CN106752872A - 一种兼具防污自洁功效的水性聚氨酯涂层剂及其制备方法 - Google Patents

一种兼具防污自洁功效的水性聚氨酯涂层剂及其制备方法 Download PDF

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CN106752872A
CN106752872A CN201611204625.5A CN201611204625A CN106752872A CN 106752872 A CN106752872 A CN 106752872A CN 201611204625 A CN201611204625 A CN 201611204625A CN 106752872 A CN106752872 A CN 106752872A
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王强
查道友
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Anqing Decheng Chemical Co Ltd
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Abstract

本发明公开一种兼具防污自洁功效的水性聚氨酯涂层剂，由以下重量份的原料组成：甲苯二异氰酸酯40‑60，聚醚二元醇12‑28，三氯氧磷8‑15，甲基丙烯酸羟乙酯5‑11，无水乙醚20‑40，三乙胺22‑35，二乙醇胺6‑14，甲醇适量，1,4‑二丁醇3‑7，二羟甲基丙酸2‑6，全氟烷基乙基醇6‑12，丙酮适量，乙醇适量，季戊四醇2‑5，氧化石墨烯3‑8，钛白粉2‑4，KH550 0.2‑0.6，去离子水适量。本发明在聚氨酯的大分子链中引入膦酸酯阻燃中间体，形成了无卤、低毒阻燃大分子，应用涂层剂后的海绵、织物等具有较高的阻燃性能，同时将氟元素引入水性聚氨酯分子中，提高水性聚氨酯涂层剂的耐水性。

