CN106750239A - 一种含磷氮氟聚合物阻燃剂及其制备方法与应用 - Google Patents

一种含磷氮氟聚合物阻燃剂及其制备方法与应用 Download PDF

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CN106750239A
CN106750239A CN201611037090.7A CN201611037090A CN106750239A CN 106750239 A CN106750239 A CN 106750239A CN 201611037090 A CN201611037090 A CN 201611037090A CN 106750239 A CN106750239 A CN 106750239A
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戴李宗
陈婷
刘诚
王世成
陈国荣
袁丛辉
许婷
许一婷
曾碧榕
罗伟昂
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Xiamen University
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Abstract

本发明公开了一种含磷氮硅聚合物阻燃剂及其制备方法和应用，其化学式结构为：其中，m＝10～100，n＝10～100。本发明的含磷氮硅聚合物阻燃剂中磷、氮、硅三者之间的协同阻燃效果提高了环氧树脂的阻燃性能。

Description

一种含磷氮氟聚合物阻燃剂及其制备方法与应用
技术领域
本发明属于有机阻燃剂技术领域，具体涉及一种含磷氮氟聚合物阻燃剂及其制备方法与应用。
背景技术
环氧树脂是一类具有强度高、粘结性能好、耐腐蚀性好及介电性能优异等优点的高分子材料，被广泛应用于土木建筑、电子电器、航天航空及汽车机械等领域中，在国民经济各部门中起着不可或缺的位置。然而，环氧树脂是一类相对易燃的材料，这个缺点也大大限制了环氧树脂的应用，环氧树脂的阻燃也一直是研究者们不懈探讨的课题。
多元素阻燃剂是近年来兴起的一类阻燃技术，CN201510132367.3公开了一种含磷、氮膨胀型阻燃剂，作为一种环氧树脂反应型阻燃剂固化剂，不仅具有阻燃效果，还可以固化环氧树脂，固化物力学性能好。CN201510132367.3公开了一种DOPO衍生阻燃剂，利用磷氮阻燃剂的磷氮协同阻燃作用，及其较好的热稳定性和良好的成炭作用，用于环氧树脂等高分子材料的阻燃，阻燃效果好，拓展了DOPO阻燃剂的应用范围。含有多元素阻燃剂的阻燃效果良好，但现有的阻燃剂大多以小分子为主，往往存在着降低材料热稳定性或机械性能的缺点。
发明内容
本发明目的在于提供一种含磷氮硅聚合物阻燃剂。
本发明的另一目的在于提供上述含磷氮硅聚合物阻燃剂的制备方法。
本发明的目的在于提供上述含磷氮硅聚合物阻燃剂的应用。
本发明的技术方案如下：
一种含磷氮硅聚合物阻燃剂，其化学式结构为：
其中，m＝10～100，n＝10～100。
上述含磷氮硅聚合物阻燃剂的制备方法，其合成路线如下所示：
具体包括如下步骤：
(1)在冰浴下依次向反应容器中加入缩水甘油、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、三乙胺和第一有机溶剂，室温反应4～16h，接着用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后，得含磷环氧单体EP-DOPO；上述缩水甘油、DOPO和三乙胺的摩尔比为1∶0.5～2.5∶0.5～2.5
(2)依次向另一反应容器中加入步骤(1)中所得的含磷环氧单体EP-DOPO、氨丙基笼型聚倍半硅氧烷(POSS-NH2)、甲醇钠和第二有机溶剂，加热至60～120℃，通氮气保护，反应4～24h，接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂；上述含磷环氧单体EP-DOPO、氨丙基笼型聚倍半硅氧烷和甲醇钠的摩尔比为1∶0.01～0.1∶0.01～0.1。
在本发明的一个优选实施方案中，所述第一有机溶剂为二氯甲烷、甲苯或四氯化碳。
在本发明的一个优选实施方案中，所述第二有机溶剂为甲苯、N，N-二甲基甲酰胺或1，4-二氧六环。
上述含磷氮硅聚合物阻燃剂在制备阻燃性环氧树脂中的应用。
在本发明的一个优选实施方案中，具体为：称取环氧树脂预聚体升温至70～110℃，加入0.1～50wt％的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，接着按化学计量比加入固化剂4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
进一步优选的，所述环氧树脂预聚体为E51双酚A型环氧树脂。
进一步优选的，所述环氧树脂预聚体与固化剂4，4-二氨基二苯甲烷的质量比为8∶2.02。
进一步优选的，所述升温程序为：120℃固化4h，140℃固化2h，180℃固化2h。
本发明的有益效果是：
1、本发明的制备方法通过制备含磷的环氧单体，以POSS-NH2为引发剂，利用环氧丙烷的开环反应制备出磷氮硅一体的聚合物阻燃剂，聚合物分子链中含有大量的-C-O-键，使聚合物分子链具有一定的柔软性，与高分子基体共混过程中表现出较好的相容性；同时固化后的阻燃性环氧树脂热稳定性与机械性能好；
2、本发明的含磷氮硅聚合物阻燃剂中磷、氮、硅三者之间的协同阻燃效果提高了环氧树脂的阻燃性能；
3、本发明的含磷氮硅聚合物阻燃剂的分子量可控，通过聚合物的分子量的调节可以控制体系中的磷、氮、硅含量比；
4、本发明的制备方法的合成反应较简单，原料成本低，产物的产率高。
附图说明
图1为实施例1中含磷氮硅聚合物阻燃剂的核磁共振氢谱图；
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述
下述实施例中，环氧树脂预聚体为E51双酚A型环氧树脂。
实施例1
(1)在冰浴下依次向单口瓶中加入2.88g(38.89mmol)缩水甘油、7g(32.41mmol)DOPO、3.94g(38.89mmol)三乙胺和50mL二氯甲烷，室温反应8h；接着用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后得单体EP-DOPO。
