CN101495574A - 具有高的热机械应力耐受性且防火的柔性无卤素热塑性组合物 - Google Patents
具有高的热机械应力耐受性且防火的柔性无卤素热塑性组合物 Download PDFInfo
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- CN101495574A CN101495574A CNA2007800279520A CN200780027952A CN101495574A CN 101495574 A CN101495574 A CN 101495574A CN A2007800279520 A CNA2007800279520 A CN A2007800279520A CN 200780027952 A CN200780027952 A CN 200780027952A CN 101495574 A CN101495574 A CN 101495574A
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- ethene
- polyamide
- zeolite
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Abstract
本发明涉及柔性的具有高热机械应力耐受性且阻燃的无卤素热塑性组合物,所述组合物包含由主链和平均至少一个聚酰胺接枝组成的聚酰胺嵌段接枝共聚物,其中所述接枝通过具有能够与胺端基聚酰胺反应的官能团的不饱和单体(X)的残基而结合到所述主链上,该不饱和单体残基(X)通过其双键接枝或共聚结合到所述主链上。本发明的特征在于所述组合物包含下列物质的混合物:50~70重量%的聚酰胺嵌段共聚物、25~35重量%的选自磷酸铵、次膦酸铵、焦磷酸铵和多磷酸铵的阻燃剂、约2重量%的沸石或水滑石分子筛。所述组合物特别可用于制造电缆、电子元件;用于模塑电工外壳;或用于制造汽车工业中流体输送管线用的涂层或热防护套。
Description
本发明涉及具有高热机械强度的阻燃柔性热塑性组合物,该组合物基于接枝有聚酰胺单元的官能化聚烯烃、含有至少一种阻燃剂(更具体地说是基于多磷酸铵的阻燃剂)和沸石,并且不含卤素化合物、磷增塑剂或红磷。
对于缆线,这些组合物可用于电缆和光纤的绝缘和保护,而且,这些组合物可用于电子元件如电连接器的制造,此外,在电气工程中,这些组合物可用于诸如壳体的制品的模塑。
热塑性聚合物如聚乙烯、聚酰胺或其共混物是良好的电绝缘体并且易于利用。它们用于制造壳体和电连接器以及电缆涂层。电气系统可为短路的来源并可能着火,并且电气系统还可与火焰接触并因此着火和沿着电缆路线传播火焰。存在使这些材料不可燃的多种添加剂,一些所述添加剂基于卤化产品,其它添加剂不含卤素。由于生态毒理学和毒理学(在燃烧期间释放的蒸气的毒性和侵蚀性)的原因,卤化添加剂的使用日益受到禁止。
根据符合标准ISO 1210的UL 94火焰传播试验,V0级是最好的级别,对应于难以点燃且在试验期间不产生燃烧液滴的材料。
对于V1级,材料更易于点燃但在试验期间不产生燃烧液滴。至于V2级,除了比V0更容易点燃之外,在试验期间还可能产生燃烧液滴。
甚至更可燃的材料标记为NC(不分级)。
专利EP629678描述了包含聚酰胺和聚丙烯的共混物的热塑性合金,其中加入沸石和多磷酸铵(脱水剂)以使得所述合金阻燃。聚酰胺和聚烯烃的共混物由57重量%的聚酰胺6(PA6)、33重量%的丙烯均聚物、和10重量%的用马来酸酐接枝并然后与单氨基聚酰胺低聚物缩合的聚丙烯组成。将30重量份的多磷酸铵(APP)和1重量份的沸石加入到69重量份的上述混合物中,之后,通过注射成型生产厚度为3.2mm的测试样品。这些测试样品经历根据标准ISO 1210的UL 94火焰传播试验,所获得的级别为V0。V0是该试验中的最佳级别。这些由PA基体组成的共混物不含磷增塑剂,并且未显示出任何机械特性,特别是例如断裂伸长率。
