CN106750116B - 一种聚氨酯纳米阻燃复合材料及其制备方法 - Google Patents

一种聚氨酯纳米阻燃复合材料及其制备方法 Download PDF

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CN106750116B
CN106750116B CN201611046044.3A CN201611046044A CN106750116B CN 106750116 B CN106750116 B CN 106750116B CN 201611046044 A CN201611046044 A CN 201611046044A CN 106750116 B CN106750116 B CN 106750116B
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韩永芹
王圣武
李廷希
王天琪
高萧萧
张宗霖
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Shandong University of Science and Technology
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Abstract

本发明公开了一种聚氨酯纳米阻燃复合材料及其制备方法，所述复合材料包括A、B两组分，其中A组分含有聚醚多元醇、反应型阻燃剂、氧化石墨烯接枝聚苯胺、催化剂、增塑剂、纳米改性剂，B组分为有机异氰酸酯。本发明解决了煤矿岩层用聚氨酯加固材料的阻燃性能，得到的聚氨酯纳米复合材料具有高强度、高阻燃性和抗静电性，为矿用聚氨酯加固材料的安全性提供保障。

Description

一种聚氨酯纳米阻燃复合材料及其制备方法
技术领域
本发明属于高分子材料技术领域，具体涉及一种煤矿用加固聚氨酯纳米阻燃复合材料及其制备方法。
背景技术
煤炭是我国的主体能源，煤炭能源占我国当前整个能源供应体系的70％左右，煤炭开采业的发展直接影响到我国经济的发展。煤矿的下煤层抗压强度低，易破碎变形，容易产生裂缝和较大的断裂带；破碎松散岩区和裂隙发育带在动压增大情况下极易冒顶、产生地下水灾等。煤矿安全生产关系煤炭工业持续发展和国家能源安全，关系数百万矿工生命安全。在煤层破碎岩层中注入高分子材料煤岩体加固剂可将裂缝和裂纹粘结在一起，注入的浆体物料可被强劲地锁紧在一起，防止相互已锁紧的岩块之间发生移动，最终达到煤岩加固的目的。
常用的煤岩加固剂主要有聚氨酯类、环氧树脂类、丙烯酰胺类、丙烯酸盐类、脲醛树脂类等。在所有类型的加固剂中聚氨酯类加固剂具有固化速度快且可控、发泡倍率高、粘结能力强、施工快捷等特点，在破碎煤岩体的固结、采空区快速密闭、封堵矿井漏水、瓦斯封孔等方面具有独特的优点，具有广阔的市场前景。纯聚氨酯泡沫的极限氧指数(LOI)在18左右，属于易燃材料。但煤矿矿井中含有大量瓦斯，对聚氨酯材料的阻燃和抗静电性提出了较高的要求。
聚氨酯材料的阻燃剂主要有三聚氰胺、磷酸酯、无机或其它含卤素的阻燃剂，含卤素的阻燃剂由于在燃烧过程中会释放有毒气体而逐渐被禁用，添加型阻燃剂又会面临着在使用过程中阻燃组分会逐渐向制品表面迁移，进而导致聚氨酯阻燃及力学性能的下降。因此非常有必要开发高阻燃、高强度的矿用聚氨酯加固材料。
发明内容
为了实现上述的发明目的，本发明提供的技术方案如下：一种聚氨酯纳米阻燃复合材料，包括A组分和B组分，其中A组分按照重量百分数计含有：
聚醚多元醇：80-90％
反应型阻燃剂 1-10％
氧化石墨烯接枝聚苯胺 2-5％
催化剂 0.1-2％
增塑剂 1-6％
纳米改性剂 3-10％
B组分为有机异氰酸酯。
进一步，所述A、B组份的体积比为A:B＝1:1
进一步，所述的聚醚多元醇为405，4110，330N,ZN-8304中的一种；
进一步，所述的反应型阻燃剂为四溴双酚A、四羟甲基氯化鏻(THPC)、四羟甲基氢氧化鏻(THPOH)、O,O′-二乙基-N,N-二(2-羟乙基)氨基甲基磷酸酯(无色溶液，商品名称Fyrol-6)、三(一缩二丙二醇)亚磷酸酯(P430)，10-(2,5-二羟基苯基)-10-二氢-9-氧杂-10-磷菲-10-氧化物中的一种。
进一步，所述的氧化石墨烯接枝聚苯胺是由氧化石墨烯酰氯化后接枝的方法制备的，其结构式如下；
进一步，所述的催化剂选自N，N-二甲基环已胺、N，N-二甲基苄胺、二乙烯三胺、五甲基二亚乙基三胺、二月桂酸二丁基锡、二醋酸二丁基锡中的一种。
进一步，所述的增塑剂选自邻苯二甲酸二辛酯、邻苯二甲酸二异壬酯、甘油三醋酸酯、柠檬酸三乙酯、柠檬酸三丁酯、磷酸三芳基酯中的一种。
进一步，所述的纳米改性剂为纳米蒙脱土、纳米层状双氢氧化物、碳纳米管、纳米二氧化硅中的一种或一种以上的混合物；
进一步，所述的有机异氰酸酯为二苯基甲烷二异氰酸酯、多亚甲基多苯多异氰酸酯，六亚甲基二异氰酸酯、萘二异氰酸酯中的一种。
本发明还提供上述聚氨酯纳米阻燃复合材料的制备方法，包括以下步骤：
(1)制备A组份料：将称量好的A组份原料在常温搅拌均匀，备用；
(2)将A、B组份料按A:B＝1:1的体积比在现场混合均匀，即得聚氨酯纳米阻燃复合材料。该材料可用作煤矿岩层的加固材料，使用时只需专用双液注浆泵进行注浆即可。
