CN111793358A - 一种耐火烧无卤阻燃增强尼龙复合材料 - Google Patents
一种耐火烧无卤阻燃增强尼龙复合材料 Download PDFInfo
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- CN111793358A CN111793358A CN202010651160.8A CN202010651160A CN111793358A CN 111793358 A CN111793358 A CN 111793358A CN 202010651160 A CN202010651160 A CN 202010651160A CN 111793358 A CN111793358 A CN 111793358A
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Abstract
本发明涉及一种耐火烧无卤阻燃增强尼龙复合材料，包括如下组分：聚酰胺树脂、阻隔剂、填充剂、次膦酸盐、三聚氰胺衍生物、硼酸锌和其他助剂。本发明通过向无卤有机次膦酸盐阻燃的聚酰胺体系中，引入提高灼烧后碳层阻隔作用的阻隔剂，能够有效提高碳层的隔热性能，延长材料的阻燃性能和耐火烧时间，在部分应用领域中达到替换热固性材料的效果，同时实施难度小，效果明显，具有良好的应用前景。
Description
技术领域
本发明属于工程塑料领域，特别涉及一种耐火烧无卤阻燃增强尼龙复合材料。
背景技术
玻纤增强的聚酰胺具有力学性能好，耐化学腐蚀，电性能优等一系列优点，成为众多工程领域应用的首选材料。不同种类的聚酰胺的阻燃性能差别较大，大多数聚酰胺的阻燃性能无法满足日常需求，加之引入玻纤后带来的“烛芯效应”会劣化聚酰胺自身的阻燃性能，所以众多诸如电子电器、消费电器等领域对玻纤增强聚酰胺的阻燃性能提出了更高的要求。
由于无卤阻燃体系材料在燃烧过程中产生的有害物质少，发烟量低等优点，是近年来阻燃聚酰胺发展的重要方向之一。含磷化合物是一类在聚酰胺材料中非常具有应用前景的高效无卤阻燃剂，如以二乙基次膦酸铝为主要成分的商业化阻燃剂。为了获得较高的阻燃效率，在其使用过程中往往同时引入协效剂，如三聚氰胺衍生物和硼酸盐等。
火烧实验是模拟部分产品实际使用工况的一种阻燃性测试，这类产品往往对阻燃有着极为苛刻的要求。如部分家用及工业电器的电控盒外壳仍然采用传统的BMC(BulkMolding Compound)热固性材料，其往往具有较高的力学强度，同时具有十分优异的耐电弧能力和阻燃性能，具有优异的耐火烧性能，高温火焰烧灼后不变形。但是缺点也十分明显，如加工成本高，生产周期长，有毒的小分子单体含量高，且后期会逐渐释放，材料品质难以控制等。采用具有高耐热性的热塑性聚酰胺代替传统的BMC热固性材料是众多新产品的发展趋势。再如新能源汽车行业中，锂离子电池是非常关键的组成结构之一，根据安全要求和实际使用工况，人们制定了GB/T 31467.3-2015等国家标准，其中对火烧实验有着明确的标准和规定。以上标准和行业均要求材料在实际使用过程中具有足够好的耐火烧性能，保证内部结构和功能即使在火烧过程中也能不过度受损。
目前关于耐火烧聚酰胺材料开发的报道相对较少。如专利CN109353031中的耐火烧电池箱盖仍然采用SMC(Sheet molding compound)材料，这种材料和BMC材料相似，虽然拥有较好的力学性能和耐火烧性能，但是制备工艺复杂，不环保以及无法回收的特点使其难以在众多新产品中使用。专利CN110183931中采用三嗪成碳剂、二乙基次膦酸铝、三苯基氧化膦、环氧树脂和有机硅胶混合搅拌，涂覆在电池模组的顶面和侧面，固化12h后起到阻燃层作用，这种工艺复杂且阻燃效果不佳。耐火电缆也是常见的对耐火烧有需求的产品，采用云母带作为防火层，提高线缆的防火性能，使线缆在火烧过程中也能连续运行，这种方法在专利CN1031238188、CN109920600都有提到。