专利EP704489描述了由聚酰胺基体组成的组合物,所述聚酰胺基体含有分散在其中的交联聚烯烃球状粒(nodule)和阻燃剂,所述阻燃剂选自氢氧化镁、十溴二苯醚、氰尿酸三聚氰胺、和季戊四醇。这些组合物可用于包覆电缆。它们不含多磷酸盐、不含磷增塑剂、且不含沸石。
然而,这些现有技术的组合物的阻燃性能一般是在损害材料延展性(断裂伸长率的显著损失、在环境温度下的脆性冲击性能)的情况下获得的。而且,发现这些材料的热稳定性不足。热稳定性是指在各种形式的热老化(例如在热空气中在120℃下1周)之后的机械性能(且更具体地说是断裂伸长率)的保持性。
本申请人的文献EP1375594描述了具有阻燃性的不含卤素化合物的组合物,其包含总计100份的下列物质(按重量计):
-50~75份聚酰胺(A)和聚烯烃(B)的共混物,其包含(i)高密度聚乙烯(HDPE)以及(ii)聚乙烯(C1)与选自弹性体、极低密度聚乙烯和乙烯共聚物的聚合物(C2)的共混物,共混物(C1)+(C2)通过不饱和羧酸共接枝,
-25~50份混合物,其包含:
-0.1~48.8份多磷酸铵型阻燃剂,
-0.1~30份磷增塑剂,
-0.1~10份沸石。
当燃烧试验在厚度为1.6mm的测试样品上进行时,根据UL 94试验,这些组合物显示出V0或V1级别,并且根据ISO R 527-1B测得的它们的断裂伸长率超过100%。
(A)+(B)的共混物包括60重量%~70重量%的构成共混物基体的聚酰胺(A)。
这些配制物含有磷增塑剂,已知原子元素磷对材料的阻燃性有贡献。另一方面,这些作为小分子的增塑剂具有可观测到的脱离所得材料(渗出)的趋势,这对于期望的应用是不可接受的。因此,目前已经开发出未进行增塑(因此不会渗出)然而具有相同水平的阻燃性的新配制物。
而且,官能化聚烯烃的无卤素阻燃是公知的,在缆线应用中更是如此。其涉及引入非常大量(60重量%~65重量%)的水合物填充剂如三水合铝(ATH)或二氢氧化镁(magnesium dihydroxide,MDH)以提供期望的阻燃水平。这种阻燃配制物向描述于申请人的文献WO02/028959中的那些类型的PA-接枝乙烯-(甲基)丙烯酸烷基酯-马来酸酐共聚物材料的变换导致该组合物的机械性质的灾难性损失,对于断裂伸长率来说尤其如此(数值<100%),其中,所述文献WO02/028959涉及含有聚酰胺嵌段并由聚烯烃主链和平均至少一个聚酰胺接枝组成的接枝共聚物与柔性聚烯烃的共混物。
然而,这些材料的某些目标应用(缆线、电子和电工元件、汽车)需要这些性质的组合。
本发明的目的是寻找基于聚酰胺接枝的官能化聚烯烃且不使用卤素进行阻燃的组合物,其能够生产这样的材料,该材料具有高性能的抗火焰传播性(根据UL 94试验)并还具有高水平的机械和热机械性能、以及高的热稳定性和令人满意的流变性(没有过量的粘度增加、高MFI(熔体流动指数)),并且在所得材料上不产生渗出。
对于高水平的机械和热机械性能,提及这样的材料,该材料具有在环境温度下的小于或等于400MPa的弯曲模量,且具有由动态力学分析(DMA)测定的在150℃下的至少0.5MPa的弹性模量。DMA分析在于:使待分析材料在-100℃~250℃的温度下以3℃/min的速率经历动态(1Hz)拉伸,并记录弹性模量和损耗值以及它们的比,该比值对应于损耗角的正切。
类似地,当该材料在热氧化条件下老化之后仍保持其断裂伸长率和断裂应力的初始机械性能的约70%的时候,认为该材料显示出高的热稳定性。
而且,当该材料与用于将本发明组合物转化为材料的典型方法(挤出、注射成型等)相适应时,则认为所讨论的材料的流变性是令人满意的。