Description

一种兼具防污自洁功效的水性聚氨酯涂层剂及其制备方法
技术领域
本发明涉及水性聚氨酯阻燃涂层剂及其制备方法，特别涉及一种兼具防污自洁功效的水性聚氨酯涂层剂及其制备方法。
技术背景
海绵遇到明火容易燃烧，如在海绵表面经过特殊的聚氨酯材料处理以后，海绵表面可以良好的阻燃效果。传统用于机械防震、隔热阻燃的海绵表面涂层处理大多是油性聚氨酯，众所周知，油性聚胺酯中的VOC有损于人类身体健康，随着人类环保意识的增强，寻求绿色环保的海绵表面涂层已势在必然。
阻燃整理剂，又称阻燃剂，难燃剂，耐火剂或防火剂，是一种能够赋予织物、海绵等易燃物难燃性的功能性助剂；依其应用方式分为添加型阻燃剂和反应型阻燃剂。相对填料阻燃技术而言，反应型阻燃技术更能达到高效高阻燃低发烟低毒性的目标。反应型阻燃技术通过将阻燃元素（卤素、磷、锑、硅、氮）引入易燃物表面涂层中从而达到阻燃目的。
于丹琦、陈国强等人在其《新型磷系阻燃剂的合成及对真丝的微波接枝》一文中，使用三氯氧磷与甲基丙烯酸羟乙酯、无水甲醇分两步反应合成具有双键的含磷丙烯酸酯有机磷系阻燃剂，之后采用微波辐照的方法对真丝进行接枝共聚处理，获得较好的阻燃性能，且水洗30次后织物仍具有较好的阻燃性，说明该种阻燃整理的耐久性较好。
本发明在含磷丙烯酸酯链上引入端羟基，部分取代多元醇与异氰酸酯反应，在聚氨酯的大分子链中引入膦酸酯阻燃中间体，形成了无卤、低毒阻燃大分子，应用涂层剂后的海绵、织物等具有较高的阻燃性能，同时将氟元素引入水性聚氨酯分子中，降低水性聚氨酯的表面能，提高水性聚氨酯涂层剂的耐水性。
发明内容
针对现有技术的不足，本发明提供一种兼具防污自洁功效的水性聚氨酯涂层剂及其制备方法。
一种兼具防污自洁功效的水性聚氨酯涂层剂，由以下重量份的原料组成：甲苯二异氰酸酯40-60份，聚醚二元醇12-28份，三氯氧磷8-15份，甲基丙烯酸羟乙酯5-11份，无水乙醚20-40份，三乙胺22-35份，二乙醇胺6-14份，甲醇适量，1,4-二丁醇3-7份，二羟甲基丙酸2-6份，全氟烷基乙基醇6-12份，丙酮适量，乙醇适量，季戊四醇2-5份，氧化石墨烯3-8份，钛白粉2-4份，KH550 0.2-0.6份，去离子水适量。
具体步骤如下：
（1）端羟基含磷阻燃剂的制备：
①、将三口烧瓶置于低温反应浴中，加入三氯氧磷和无水乙醚，当温度降至0-5℃，开始滴加甲基丙烯酸羟乙酯和1/7份三乙胺的混合液，边滴加边搅拌，当滴加完毕后继续搅拌1-2小时，之后滴加甲醇与1/7份三乙胺混合液，继续搅拌反应5-7小时，将其静置过夜，抽滤直至得到澄清的透明溶液，浓缩得到甲基丙烯酰氧乙基二甲基磷酸酯；
②、在三口瓶加入上述产物和二乙醇胺、甲醇，通氮气保护，在室温条件下低速搅拌50-70分钟，之后升温至40-50℃反应4-5小时，蒸馏去除溶剂，得到端羟基含磷阻燃单体；
（2）含磷阻燃型的端-NCO聚氨酯预聚体的制备：
在装有搅拌器、冷凝回流管和温度计的四口烧瓶中加入甲苯二异氰酸酯、聚醚二元醇以及步骤（1）端羟基含磷阻燃单体，70-80℃下反应1-3小时，降温至65-70℃下逐步与1,4-二丁醇、二羟甲基丙酸反应2-4小时，制得含磷阻燃型的端-NCO基聚氨酯预聚体；
（3）含磷阻燃型的有机氟封端水性聚氨酯乳液的制备：
向上述聚氨酯预聚体反应液中加入全氟烷基乙基醇，在水浴温度65-80℃下反应25-40分钟，加入丙酮调节体系粘度，并降温至室温，加入余下三乙胺中和搅拌15-25分钟，得到含磷阻燃型的有机氟封端水性聚氨酯乳液；
（4）将氧化石墨烯与钛白粉混合均匀，之后溶于乙醇中配制成浓度为0.5-1mg/ml的悬浮液，加入KH550搅拌10-20分钟，继续超声处理1-2小时，得到杂化的氧化石墨烯混合液，备用；
（5）常温下，向步骤（3）乳液中加入乙醇、季戊四醇混合，升温至40-60℃，加入步骤（4）杂化的氧化石墨烯混合液，在7000-8000rpm强剪切下搅拌0.5-1.5小时，即得一种兼具防污自洁功效的水性聚氨酯涂层剂。
与现有技术相比，本发明具有以下优点：
（1）本发明使用三氯氧磷与甲基丙烯酸羟乙酯、无水甲醇反应合成具有双键的含磷丙烯酸酯，之后利用双键与二乙醇胺反应在含磷丙烯酸酯链上引入端羟基，部分取代多元醇与异氰酸酯反应，在聚氨酯的大分子链中引入膦酸酯阻燃中间体，形成了无卤、低毒阻燃大分子，应用涂层剂后的海绵、织物等具有较高的阻燃性能，高温下无卤素释放，无毒，低烟。
（2）同时有机氟化合物中的-CF3的表面能低，使含有C-F键的聚合物物分子间的作用力较弱，因而含氟的聚合物具有较低的表面自由能，具有较好的拒水、拒油性，因此将全氟烷基乙基醇对水性聚氨酯分子进行封端，含氟的碳链处在水性聚氨酯分子的两端，可以降低水性聚氨酯的表面能，提高水性聚氨酯胶膜的耐水、抗污性。
（3）本发明利用钛白粉和氧化石墨烯杂化改性的氧化石墨烯掺杂到水性聚氨酯涂层剂中，提高了涂层剂的疏水亲油性，同时兼具一定的防污自洁性能，能够避免多次洗涤对面料等的损害。
具体实施方式
一种兼具防污自洁功效的水性聚氨酯涂层剂，由以下重量份的原料组成：甲苯二异氰酸酯55，聚醚二元醇25，三氯氧磷12，甲基丙烯酸羟乙酯8，无水乙醚34，三乙胺30，二乙醇胺10，甲醇适量，1,4-二丁醇6，二羟甲基丙酸4，全氟烷基乙基醇10，丙酮适量，乙醇适量，季戊四醇4，氧化石墨烯7，钛白粉3，KH550 0.5，去离子水适量。
具体步骤如下：
（1）端羟基含磷阻燃剂的制备：
①、将三口烧瓶置于低温反应浴中，加入三氯氧磷和无水乙醚，当温度降至0℃，开始滴加甲基丙烯酸羟乙酯和1/7份三乙胺的混合液，边滴加边搅拌，当滴加完毕后继续搅拌1小时，之后滴加甲醇与1/7份三乙胺混合液，继续搅拌反应6小时，将其静置过夜，抽滤直至得到澄清的透明溶液，浓缩得到甲基丙烯酰氧乙基二甲基磷酸酯；
②、在三口瓶加入上述产物和二乙醇胺、甲醇，通氮气保护，在室温条件下低速搅拌60分钟，之后升温至45℃反应5小时，蒸馏去除溶剂，得到端羟基含磷阻燃单体；
（2）含磷阻燃型的端-NCO聚氨酯预聚体的制备：
在装有搅拌器、冷凝回流管和温度计的四口烧瓶中加入甲苯二异氰酸酯、聚醚二元醇以及步骤（1）端羟基含磷阻燃单体，75℃下反应2小时，降温至67℃下逐步与1,4-二丁醇、二羟甲基丙酸反应3小时，制得含磷阻燃型的端-NCO基聚氨酯预聚体；
（3）含磷阻燃型的有机氟封端水性聚氨酯乳液的制备：
向上述聚氨酯预聚体反应液中加入全氟烷基乙基醇，在水浴温度75℃下反应30分钟，加入丙酮调节体系粘度，并降温至室温，加入余下三乙胺中和搅拌20分钟，得到含磷阻燃型的有机氟封端水性聚氨酯乳液；
（4）将氧化石墨烯与钛白粉混合均匀，之后溶于乙醇中配制成浓度为0.8mg/ml的悬浮液，加入KH550搅拌15分钟，继续超声处理1.5小时，得到杂化的氧化石墨烯混合液，备用；
（5）常温下，向步骤（3）乳液中加入乙醇、季戊四醇混合，升温至50℃，加入步骤（4）杂化的氧化石墨烯混合液在8000rpm强剪切下搅拌1小时，即得一种兼具防污自洁功效的水性聚氨酯涂层剂。
阻燃性能测试：以涤纶牛津帐篷布为处理和测试织物，采用GB/T5455-1997垂直燃烧法实验检测，须燃时间0s，阴燃时间0s；损毁炭长10.8cm。

