CN112778957B - 单组分无卤阻燃聚氨酯泡沫填缝剂及其制备方法 - Google Patents

单组分无卤阻燃聚氨酯泡沫填缝剂及其制备方法 Download PDF

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CN112778957B
CN112778957B CN202011609011.1A CN202011609011A CN112778957B CN 112778957 B CN112778957 B CN 112778957B CN 202011609011 A CN202011609011 A CN 202011609011A CN 112778957 B CN112778957 B CN 112778957B
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李剑锋
孙兆任
戈欢
王浩
王腾
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Shandong Inov New Material Co Ltd
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Abstract

本发明涉及一种单组分无卤阻燃聚氨酯泡沫填缝剂及其制备方法，属于高分子合成技术领域。所述的填缝剂由改性聚多元醇混合物、含磷聚酯多元醇、聚醚多元醇、泡沫稳定剂、抛射剂、催化剂、改性填料和异氰酸酯制得；其制备方法为：利用气雾剂灌装设备，将改性聚多元醇混合物、含磷聚酯多元醇、聚醚多元醇、改性填料、催化剂、泡沫稳定剂及异氰酸酯加入气雾罐中，封口后冲入抛射剂，振摇混合均匀，常温存放后，即得产品。本发明的填缝剂不需要额外添加非反应型阻燃剂，阻燃性能优异，产品储存稳定性好；其制备方法，科学合理、简单易行。