根据本发明通过阻燃柔性热塑性组合物达到该目的,它们的柔韧性意味着弯曲模量不大于400MPa,所述组合物具有高的热机械强度且不含卤素化合物,该组合物包含含有聚酰胺嵌段并由聚烯烃主链和平均至少一个聚酰胺接枝组成的接枝共聚物,其中所述接枝通过具有能够与胺端基聚酰胺反应的官能团的不饱和单体(X)的基团连接到所述主链上,所述不饱和单体(X)的基团通过其双键接枝或共聚而固定到所述主链上,其中所述组合物包含下列物质的混合物:
-50~70重量%的含有聚酰胺嵌段的接枝共聚物,
-25~35重量%的选自磷酸铵、次膦酸铵、焦磷酸铵和多磷酸铵的阻燃剂,
-约2重量%的分子筛,例如沸石或水滑石。
优选地,根据本发明,含有聚酰胺嵌段的接枝共聚物的含有X的聚烯烃主链选自乙烯-马来酸酐和乙烯-(甲基)丙烯酸烷基酯-马来酸酐共聚物。
优选地,平均至少1.3摩尔的X连接到所述聚烯烃主链上。
特别地,聚酰胺接枝具有1000~5000g/mol且优选2000~3000g/mol的摩尔质量Mn。
更具体地说,阻燃剂是多磷酸铵。
根据一个优选实施方式,沸石为3A、4A、5A、10X和13X沸石。
根据本发明的阻燃热塑性组合物可进一步含有氰尿酸三聚氰胺和/或季戊四醇的混合物。
而且,以聚烯烃主链和/或聚酰胺接枝各自与纳米填充剂(例如,尤其是纳米粘土或碳纳米管)的混合物来部分或完全替代聚烯烃主链和/或聚酰胺接枝不脱离本发明的范围,本领域技术人员将所述混合物称为术语“纳米复合材料”。
本发明的阻燃组合物有利地用于缆线以及电子元件如电连接器的制造,或者,在电气工程中,本发明的阻燃组合物有利地用于诸如壳体的制品的模塑。
然而,这些组合物还可用于生产汽车工业中的流体(特别是燃料或冷却剂)的输送管线(或管道)的保护层或热保护套。
含有聚酰胺嵌段的接枝共聚物可以通过使胺端基聚酰胺与不饱和单体X的残基反应而获得,该不饱和单体X通过接枝或共聚连接到聚烯烃主链上。
该单体X可以是例如不饱和环氧化物或不饱和羧酸酐。所述不饱和羧酸酐可选自例如马来酸酐、衣康酸酐、柠康酸酐、烯丙基琥珀酸酐、环己-4-烯-1,2-二羧酸酐、4-亚甲基-环己-4-烯-1,2-二羧酸酐、双环[2.2.1]庚-5-烯-2,3-二羧酸酐、和x-甲基双环[2.2.1]庚-5-烯-2,2-二羧酸酐。有利地,使用马来酸酐。以不饱和羧酸例如(甲基)丙烯酸替代部分或全部酸酐不脱离本发明的范围。
至于聚烯烃主链,聚烯烃定义为α-烯烃或二烯烃均聚物或共聚物,例如乙烯、丙烯、1-丁烯、1-辛烯或丁二烯的均聚物或共聚物。实例可包括:
-聚乙烯的均聚物和共聚物,特别是LDPE、HDPE、LLDPE(线性低密度聚乙烯)、VLDPE(极低密度聚乙烯)、和茂金属聚乙烯;
-丙烯的均聚物或共聚物;
-乙烯/α-烯烃共聚物,例如乙烯/丙烯、EPR(乙丙橡胶)和乙烯/丙烯/二烯(EPDM)共聚物;
-苯乙烯/乙烯-丁烯/苯乙烯(SEBS)、苯乙烯/丁二烯/苯乙烯(SBS)、苯乙烯/异戊二烯/苯乙烯(SIS)、和苯乙烯/乙烯-丙烯/苯乙烯(SEPS)嵌段共聚物;
-乙烯与选自不饱和羧酸的盐或酯(如(甲基)丙烯酸烷基酯(例如丙烯酸甲酯))或饱和羧酸的乙烯基酯(如乙酸乙烯酯)中的至少一种产品的共聚物,共聚单体的比例可为40重量%。
连接有X残基的聚烯烃主链有利地是接枝有X的聚乙烯或例如通过自由基聚合获得的X和乙烯的共聚物。
至于接枝有X的聚乙烯,该聚乙烯包括均聚物或共聚物。
共聚单体可以包括下列物质:
-α-烯烃,有利地是具有3~30个碳原子的那些。实例在上文中已给出。这些α-烯烃可单独使用或以两种或更多种的混合物使用;