Claims (2)

1.一种兼具防污自洁功效的水性聚氨酯涂层剂，其特征在于，由以下重量份的原料组成：甲苯二异氰酸酯40-60份，聚醚二元醇12-28份，三氯氧磷8-15份，甲基丙烯酸羟乙酯5-11份，无水乙醚20-40份，三乙胺22-35份，二乙醇胺6-14份，甲醇适量，1,4-二丁醇3-7份，二羟甲基丙酸2-6份，全氟烷基乙基醇6-12份，丙酮适量，乙醇适量，季戊四醇2-5份，氧化石墨烯3-8份，钛白粉2-4份，KH550 0.2-0.6份，去离子水适量。
2.根据权利要求书1所述的一种兼具防污自洁功效的水性聚氨酯涂层剂的制备方法，其特征在于，具体步骤如下：
（1）端羟基含磷阻燃剂的制备：
①、将三口烧瓶置于低温反应浴中，加入三氯氧磷和无水乙醚，当温度降至0-5℃，开始滴加甲基丙烯酸羟乙酯和1/7份三乙胺的混合液，边滴加边搅拌，当滴加完毕后继续搅拌1-2小时，之后滴加甲醇与1/7份三乙胺混合液，继续搅拌反应5-7小时，将其静置过夜，抽滤直至得到澄清的透明溶液，浓缩得到甲基丙烯酰氧乙基二甲基磷酸酯；
②、在三口瓶加入上述产物和二乙醇胺、甲醇，通氮气保护，在室温条件下低速搅拌50-70分钟，之后升温至40-50℃反应4-5小时，蒸馏去除溶剂，得到端羟基含磷阻燃单体；
（2）含磷阻燃型的端-NCO聚氨酯预聚体的制备：
在装有搅拌器、冷凝回流管和温度计的四口烧瓶中加入甲苯二异氰酸酯、聚醚二元醇以及步骤（1）端羟基含磷阻燃单体，70-80℃下反应1-3小时，降温至65-70℃下逐步与1,4-二丁醇、二羟甲基丙酸反应2-4小时，制得含磷阻燃型的端-NCO基聚氨酯预聚体；
（3）含磷阻燃型的有机氟封端水性聚氨酯乳液的制备：
向上述聚氨酯预聚体反应液中加入全氟烷基乙基醇，在水浴温度65-80℃下反应25-40分钟，加入丙酮调节体系粘度，并降温至室温，加入余下三乙胺中和搅拌15-25分钟，得到含磷阻燃型的有机氟封端水性聚氨酯乳液；
（4）将氧化石墨烯与钛白粉混合均匀，之后溶于乙醇中配制成浓度为0.5-1mg/ml的悬浮液，加入KH550搅拌10-20分钟，继续超声处理1-2小时，得到杂化的氧化石墨烯混合液，备用；
（5）常温下，向步骤（3）乳液中加入乙醇、季戊四醇混合，升温至40-60℃，加入步骤（4）杂化的氧化石墨烯混合液，在7000-8000rpm强剪切下搅拌0.5-1.5小时，即得一种兼具防污自洁功效的水性聚氨酯涂层剂。
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