本发明的优点在于：(1)本发明通过配方设计，固化速度可控，固化后材料具有高抗压强度；原料液粘度低，在煤岩中有良好的渗透性；(2)本发明采用反应型阻燃剂、氧化石墨烯接枝聚苯胺，可在聚氨酯分子骨架中同时引入阻燃及增强组分，同时获得良好的力学强度及阻燃性能；(3)本发明材料的原料无污染，不含有挥发性溶剂，不产生任何有毒气体，绿色环保。
附图说明
图1为本发明聚氨酯纳米阻燃复合材料抗压强度测试前后的数码照片。
具体实施方式
以下通过具体实施例对本发明作进一步详细说明。但不应将此理解为本发明的保护范围仅限于下述实施例。
实施例1一种聚氨酯纳米阻燃复合材料的制备方法，步骤如下：
A组分按照重量百分数计含有：
聚醚多元醇4110(汕头市成霖化工有限公司)：80％
THPC(道尔化工有限公司) 10％
氧化石墨烯接枝聚苯胺 2％
N，N-二甲基环己胺(国药集团化学试剂有限公司) 0.1％
邻苯二甲酸辛酯(国药集团化学试剂公司) 1％
纳米蒙脱土(浙江丰虹化工有限公司) 5％
纳米二氧化硅(山东寿光宝特化工有限公司) 1.9％
B组分为二苯基甲烷二异氰酸酯(青岛鹏源化工原料有限公司)
A组分中氧化石墨烯接枝聚苯胺参照文献Kumar NA,Choi HJ,Shin YR,Chang DW,Dai LM,Baek JB.Polyaniline-grafted reduced graphene oxide for efficientelectrochemical supercapacitors.ACS Nano,2012,6(2):1715-1723.方法制备得到。
将称量好的A组分原料在常温搅拌均匀，备用；
将A、B组份料按A:B＝1:1的体积比在现场混合均匀，即得聚氨酯纳米阻燃复合材料，可用作煤矿岩层的加固材料。
实施例2一种聚氨酯纳米阻燃复合材料制备方法，步骤如下：
A组分按照重量百分数计含有：
聚醚多元醇405：85％
阻燃剂THPOH 1％
氧化石墨烯接枝聚苯胺 2％
二乙烯三胺 0.3％
甘油三醋酸酯 1.7％
层状双氢氧化物 5％
纳米蒙脱土 5％
B组分为多亚甲基多苯多异氰酸酯
将称量好的A组分原料在常温搅拌均匀，备用；
将A、B组份料按A:B＝1:1的体积比在现场混合均匀，即得聚氨酯纳米阻燃复合材料，可用作煤矿岩层的加固材料。
实施例3一种聚氨酯纳米阻燃复合材料制备方法，步骤如下：
A组分按照重量百分数计含有：
聚醚多元醇330N：80％
四溴双酚A 5％
氧化石墨烯接枝聚苯胺 3％
N，N-二甲基苄胺 2％
邻苯二甲酸二异壬酯 3％
纳米层状双氢氧化物 2％
碳纳米管 5％
B组分为六亚甲基二异氰酸酯
将称量好的A组分原料在常温搅拌均匀，备用；
将A、B组份料按A:B＝1:1的体积比在现场混合均匀，即得聚氨酯纳米阻燃复合材料，可用作煤矿岩层的加固材料。
实施例4一种聚氨酯纳米阻燃复合材料制备方法，步骤如下：
A组分按照重量百分数计含有：
聚醚多元醇ZN-8304：90％
阻燃剂Fyrol-6 2％
氧化石墨烯接枝聚苯胺 3％
五甲基二亚乙基三胺 0.5％
柠檬酸三乙酯 1.5％
碳纳米管 3％
B组分为六亚甲基二异氰酸酯
将称量好的A组分原料在常温搅拌均匀，备用；
将A、B组份料按A:B＝1:1的体积比在现场混合均匀，即得聚氨酯纳米阻燃复合材料，可用作煤矿岩层的加固材料。
实施例5一种聚氨酯纳米阻燃复合材料制备方法，步骤如下：
A组分按照重量百分数计含有：
聚醚多元醇405：82％
阻燃剂P430 4％
氧化石墨烯接枝聚苯胺 3.4％
二月桂酸二丁基锡 0.6％
柠檬酸三丁酯 6％
纳米蒙脱土 4％
B组分为萘二异氰酸酯
将称量好的A组分原料在常温搅拌均匀，备用；
将A、B组份料按A:B＝1:1的体积比在现场混合均匀，即得聚氨酯纳米阻燃复合材料，可用作煤矿岩层的加固材料。
实施例6一种聚氨酯纳米阻燃复合材料制备方法，步骤如下：
A组分按照重量百分数计含有：
聚醚多元醇4110：80％
10-(2,5-二羟基苯基)-10H-9-氧杂-10-磷菲-10-氧化物 7％
氧化石墨烯接枝聚苯胺 5％
二醋酸二丁基锡 1.5％
磷酸三芳基酯 3％
层状双氢氧化物 3.5％
其中A组分中层状双氢氧化物参照文献Faour,Azzam，Prévot Vanessa,Taviot-Gueho,Christine.Microstructural study of different LDH morphologies obtainedvia different synthesis routes.Journal of Physics and Chemistry of Solids2010；71:487-490方法制备得到。
B组分为萘二异氰酸酯
将称量好的A组分原料在常温搅拌均匀，备用；
将A、B组份料按A:B＝1:1的体积比在现场混合均匀，即得聚氨酯纳米阻燃复合材料，可用作煤矿岩层的加固材料。
实施例1-6制备的复合材料性能参数如表1所示
表1
材料 抗压强度(MPa) 极限氧指数(LOI)
实施例1 121.7 32
实施例2 95.6 30
实施例3 88.2 29
实施例4 102.5 31
实施例5 100.8 32
实施例6 95.6 31
图1为本发明聚氨酯纳米阻燃复合材料抗压强度测试前后的数码照片，可以看出,抗压强度测试后，样品破坏程度较小。
上述实施例对本发明的技术方案进行了详细说明。显然，本发明并不局限于所描述的实施例。熟悉本技术领域的人员还可据此做出多种变化，但任何与本发明等同或相类似的变化都属于本发明保护的范围。