Description

单组分无卤阻燃聚氨酯泡沫填缝剂及其制备方法
技术领域
本发明涉及一种单组分无卤阻燃聚氨酯泡沫填缝剂及其制备方法，属于高分子合成技术领域。
背景技术
聚氨酯本身而言属于易燃材料，通过常规方法想要提升材料阻燃性能比较困难。对于单组分聚氨酯填缝剂而言，由于其主要成分为聚氨酯和极度易燃的烷烃，想要提高其阻燃性能更是难上加难。目前最常见的技术思路主要是依赖添加型阻燃剂。如常见的含磷液体阻燃剂TCPP、DMMP等。该类阻燃剂磷含量较高，对于提高材料阻燃性能的确有很大帮助。但是由于材料结构易水解的特点，添加大量的阻燃剂后不仅会影响材料性能，还会影响材料的储存稳定性。还有一些阻燃OCF填缝剂借助固体添加型阻燃剂，如膨胀石墨、Al(OH)3、Sb2O3等。添加上述物质后填缝剂粘度会有所提升，最主要的是长期存放填料会下沉、打胶时容易堵枪。
专利CN106977684B中公告了一种氧指数≥32的高阻燃无卤低烟低毒单组分聚氨酯泡沫填缝剂及其制备方法，主要借助含有磷、氮、硅、芳杂环而无卤素的反应型阻燃剂、膨胀型固体添加型阻燃剂、和无卤素的液体添加型阻燃剂等阻燃剂来提高填缝剂氧指数、降低填缝剂烟密度和烟毒性。专利CN 110423458 A中公开了一种B1级阻燃型单组分聚氨酯泡沫材料，主要借助结构不详的阻燃组合聚醚和含溴的阻燃石蜡来提高填缝剂阻燃性能。专利CN 106800633 B公告了一种氧指数≥32的高阻燃单组分聚氨酯泡沫填缝剂，该填缝材料核心原料是含溴的多元醇、含磷和卤液体阻燃剂以及可膨胀石墨。专利CN 111363113 A公开了一种防火单组分聚氨酯泡沫填缝剂及其制备方法，其技术路线是采用阻燃聚醚、添加型阻燃剂以及大量具有阻燃特性的无机填料。
目前为止，阻燃聚氨酯填缝剂技术路线主要依赖于液体添加型阻燃剂、固体添加型阻燃剂。
发明内容
针对现有技术的不足，本发明的目的是提供一种单组分无卤阻燃聚氨酯泡沫填缝剂，不需要额外添加非反应型阻燃剂，阻燃性能优异，产品储存稳定性好；本发明还提供其制备方法，科学合理，简单易行。
本发明所述的单组分无卤阻燃聚氨酯泡沫填缝剂，由下列质量份数的物质组成：
Figure BDA0002870809210000011
Figure BDA0002870809210000021
其中：
所述改性聚多元醇混合物是将TDI多聚体、乙酸丁酯溶液、有机磷酸酯二醇在反应釜中，75-80℃条件下，反应2-3h，测试NCO％为0，降温放料制备。通过两者的反应，将N、P阻燃元素引入材料结构中。改性后产物中多元醇占比70％-90％，乙酸丁酯占比10％-30％。所述改性聚多元醇混合物羟值50-80mgKOH/g。所述TDI多聚体为TDI二聚体或TDI三聚体中的一种。所述有机磷酸酯二醇是由乙二醇或1,4丁二醇与甲基膦酸二甲酯或乙基磷酸二乙酯，通过在钛酸四丁酯催化剂作用下进行酯交换，蒸除小分子物质，控制馏分的质量，得到目标产物。所述的改性聚多元醇的结构如结构式1或结构式2所示：
Figure BDA0002870809210000022
R1为C2H4或C4H8；R2为CH3或C2H5；2＜n＜10；
所述的含磷聚酯多元醇羟值为80-550mgKOH/g；所述的含磷聚酯多元醇的结构如结构式3或结构式4所示，苯环和磷元素的有机结合，可以提高材料的阻燃性能。所述含磷聚酯多元醇是由邻苯二甲酸酐与有机磷酸酯二醇或THPO采用常规的聚酯多元醇制备方法制备。
Figure BDA0002870809210000031
1≤n1＜5；1≤n2＜5；1≤n＜5；
所述的聚醚多元醇数均分子量为300-2000，官能度为2-3；优选的，官能度2，分子量400～1000。
所述的泡沫稳定剂为AK8871、AK8872或AK8876中的一种或多种。
所述的抛射剂为丙丁烷和二甲醚的混合物，丙丁烷与二甲醚质量比为1.5：1-1.5。
所述的催化剂为DMDEE。
所述的改性填料是由偶联剂与膨胀石墨按质量比1-10:100-150在高速搅拌机上研磨分散0.5h，然后100-120℃烘干0.5h以上制备。
所述的偶联剂为新烷氧基三(二辛基焦磷酸酰氧基)钛酸酯、异丙基三(二辛基焦磷酸酰氧基)钛酸酯、新烷氧基三(十二烷基苯磺酰氧基)锆酸酯或双新烷氧基双(4-氨基苯甲酸酰氧基)锆酸酯中的一种。
所述异氰酸酯为多亚甲基多苯基多异氰酸酯，NCO质量分数为30-32％。
本发明所述的单组分无卤阻燃聚氨酯泡沫填缝剂的制备方法，包括以下步骤：
利用气雾剂灌装设备，将改性聚多元醇混合物、含磷聚酯多元醇、聚醚多元醇、改性填料、催化剂、泡沫稳定剂及异氰酸酯加入气雾罐中，封口后冲入抛射剂，振摇混合均匀，常温存放后，即得单组分无卤阻燃聚氨酯泡沫填缝剂。