-不饱和羧酸的酯,例如,(甲基)丙烯酸烷基酯,烷基可具有最高达24个碳原子;丙烯酸烷基酯或甲基丙烯酸烷基酯的实例更具体地说为甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、和丙烯酸2-乙基己酯;
-饱和羧酸的乙烯基酯,例如乙酸乙烯酯或丙酸乙烯酯;
-二烯,例如1,4-己二烯;
-该聚乙烯可包含两种或更多种上述共聚单体。
可为两种或更多种聚合物的共混物的聚乙烯有利地包含至少50摩尔%且优选75摩尔%的乙烯,并且其密度可为0.86~0.98g/cm3。MFI(在190℃、2.16kg下的粘度指数)有利地为20~1000g/10min。
可能的聚乙烯的实例包括下列物质:
-低密度聚乙烯(LDPE)
-高密度聚乙烯(HDPE)
-线性低密度聚乙烯(LLDPE)
-极低密度聚乙烯(VLDPE)
-通过茂金属催化获得的聚乙烯
-EPR(乙丙橡胶)弹性体
-EPDM(乙烯-丙烯-二烯)弹性体
-聚乙烯和EPR或EPDM的共混物
-含有最高达60重量%且优选2~40重量%的(甲基)丙烯酸酯的乙烯-(甲基)丙烯酸烷基酯共聚物。
就接枝来说,其本身是一种已知的操作。
至于乙烯和X的共聚物(即,未接枝有X的那些),它们是乙烯、X、和任选的其它单体的共聚物,所述其它单体可选自以上给出的用于待接枝乙烯的共聚物的共聚单体。
有利地,使用乙烯-马来酸酐和乙烯-(甲基)丙烯酸烷基酯-马来酸酐共聚物。这些共聚物含有0.2重量%~10重量%的马来酸酐、0重量%~40重量%且优选5重量%~40重量%的(甲基)丙烯酸烷基酯。它们的MFI为5~100(190℃、2.16kg)。已在上文中描述了(甲基)丙烯酸烷基酯。熔融温度为80~120℃。
在每条链上,有利地具有平均至少2摩尔、优选2~5摩尔的连接到聚烯烃主链上的X。本领域技术人员能够容易地通过FTIR分析确定X的这些摩尔数。例如,如果X是马来酸酐且聚烯烃的Mw为95000g/ml,发现这对应于含有X的全部聚烯烃主链的至少1.5重量%、优选2.5重量%~4重量%的酸酐比例。与胺端基聚酰胺的质量相结合的这些值决定了在含有聚酰胺嵌段的接枝共聚物中的聚酰胺和主链的比例。
至于胺端基聚酰胺,聚酰胺是指:
-一种或多种氨基酸(如氨基己酸、7-氨基庚酸、11-氨基十一酸、和12-氨基十二酸)与一种或多种内酰胺(如己内酰胺、庚内酰胺、和十二内酰胺)的缩合产物;
-二胺(如六亚甲基二胺、十二亚甲基二胺、间苯二甲二胺、双-对-氨基环己基甲烷、和三甲基六亚甲基二胺的一种或多种盐或混合物)与二元酸(如间苯二甲酸、对苯二甲酸、己二酸、壬二酸、辛二酸、癸二酸、和十四双酸)的缩合产物;或者
-两种或更多种单体的混合物的缩合产物,由此获得共聚酰胺。
可使用聚酰胺的共混物。有利地,使用PA6、PA11、PA12、具有6单元和11单元的共聚酰胺(PA6/11)、具有6单元和12单元的共聚酰胺(PA6/12)、和基于己内酰胺、六亚甲基二胺、和己二酸的共聚酰胺(PA6/6-6)。
聚合度可以在宽的比例内变化;根据聚合度的值,产物为聚酰胺或聚酰胺低聚物。在本文的剩余部分,这两种表达将同义地用于接枝。
为使聚酰胺具有单胺末端,使用下式的链终止剂是足够的:
其中:
R1是氢或含有最高达20个碳原子的线型或支化的烷基,
R2是具有最高达20个碳原子的线型或支化的烷基或链烯基、饱和或不饱和的脂环族基团、芳族基团或这些基团的组合。所述终止剂可为例如月桂胺或油胺。
有利地,胺端基的聚酰胺具有1000~5000g/mol且优选2000~3000g/mol的摩尔质量。
根据本发明的用于合成单氨基低聚物的优选的氨基酸或内酰胺单体选自己内酰胺、11-氨基十一酸、和十二内酰胺。优选的单官能聚合终止剂为月桂胺和油胺。
根据常规已知方法,在例如通常为200~300℃的温度下、在真空或惰性气氛中,搅拌反应混合物进行上述缩聚。低聚物的平均链长由可缩聚单体或内酰胺与单官能聚合终止剂之间的初始摩尔比确定。为计算平均链长,通常计数为:一个链终止剂分子用于一条低聚物链。
