CN108948477B - 一种多聚均三嗪及无卤抗静电阻燃超高分子量聚乙烯复合材料 - Google Patents
一种多聚均三嗪及无卤抗静电阻燃超高分子量聚乙烯复合材料 Download PDFInfo
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- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003063 flame retardant Substances 0.000 title abstract description 55
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明公开了一种多聚均三嗪及无卤抗静电阻燃超高分子量聚乙烯复合材料。所述多聚均三嗪具有很好的阻燃抗静电效果,可作为抗静电剂和阻燃剂添加在组合物中用于制备抗静电阻燃复合材料。本发明还公开了一种含有多聚均三嗪的超高分子量聚乙烯复合材料,其组成成分的重量份数为:超高分子量聚乙烯50~85份,多聚均三嗪及其衍生物2~20份,聚磷酸胺5~30份,多羟基化合物2~30份,流动改性剂0.1~10份,成核剂0.05~1份,偶联剂0.03~5份,抗氧剂0.02~5份。该复合材料的阻燃抗静电效果得到显著提升,且具有很好的力学性能,能广泛应用于电力、煤炭、冶金、化工、石油开采、海洋和市政等领域,尤其适用于煤炭、海洋等具有特殊要求的行业。
Description
技术领域
本发明属于功能复合材料技术领域。更具体地,涉及一种多聚均三嗪及无卤抗静电阻燃超高分子量聚乙烯复合材料。
背景技术
随着工程塑料的应用日益广泛,现代社会对塑料防火阻燃抗静电的性能要求也越来越高。超高分子量聚乙烯(UHMWPE)是一种具有优良耐磨性、耐冲击性、化学稳定性、耐疲劳性、耐应力开裂性和耐腐蚀性的热塑性工程塑料。上述特性使其广泛应用于纺织、造纸、食品机械、运输、医疗、煤矿、化工等领域。但它的阻燃性能较差,限制了其应用。特别是近年来,部分溴系阻燃剂由于Dioxin问题被欧盟RoSH指令禁用,这就对我国超高分子量聚乙烯产品提出了更高的要求。另外,UHMWPE的体积电阻率非常高,可作为良好的电气绝缘材料。但由于其表面经摩擦后易产生静电,所以在用其作为非电气绝缘材料时,就要对其进行抗静电改性。
现有技术中针对UHMWPE的阻燃性和抗静电改性的研究报道很多。随着环保政策的不断出台和实施,无卤阻燃同时有着抗静电效果的UHMWPE是市场的需求。因此制备综合性能优异的无卤阻燃抗静电UHMWPE复合材料具有重要的意义。
均三嗪及其衍生物是一大类含叔氮结构的化合物,具有无卤、低毒、分解温度高、抗渗出、阻燃等优点,均三嗪系列阻燃剂已多有报道,如CN103882698A、CN105732712B。然而,现有均三嗪及其衍生物的制作过程复杂,无法通过一步法或一锅法合成。而且,现有阻燃剂配方多集中在阻燃元素的复杂搭配上,单一种类难以达到优良阻燃效果,卤系阻燃剂又因其环境缺陷而使用越来越少。如CN103882698A所研制的阻燃剂,在阻燃剂制作过程上和本阻燃剂完全不一样,且阻燃剂结构也不类似,本阻燃剂是一种具有重复单元的聚合物结构物质,而CN103882698A所研制的阻燃剂只能算是一种小分子化合物。
发明内容
本发明要解决的技术问题是克服上述现有技术的缺陷和不足,提供一种多聚均三嗪聚合物,在超高分子量聚乙烯添加量较少便能达到优良阻燃效果,节约成本。将其作为添加剂加入到超高分子量聚乙烯中,所得多聚均三嗪无卤抗静电阻燃剂复合材料在拥有优异阻燃性能的同时,在没有添加其它抗静电剂的前提下,多聚均三嗪在发挥了阻燃效能时同时扮演了抗静电剂的角色,并且所有添加物不含任何有害物质,不影响超高分子量聚乙烯原先的优良耐老化性及耐腐蚀性。而且该多聚均三嗪聚合物制作简单,原料来源广,成本低廉,制作方式简单,有成熟的产业化制造能力;应用于超高分子聚乙烯时,符合现在人们的环保理念,不含卤素,只有C、N、H三种元素。
本发明的目的是提供一种多聚均三嗪聚合物。
本发明另一目的是提供一种无卤抗静电阻燃超高分子量聚乙烯复合材料。
