CN105646811A - 一种有机氟改性聚氨酯乳液的制备方法 - Google Patents

一种有机氟改性聚氨酯乳液的制备方法 Download PDF

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CN105646811A
CN105646811A CN201610003644.5A CN201610003644A CN105646811A CN 105646811 A CN105646811 A CN 105646811A CN 201610003644 A CN201610003644 A CN 201610003644A CN 105646811 A CN105646811 A CN 105646811A
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王学川
王莎
许伟
强涛涛
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Shaanxi University of Science and Technology
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Abstract

本发明属于改性聚氨酯材料领域，具体涉及一种有机氟改性聚氨酯乳液的制备方法。可有效降低含氟单体的用量，在保证有两耐水性的前提下大幅降低制备成本。本发明采用的技术方案不步骤为：1)NCO封端的聚氨酯预聚体的合成；2)超支化聚氨酯的合成；3)有机氟改性超支化聚氨酯的合成；4)HBPUF乳液的制备。

Description

一种有机氟改性聚氨酯乳液的制备方法
一、技术领域：
本发明属于改性聚氨酯材料领域，具体涉及一种有机氟改性聚氨酯乳液的制备方法。
二、背景技术：
聚氨酯材料具有很多优异的性能，如良好的力学性能、粘附性、成膜性、柔韧性等，因而被广泛应用于纺织、印染、皮革加工、胶黏剂、涂料等领域。溶剂型聚氨酯，由于含有大量有机溶剂，不利于运输、储存，且不利于环保，因而现在人们致力于水性聚氨酯的研究，水性聚氨酯以水为分散介质，大大降低了有机溶剂的用量，且依然保持了聚氨酯优异的综合性能，但由于亲水扩链剂的引入，使得制得的聚氨酯胶膜耐水性变差。众所周知，氟是自然界中电负性最强的元素，氟原子吸引电子的能力非常强，所以有机氟中C-F键具有键能大、键长短的特点，有机氟聚合物分子间作用力低，聚合物表面能低，材料表现出优异的疏水疏油性。但是有机氟单体价格昂贵，近年来用有机氟改性聚氨酯的研究国内外均有报道。有人将二元氟醇、一元氟醇或含氟丙烯酸酯引入聚氨酯中，得到线型有机氟改性聚氨酯，有效地改善了聚氨酯的耐水性，但此种改性有机氟的用量依然较大。
三、发明内容
本发明的提供一种有机氟改性聚氨酯乳液的制备方法，可有效降低含氟单体的用量，在保证有两耐水性的前提下大幅降低制备成本。
为实现上述目的，本发明采用的技术方案为：一种有机氟改性聚氨酯乳液的制备方法，其特征在于：所述方法包括以下步骤：
1)NCO封端的聚氨酯预聚体的合成：以异佛尔酮二异氰酸酯和聚酯或聚醚二元醇为原料，二月桂酸二丁基锡做催化剂，在80-90℃下反应1-2小时，然后加2,2-二羟甲基丙酸扩链，同时加入丙酮作为溶剂，在60-70℃下反应2.5-3小时，制得聚氨酯预聚体；
2)超支化聚氨酯的合成：将超支化聚合物用N,N-二甲基甲酰胺溶解，滴加到聚氨酯预聚体中，在80℃下反应三小时，使聚氨酯预聚体完全接到超支化聚合物的活性末端；
3)有机氟改性超支化聚氨酯的合成：在温度为80℃的条件下，将有机氟逐渐滴加至上述反应体系，加热搅拌三小时，至反应完全；
4)HBPUF乳液的制备：将体系温度降至40-50℃，加三乙胺中和用高速搅拌机分散，然后在50℃下旋蒸半小时除去溶剂，制得固含量在30％-50％的有机氟改性聚氨酯乳液。
步骤(1)中的聚酯或聚醚二元醇为聚四氢呋喃、聚乙二醇、聚丙二醇、聚己二酸丁二醇酯、聚己二酸新戊二醇酯、聚己二酸己二醇酯中的一种。
步骤(2)中的超支化聚合物选自0代、1代或2代端羟基超支化聚合物中的一种。
步骤(3)中的有机氟为单官能团的有机氟。
所述的单官能团的有机氟选自全氟己基乙醇、全氟乙基辛醇中的一种。
步骤(4)中的中和剂三乙胺的用量与扩链剂二羟甲基丙酸的物质的量相等。
与现有技术相比，本发明具有如下优点和效果：