通过低聚物的胺官能团与X的反应,将单氨基聚酰胺低聚物加到含有X的聚烯烃主链上。X有利地带有酸或酸酐官能团,因此产生酰胺或酰亚胺连接。
胺端基低聚物加到含有X的聚烯烃主链上优选地在熔融态下进行。以这种方法,可在通常为230~300℃的温度下、在挤出机中捏合低聚物和主链。熔融材料在挤出机中的平均停留时间可为5秒~5分钟,且优选20秒~1分钟。该加合的效率通过游离聚酰胺低聚物(即,还未反应形成含有聚酰胺嵌段的最终接枝共聚物的那些)的选择性提取而进行评价。
这种胺端基聚酰胺的制备以及将它们加到含有X的聚烯烃主链上描述于专利US3976720、US3963799、US5342886、和FR2291225中。
本发明的含有聚酰胺嵌段的接枝共聚物的特征在于具有厚度为10~50纳米的聚酰胺薄片的纳米结构化排列。
相对于85%~50%的柔性聚烯烃,含有聚酰胺嵌段的接枝共聚物的比例有利地相应为15%~50%。
本发明的共混物在至少80℃和可能的最高达130℃的温度下非常地抗流动(resistant to flow),就是说它们在25kPa下不显示出破裂。
本发明的共混物可以通过在挤出机(单螺杆或双螺杆)、Buss捏合机、布拉本德混合机、以及一般用于共混热塑性聚合物的常规设备中,且优选在同向双螺杆挤出机中通过熔融共混制备。本发明的共混物还可包含自由流动剂例如二氧化硅、亚乙基双酰胺、硬脂酸钙或硬脂酸镁。它们可进一步包含抗氧化剂、UV吸收剂、无机填料、和着色颜料。
本发明的共混物可以在挤出机中一步制备。将含有X的主链(例如乙烯-(甲基)丙烯酸烷基酯-马来酸酐共聚物)和胺端基聚酰胺引入到第一区段中,然后,在许多后面的区段中,通过侧进料引入阻燃剂。还可将所有成分引入到挤出机的第一区段中。
至于阻燃剂,其包含在燃烧时能够形成酸如H3PO4(正磷酸)、(HPO3)n(偏磷酸)、和H4P2O7(焦磷酸)的化合物。这种试剂的示例性实例包括磷酸铵、次膦酸铵、焦磷酸铵、和多磷酸铵、三聚氰胺磷酸酯、三聚氰胺亚磷酸酯、哌嗪亚磷酸酯和哌嗪二亚磷酸酯、胍基(guanazole)磷酸酯、三聚氰胺焦磷酸酯、和哌嗪焦磷酸酯。
有利地,使用多磷酸铵,其是通式(NH4)n+2PnO3n+1的单链聚合物,其中n表示大于或等于2的整数。
多磷酸铵可以包封在基于三聚氰胺的树脂中。使用上述阻燃剂的混合物不脱离本发明的范围。该阻燃剂可以是官能化的,例如,其可带有硅烷官能团。
至于沸石,它们描述于ULLMANN’S Encyclopedia of Industrial Chemistry,1996,第五版,第28卷,第475~504页。可使用A、X、Y、L、ZSM或ZM沸石或者天然沸石例如菱沸石、丝光沸石、和八面沸石。有利地,使用3A、4A、5A、10X和13X沸石。使用这些各种沸石的混合物不脱离本发明的范围。
沸石一般以大于1μm且优选2~50μm粉末的形式使用。
用称为“酸清除剂”或水滑石的无机添加剂替代这些沸石不脱离本发明的范围。一种可能的实例为得自KYOWA Chemical的DHT 4A。
本发明的具有特殊优点的组合物还可包含乙烯与羧酸或烯属不饱和酯共聚单体的至少一种共聚物。
该羧酸或烯属不饱和酯共聚单体有利地以5~40摩尔%、优选15~35摩尔%的比例存在,以该共聚物的总摩尔数计。
该共聚单体可包含选自乙酸乙烯酯(VA)、丙烯酸乙酯(EA)、丙烯酸甲酯(MA)、丙烯酸正丁酯(BA)、丙烯酸异丁酯、甲基丙烯酸甲酯、丙烯酸2-乙基己酯(AE2H或EH)、丙烯酸、和甲基丙烯酸中的至少一种。
优选地,乙烯与羧酸或烯属不饱和酯共聚单体的这种共聚物以能够最高达20份/100份本发明组合物的比例引入。
