CN115505093A - 一种磷氮硅阻燃水性聚氨酯的制备方法 - Google Patents

一种磷氮硅阻燃水性聚氨酯的制备方法 Download PDF

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CN115505093A
CN115505093A CN202211125620.9A CN202211125620A CN115505093A CN 115505093 A CN115505093 A CN 115505093A CN 202211125620 A CN202211125620 A CN 202211125620A CN 115505093 A CN115505093 A CN 115505093A
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retardant
waterborne polyurethane
phosphorus
silicon
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徐志伟
冯莲
王维
庄君新
宋兵
朱雪利
王亮
钱晓明
孙国旗
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Jiangsu Huron New Materials Co ltd
Mingxin Menorca Jiangsu New Materials Co ltd
Mingxin Xuteng Jiangsu Innovation Research Institute Co ltd
Jiangsu Mill Chemical Technology Co ltd
Tianjin Polytechnic University
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Jiangsu Huron New Materials Co ltd
Mingxin Menorca Jiangsu New Materials Co ltd
Mingxin Xuteng Jiangsu Innovation Research Institute Co ltd
Jiangsu Mill Chemical Technology Co ltd
Tianjin Polytechnic University
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Abstract

本发明涉及阻燃高分子材料领域，公开了一种磷氮硅阻燃水性聚氨酯的制备方法，包括以下步骤：步骤一：将阻燃多元醇和聚丙二醇混合均匀，并且进行真空脱水；步骤二：向容器中加入异氟尔酮二异氰酸酯、阻燃单体进行预聚反应；然后进行扩链反应，制备得到阻燃水性聚氨酯预聚体；步骤三：将阻燃水性聚氨酯预聚体倒入乳化桶中，同时进行后扩链反应和乳化反应，制备得到阻燃水性聚氨酯乳液；步骤四：将阻燃水性聚氨酯乳液置于聚四氟乙烯模具中，常温固化，并烘干至恒重制备得到阻燃水性聚氨酯胶膜，本发明制备得到一种磷‑硅‑氮协同阻燃水性聚氨酯，力学性能优异、阻燃效果较好，合成方法简单通用，对环境污染小，在皮革领域具有潜在的应用价值。