(2)依次向双口瓶中加入5.72g(19.86mmol)步骤(1)中所得单体EP-DOPO、0.35g(0.40mmol)POSS-NH2、0.01g(0.20mmol)甲醇钠和30mL N，N-二甲基甲酰胺，加热至80℃，通氮气保护，反应进行12h；接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂(如图1所示)。
(3)称取20g环氧树脂预聚体升温至70℃，加入1.32g的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，接着加入5.05g4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
根据GB/T 2406-2009测得本实施例的阻燃性环氧树脂的氧指数为28.1％。
实施例2
(1)在冰浴下依次向单口瓶中加入2.88g(38.89mmol)缩水甘油、7g(32.41mmol)DOPO、3.94g(38.89mmol)三乙胺和50mL二氯甲烷，反应8h；接着用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后得单体EP-DOPO。
(2)依次向双口瓶中加入5.72g(19.86mmol)步骤(1)中所得单体EP-DOPO、0.35g(0.40mmol)POSS-NH2、0.01g(0.20mmol)甲醇钠和30mL N，N-二甲基甲酰胺，加热至80℃，通氮气保护，反应进行12h；接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂。
(3)称取20g环氧树脂预聚体升温至70℃，加入0.61g的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，接着加入5.05g4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
根据GB/T 2406-2009测得本实施例的阻燃性环氧树脂的氧指数为27.5％。
实施例3
(1)在冰浴下依次向单口瓶中加入2.88g(38.89mmol)缩水甘油、7g(32.41mmol)DOPO、3.94g(38.89mmol)三乙胺和50mL二氯甲烷，反应8h；接着水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后得单体EP-DOPO。
(2)依次向双口瓶中加入5.72g(19.86mmol)步骤(1)中所得单体EP-DOPO、0.35g(0.40mmol)POSS-NH2、0.01g(0.20mmol)甲醇钠和30mL N，N-二甲基甲酰胺，加热至80℃，通氮气保护，反应进行12h；反接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂。
(3)称取20g环氧树脂预聚体升温至70℃，加入1.88g的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，接着加入5.05g4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
根据GB/T 2406-2009测得本实施例的阻燃性环氧树脂的氧指数为28.8％。
实施例4
(1)在冰浴下依次向单口瓶中加入2.88g(38.89mmol)缩水甘油、8g(37.04mm0l)DOPO、3.94g(38.89mmol)三乙胺和50mL甲苯，步骤(1)2h；接着用水反复淬洗三次，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后得单体EP-DOPO。
(2)依次向双口瓶中加入5.72g(19.86mmol)步骤(1)中所得单体EP-DOPO、0.35g(0.40mmol)POSS-NH2、0.01g(0.20mmol)甲醇钠和30mL甲苯，加热至80℃，通氮气保护，反应进行12h；接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂。
(3)称取20g环氧树脂预聚体升温至70℃，加入1.32g的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，接着加入5.05g4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
根据GB/T 2406-2009测得本实施例的阻燃性环氧树脂的氧指数为28.3％。
实施例5
(1)在冰浴下依次向单口瓶中加入2.88g(38.89mmol)缩水甘油、7g(32.41mmol)DOPO、3.94g(38.89mmol)三乙胺和50mL二氯甲烷，反应8h；接着用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后得单体EP-DOPO。
(2)依次向双口瓶中加入5.72g(19.86mmol)步骤(1)中所得单体EP-DOPO、0.70g(0.80mmol)POSS-NH2、0.02g(0.40mmol)甲醇钠和30mL N，N-二甲基甲酰胺，加热至80℃，通氮气保护，反应进行12h；接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂。
(3)称取20g环氧树脂预聚体升温至70℃，加入1.32g的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，接着加入5.05g4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
根据GB/T 2406-2009测得本实施例的阻燃性环氧树脂的氧指数为28.2％。
本领域普通技术人员可知，本发明的技术方案在下述范围内变化时，仍然能够得到与上述实施例相同或相近的技术效果，仍然属于本发明的保护范围：
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (9)