本发明借助超支化聚合物的三维立体结构，让聚氨酯预聚体一端与超支化聚合物的末端活性基团反应，最后再将一元氟醇接到聚氨酯另一末端，有效地促进氟原子的表面迁移，有机氟单体的用量降低为原来的一半，乳液在3000r/min的转速下离心半小时无沉淀或分层现象，说明乳液具有良好的离心稳定性，改性前聚氨酯胶膜的接触角仅为70°左右，经有机氟改性后胶膜接触角增大到110°左右，胶膜的拒水性有了显著地提高。
四、具体实施方式
一种有机氟改性聚氨酯乳液的制备方法包括以下步骤：
1)NCO封端的聚氨酯预聚体(PU)的合成：以异佛尔酮二异氰酸酯和聚酯或聚醚二元醇为原料，二月桂酸二丁基锡(DBTDL)做催化剂，在80-90℃下反应1-2小时，然后加2,2-二羟甲基丙酸(DMPA)扩链，同时加入丙酮作为溶剂，在60-70℃下反应2.5-3小时，制得聚氨酯预聚体；
所述的的聚酯或聚醚二元醇为聚四氢呋喃、聚乙二醇、聚丙二醇、聚己二酸丁二醇酯、聚己二酸新戊二醇酯、聚己二酸己二醇酯中的一种；
2)超支化聚氨酯(HBPU)的合成：将超支化聚合物用N,N-二甲基甲酰胺(DMF)溶解，滴加到聚氨酯预聚体中，在80℃下反应三小时，使聚氨酯预聚体完全接到超支化聚合物的活性末端；
所述的超支化聚合物选自0代、1代或2代端羟基超支化聚合物中的一种；
3)有机氟改性超支化聚氨酯(HBPUF)的合成：在温度为80℃的条件下，将有机氟逐渐滴加至上述反应体系，加热搅拌三小时，至反应完全；
所述的步骤(3)中的有机氟为单官能团的有机氟，单官能团的有机氟选自全氟己基乙醇、全氟乙基辛醇中的一种；
4)HBPUF乳液的制备：将体系温度降至40-50℃，加三乙胺中和用高速搅拌机分散，然后在50℃下旋蒸半小时除去溶剂，制得固含量在30％-50％的有机氟改性聚氨酯乳液；
所述的中和剂三乙胺的用量与扩链剂二羟甲基丙酸的物质的量相等；
所述的高速搅拌的转速为3000r/min。
步骤(1)中合成NCO封端的聚氨酯预聚体(PU)的反应方程式如下：
步骤(2)合成HBPU的反应方程式如下：
步骤(3)(4)合成HBPUF的反应方程式如下：
下面结合具体实施例来进一步说明本发明。
实例中的试剂在使用前均需进行干燥处理，排除水分对反应的影响，所用的聚己二酸丁二醇酯的相对分子质量为1000，聚乙二醇的相对分子质量为1000。所用的二月桂酸二丁基锡作催化剂。
实施例一：
准确称取15g异佛尔酮二异氰酸酯(IPDI)和24.27g聚己二酸丁二醇酯(CMA-1044),加入三口烧瓶中，油浴加热，在N2保护条件下进行加热搅拌，待体系温度达到80℃，加二月桂酸二丁基锡(DBTDL)两滴，继续反应1h后，开始降温，待体系温度降至60℃，加3.71g2,2-二羟甲基丙酸(DMPA)扩链，同时加入20ml丙酮做溶剂来降低体系黏度，并通冷凝水，持续反应2.5h后升温，待体系温度达到80℃，称取2.03g0代超支化聚合物用10mlN,N-二甲基甲酰胺(DMF)溶解，1h内滴加至反应体系，持续加热搅拌2h后，再称取5.67g全氟己基乙醇,1h内滴加至反应体系，持续加热搅拌2h后，对体系降温，当温度将至40℃，加2.78g三乙胺进行中和，中和反应持续0.5h,最后称取125g去离子水边搅拌边滴加进行乳化，将制备的乳液在50℃，-0.1MPa条件下旋蒸0.5h,除去有机溶剂，最终制得有机氟改性聚氨酯乳液HBPUF-0，取20g乳液平铺于聚四氟乙烯板中自然干燥制成聚氨酯胶膜。
实施例二：
准确称取20.00g异佛尔酮二异氰酸酯(IPDI)和39.13g聚乙二醇(PEG),加入三口烧瓶中，油浴加热，在N2保护条件下进行加热搅拌，待体系温度达到90℃，加二月桂酸二丁基锡(DBTDL)两滴，继续反应1h后，开始降温，待体系温度降至60℃，加4.03g2,2-二羟甲基丙酸(DMPA)扩链，同时加入20ml丙酮做溶剂来降低体系黏度，并通冷凝水，持续反应3h后升温，待体系温度达到80℃，称取7.46g1代超支化聚合物用15mlN,N-二甲基甲酰胺(DMF)溶解，1h内滴加至反应体系，持续加热搅拌2h后，再称取9.30g全氟己基辛醇,1h内滴加至反应体系，持续加热搅拌2h后，对体系降温，当温度将至50℃，加3.05g三乙胺进行中和，中和反应持续0.5h,最后称取193g去离子水边搅拌边滴加进行乳化，将制备的乳液在50℃，-0.1MPa条件下旋蒸0.5h,除去有机溶剂，最终制得有机氟改性聚氨酯乳液HBPUF-1，取20g乳液平铺于聚四氟乙烯板中自然干燥制成聚氨酯胶膜。

Claims (6)