Description

一种磷氮硅阻燃水性聚氨酯的制备方法
技术领域
本发明涉及阻燃高分子材料领域，更具体地说，它涉及一种磷氮硅阻燃水性聚氨酯的制备方法。
背景技术
水性聚氨酯以水为介质，无毒绿色环保，在涂料、胶粘剂、皮革等各个领域应用较为广泛。但未经阻燃整理的水性聚氨酯胶膜的极限氧指数仅有18％左右，不具有阻燃性能,遇火会燃烧并分解,产生大量有毒烟雾和气体。因此，开发阻燃性能优良的水性聚氨酯是整个行业亟待解决的问题之一。
根据阻燃单体加入方式的不同，阻燃水性聚氨酯包括添加型阻燃水性聚氨酯和本征型阻燃水性聚氨酯。添加型阻燃水性聚氨酯由于阻燃单体与树脂相容性不佳，共混后阻燃元素极易迁移，严重影响胶膜的阻燃、力学等性能。本征型阻燃水性聚氨酯根据阻燃单体接枝链段的不同，分为软段改性、硬段改性、软硬段共改性和后扩链改性。软段改性、硬段改性和软硬段共改性三种方式可以引入较多的阻燃元素，工艺灵活，性能较佳。由于后扩链改性受后扩链系数的影响，导致引入的阻燃元素受限，关注度较低。目前在改善水性聚氨酯阻燃性能的过程中，引入磷、氮、硅等具有阻燃性的元素，通过单独阻燃或协同阻燃来改善水性聚氨酯的阻燃性能和热稳定性能。在研究过程中，为了获得更好的阻燃效果，多元素协同阻燃成为了开发本征阻燃水性聚氨酯的重要渠道。
公开号专利CN112279995B公布了一种以由甘氨酸、多聚甲醛、亚磷酸二甲酯为原料制得的磷氮一体化功能化合物与双环氧化合物反应制得的双羟基高磷氮含量阻燃功能单体为扩链单体制备得到阻燃水性聚氨酯。阻燃单体的合成过程过于复杂，副反应较多，不易于产业化。公开号专利CN113621173A公布了一种由三聚氰胺、聚磷酸铵、氢氧化镁等组成的复合阻燃剂和硅凝胶复配对单组份水性聚氨酯进行阻燃改性。该方法制备得到的阻燃水性聚氨酯乳液不稳定、阻燃元素易迁移，阻燃耐久性差。公开号专利CN111825824A公布了一种以含磷多元醇、含磷稳定剂和含磷扩链剂为阻燃单体制备得到阻燃水性聚氨酯的方法。该方法仅仅引入磷一种元素，会增强聚氨酯胶膜的吸湿性能，严重影响水性聚氨酯在皮革上的应用。
发明内容
本发明提供了一种磷-氮-硅协同阻燃水性聚氨酯的制备方法。此方法制备得到的阻燃水性聚氨酯阻燃性能优异，制备得到的乳液在皮革方面具有潜在的应用价值，适合放大合成和实际生产。
本发明提出的一种磷氮硅阻燃水性聚氨酯的制备方法，包括以下步骤：
步骤一：将阻燃多元醇和聚丙二醇置于容器中搅拌混合均匀，并且进行真空脱水；
步骤二：向容器中加入异氟尔酮二异氰酸酯、阻燃单体进行预聚反应；
然后加入二羟甲基丙酸和1，4-丁二醇进行扩链反应，在反应过程中加入适量丙酮降低黏度；
降温至65℃，加入有机铋催化剂，反应2h；
降温加入KH-550和三乙胺，中和反应一段时间，制备得到阻燃水性聚氨酯预聚体；
步骤三：将阻燃水性聚氨酯预聚体倒入乳化桶中，同时加入二乙胺和去离子水进行后扩链反应和乳化反应，制备得到阻燃水性聚氨酯乳液；
步骤四：将阻燃水性聚氨酯乳液置于聚四氟乙烯模具中，常温固化，并烘干至恒重制备得到阻燃水性聚氨酯胶膜。
进一步地：在步骤一中，阻燃多元醇为含磷聚醚多元醇、含硅多元醇其中的一种或两种组合。
进一步地：含磷聚醚多元醇为下式所示的化合物
Figure BDA0003848492090000031
进一步地：含硅多元醇为下所示的化合物
Figure BDA0003848492090000032
进一步地：步骤一中，阻燃多元醇和普通聚醚多元醇的摩尔比为(2：3)～(1：4)。
进一步地：步骤二中，阻燃单体为10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和三聚氰胺的任意一种或两种组合。
进一步地：步骤二中，所述的阻燃单体占总反应物质量的2％～10％。
进一步地：步骤二中，在下述工艺条件下进行真空脱水，该工艺条件为：预聚反应温度90℃，时间2h；扩链反应80℃，时间3h；中和反应温度40℃，时间0.5h。
本发明的有益效果在于：本发明提出磷-氮-硅阻燃水性聚氨酯的制备方法的以含磷多元醇、含硅多元醇、三聚氰胺、KH-550为阻燃单体制备得到阻燃水性聚氨酯，避免了自制阻燃剂的复杂工艺和较多副反应的发生，可以获得稳定、阻燃元素不迁移、阻燃性能优异的水性聚氨酯乳液，可适用于织物涂层和皮革含浸用等各个领域。
附图说明
图1是本发明提出的一种磷氮硅阻燃水性聚氨酯的制备方法的流程示意图；
图2是实施例1制备的磷氮硅阻燃水性聚氨酯(P-N-SiWPU)和对比实施例制备的水性聚氨酯(WPU)的Tg图；
图3是实施例1制备的磷氮硅阻燃水性聚氨酯(P-N-SiWPU)和对比实施例制备的水性聚氨酯(WPU)的DTG图；
图4是实施例1制备的磷氮硅协同阻燃水性聚氨酯和对比实施例制备的水性聚氨酯红外光谱图。
具体实施方式
现在将参考示例实施方式讨论本文描述的主题。应该理解，讨论这些实施方式只是为了使得本领域技术人员能够更好地理解从而实现本文描述的主题，并非是对权利要求书中所阐述的保护范围、适用性或者示例的限制。可以在不脱离本说明书内容的保护范围的情况下，对所讨论的元素的功能和排列进行改变。各个示例可以根据需要，省略、替代或者添加各种过程或组件。另外，相对一些示例所描述的特征在其他例子中也可以进行组合。
实施例1
参考附图1，在本实施例中提出了一种磷氮硅阻燃水性聚氨酯的制备方法，制备步骤如下：
步骤一：将68.7g聚丙二醇、17.3聚硅氧烷多元醇和80g含磷阻燃聚醚多元醇Frol-326置于四口烧瓶中搅拌混合均匀，并且在温度105℃、压力-0.1KPa的条件下真空脱水1h。
步骤二：降温至40℃，向四口烧瓶中加入55.57g异氟尔酮二异氰酸酯、7.26g10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物和5g三聚氰胺，升温至85℃，保温搅拌2h；降温至40℃，加入7g二羟甲基丙酸和3.03g1，4-丁二醇，升温至80℃，保温反应2h；降温至60℃，加入0.37g有机铋催化剂，保温反应3h，加入100g丙酮降低黏度；降温至40℃，加入2.75gKH-550和5.69g三乙胺，反应0.5h；降温至20℃，制备得到阻燃水性聚氨酯预聚体。
