方法，其特征步骤为：
(1)侧链含氟硅预聚体的制备：将计量含氟丙烯酸酯、有机硅丙烯酸酯、甲基丙烯酸羟乙酯、N，N-二甲基甲酰胺和引发剂加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中，通入氮气保护，升温至75-80℃反应7-8小时，得到侧链含氟硅预聚体；
(2)NCO半封端聚氨酯预聚物的制备：将计量HDI三聚体(HDT)、催化剂和丙酮加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中，升温至50-55℃滴加一定量的聚酯二元醇，反应3-4h，采用二正丁胺法滴定体系中游离的-NCO含量，当-NCO达到理论值时，升温至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NCO半封端聚氨酯预聚物；
(3)侧链含氟硅水性聚氨酯乳液的制备：将计量侧链含氟硅预聚体、NCO半封端聚氨酯预聚物、催化剂、丙酮加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中，升温至60℃反应4h，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，剪切乳化30min，减压旋蒸除去溶剂，即得侧链含氟水性聚氨酯乳液。
2.如权利要求1所述的一种高耐水性侧链含氟-硅UV固化水性聚氨酯树脂的制备方法，其特征在于：
步骤(1)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(1)中所述有机硅丙烯酸酯为3-(三甲氧基甲硅烷基)丙基-2-甲基-2-丙烯酸酯、三异丙基硅烷基甲基丙烯酸酯中的至少一种；
步骤(1)中所述引发剂为偶氮二异丁腈、过氧化二苯甲酰中的至少一种；
步骤(2)和(3)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(2)中所述阻聚剂为对苯二酚、对甲氧基苯酚中的至少一种；
步骤(2)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(2)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(2)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。
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