本发明上述目的通过以下技术方案实现:
本发明公开了一种聚合物,即多聚均三嗪,其主链为含均三嗪稠环结构的高聚物,所述高聚物结构如下式(I)所示:
进一步优选地,n的取值范围为2~1000。
本发明的多聚均三嗪是由马弗炉、管式炉烧结而成,控制坩埚厚度1~20mm,烧结温度为500~650℃,烧结时间为2~10小时,其烧结前驱体为尿素、单氰胺、双氰胺、三聚氰胺、三聚氰胺氰尿酸盐、三聚氰胺磷酸盐、三聚氰胺焦磷酸盐或磷酸双季戊四醇酯三聚氰胺盐中的一种或几种。
另外,所述聚合物在制备抗静电剂和/或阻燃剂方面的应用,以及在制备具有抗静电和/或阻燃性能的材料方面的应用,也都应在本发明的保护范围之内。
本发明还提供了一种含多聚均三嗪的组合物,即一种无卤抗静电阻燃超高分子量聚乙烯复合材料,包括如下重量份的组分:
超高分子量聚乙烯 50~85份
上述多聚均三嗪 2~20份
聚磷酸胺 5~30份
多羟基化合物 2~30份
流动改性剂 0.1~10份
成核剂 0.05~1份
偶联剂 0.03~5份
抗氧剂 0.02~5份。
其中,优选地,所述的多羟基化合物是季戊四醇、双季戊四醇、三季戊四醇、甘露醇、木糖醇、蔗糖、淀粉、糊精、纤维素及其衍生物中的一种或几种。
优选地,所述的流动改性剂是高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯、马来酸酐接枝聚乙烯中的一种或几种。
优选地,所述的成核剂是滑石粉、碳酸钙、硅石、硬脂酸锌中的一种或几种。
优选地,所述的偶联剂是硅烷偶联剂、钛酸酯偶联剂或其它偶联剂中的一种。
优选地,所述的抗氧剂是抗氧剂1010、抗氧剂164、抗氧剂TNP、抗氧剂164中的一种。
另外,所述超高分子量聚乙烯(UHMWPE)是分子量150万以上的无支链的线性聚乙烯。在本发明的方案中,优选地,超高分子量聚乙烯的粘均分子量为300~600万。
本发明具有以下有益效果:
本发明首先合成了一种多聚均三嗪聚合物,与传统卤素阻燃剂、无卤阻燃剂或膨胀型阻燃剂不同,本发明采用一锅法烧制了多聚均三嗪阻燃抗静电剂,热重图显示多聚均三嗪有三个明显的不同热失重峰,其中550℃以上稳定的部分有48.22%,查文献可知为一类层状半导体氮化碳化合物,该化合物有着良好的化学稳定性,它的二维纳米片层可以减少热传导和限制聚合物分子链的运动,同时剩下的部分也具有氮系阻燃剂特有的气相阻燃特征。而且,使其在即使没有添加额外抗静电剂的情况下,也能达到好的抗静电效果。
本发明的多聚均三嗪聚合物可以通过简单的一步法一锅法合成,产率高,阻燃效果显著,具有不可比拟的优势;而且是一种优良的多聚合度的聚三嗪化合物,整体不含卤素,加工不影响成品机械性能,这是大多阻燃剂所做不到的。且与传统卤素阻燃剂、无卤阻燃剂或膨胀型阻燃剂相比,在超高分子量聚乙烯添加量较少便能达到优良阻燃效果,可节约成本;而且该多聚均三嗪聚合物制作简单,原料来源广,成本低廉,制作方式简单,有成熟的产业化制造能力;应用于超高分子聚乙烯时,符合现在人们的环保理念,不含卤素,只有C、N、H三种元素。
本发明制备的超高分子量聚乙烯复合材料,不含卤素,阻燃性和抗静电性能佳;且所得超高分子量聚乙烯复合材料,在提高阻燃抗静电效果的同时,其力学性能也得到了保持,拉伸强度≥22MPa,冲击强度≥100kJ/m2 ,并且不影响超高分子量聚乙烯原先的优良耐老化性及耐腐蚀性,能广泛应用于电力、煤炭、冶金、化工、石油开采、海洋和市政等领域,尤其适用于煤炭、海洋等具有特殊要求的行业,具有很好的应用前景。
附图说明
图1为多聚均三嗪及其衍生物的热重和DTG图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明,以下实施例所用试剂和材料均为市购。
实施例1 制备多聚均三嗪
本发明的多聚均三嗪由马弗炉、管式炉烧结而成,控制坩埚厚度1~20mm,烧结温度为500~650℃,烧结时间为2~10小时,其烧结前驱体为尿素、单氰胺、双氰胺、三聚氰胺、三聚氰胺氰尿酸盐、三聚氰胺磷酸盐、三聚氰胺焦磷酸盐或磷酸双季戊四醇酯三聚氰胺盐中的一种或几种。
所制备得到的多聚均三嗪的结构式如下式(I)所示:
实施例2 制备多聚均三嗪无卤抗静电阻燃剂超高分子量聚乙烯复合材料