1.一种有机氟改性聚氨酯乳液的制备方法，其特征在于：所述方法包括以下步骤：
1)NCO封端的聚氨酯预聚体的合成：以异佛尔酮二异氰酸酯和聚酯或聚醚二元醇为原料，二月桂酸二丁基锡做催化剂，在80-90℃下反应1-2小时，然后加2,2-二羟甲基丙酸扩链，同时加入丙酮作为溶剂，在60-70℃下反应2.5-3小时，制得聚氨酯预聚体；
2)超支化聚氨酯的合成：将超支化聚合物用N,N-二甲基甲酰胺溶解，滴加到聚氨酯预聚体中，在80℃下反应三小时，使聚氨酯预聚体完全接到超支化聚合物的活性末端；
3)有机氟改性超支化聚氨酯的合成：在温度为80℃的条件下，将有机氟逐渐滴加至上述反应体系，加热搅拌三小时，至反应完全；
4)HBPUF乳液的制备：将体系温度降至40-50℃，加三乙胺中和用高速搅拌机分散，然后在50℃下旋蒸半小时除去溶剂，制得固含量在30％-50％的有机氟改性聚氨酯乳液。
2.根据权利要求1所述的有机氟改性聚氨酯乳液的制备方法，其特征在于步骤(1)中的聚酯或聚醚二元醇为聚四氢呋喃、聚乙二醇、聚丙二醇、聚己二酸丁二醇酯、聚己二酸新戊二醇酯、聚己二酸己二醇酯中的一种。
3.根据权利要求1所述的有机氟改性聚氨酯乳液的制备方法，其特征在于：步骤(2)中的超支化聚合物选自0代、1代或2代端羟基超支化聚合物中的一种。
4.根据权利要求1所述的有机氟改性聚氨酯乳液的制备方法，其特征在于：步骤(3)中的有机氟为单官能团的有机氟。
5.根据权利要求4所述的有机氟改性聚氨酯乳液的制备方法，其特征在于：所述的单官能团的有机氟选自全氟己基乙醇、全氟乙基辛醇中的一种。
6.根据权利要求5所述的有机氟改性聚氨酯乳液的制备方法，其特征在于：步骤(4)中的中和剂三乙胺的用量与扩链剂二羟甲基丙酸的物质的量相等。
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106349452A (zh) * 2016-08-19 2017-01-25 陕西科技大学 端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法
CN107118327A (zh) * 2017-06-16 2017-09-01 陕西科技大学 一种耐黄变的氟醇封端型超支化聚氨酯及其制备方法
CN108505394A (zh) * 2017-12-26 2018-09-07 刘超 一种超支化含氟聚合物材料的制造工艺
CN109385199A (zh) * 2018-10-22 2019-02-26 陕西科技大学 一种阳离子端氟烷基超支化聚氨酯皮革涂饰剂的制备方法
CN109438643A (zh) * 2018-11-08 2019-03-08 合众（佛山）化工有限公司 一种生物基氟改性水性聚氨酯树脂及其制备方法
CN109749048A (zh) * 2019-02-28 2019-05-14 陕西科技大学 端氟烷基和侧链氟烷基双改性聚氨酯乳液及其制备方法
CN110330634A (zh) * 2019-06-18 2019-10-15 湖北大学 一种新型的耐水解超支化含氟水性聚氨酯的制备方法
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103865026A (zh) * 2014-03-18 2014-06-18 山东大学 一种含短氟碳链的有机氟硅改性聚氨酯乳液的制备方法
CN104448211A (zh) * 2014-12-19 2015-03-25 江南大学 一种uv固化含氟超支化水性聚氨酯树脂的制备方法
CN104877099A (zh) * 2015-05-22 2015-09-02 安徽大学 一种有机氟改性超支化水性聚氨酯的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103865026A (zh) * 2014-03-18 2014-06-18 山东大学 一种含短氟碳链的有机氟硅改性聚氨酯乳液的制备方法
CN104448211A (zh) * 2014-12-19 2015-03-25 江南大学 一种uv固化含氟超支化水性聚氨酯树脂的制备方法
CN104877099A (zh) * 2015-05-22 2015-09-02 安徽大学 一种有机氟改性超支化水性聚氨酯的制备方法

Cited By (10)

* Cited by examiner, † Cited by third party
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CN106349452B (zh) * 2016-08-19 2019-01-25 陕西科技大学 端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法
CN107118327A (zh) * 2017-06-16 2017-09-01 陕西科技大学 一种耐黄变的氟醇封端型超支化聚氨酯及其制备方法
CN108505394A (zh) * 2017-12-26 2018-09-07 刘超 一种超支化含氟聚合物材料的制造工艺
CN108505394B (zh) * 2017-12-26 2021-02-19 刘超 一种超支化含氟聚合物材料的制造工艺
CN109385199A (zh) * 2018-10-22 2019-02-26 陕西科技大学 一种阳离子端氟烷基超支化聚氨酯皮革涂饰剂的制备方法
CN109438643A (zh) * 2018-11-08 2019-03-08 合众（佛山）化工有限公司 一种生物基氟改性水性聚氨酯树脂及其制备方法
CN109749048A (zh) * 2019-02-28 2019-05-14 陕西科技大学 端氟烷基和侧链氟烷基双改性聚氨酯乳液及其制备方法
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