关于聚酰胺的报道更多地是关于如何提高材料的常规性能。如专利CN 106675007中采用新型反应型磷系阻燃剂获得的阻燃聚酰胺的极限氧指数大于29％；专利CN109844001中采用矿物填料提高聚酰胺的灼热丝(GWFI，0.5mm)性能；专利CN 106133043中采用硅酸铝提高阻燃聚酰胺的GWFI性能，使其特别适用于家用电器中用于电流和电压传导部件的带电部件。类似地，采用新型阻燃剂、协效剂和填料等手段，提高聚酰胺的垂直燃烧、灼热丝性能(GWFI/GWIT)、电性能、力学性能、耐老化性能、流动性的专利和文章不胜枚举，但是对于新产生的诸如耐火烧需求，甚至代替热固性材料并未进行具有针对性的性能提升。
综上所述，基于热塑性材料代替热固性材料的趋势，以及新能源汽车快速发展的背景，如何提高聚酰胺材料的耐火烧性能以满足行业和产品需求，是人们需要考虑的一个技术问题。
发明内容
本发明所要解决的技术问题是提供一种耐火烧无卤阻燃增强尼龙复合材料，该复合材料具备优异的耐火烧性能和阻燃性能。
本发明提供一种耐火烧无卤阻燃增强尼龙复合材料，按质量百分比，包括如下组分：
所述聚酰胺树脂为脂肪族聚酰胺、芳香族聚酰胺、半芳香族聚酰胺中的至少一种。
所述聚酰胺树脂包括但不限于如下种类的聚酰胺树脂：通过至少一种脂肪族二元羧酸与脂肪族的或环的或脂环族的或芳基脂肪族的二元胺的缩聚作用获得的聚酰胺类，比如PA66、PA610、PA612、PA1010、PA106、PA1212、PA46、MXD6、PA92、PA102；或至少一种芳香族的二元羧酸与脂肪族的或芳香族的二元胺之间的缩聚作用获得的聚酰胺类，比如以下类型的聚对苯二甲酰胺类，如PA9T、PA10T、PA11T、PA12T、PA13T或PA6T/MT、PA6T/6I、PA6T/66、PA66/6T，以下类型的聚间苯二甲酰胺类，如PA6I、PA6I/6T，以下类型的聚萘亚甲基酰胺类，如PA10N、PA11N、PA12N，聚芳酰胺类，如芳纶，或其共混物以及其(共)聚酰胺树脂。本发明的聚酰胺树脂还可以选自通过将至少一种氨基酸或内酰胺与其本身进行缩聚而获得的聚酰胺树脂，对于这种氨基酸有可能的是通过内酰胺环的水解打开而产生，如PA6、PA7、PA11、PA12或者PA13、或者其共混物以及其(共)聚酰胺树脂。尤其可以提及的共聚酰胺树脂的类型包括聚酰胺6/66、聚酰胺6/11、聚酰胺6/12以及聚酰胺11/12。
所述阻隔剂为层状结构类物质、熔融后形成玻璃态的物质、水合金属氧化物中的至少一种。
所述层状结构类物质为粘土类物质、层状双金属氢氧化物、类石墨烯二维材料、层状碳酸钙、层状陶瓷中的至少一种。优选的，所述层状结构类物质含量为2％-30％。
所述粘土类物质为蒙脱土、高岭土、伊利土、凹凸棒土、海泡石中的至少一种。优选的，所述粘土类物质含量为2％-25％。
所述层状双金属氢氧化物包含但不限于水滑石类层状物，遵循化学式[M2+ 1-xN3+ x(OH)2]z+[An-]z/n·mH2O，其中M为二价金属元素，N为三价金属元素，A为层间阴离子。其中二价金属元素M包含但不限于Mg、Zn、Ni、Co、Cu、Ca、Mn等，三价金属元素N包含但不限于Al、Cr、Co、Fe、Sc、V等，A表示进入层间的阴离子，包含但不限于无机阴离子，如CO3 2-、NO3 -、F-、Cl-、Br-、I-、CrO4 2-、H2PO4-、PO4 3-、SO4 2-、SO3 2-等；有机阴离子，如对苯二甲酸根、己二酸根等；配合物阴离子，如Fe(CN)6 3-、Fe(CN)6 4-、Zn(BPS)3 4-、Ru(BPS)3 3-等；同多和杂多阴离子，如Mo7O24 6-、V10O28 6-、PW11CuO39 6-、W9V3O40 7-等。x为层状氢氧化物的结构参数，x＝N3+/[M2++N3+]，z为阳离子价态，n阴离子价态。优选的，所述层状双金属氢氧化物含量为2％-30％。
所述类石墨烯二维材料为石墨烯、多层石墨烯微片、二硫化钼、二硫化钨、氮化硼、黑磷中的至少一种。优选的，所述类石墨烯二维材料含量为2％-25％。
所述熔融后形成玻璃态的物质为低熔点玻璃粉(玻璃化转变终止温度＜600℃，熔程＜1000℃)、硼酸钠、硼酸镁、硼酸钙、硼酸钾和硼酸锂的至少一种，含量为2％-30％。
所述水合金属氧化物为水合氧化镁、水合氧化硅、水合氧化铁、水合氧化锆中的至少一种，含量为2％-30％。
所述填充剂为玻纤、碳纤维中的至少一种。
所述次膦酸盐为以下结构的次膦酸盐：
以下结构的二次膦酸盐式：
和/或它们的聚合物；