除了上述产品之外,还可加入聚酰胺领域的技术人员所公知的任何不含卤素的添加剂,例如氰尿酸三聚氰胺、季戊四醇氰尿酸酯、和有机硅或氟化型防滴剂。这种添加剂可以最高达总组合物的20重量%的比例引入。
根据本发明的组合物可进一步包含选自染料、颜料、光学增亮剂、抗氧化剂、UV稳定剂、和热稳定剂中的至少一种添加剂。
本发明的组合物通过以“直接”法混合所有组分(共聚物、阻燃剂、沸石)而制备,或者通过将阻燃剂和沸石加入到已经制备好的共聚物和PA的共混物中制备(“再加工”法)。
配制物的配混:
下面描述的配制物通过使用Coperion Werner andZSK 40同向双螺杆挤出机进行配混而制备(“双螺杆”法,在下表中表示为“双螺杆”),按照240℃下的平坦曲线加热挤出机的筒体部件;转速为300rpm,产量为70kg/h;添加剂通过侧进料加入到筒体4中的熔融聚合物内。
另一配混法采用了Buss PR46共捏合机(“共捏合机法”,在表中表示为“共捏合”)。对于该“共捏合机”法,金属温度曲线为220/250/250/250/240;共捏合机的转速为280rpm且产量固定为15kg/h,将一半的阻燃填充剂与第一井中的聚合物一起引入,然后,引入第二井中的另一半阻燃填充剂,同时对第三井进行排气。
所采用的材料:
7500:乙烯、丙烯酸乙酯(17.5重量%)和马来酸酐(2.8重量%)的三元共聚物,由ARKEMA生产,具有70g/10min的MFI(在190℃、2.16kg下,通过ISO 1133测量)。
PA6:用胺官能团封端的聚酰胺6,具有通过GPC测量的2500g/mol的Mn。
Irganox 1098:由CIBA生产的受阻酚热稳定剂。
Irganox 1010:由CIBA生产的受阻酚热稳定剂。
Irgafos 168:由CIBA生产的亚磷酸酯热稳定剂。
PER:由CELANESE生产的单季戊四醇。
Magnifin H5:由MARTINSWERK生产的二氢氧化镁。
Magnifin H5KV:由MARTINSWERK生产的二氢氧化镁。
Stavinor CA PSE:由CECA生产的硬脂酸钙。
材料的表征:
通过挤出生产长条:使用配有片材口模并在210℃下加热的ThermoHaake Rheocord System 40实验室双螺杆挤出机,使从“双螺杆”和“共捏合机”合成法获得的粒料形成长条,从该长条切割表征材料所需的测试样品。
MFI的测量:除非另有说明,该测量根据标准ISO 1133在下列条件(230℃、2.16kg)下进行。
抗流动性的测量:从上述长条切割的测试样品在温度调节烘箱中经历相当于2巴的压力的质量。如果测试样品耐受该负载15分钟,则将该测试评定为肯定性的,并记录最大耐受温度。如果测试样品不耐受这些条件,则测量测试样品发生断裂前的时间。
断裂伸长率和断裂应力:根据标准ISO 527:93-1BA在从上述长条切割的测试样品上进行测量。
硬度:根据标准ISO 868以肖式D级测量。
极限氧指数(LOI):根据标准ISO 4589测量。
抗火焰传播性:根据标准ISO 1210通过UL 94试验测量。
渗出:观察并记录为是或否(是/否)
根据本发明的组合物(实施例1~5)和现有技术的组合物(对比例CE1~CE9)的结果集中在下表1中:
Claims (10)
1.一种不含卤素化合物的阻燃柔性热塑性组合物,其包含含有聚酰胺嵌段并由聚烯烃主链和平均至少一个聚酰胺接枝组成的接枝共聚物,其中所述接枝通过具有能够与胺端基聚酰胺反应的官能团的不饱和单体(X)的基团而连接到所述主链上,所述不饱和单体(X)的基团通过其双键接枝或共聚固定到所述主链上,其中所述组合物包含下列物质的混合物:
-50~70重量%的所述含有聚酰胺嵌段的接枝共聚物,
-25~35重量%的选自磷酸铵、次膦酸铵、焦磷酸铵和多磷酸铵的阻燃剂,