与现有技术相比，本发明有益效果如下：
1、本发明将氮、磷、苯环等阻燃效果理想的元素或基团直接引入聚氨酯填缝剂分子结构中，不需要额外添加非反应型阻燃剂，阻燃性能优异，产品储存稳定性好。
2、本发明将固体添加型阻燃剂进行改性，改善其在聚氨酯材料中的分散性，便于储存，同时有助于提高填缝剂阻燃性能。
3、本发明借助改性的含磷多元醇将氮、磷阻燃元素直接引入到材料分子结构中，同时辅以改性填料来提高材料的阻燃性能，不需要额外添加大量的无卤或含卤的添加型阻燃剂，制备的填缝剂材料储存期长，阻燃性能优异。
4、本发明的制备方法，科学合理、简单易行。
具体实施方式
以下结合实施例对本发明做进一步描述，但其并不限制本发明的实施。
实施例中所用材料，除特殊说明外，均为市售原料。
实施例1
利用气雾剂灌装设备，按表1中实施例1配方将具有结构式1结构(R1为C2H4，R2为CH3)的改性聚多元醇混合物(乙酸丁酯占比15％)、具有结构式3结构的含磷聚酯多元醇、聚醚多元醇(INOVOL C204，羟值278mgKOH/g)、泡沫稳定剂、DMDEE、改性填料(新烷氧基三(二辛基焦磷酸酰氧基)钛酸酯与膨胀石墨按质量比1:120进行改性)及多异氰酸酯加入气雾罐中，封口后冲入抛射剂(丙丁烷与二甲醚质量比为1.5：1)，振摇混合均匀，常温存放后，即得单组分聚氨酯泡沫填缝剂。
实施例2
利用气雾剂灌装设备，按表1中实施例2配方将具有结构式2结构(R1为C2H4，R2为C2H5)的改性聚多元醇混合物(乙酸丁酯占比20％)、具有结构式3结构的含磷聚酯多元醇、聚醚多元醇(INOVOL C204，羟值278mgKOH/g)、泡沫稳定剂、DMDEE、改性填料(异丙基三(二辛基焦磷酸酰氧基)钛酸酯与膨胀石墨按质量比1:40进行改性)及多异氰酸酯加入气雾罐中，封口后冲入抛射剂(丙丁烷与二甲醚质量比为1.5：1.1)，振摇混合均匀，常温存放后，即得单组分聚氨酯泡沫填缝剂。
实施例3
利用气雾剂灌装设备，按表1中实施例3配方将具有结构式1结构(R1为C4H8，R2为CH3)的改性聚多元醇混合物(乙酸丁酯占比25％)、具有结构式4结构的含磷聚酯多元醇、聚醚多元醇(市售INOVOL S207H，羟值160mgKOH/g)、泡沫稳定剂、DMDEE、改性填料(新烷氧基三(十二烷基苯磺酰氧基)锆酸酯与膨胀石墨按质量比1:60进行改性)及多异氰酸酯加入气雾罐中，封口后冲入抛射剂(丙丁烷与二甲醚质量比为1.5：1.2)，振摇混合均匀，常温存放后，即得单组分聚氨酯泡沫填缝剂。
实施例4
利用气雾剂灌装设备，按表1中实施例4配方将具有结构式2结构(R1为C4H8，R2为C2H5)的改性聚多元醇混合物(乙酸丁酯占比25％)、具有结构式4结构的含磷聚酯多元醇、聚醚多元醇(市售INOVOL C310，羟值168mgKOH/g)、泡沫稳定剂、DMDEE、改性填料(新烷氧基三(二辛基焦磷酸酰氧基)钛酸酯与膨胀石墨按质量比1:15进行改性)及多异氰酸酯加入气雾罐中，封口后冲入抛射剂(丙丁烷与二甲醚质量比为1.5：1.0)，振摇混合均匀，常温存放后，即得单组分聚氨酯泡沫填缝剂。
实施例5
利用气雾剂灌装设备，按表1中实施例5配方将具有结构式2结构(R1为C2H4，R2为CH3)的改性聚多元醇混合物(乙酸丁酯占比25％)、具有结构式4结构的含磷聚酯多元醇、聚醚多元醇(市售INOVOL C204，羟值278mgKOH/g)、泡沫稳定剂、DMDEE、改性填料(异丙基三(二辛基焦磷酸酰氧基)钛酸酯与膨胀石墨按质量比1:10进行改性)及多异氰酸酯加入气雾罐中，封口后冲入抛射剂(丙丁烷与二甲醚质量比为1：1)，振摇混合均匀，常温存放后，即得单组分聚氨酯泡沫填缝剂。
实施例6
利用气雾剂灌装设备，按表1中实施例6配方将具有结构式2结构(R1为C4H8，R2为C2H5)的改性聚多元醇混合物(乙酸丁酯占比20％)、具有结构式4结构的含磷聚酯多元醇、聚醚多元醇(市售INOVOL C207，羟值160mgKOH/g)、泡沫稳定剂、DMDEE、改性填料(新烷氧基三(二辛基焦磷酸酰氧基)钛酸酯与膨胀石墨按质量比1:15进行改性)及多异氰酸酯加入气雾罐中，封口后冲入抛射剂(丙丁烷与二甲醚质量比为1.5：1.0)，振摇混合均匀，常温存放后，即得单组分聚氨酯泡沫填缝剂。
将市售B1级阻燃聚氨酯填缝剂与实施例1-6制备的聚氨酯填缝剂同步进行阻燃性能测试，测试数据见表1。
表1实施例配方及阻燃性能测试
Figure BDA0002870809210000061