其中，R6和R7为结构相同或不同的线性或支化的C1～C6烷基和/或芳基；R3为线性或支化的C1～C10–亚烷基、C6～C10-亚芳基、-烷基亚芳基或-芳基亚烷基；M选自碱金属、碱土金属、Al、Zn、Fe和硼中的一个或多个，特别优选为Ca或Mg，其中m为1～4；n为1或3；x为1或2。R1和R2优选甲基、乙基、正丙基、异丙基、正丁基、叔丁基、正戊基、苯基中的一个或多个。R3优选为亚甲基、亚乙基、正亚丙基、异亚丙基、正亚丁基、叔亚丁基、正亚戊基、正亚辛基、正亚十二烷基、亚苯基、亚萘基、甲基亚苯基、乙基亚苯基、叔丁基亚苯基、甲基亚荼基、乙基亚荼基、叔丁基亚荼基、苯基亚甲基、苯基亚乙基，苯基亚丙基或苯基亚丁基。本发明优选二乙基次膦酸铝。
所述三聚氰胺衍生物为三聚氰胺多聚磷酸盐，平均缩合度为20～200，磷含量为10～15wt％。优选12～14wt％。且水含量优选低于0.3wt％，密度为1.83至1.86g/cm3。更优选的为衍生自1,3,5-三嗪化合物的三聚氰胺多磷酸盐，其平均缩合度为20至200，且1,3,5-三嗪含量为每摩尔磷原子1.1至2.0mol的选自三聚氰胺、蜜白胺、蜜勒胺、氰尿酰胺(melon)、三聚氰胺二酰胺、三聚氰胺一酰胺、2-脲基三聚氰胺、酰代三聚氰胺、苯代三聚氰胺，和二氨苯基三嗪的1,3,5-三嗪化合物。最优选的其平均缩合度为40至150且1,3,5-三嗪化合物：摩尔磷原子的比例为1.2～1.8。10wt％盐的水浆体(如EP1095030B1中制备)的pH通常高于4.5，优选地至少5.0。
所述其他助剂包括热稳定剂和/或润滑剂。
所述热稳定剂为受阻酚类、胺类、磷酸酯类中的至少一种；所述润滑剂为硬脂酸酰胺类、硬脂酸醇酯类、硬脂酸盐类、长链饱和线性羧酸盐类中的至少一种。
本发明还提供了一种耐火烧无卤阻燃增强尼龙复合材料的应用。
有益效果
本发明通过向无卤有机次膦酸盐阻燃的聚酰胺体系中，引入提高灼烧后碳层阻隔作用的阻隔剂，能够有效提高碳层的隔热性能，延长材料的阻燃性能和耐火烧时间，在部分应用领域中达到替换热固性材料的效果，同时实施难度小，效果明显，具有良好的应用前景。
附图说明
图1是对比例2火烧实验30s后火烧面(a)和背面(b)照片。
图2是实施例4火烧实验600s火烧面(a)和背面(b)照片。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
PA66、PA6、PA10T：市售。
二乙基次膦酸铝：购自科莱恩化工(Clariant)，牌号为OP 1230。
三聚氰胺聚膦酸盐：购自巴斯夫，牌号为Melapur 200 70。
硼酸锌：购自美国力拓公司，牌号为Firebrake ZB。
水合氧化镁：改性超细氢氧化镁(2500-G)，购自营口环球粉体工程有限公司。
低熔点玻璃粉：牌号为Flamtard V 300，购自威姆宝莱有限公司(William BlytheLtd)。
蒙脱土：牌号为YH-170，购自宇宏新材料有限公司。
水滑石：牌号为AC-106，购自呈和科技。
TR044W：购自Struktol公司。
IRGANOX 1098：购自巴斯夫公司。
下面将结合对比例1～2和实施例1～19，对本发明作进一步说明。
按表1和表2配比称取各原料，在高混机中进行混合，然后通过双螺杆进行挤出造粒成复合材料。将上述各实施例和对比例所制得的复合材料先注塑成方板，然后进行火烧测试。
性能测试方法：
挤出的粒料注塑成100mm×100mm×3.0mm尺寸方板，采用液化石油气进行灼烧实验，通过固定减压阀压力为0.5MPa控制气体流速，通过激光红外测温仪固定火焰温度为1000℃，将方板平架于两根钢条上，钢条间距固定为80mm，喷火枪距离方板距离固定为40mm，持续灼烧，考察方板背面状况，背面被灼烧脱落时记录灼烧时间，以及离火后火焰持续的时间。若耐火烧效果良好，灼烧时间足够长可停止灼烧(本发明中灼烧超过10min若背面未脱落，且未烧穿则停止灼烧，则记录灼烧时间为600s)。
表1对比例1-2和实施例1-9配比和性能测试结果
表2实施例10-19配比和性能测试结果