Claims (10)

1.一种聚氨酯纳米阻燃复合材料，其特征在于，所述复合材料包括A组分和B组分，其中A组分按照重量百分数计含有：
聚醚多元醇：80-90%
反应型阻燃剂 1-10%
氧化石墨烯接枝聚苯胺2-5%
催化剂0.1-2%
增塑剂1-6%
纳米改性剂 3-10%
B组分为有机异氰酸酯。
2.根据权利要求1所述聚氨酯纳米阻燃复合材料，其特征在于，所述A、B 组份的体积比为A:B ＝1:1。
3.根据权利要求1所述聚氨酯纳米阻燃复合材料，其特征在于，所述的聚醚多元醇为405， 4110，330N中的一种。
4.根据权利要求1所述聚氨酯纳米阻燃复合材料，其特征在于，所述的反应型阻燃剂为四溴双酚A、四羟甲基氯化鏻、四羟甲基氢氧化鏻、O,O′-二乙基-N,N-二（2-羟乙基）氨基甲基磷酸酯、三（一缩二丙二醇）亚磷酸酯，10-（2,5-二羟基苯基）-10-二氢-9-氧杂-10-磷杂菲-10-氧化物中的一种。
5.根据权利要求1所述聚氨酯纳米阻燃复合材料，其特征在于，所述的氧化石墨烯接枝聚苯胺是由氧化石墨烯酰氯化后接枝的方法制备的。
6.根据权利要求1所述聚氨酯纳米阻燃复合材料，其特征在于，所述的催化剂选自N，N-二甲基环已胺、N，N-二甲基苄胺、二乙烯三胺、五甲基二亚乙基三胺、二月桂酸二丁基锡、二醋酸二丁基锡中的一种。
7.根据权利要求1所述聚氨酯纳米阻燃复合材料，其特征在于，所述的增塑剂选自邻苯二甲酸二辛酯、邻苯二甲酸二异壬酯、甘油三醋酸酯、柠檬酸三乙酯、柠檬酸三丁酯、磷酸三芳基酯中的一种。
8.根据权利要求1所述聚氨酯纳米阻燃复合材料，其特征在于，所述的纳米改性剂为纳米蒙脱土、纳米层状双氢氧化物、碳纳米管、纳米二氧化硅中的一种或一种以上的混合物。
9.根据权利要求1所述聚氨酯纳米阻燃复合材料，其特征在于，所述的有机异氰酸酯为二苯基甲烷二异氰酸酯、多亚甲基多苯基多异氰酸酯，六亚甲基二异氰酸酯、萘二异氰酸酯中的一种。
10.权利要求1-9任一项所述聚氨酯纳米阻燃复合材料的制备方法，其特征在于：包括以下步骤：
(1) 制备A 组份料：将称量好的A 组份原料在常温搅拌均匀，备用；
(2) 将A、B 组份料按A:B ＝1:1 的体积比在现场混合均匀，即得聚氨酯纳米阻燃复合材料。
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