-约2重量%的分子筛,例如沸石或水滑石。
2.权利要求1的组合物,其中所述含有(X)的聚烯烃主链选自乙烯-马来酸酐和乙烯-(甲基)丙烯酸烷基酯-马来酸酐共聚物。
3.权利要求1或2的组合物,其中存在至少1.3摩尔的连接到所述聚烯烃主链上的(X)。
4.权利要求1-3中任一项的组合物,其中所述聚酰胺接枝具有1000~5000g/mol且优选2000~3000g/mol的摩尔质量。
5.权利要求1-4中任一项的组合物,其中所述阻燃剂是多磷酸铵。
6.前述权利要求中任一项的组合物,其中所述沸石为3A、4A、5A、10X和13X沸石。
7.前述权利要求中任一项的组合物,其中所述混合物进一步包含氰尿酸三聚氰胺和/或季戊四醇。
8.权利要求1-7中任一项的组合物,进一步包含乙烯与羧酸或烯属不饱和酯共聚单体的至少一种共聚物。
9.权利要求1-8中任一项的阻燃热塑性组合物在电缆、电子元件如连接器的制造中的用途、或者在电气工程的壳体的模塑中的用途。
10.权利要求1-8中任一项的阻燃热塑性组合物在制造汽车流体输送管线用保护层或热防护套中的用途。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0652014A FR2901799B1 (fr) | 2006-06-02 | 2006-06-02 | Compositions thermoplastiques souples a haute tenue thermomecanique et ignifugees sans halogene |
FR0652014 | 2006-06-02 | ||
PCT/FR2007/051365 WO2007141449A2 (fr) | 2006-06-02 | 2007-06-01 | Compositions thermoplastiques souples a haute tenue thermo-mecanique et ignifugees sans halogene |
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CN101495574A true CN101495574A (zh) | 2009-07-29 |
CN101495574B CN101495574B (zh) | 2012-06-27 |
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US (1) | US7897673B2 (zh) |
EP (1) | EP2029672B1 (zh) |
JP (1) | JP5129243B2 (zh) |
CN (1) | CN101495574B (zh) |
DK (1) | DK2029672T3 (zh) |
ES (1) | ES2385057T3 (zh) |
FR (1) | FR2901799B1 (zh) |
PL (1) | PL2029672T3 (zh) |
WO (1) | WO2007141449A2 (zh) |
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CN110214158A (zh) * | 2017-01-27 | 2019-09-06 | 阿科玛法国公司 | 具有高热机械强度和改进的热老化性的柔性、防火的热塑性组合物 |
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-
2006
- 2006-06-02 FR FR0652014A patent/FR2901799B1/fr not_active Expired - Fee Related