1、多聚均三嗪无卤抗静电阻燃剂超高分子量聚乙烯复合材料的制备:
(1)选取厚度为1mm的坩埚放入马弗炉内,设置温度为500℃,烧结时间为3小时,选取单氰胺作为烧结前驱体,所得产物即为单氰胺前驱体多聚均三嗪;
(2)将77份超高分子量聚乙烯、10份单氰胺前驱体多聚均三嗪、8份聚磷酸铵、2份季戊四醇、2份高密度聚乙烯、0.3份硅烷偶联剂、0.5份滑石粉、0.2份抗氧剂1010在高速混合机中混匀;
(3)将上步骤中混匀的物料用双螺杆挤出机挤出造粒,挤出机各段温度为180~190℃,螺杆转速350转/分钟。
2、所得产品采用国标(GB/T)标准方法测试其各项性能。数据见表1。
表1
实施例3 制备多聚均三嗪无卤抗静电阻燃剂超高分子量聚乙烯复合材料
1、多聚均三嗪无卤抗静电阻燃剂超高分子量聚乙烯复合材料的制备:
(1)选取厚度为0.8mm的坩埚放入马弗炉内,设置温度为600℃,烧结时间为2小时,选取三聚氰胺作为烧结前驱体,所得产物即为三聚氰胺前驱体多聚均三嗪;
(2)将70份超高分子量聚乙烯、15份三聚氰胺前驱体多聚均三嗪、10份聚磷酸铵、2份双季戊四醇、2份低密度聚乙烯、0.2份硅烷偶联剂、0.5份碳酸钙、0.3份抗氧剂1010在高速混合机中混匀;
(3)将上步骤中混匀的物料用双螺杆挤出机挤出造粒,挤出机各段温度为180~190℃,螺杆转速350转/分钟。
2、所得产品采用国标(GB/T)标准方法测试其各项性能。数据见表2。
表2
实施例4 制备多聚均三嗪无卤抗静电阻燃剂超高分子量聚乙烯复合材料
1、多聚均三嗪无卤抗静电阻燃剂超高分子量聚乙烯复合材料的制备:
(1)选取厚度为2mm的坩埚放入马弗炉内,设置温度为650℃,烧结时间为4小时,选取尿素作为烧结前驱体,所得产物即为尿素前驱体多聚均三嗪;
(2)将60份超高分子量聚乙烯、18份尿素前驱体聚均三嗪、12份聚磷酸铵、7份双季戊四醇、2份低密度聚乙烯、0.2份钛酸酯偶联剂、0.5份碳酸钙、0.3份抗氧剂164在高速混合机中混匀;
(3)将上步骤中混匀的物料用双螺杆挤出机挤出造粒,挤出机各段温度为180~190℃,螺杆转速350转/分钟。
2、所得产品采用国标(GB/T)标准方法测试其各项性能。数据见表3。
表3
实施例5 制备多聚均三嗪无卤抗静电阻燃剂超高分子量聚乙烯复合材料
1、多聚均三嗪无卤抗静电阻燃剂超高分子量聚乙烯复合材料的制备:
(1)选取厚度为15mm的坩埚放入马弗炉内,设置温度为580℃,烧结时间为10小时,选取三聚氰胺氰尿酸盐作为烧结前驱体,所得产物即为三聚氰胺氰尿酸盐前驱体多聚均三嗪;
(2)将65份超高分子量聚乙烯、15份三聚氰胺氰尿酸盐前驱体多聚均三嗪、10份聚磷酸铵、7份三季戊四醇、2份低密度聚乙烯、0.3份钛酸酯偶联剂、0.5份硅石、0.2份抗氧剂164在高速混合机中混匀;
(3)将上步骤中混匀的物料用双螺杆挤出机挤出造粒,挤出机各段温度为180~190℃,螺杆转速350转/分钟。
2、所得产品采用国标(GB/T)标准方法测试其各项性能。数据见表4。
表4
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (6)
2.如权利要求1所述含多聚均三嗪的组合物,其特征是,所述的多羟基化合物是季戊四醇、双季戊四醇、三季戊四醇、甘露醇、木糖醇、蔗糖、淀粉、糊精、纤维素及其衍生物中的一种或几种。
3.如权利要求1所述含多聚均三嗪的组合物,其特征是,所述的流动改性剂是高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯、马来酸酐接枝聚乙烯中的一种或几种。
4.如权利要求1所述含多聚均三嗪的组合物,其特征是,所述的成核剂是滑石粉、碳酸钙、硅石、硬脂酸锌中的一种或几种。
5.如权利要求1所述含多聚均三嗪的组合物,其特征是,所述的偶联剂是硅烷偶联剂、钛酸酯偶联剂中的一种。
6.如权利要求1所述含多聚均三嗪的组合物,其特征是,所述的抗氧剂是抗氧剂1010、抗氧剂TNP、抗氧剂164中的一种。
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