CN107987320B - 一种磷氮杂化协效膨胀阻燃剂及其制备方法 - Google Patents
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Abstract
本发明公开了一种磷氮杂化协效膨胀阻燃剂及其制备方法，本发明提供一种通过原位交联/接枝反应，形成具有磷氮杂化结构的集酸源、气源和碳源为一体的协效膨胀型阻燃剂，该阻燃剂通过物理和化学阻燃过程，可达到优异的阻燃效果，并且吸水率低和稳定性好，可广泛应用于ABS等塑料以及有机泡沫制品。
Description
技术领域
本发明属于高分子阻燃技术领域，涉及磷氮杂化协效膨胀阻燃剂及其制备方法。
技术背景
磷氮膨胀型阻燃剂主要以磷氮为主要成分，引起发烟量和有毒气体少，并能起到优异的阻燃效果，被认为是阻燃剂今后发展得重要方向之一。膨胀阻燃体系一般由酸源（脱水剂）、炭源（成炭剂）和气源（发泡剂）3部分组成，炭源是指在燃烧过程中能被脱水剂夺走水分而被炭化的物质。炭源是形成泡沫炭层物质的基础，炭源是否优良直接决定了阻燃效果。氧化石墨烯是主要的碳源候选材料，并常用作塑料、橡胶等高分子材料的阻燃剂。
以往的报道大多都是将氧化石墨烯与其他阻燃剂进行简单混合并用后应用于聚合物中，虽然在一定程度上能够提升阻燃效果，但因为氧化石墨烯难以良好分散而损害了基体聚合物的力学性能。
发明内容
本发明的目的是供一种通过在氧化石墨烯表面进行原位反应包覆，形成核壳结构的集酸源、气源和碳源为一体的高效膨胀型阻燃剂，可以有效提升橡塑材料阻燃效果的同时，并能改善基体材料的力学性能。为了实现上述目的，本发明提供如下技术方案：
一种磷氮杂化协效膨胀阻燃剂，按照质量百分数，包括以下组分：
三聚氰氯 12%～20%
双酚化合物 28%～35%
二异丙基乙胺 18%～22%
密胺磷酸盐 10%～18.5%
氧化石墨烯 15%～25%。
优选地，双酚化合物为双酚A、双酚S和双酚酸中的一种或几种的组合。
优选地，蜜胺磷酸盐为蜜胺氰尿酸盐、蜜胺正磷酸盐、二蜜胺磷酸盐、蜜胺焦磷酸盐和蜜胺聚磷酸盐中的一种或几种的组合。
优选地，氧化石墨烯的直径为0.1-5µm，层数为1-5层，厚度为1-2nm。
一种制备如上述磷氮杂化协效膨胀阻燃剂的方法，包括以下步骤：
（1）在反应器中，按照配比将三聚氰氯、双酚化合物和密胺磷酸盐加入四氢呋喃中，搅拌至完全溶解，将配制分散后的氧化石墨烯THF溶液倒入上述反应器中；
（2）边搅拌边加入二异丙基乙胺THF溶液，反应1-3小时；
（3）除去溶剂，并用去离子水洗涤1-3次；
（4）用硅胶柱层析法进行纯化后热空气干燥；
（5）取出制品破碎研磨，得到阻燃剂粉末。
本专利选取具有三嗪结构的三聚氰氯和双酚在氧化石墨烯表面进行原位交联反应，生长成环状或笼形结构，并同时对密胺磷酸盐进行包覆，形成一体结构，形成集酸源、气源和碳源为一体的高效膨胀型阻燃剂，最主要的是经过表面改性的氧化石墨烯亲油性提高，与橡塑材料的相容性明显改善。阻燃机理为：在250～300度左右时蜜胺磷酸盐分解，生成的磷酸催化基体成炭，生成的氮气没有烟气毒性，可以作为安全的起泡剂，使氧化石墨烯等碳源形成泡沫炭层物质，阻隔氧气从而起到优异的阻燃效果。本产品具有较小的水溶解度和很好的热稳定性，可广泛应用于塑料以及有机泡沫制品。
本发明的有益效果：
1、通过合理设计，将三嗪类和双酚类阻燃成分成功原位接枝和交联生长在氧化石墨烯表面，原位反应、包覆的方式制备真正意义上的协效膨胀阻燃剂，该阻燃剂兼具酸源、气源、碳源组分，摒弃了以往简单共混并用的方式，有效弥补了各阻燃组分的缺点，增加了其与有机高分子材料的相容性的同时补强力学强度，燃效果提升显著；
2、本发明涉及方法均在常压下进行，简单易行，便于大规模制备。
具体实施方式
实施例1
一种协效膨胀阻燃剂，按照质量百分数，包括以下组分：
三聚氰氯 12.2%
双酚A 30.4%
二异丙基乙胺 19.4%
密胺正磷酸盐 16%
氧化石墨烯 22%
其中，氧化石墨烯的直径为0.1µm，层数为5层，厚度为2nm。
一种制备如上述磷氮杂化协效膨胀阻燃剂的方法，包括以下步骤：
（1）在反应器中，按照配比将三聚氰氯、双酚A和密胺正磷酸盐加入四氢呋喃中，搅拌至完全溶解，将配制分散后的氧化石墨烯THF溶液倒入上述反应器中；
（2）边搅拌边加入二异丙基乙胺THF溶液，反应2.5小时；
（3）除去溶剂，并用去离子水洗涤2次；
（4）用硅胶柱层析法进行纯化后，再进行热空气干燥；
（5）取出制品破碎研磨，得到阻燃剂粉末。