-
2007
- 2007-06-01 JP JP2009512653A patent/JP5129243B2/ja not_active Expired - Fee Related
- 2007-06-01 PL PL07788952T patent/PL2029672T3/pl unknown
- 2007-06-01 DK DK07788952.5T patent/DK2029672T3/da active
- 2007-06-01 ES ES07788952T patent/ES2385057T3/es active Active
- 2007-06-01 WO PCT/FR2007/051365 patent/WO2007141449A2/fr active Application Filing
- 2007-06-01 US US12/303,174 patent/US7897673B2/en active Active
- 2007-06-01 EP EP07788952A patent/EP2029672B1/fr active Active
- 2007-06-01 CN CN2007800279520A patent/CN101495574B/zh not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102975445A (zh) * | 2011-09-05 | 2013-03-20 | 施耐德电器工业公司 | 包括防火涂层的塑料部件及其生产方法 |
CN102975445B (zh) * | 2011-09-05 | 2016-12-07 | 施耐德电器工业公司 | 包括防火涂层的塑料部件及其生产方法 |
CN104910630A (zh) * | 2015-07-06 | 2015-09-16 | 刘雷 | 一种含阻燃增效组合物的阻燃剂及其制备方法 |
CN107057491A (zh) * | 2016-12-29 | 2017-08-18 | 广州凯耀资产管理有限公司 | 一种水性石墨烯膨胀型防火涂料及其制备方法 |
CN110214158A (zh) * | 2017-01-27 | 2019-09-06 | 阿科玛法国公司 | 具有高热机械强度和改进的热老化性的柔性、防火的热塑性组合物 |
Also Published As
Publication number | Publication date |
---|---|
JP5129243B2 (ja) | 2013-01-30 |
US20090253836A1 (en) | 2009-10-08 |
ES2385057T3 (es) | 2012-07-17 |
US7897673B2 (en) | 2011-03-01 |
CN101495574B (zh) | 2012-06-27 |
WO2007141449A2 (fr) | 2007-12-13 |
WO2007141449A3 (fr) | 2008-01-31 |
JP2009538954A (ja) | 2009-11-12 |
DK2029672T3 (da) | 2012-07-02 |
EP2029672A2 (fr) | 2009-03-04 |
PL2029672T3 (pl) | 2012-09-28 |
FR2901799B1 (fr) | 2008-08-01 |
FR2901799A1 (fr) | 2007-12-07 |
EP2029672B1 (fr) | 2012-05-30 |
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