CN113512295A - 基于聚磷腈体系的低热释放阻燃热塑性材料及制备方法 - Google Patents
基于聚磷腈体系的低热释放阻燃热塑性材料及制备方法 Download PDFInfo
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Abstract
基于聚磷腈体系的低热释放阻燃热塑性材料及制备方法,属于阻燃材料技术领域。由聚磷腈和共混聚合物及添加剂组成;所选用的聚磷腈重量占比5‑85%,共混聚合物重量占比15‑95%,添加剂重量占比0‑5%。所述热塑性材料微型量热测试峰值热释放率(PHRR)比纯聚偏氟乙烯、聚甲基丙烯酸甲酯、聚碳酸酯下降幅度在30‑70%。
Description
技术领域
本发明涉及的是低热释放率阻燃材料,属于一种聚磷腈改性热塑性新型阻燃高分子材料,相比常规阻燃高分子材料,具有更优异的低热释放率和更宽温域的弹性性能。
背景技术
对于防火/阻燃材料而言,常规应用领域普遍采用UL(美国保险商实验室)体系来评估材料的防火性能,该体系着重于评估材料本身的可燃性。但对某些特殊应用场合,如空间封闭、狭小及人员高度集中的航空客舱、船舱以及高能量密度电池而言,不仅需要考察材料的可燃性(起火初期),还需要对其燃烧释放的热量进行评价(起火扩展期),以尽量避免因热量集中释放所产生的局部高温环境所引发的更大危害,如对于有人员的客舱而言,局部高温环境会严重影响到人员紧急逃生,造成重大人员伤亡事故;对于高能量密度电池而言,电池内部的局部高温环境会大幅增加电池的爆炸几率,危害性极大。因此,低热释放率阻燃材料具有极其重要的应用价值。
与通过添加各种阻燃剂和在分子结构上引入功能基团的普通阻燃方式类似,低热释放率阻燃材料主要也是采用引入阻燃剂或分子结构改性,但可供选择的成熟技术不多,多数集中在引入氢氧化铝和氢氧化镁为主的无机阻燃剂,如专利CN106589750B,虽然通过加入氢氧化铝使某聚烯烃热塑性弹性体材料达到了低热释放率效果,但其1倍以上的添加量,对材料加工性能和机械力学性能的影响是显而易见的;专利CN106832554 B也是通过添加大量的氢氧化铝、氢氧化镁实现低热释放率阻燃效果的。其它方式包括引入有机磷、硅氧烷等,如专利CN107001796B采用的是结合硅氧烷改性和酞酮化合物来降低聚碳酸酯热释放率。专利CN106488954B通过引入有机磷、聚醚酰亚胺等与纯聚碳酸酯组合,制备出低热释放率聚碳酸酯材料。专利CN107033400B通过成炭剂、硼酸三聚氰胺和红磷的组合物对天然橡胶改性,获得低热释放率效果。专利CN108383987B是通过设计一种芳酮结构的聚酯,可以形成稳定的芳香杂环从而获得高成碳能力,阻隔热释放来实现低热释放性能。
磷腈是一种综合性能非常优异的阻燃剂材料,但目前涉及磷腈的阻燃材料技术尽管很多,但是基本都是环磷腈等小分子磷腈、低聚合度聚磷腈或聚磷腈微球。如专利CN109370190B将含有至少一种烯丙基取代的苯基磷腈阻燃添加剂加入到聚碳酸酯中制成一种阻燃等级和耐漏电起痕性能提高的聚碳酸酯材料。专利CN107011501B将六(4-羟甲基苯氧基)环三磷腈与十六烷基三甲基溴化铵、环氧氯丙烷混合后,反应制得含磷环氧树脂,然后加入固化剂于120℃、160℃固化得到一种无卤低烟阻燃环氧树脂复合材料。专利CN106633794B公开了一种复合阻燃剂(聚二磷腈、磷酸三乙酯和协效剂)。专利CN106133056B公开了一种聚酯组合物,引入了有机膦氧化物、低聚或聚合的双(苯氧基)磷腈、有机磷酸酯或它们的组合作为阻燃增效剂,可用于制造电气和电子设备的部件。