Claims (6)

1.一种单组分无卤阻燃聚氨酯泡沫填缝剂，其特征在于：由下列质量份数的物质组成：
改性聚多元醇混合物 60-80；
含磷聚酯多元醇 15-30；
聚醚多元醇 5-10；
泡沫稳定剂 1-10；
抛射剂 40-100；
催化剂 0.1-2.0；
改性填料 10-40；
异氰酸酯 120-200；
其中：
所述的改性聚多元醇混合物是由TDI二聚体或TDI三聚体在乙酸丁酯溶液中与有机磷酸酯二醇反应制备，改性产物中改性聚多元醇占比70-90%，乙酸丁酯占比10%-30%，所述改性聚多元醇混合物羟值为50-80mgKOH/g；所述的改性聚多元醇的结构如结构式1或结构式2所示：
Figure DEST_PATH_IMAGE002
结构式1，
Figure DEST_PATH_IMAGE004
结构式2，
R1为C2H4或C4H8；R2为CH3或C2H5；2＜n＜10；
所述的含磷聚酯多元醇羟值为80-550 mgKOH/g；所述的含磷聚酯多元醇的结构如结构式3或结构式4所示：
Figure DEST_PATH_IMAGE006
结构式3，
Figure DEST_PATH_IMAGE008
结构式4，
1≤n1＜5；1≤n2＜5；1≤n＜5；
所述的聚醚多元醇数均分子量为300-2000，官能度为2-3；
所述的改性填料是由偶联剂与膨胀石墨按质量比1-10:100-150在高速搅拌机上研磨分散0.5h，然后100-120℃烘干0.5h以上制备。
2.根据权利要求1所述的单组分无卤阻燃聚氨酯泡沫填缝剂，其特征在于：所述的抛射剂为丙丁烷和二甲醚的混合物，丙丁烷与二甲醚质量比为1.5：1-1.5。
3.根据权利要求1所述的单组分无卤阻燃聚氨酯泡沫填缝剂，其特征在于：所述的催化剂为DMDEE。
4.根据权利要求1所述的单组分无卤阻燃聚氨酯泡沫填缝剂，其特征在于：所述的偶联剂为新烷氧基三(二辛基焦磷酸酰氧基)钛酸酯、异丙基三(二辛基焦磷酸酰氧基)钛酸酯、新烷氧基三(十二烷基苯磺酰氧基)锆酸酯或双新烷氧基双(4-氨基苯甲酸酰氧基)锆酸酯中的一种。
5.根据权利要求1所述的单组分无卤阻燃聚氨酯泡沫填缝剂，其特征在于：所述异氰酸酯为多亚甲基多苯基多异氰酸酯，NCO质量分数为30-32%。
6.一种权利要求1-5任一所述的单组分无卤阻燃聚氨酯泡沫填缝剂的制备方法，其特征在于：包括以下步骤：
利用气雾剂灌装设备，将改性聚多元醇混合物、含磷聚酯多元醇、聚醚多元醇、改性填料、催化剂、泡沫稳定剂及异氰酸酯加入气雾罐中，封口后冲入抛射剂，振摇混合均匀，常温存放后，即得单组分无卤阻燃聚氨酯泡沫填缝剂。
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