经过热重分析，该阻燃剂开始分解温度为265℃，热失重最快温度为365℃，800℃质量剩余52%，1000℃质量剩余46.1%。在水中的溶解度为0.03g/100ml水。
实施例2
一种协效膨胀阻燃剂按照质量百分数，包括以下组分：
三聚氰氯 18.4%
双酚S 34.3%
二异丙基乙胺 20.4%
密胺聚磷酸盐 11.2%
氧化石墨烯 15.7%
其中，氧化石墨烯的直径为3µm，层数为3层，厚度为1.5nm。
一种制备如上述磷氮杂化协效膨胀阻燃剂的方法，包括以下步骤：
（1）在反应器中，按照配比将三聚氰氯、双酚S和密胺聚磷酸盐加入四氢呋喃中，搅拌至完全溶解，将配制分散后的氧化石墨烯THF溶液倒入上述反应器中；
（2）边搅拌边加入二异丙基乙胺THF溶液，反应2小时；
（3）除去溶剂，并用去离子水洗涤3次；
（4）用硅胶柱层析法进行纯化后，再进行热空气干燥；
（5）取出制品破碎研磨，得到阻燃剂粉末。
经过热重分析，该阻燃剂开始分解温度为256℃，热失重最快温度为389℃，800℃质量剩余51.2%， 1000℃质量剩余44.2%。在水中的溶解度为0.018g/100ml水。
实施例3
一种协效膨胀阻燃剂按照质量百分数，包括以下组分：
三聚氰氯 12%
双酚S 15%
双酚酸 20%
二异丙基乙胺 18%
蜜胺氰尿酸盐 10.5%
二蜜胺磷酸盐 8.0%
氧化石墨烯 16.5%
其中，氧化石墨烯的直径为5µm，层数为1层，厚度为1nm。
一种制备如上述磷氮杂化协效膨胀阻燃剂的方法，包括以下步骤：
（1）在反应器中，按照配比将三聚氰氯、双酚S、双酚酸蜜胺氰尿酸盐和二蜜胺磷酸盐加入四氢呋喃中，搅拌至完全溶解，将配制分散后的氧化石墨烯THF溶液倒入上述反应器中；
（2）边搅拌边加入二异丙基乙胺THF溶液，反应3小时；
（3）除去溶剂，并用去离子水洗涤1次；
（4）用硅胶柱层析法进行纯化后，再进行热空气干燥；
（5）取出制品破碎研磨，得到阻燃剂粉末。
经过热重分析，该阻燃剂开始分解温度为277℃，热失重最快温度为382℃，800℃质量剩余50.8%， 1000℃质量剩余45.4%。在水中的溶解度为0.015g/100ml水。
对比试验：
分别将本申请实施例1-3制得的阻燃剂和纯氧化石墨烯以10%（质量分数）添加到ABS塑料中，分别测定抗拉强度和氧指数，结果如下表1：
表1
| 项目 | 实施例1 | 实施例2 | 实施例3 | 氧化石墨烯 |
| 抗拉强度/MPa | 62 | 64 | 63 | 56 |
| 氧指数/% | 31 | 30 | 31 | 25 |
由表中可以直观看出，单纯添加氧化石墨烯对于实施例产品对基体材料的压缩强度的改善效果差，原因是实施例产品因为与基体材料相容性的提高，有效的弥补了氧化石墨烯分散性差对复合材料强度的影响。
本发明提供一种通过原位交联/接枝反应，形成具有磷氮杂化结构的集酸源、气源和碳源为一体的协效膨胀型阻燃剂，该阻燃剂通过物理和化学阻燃过程，可达到优异的阻燃效果，并且吸水率低、稳定性好，可广泛应用于ABS等塑料以及有机泡沫制品。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
Claims (5)
1.一种磷氮杂化协效膨胀阻燃剂，其特征在于，按照质量百分数，包括以下组分：
三聚氰氯 12%～20%
双酚化合物 28%～35%
二异丙基乙胺 18%～22%
蜜胺磷酸盐 10%～18.5%
氧化石墨烯 15%～25%
选取具有三嗪结构的三聚氰氯和双酚在氧化石墨烯表面进行原位交联反应。
2.根据权利要求1所述的磷氮杂化协效膨胀阻燃剂，其特征在于，双酚化合物为双酚A、双酚S和双酚酸中的一种或几种的组合。
3.根据权利要求1所述的磷氮杂化协效膨胀阻燃剂，其特征在于，蜜胺磷酸盐为蜜胺正磷酸盐、二蜜胺磷酸盐、蜜胺焦磷酸盐和蜜胺聚磷酸盐中的一种或几种的组合。
4.根据权利要求1所述的磷氮杂化协效膨胀阻燃剂，其特征在于，氧化石墨烯的直径为0.1-5µm，层数为1-5层，厚度为1-2nm。
5.一种制备如权利要求1-4任一所述磷氮杂化协效膨胀阻燃剂的方法，其特征在于，包括以下步骤：
（1）在反应器中，按照配比将三聚氰氯、双酚化合物和密胺磷酸盐加入四氢呋喃中，搅拌至完全溶解，将配制分散后的氧化石墨烯THF溶液倒入上述反应器中；
（2）边搅拌边加入二异丙基乙胺THF溶液，反应1-3小时；
（3）除去溶剂，并用去离子水洗涤1-3次；
（4）用硅胶柱层析法进行纯化后，再进行热空气干燥；
（5）取出制品破碎研磨，得到阻燃剂粉末。
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