相比以上专利所提到的环磷腈等小分子磷腈以及低聚合度聚磷腈,本发明采用分子量10000以上的聚磷腈,其独特的优势体现在两个方面:1.可以与本体材料(如聚甲基丙烯酸甲酯或聚偏氟乙烯、聚碳酸酯等在内的一系列热塑性材料)的结合能够保持长期稳定性;2.高温燃烧条件下,通过交联生成多层堆叠结构化的连续相耐高温致密材料,使其具备更高的固体残留率,从而有助于抑制热量释放和阻挡火焰进一步侵蚀。
发明内容
本发明利用聚磷腈的磷氮结构阻燃性、结构多样性和高致密燃烧产物特点,将其与聚偏氟乙烯、聚甲基丙烯酸甲酯、聚碳酸酯一种和添加剂共混形成组合物,得到了一种可溶解、可热加工成型的具有优异低热释放性能的阻燃热塑性材料。
本发明提供的一种低热释放率阻燃材料是由聚磷腈和共混聚合物及添加剂组成;所选用的聚磷腈重量占比85-5%,共混聚合物重量占比15-95%,添加剂重量占比0-5%。
其中聚磷腈结构为:
式中,R1为不含氟的芳氧基(包括苯氧基、烷基苯氧基、环状烯基取代的苯氧基、链状烯基取代的苯氧基等)、含氟或不含氟的烷氧基。
式中,R2为不含氟的芳氧基(包括苯氧基、烷基苯氧基、环状烯基苯氧基和链状烯基苯氧基等)和含氟或不含氟的烷氧基。
式中,聚合物分子中单个氮磷段上的R1、R2可以相同也可以不同,同一聚合物分子中的不同氮磷链段上R1可以相同也可以不同,同一聚合物分子中的不同氮磷链段上R2可以相同也可以不同,且同一聚合物分子中可能含有一种或一种以上的R1或R2基团。100≥n≥20,优选≥50;
举例聚磷腈结构如;
本发明提供的基于聚磷腈体系的低热释放阻燃热塑性材料,所选用的聚磷腈分子量Mn≥10000。
本发明提供的基于聚磷腈体系的低热释放阻燃热塑性材料,所选用的添加剂为石墨粉、炭黑、蒙脱石、硅酸铝一种或几种组合物。
本发明提供的基于聚磷腈体系的低热释放阻燃热塑性材料,所选用的共混聚合物为聚偏氟乙烯、聚甲基丙烯酸甲酯或聚碳酸酯中的一种或几种。
上述所述的基于聚磷腈体系的低热释放阻燃热塑性材料制备方法,包括如下步骤:
步骤一:采用溶液或本体聚合法制备聚二氯磷腈,通过亲核试剂反应制备所述的聚磷腈;
步骤二:将步骤一制备的聚磷腈产物干燥处理,再经溶剂溶解后,在溶液状态下与共混聚合物及添加剂进行混合分散处理,烘干造粒后得到一种新型低热释放阻燃热塑性材料。
上述步骤二所选用的溶剂为四氢呋喃、N-甲基吡咯烷酮、二甲苯、二甲基亚砜中的一种。
所述热塑性材料微型量热测试峰值热释放率(PHRR)比纯聚偏氟乙烯、聚甲基丙烯酸甲酯、聚碳酸酯下降幅度在30-70%。
以上所述基于聚磷腈体系的低热释放阻燃热塑性材料可直接作为工程塑料、薄膜材料和3D打印原料使用,也可作为防火功能添加剂使用。
附图说明
图1为本发明材料高温(用氧乙炔火焰)燃烧后的固体残留物微观结构图,其中a,b均为聚磷腈烧蚀后的形貌图,a为断面形貌,b为烧蚀产物中心区域形貌。
具体实施方式
下面对本发明的实施例作进一步描述。
实施例1:使用前所有固体原料都要在80℃烘箱中干燥12h。称取5g聚偏氟乙烯和30g乙氧基聚磷腈的低热释放阻燃热塑性材料,加入N-甲基吡咯烷酮,分别配制成溶液,将两种溶液充分混合搅拌后加入1g石墨粉,待其分散完成后进行烘干造粒,出料。
该阻燃热塑性材料微型量热测试热释放率峰值(PHRR)为80W/g,相比单纯聚偏氟乙烯热释放率峰值(PHRR)~210W/g,降低幅度为61%。
实施例2:使用前所有固体原料都要在80℃烘箱中干燥12h。称取15g聚甲基丙烯酸甲酯和30g三氟乙氧基聚磷腈的低热释放阻燃热塑性材料,加入N-甲基吡咯烷酮,分别配制成溶液,将两种溶液充分混合搅拌后加入2g石墨粉,待其分散完成后进行烘干造粒,出料。