1.一种含磷氮硅聚合物阻燃剂，其特征在于：其化学式结构为：
其中，m＝10～100，n＝10～100。
2.如权利要求1所述的一种含磷氮硅聚合物阻燃剂的制备方法，其特征在于：其合成路线如下所示：
具体包括如下步骤：
(1)在冰浴下依次向反应容器中加入缩水甘油、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、三乙胺和第一有机溶剂，室温反应4～16h，接着用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后，得含磷环氧单体EP-DOPO；上述缩水甘油、DOPO和三乙胺的摩尔比为1∶0.5～2.5∶0.5～2.5
(2)依次向另一反应容器中加入步骤(1)中所得的含磷环氧单体EP-DOPO、氨丙基笼型聚倍半硅氧烷(POSS-NH2)、甲醇钠和第二有机溶剂，加热至60～120℃，通氮气保护，反应4～24h，接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂；上述含磷环氧单体EP-DOPO、氨丙基笼型聚倍半硅氧烷和甲醇钠的摩尔比为1∶0.01～0.1∶0.01～0.1。
3.如权利要求2所述的制备方法，所述第一有机溶剂为二氯甲烷、甲苯或四氯化碳。
4.如权利要求2所述的制备方法，所述第二有机溶剂为甲苯、N，N-二甲基甲酰胺或1，4-二氧六环。
5.权利要求1所述的含磷氮硅聚合物阻燃剂在制备阻燃性环氧树脂中的应用。
6.如权利要求5所述的应用，其特征在于：具体为：称取环氧树脂预聚体升温至70～110℃，加入0.1～50wt％的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，按化学计量比加入固化剂4，4-二氨基二苯甲烷(DDM)直至完全溶解，倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
7.如权利要求6所述的应用，其特征在于：所述环氧树脂预聚体为E51双酚A型环氧树脂。
8.如权利要求6所述的应用，其特征在于：所述环氧树脂预聚体与固化剂4，4-二氨基二苯甲烷的质量比为8∶2.02。
9.如权利要求6所述的应用，其特征在于：所述升温程序为：120℃固化4h，140℃固化2h，180℃固化2h。
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CN115612252A (zh) * 2022-10-14 2023-01-17 台州市黄岩区武汉理工高性能复合材料技术研究院 一种反应型阻燃环氧树脂配方及其制备方法与应用
CN115612252B (zh) * 2022-10-14 2024-05-14 台州市黄岩区武汉理工高性能复合材料技术研究院 一种反应型阻燃环氧树脂配方及其制备方法与应用

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