步骤三：将制备得到的阻燃水性聚氨酯预聚体倒入乳化桶中，加入500g去离子水和2.26g二乙胺，在3000r/min的转速下乳化0.5h，制备得到阻燃水性聚氨酯乳液。
步骤四：将阻燃水性聚氨酯乳液置于聚四氟乙烯模具中，常温固化48h，60℃下烘干至恒重。
实施例2
参考附图1，在本实施例中提出了一种磷氮硅阻燃水性聚氨酯的制备方法，制备步骤如下：
步骤一：将86g聚丙二醇和87g含磷阻燃聚醚多元醇置于四口烧瓶中搅拌混合均匀，并且在温度105℃、压力-0.1KPa的条件下真空脱水1h。
步骤二：降温至40℃，向四口烧瓶中加入55.57g异氟尔酮二异氰酸酯、9.08g10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物和5g三聚氰胺，升温至85℃，保温搅拌2h；降温至40℃，加入7g二羟甲基丙酸和3g1，4-丁二醇，升温至80℃，保温反应2h；降温至60℃，加入0.39g有机铋催化剂，保温反应3h，加入96g丙酮降低黏度；降温至40℃，加入12gKH-550和5.69g三乙胺，反应0.5h；降温至20℃，制备得到阻燃水性聚氨酯预聚体。
步骤三、将制备得到的阻燃水性聚氨酯预聚体倒入乳化桶中，加入499g去离子水和2.26g二乙胺，在3000r/min的转速下乳化30min反应0.5h，制备得到阻燃水性聚氨酯乳液。
步骤四、将阻燃水性聚氨酯乳液置于聚四氟乙烯模具中，常温固化48h，60℃下烘干至恒重。
实施例3
参考附图1，在本实施例中提出了一种磷氮硅阻燃水性聚氨酯的制备方法，制备步骤如下：
步骤一：将51.4g聚丙二醇、34.6g聚硅氧烷多元醇和76g含磷阻燃聚醚多元醇Frol-326置于四口烧瓶中搅拌混合均匀，并且在温度105℃、压力-0.1KPa的条件下真空脱水1h。
步骤二：降温至40℃，向四口烧瓶中加入55.57g异氟尔酮二异氰酸酯、10.90g10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物和5g三聚氰胺，升温至85℃，保温搅拌2h；降温至40℃，加入7g二羟甲基丙酸和3.04g1，4-丁二醇，升温至80℃，保温反应2h；降温至60℃，加入0.40g有机铋催化剂，保温反应3h，加入103g丙酮降低黏度；降温至40℃，加入2.75gKH550和5.69g三乙胺，反应0.5h；降温至20℃，制备得到阻燃水性聚氨酯预聚体。
步骤三、将制备得到的阻燃水性聚氨酯预聚体倒入乳化桶中，加入499g去离子水和2.26g二乙胺在3000r/min的转速下乳化0.5h，制备得到阻燃水性聚氨酯乳液。
步骤四、将阻燃水性聚氨酯乳液置于聚四氟乙烯模具中，常温固化48h，60℃下烘干至恒重。
对比实施例
在本实施例中提出了一种水性聚氨酯的制备方法，制备步骤如下：
步骤一：将173g聚丙二醇置于四口烧瓶中搅拌混合均匀，并且在温度105℃、压力-0.1KPa的条件下真空脱水1h。
步骤二：降温至40℃，向四口烧瓶中加入55.57g异氟尔酮二异氰酸酯，升温至85℃，保温搅拌2h；降温至40℃，加入7g二羟甲基丙酸和3g1，4-丁二醇，升温至80℃，保温反应2h；降温至60℃，加入0.40g有机铋催化剂，保温反应3h，加入90g丙酮降低黏度；降温至40℃，加入2.75gKH-550和5.69g三乙胺，反应0.5h；降温至20℃，制备得到阻燃水性聚氨酯预聚体。
步骤三、将制备得到的阻燃水性聚氨酯预聚体倒入乳化桶中，加入499g去离子水和2.26g二乙胺在3000r/min的转速下乳化0.5h，制备得到阻燃水性聚氨酯乳液。
步骤四、将阻燃水性聚氨酯乳液置于聚四氟乙烯模具中，常温固化48h，60℃下烘干至恒重。
将实施例1、2和3以及对比实施例制备的聚氨酯进行阻燃性能测试，具体结果如下表：
磷-氮-硅阻燃水性聚氨酯的阻燃性能测试：
Figure BDA0003848492090000071
从上可以看出，本发明制备得到的阻燃水性聚氨酯具有一定的阻燃作用，当阻燃元素达到一定含量，燃烧时滴落的熔滴不会引燃脱脂棉垫，阻燃剂添加量越多阻燃性能越好。
图2和图3分别为实施例1制备的磷-氮-硅阻燃水性聚氨酯(P-N-SiWPU)和对比实施例制备的水性聚氨酯(WPU)的Tg图和DTG图。
从图2和图3中可以看出，实施例1制备的磷-氮-硅阻燃水性聚氨酯的成炭量较大，分解温度提高，说明P、N、Si三种元素可以促进胶膜热分解性能的提高。
图4为实施例1制备的磷-氮-硅协同阻燃水性聚氨酯和对比实施例制备的水性聚氨酯红外光谱图，从图中可以看出，在240～2280cm-1处未观察到-NCO的伸缩振动峰，表明-NCO反应完全。1100cm-1是聚醚多元醇的O-C-O，1370-1380cm-1是CH3对称变形，1450cm-1是CH2变形，1540cm-1左右是N-H变形，1710cm-1是异氰酸酯的C＝O，2860和2950cm-1是CH3、CH2的伸缩振动，3330cm-1是OH\NH伸缩振动，说明水性聚氨酯合成成功。其中，P-N-SiWPU在1230cm-1处出现P＝O伸缩振动吸收峰，800-900cm-1之间出现P-O吸收峰，在650cm-1左右出现苯环特征峰，814cm-1出现三嗪环变形振动峰，1551cm-1出现三嗪环芳香族C＝N伸缩振动峰，3467和3419cm-1出现-NH2反对称伸缩振动，说明P、Si、N等元素引入了引入了阻燃水性聚氨酯链段中。
上面结合附图对本实施例的实施例进行了描述，但是本实施例并不局限于上述的具体实施方式，上述的具体实施方式仅仅是示意性的，而不是限制性的，本领域的普通技术人员在本实施例的启示下，在不脱离本实施例宗旨和权利要求所保护的范围情况下，还可做出很多形式，均属于本实施例的保护之内。