该阻燃热塑性材料微型量热测试热释放率峰值(PHRR)为125W/g,相比单纯聚甲基丙烯酸甲酯热释放率峰值(PHRR)~420W/g,降低幅度为70%。
实施例3:
使用前所有固体原料都要在80℃烘箱中干燥12h。称取30g聚碳酸酯和30g含乙氧基聚磷腈的低热释放阻燃热塑性材料,加入N-甲基吡咯烷酮,分别配制成溶液,将两种溶液充分混合搅拌后加入2g石墨粉,待其分散完成后进行烘干造粒,出料。
该阻燃热塑性材料微型量热测试热释放率峰值(PHRR)为147W/g,相比单纯聚碳酸酯热释放率峰值(PHRR)~330W/g,降低幅度为55%。
实施例4:
使用前所有固体原料都要在80℃烘箱中干燥12h。称取15g聚偏氟乙烯和30g含乙氧基聚磷腈的低热释放阻燃热塑性材料,加入N-甲基吡咯烷酮,分别配制成溶液,将两种溶液充分混合搅拌后加入1g石墨粉,待其分散完成后进行烘干造粒,出料。
该阻燃热塑性材料微型量热测试热释放率峰值(PHRR)为115W/g,相比单纯聚偏氟乙烯热释放率峰值(PHRR)~210W/g,降低幅度为45%。
实施例5:
使用前所有固体原料都要在80℃烘箱中干燥12h。称取10g聚碳酸酯和40g含乙氧基聚磷腈的低热释放阻燃热塑性材料,加入N-甲基吡咯烷酮,分别配制成溶液,将两种溶液充分混合搅拌后加入1g石墨粉,待其分散完成后进行烘干造粒,出料。
该阻燃热塑性材料微型量热测试热释放率峰值(PHRR)为161W/g,相比单纯聚碳酸酯热释放率峰值(PHRR)~330W/g,降低幅度为50%。
在引入本发明之前的本体材料(聚甲基丙烯酸甲酯、聚碳酸酯等热塑性材料)经过热测试(不同材料的分解温度不一样,如聚甲基丙烯酸甲酯在~410℃就完全分解,聚碳酸酯则在~550℃完全分解)后,近乎完全分解,固体残留物很少,而本发明材料采用氧乙炔火焰高温燃烧后,依然有很多固体残留物(如图1所示的微观形貌照片,固体残留物呈现出了很高程度的致密堆叠结构,采用本发明的技术方案得到的固体残留物基本一样),如前所述,这种致密结构对于抑制热量释放和阻挡火焰进一步侵蚀是非常有利的,从而可以有效降低燃烧过程中的材料热释放量。
最后应该说明的是,以上所述仅为本发明的优选实施例,并不构成对本发明的限制。
Claims (7)
1.基于聚磷腈体系的低热释放阻燃热塑性材料,其特征在于,由聚磷腈和共混聚合物及添加剂组成;所选用的聚磷腈重量占比85-5%,共混聚合物重量占比15-95%,添加剂重量占比0-5%。
3.按照权利要求2所述的基于聚磷腈体系的低热释放阻燃热塑性材料,其特征在于,聚磷腈分子量Mn≥10000。
4.按照权利要求1所述的基于聚磷腈体系的低热释放阻燃热塑性材料,其特征在于,所选用的添加剂为石墨粉、炭黑、蒙脱石、硅酸铝一种或几种组合物。
5.按照权利要求1所述的基于聚磷腈体系的低热释放阻燃热塑性材料,其特征在于,共混聚合物为聚偏氟乙烯、聚甲基丙烯酸甲酯或聚碳酸酯中的一种或几种。
6.权利要求1-5任一项所述的基于聚磷腈体系的低热释放阻燃热塑性材料的制备方法,其特征在于,包括如下步骤:
步骤一:采用溶液或本体聚合法制备聚二氯磷腈,通过亲核试剂反应制备所述的聚磷腈;
步骤二:将步骤一制备的聚磷腈产物干燥处理,再经溶剂溶解后,在溶液状态下与共混聚合物及添加剂进行混合分散处理,烘干造粒后得到一种新型低热释放阻燃热塑性材料。
7.按照权利要求6所述的方法,其特征在于,步骤二所选用的溶剂为四氢呋喃、N-甲基吡咯烷酮、二甲苯、二甲基亚砜中的一种。
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