由表1中的对比例1可知，市售的热固性BMC电控盒在经历70s灼烧后，壳体被烧穿，离开火焰后，壳体继续燃烧了60s，但是壳体未发生坍塌、折断或脱落等现象。而对比例2为常规阻燃增强PA66，火烧测试表现较差，仅仅灼烧30s的时间方板即被烧穿，背面发生脱落现象，离火后，火焰持续5s熄灭，无法满足耐火烧要求。实施例1-4中，随着水合氧化镁(改性超细氢氧化镁(2500-G))比例的提高，离火后火焰持续的时间基本小于6s，灼烧时间逐渐延长，水合氧化镁的比例添加至20％时，灼烧时间延长至470s，样品虽然烧穿，但是未脱落，比例提高至30％时，灼烧600s未烧穿，未脱落。添加低熔点玻璃粉(Flamtard V 300)的规律与之类似，但是比对比例1-2以及实施例1-4效果更佳，添加5％的低熔点玻璃粉，虽然存在烧穿和脱落行为，但是耐火烧时间已经延长至383s，相比对比例2有大幅度提高。添加10％以上的低熔点玻璃粉，则未发生脱落行为，这可能是低熔点玻璃粉形成的物理层具有提高碳层强度的作用。
表2中，实施例10-13中采用低熔点玻璃粉和蒙脱土(YH-170)复配，较对比例2和实施例6，灼烧时间明显延长，离火后火焰持续时间缩短，添加5％低熔点玻璃粉和10％蒙脱土，即可达到600s不烧穿不脱落。水滑石(AC-106)具有类似的效果，随着水滑石比例的提高，耐火烧时间逐渐延长，但是添加30％的水滑石时，仍然存在烧穿行为，而复配少量低熔点玻璃粉时，效果提升明显，5％低熔点玻璃粉和5％水滑石，即可达到烧穿不脱落的效果，5％低熔点玻璃粉和10％水滑石即可达到不烧穿不脱落的效果。
综上所述，本发明通过添加一些物理阻隔剂能够有效提高材料耐火烧性能，而相比市售BMC电控盒，阻隔剂的隔热作用能够有效延长材料的耐火烧时间，提高耐火烧性能。
Claims (10)
1.一种耐火烧无卤阻燃增强尼龙复合材料，其特征在于：按质量百分比，包括如下组分：
2.根据权利要求1所述的复合材料，其特征在于：所述聚酰胺树脂为脂肪族聚酰胺、芳香族聚酰胺、半芳香族聚酰胺中的至少一种。
3.根据权利要求1所述的复合材料，其特征在于：所述阻隔剂为层状结构类物质、熔融后形成玻璃态的物质、水合金属氧化物中的至少一种。
4.根据权利要求3所述的复合材料，其特征在于：所述层状结构类物质为粘土类物质、层状双金属氢氧化物、类石墨烯二维材料、层状碳酸钙、层状陶瓷中的至少一种，含量为2％-30％。
5.根据权利要求4所述的复合材料，其特征在于：所述粘土类物质为蒙脱土、高岭土、伊利土、凹凸棒土、海泡石中的至少一种；所述类石墨烯二维材料为石墨烯、多层石墨烯微片、二硫化钼、二硫化钨、氮化硼、黑磷中的至少一种。
6.根据权利要求3所述的复合材料，其特征在于：所述熔融后形成玻璃态的物质为低熔点玻璃粉、硼酸钠、硼酸镁、硼酸钙、硼酸钾、硼酸锂中的至少一种，含量为2％-30％。
7.根据权利要求3所述的复合材料，其特征在于：所述水合金属氧化物为水合氧化镁、水合氧化硅、水合氧化铁、水合氧化锆中的至少一种，含量为2％-30％。
8.根据权利要求1所述的复合材料，其特征在于：所述填充剂为玻纤、碳纤维中的至少一种；所述三聚氰胺衍生物为三聚氰胺多聚磷酸盐，平均缩合度为20～200，磷含量为10～15wt％。
9.根据权利要求1所述的复合材料，其特征在于：所述其他助剂包括热稳定剂和/或润滑剂。
10.根据权利要求9所述的复合材料，其特征在于：所述热稳定剂为受阻酚类、胺类、磷酸酯类中的至少一种；所述润滑剂为硬脂酸酰胺类、硬脂酸醇酯类、硬脂酸盐类、长链饱和线性羧酸盐类中的至少一种。
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| CN116769305A (zh) * | 2022-03-09 | 2023-09-19 | 珠海万通特种工程塑料有限公司 | 一种高温尼龙组合物及其制备方法和应用 |
| CN115353732A (zh) * | 2022-08-19 | 2022-11-18 | 东莞市华盈新材料有限公司 | 一种耐高温阻燃pa10t |
| CN115353732B (zh) * | 2022-08-19 | 2024-01-30 | 东莞市华盈新材料有限公司 | 一种耐高温阻燃pa10t |
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