Claims (7)

1.一种磷氮硅阻燃水性聚氨酯的制备方法，其特征在于，包括以下步骤：
步骤一：将阻燃多元醇和聚丙二醇置于容器中搅拌混合均匀，并且进行真空脱水；
步骤二：向容器中加入异氟尔酮二异氰酸酯、阻燃单体进行预聚反应；
然后加入二羟甲基丙酸和1，4-丁二醇进行扩链反应，在反应过程中加入适量丙酮降低黏度；
降温至65℃，加入有机铋催化剂，反应2h；
降温加入KH-550和三乙胺，中和反应一段时间，制备得到阻燃水性聚氨酯预聚体；
步骤三：将阻燃水性聚氨酯预聚体倒入乳化桶中，同时加入二乙胺和去离子水进行后扩链反应和乳化反应，制备得到阻燃水性聚氨酯乳液；
步骤四：将阻燃水性聚氨酯乳液置于聚四氟乙烯模具中，常温固化，并烘干至恒重制备得到阻燃水性聚氨酯胶膜。
2.根据权利要求1所述的一种磷氮硅阻燃水性聚氨酯的制备方法，其特征在于，在步骤一中，阻燃多元醇为含磷聚醚多元醇、含硅多元醇其中的一种或两种组合。
3.根据权利要求2所述的一种磷氮硅阻燃水性聚氨酯的制备方法，其特征在于，含磷聚醚多元醇为下式所示的化合物
Figure FDA0003848492080000011
4.根据权利要求2所述的一种磷氮硅阻燃水性聚氨酯的制备方法，其特征在于，含硅多元醇为下所示的化合物
Figure FDA0003848492080000021
5.根据权利要求1所述的一种磷氮硅阻燃水性聚氨酯的制备方法，其特征在于，步骤二中，阻燃单体为10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和三聚氰胺的任意一种或两种组合。
6.根据权利要求1所述的一种磷氮硅阻燃水性聚氨酯的制备方法，其特征在于，步骤二中，所述的阻燃单体占总反应物质量的2％～10％。
7.根据权利要求1所述的一种磷氮硅阻燃水性聚氨酯的制备方法，其特征在于，步骤二中，在下述工艺条件下进行真空脱水，该工艺条件为：预聚反应温度90℃，时间2h；扩链反应80℃，时间3h；中和反应温度40℃，时间0.5h。
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