CN107383752A - 一种改性白石墨烯复合abs材料及其制备方法 - Google Patents
一种改性白石墨烯复合abs材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及材料技术领域,具体公开了一种改性白石墨烯复合ABS材料,其原料按重量份包括:ABS 100份,改性白石墨烯0.1‑5份,抗氧剂0.1‑0.3份。还公开了该材料的具体制备方法。本发明的改性白石墨烯复合ABS材料,可以大幅度提高ABS的阻燃、导热性能和机械强度,同时不影响绝缘和加工性能,使得ABS的综合性能得到提升。可广泛应用于汽车、电子电器、家用电器等领域,提高产品附加值。
Description
技术领域
本发明涉及材料技术领域,具体涉及一种改性白石墨烯复合ABS材料及其制备方法。
背景技术
ABS树脂是丙烯腈-丁二烯-苯乙烯三元共聚物材料,结合了三种组分的优点,不仅具有聚丙烯腈优良的耐化学性、耐热性、刚性、抗拉伸性能,具有聚丁二烯优良的抗冲击性能,还具有聚苯乙烯优良的加工流动性、光泽性等优点。ABS以其卓越的综合性能广泛应用于汽车行业、电子电器行业、家用电器行业等方面。
但ABS也存在一些性能缺陷,特别是ABS阻燃性能较差(极限氧指数仅为18%左右),材料极易燃烧,在使用过程中具有一定的安全隐患。另外ABS热导率低(0.2W/m·k),在使用时易产生热量积累,影响产品的使用寿命,且使用范围受限,难以用于需要散热的配件。
目前ABS树脂的阻燃主要通过添加阻燃剂实现,普遍使用的是存在污染性的含卤阻燃剂,燃烧时会产生大量卤化氢气体,而且会有较重的浓烟,不仅不利于环保,而且一旦发生火灾还会给人体造成伤害。另一种是无卤阻燃剂,具有无毒、环保、稳定性好等优点,但需要添加较大量才能达到阻燃要求,如此会导致ABS树脂的性能受到较大影响,尤其是物理性能会大幅降低,加工流动性也会降低。
常用的提高ABS树脂导热系数的方法是在树脂基体中添加导热填料,如氧化铝、氧化硅、氮化铝、碳化硅、石墨、碳纤维等,制备方法简单,成本低。但各类导热填料的填充量一般超过30%,会影响ABS的机械性能,且大量的填料填充会导致高分子材料体系粘度急剧变大,阻碍填料分散均匀,且加工成型变得异常困难。另外部分导热填料的加入,也会导致导电性能的提高,从而降低ABS树脂的电绝缘性能。这些不足都限制了导热ABS材料的应用。
因此寻找一种添加剂,在提高ABS阻燃、导热性能的同时,又不影响其绝缘、加工及优良的力学性能就具有十分重要的现实意义。
白石墨烯这一新型二维层状纳米材料,因其独特的性能在改性ABS领域大有可为:1)白石墨烯为单层或少层六方氮化硼,具有大的比表面积,加入树脂后能更好的形成片层网结构,燃烧过程中形成紧凑、致密、均匀的层状结构,有效抑制聚合物分子链的热运动,提高复合体系的粘度,该片层网结构起到减少挥发性可燃物溢出和外界氧气进入的功效,使得复合体系的氧指数提高,阻燃性能提高且环保无毒;2)白石墨烯具有高热导率、高机械强度及绝缘性能,少量添加即可赋予树脂优异的导热性能和力学强度,同时不影响树脂的绝缘性能和加工性能。另外由于白石墨烯高的热导率,可以很好地将燃烧中产生的热量快速有效的传递出去,从而减缓燃烧速度,达到阻燃性能提高的作用;3)白石墨烯为无色或透明的,加入树脂基体后,不会影响原有颜色。
但白石墨烯作为纳米级的材料,直接加入树脂中易团聚,无法实现对ABS的良好改性效果,甚至严重影响复合材料的性能。
发明内容
有鉴于此,有必要针对上述现有ABS塑料的不足,提供一种简单有效的改性白石墨烯复合ABS材料及其制备方法,该材料具有优异的阻燃性、导热性、机械强度,同时不影响树脂的绝缘性能和加工性能。
为实现上述目的,本发明采取以下的技术方案:
本发明的改性白石墨烯复合ABS材料,其原料组成按重量份包括:ABS 100份,改性白石墨烯0.1-5份,抗氧剂0.1-0.3份。
进一步的,所述改性白石墨烯为单层或少层的改性白石墨烯,粒径5-10um,比表面积300-400m2/g。
进一步的,所述抗氧剂为抗氧剂1010、抗氧剂168、抗氧剂2912中的至少一种。
进一步的,所述改性白石墨烯为石墨烯在质量浓度为0.1%-0.5%的表面活性剂水溶液浸泡22-26h。
作为优选的,所述改性白石墨烯为石墨烯在质量浓度为0.3%的表面活性剂水溶液浸泡24h。
进一步的,所述表面活性剂包括长链路易斯碱、长链路易斯酸、季铵化物或磺酸化物。
进一步的,所述长链路易斯碱为胺类;所述长链路易斯酸为硼烷类;所述季铵化物为烷基三甲基季铵盐、烷基二甲基苄基季铵盐、二烷基二甲基季铵盐中的一种;所述磺酸化物为十二烷基苯磺酸钠、十二烷基磺酸钠、木质素磺酸钠、甘胆酸钠中的一种。
本发明的改性白石墨烯复合ABS材料的制备方法,包括:
步骤1)改性白石墨烯的制备:选用5-10层的白石墨烯制备改性白石墨烯;
步骤2)按重量份称取ABS、改性白石墨烯、抗氧剂加入高速混合机内混合均匀;然后用挤出机进行熔融共混,挤出造粒,采用切粒机切粒得到改性白石墨烯复合ABS材料。
进一步的,所述挤出机各区温度分别为:一区150-160℃、二区160-170℃、三区170-180℃、四区180-195℃、五区190-200℃、六区190-205℃、七区200-210℃、八区190-205℃、九区190-200℃、机头190-195℃。
进一步的,所述挤出机主机转速为260-280rpm,喂料转速9-10.5Hz;切粒机速度7.5-10Hz。
进一步的,步骤2)所述挤出机为单螺杆挤出机或双螺杆挤出机,优选双螺杆挤出机。
本发明的有益效果为:
1)先对白石墨烯进行表面改性,再与ABS树脂进行复合,增加了白石墨烯与ABS树脂的相容性,提高了界面粘结力和白石墨烯在ABS中的均匀分散,促进整个材料体系片层网结构的形成,从而提高了ABS树脂的性能。
2)白石墨烯为单层或少层六方氮化硼,具有大的比表面积,加入到ABS树脂后能更好的形成片层网结构,燃烧过程中形成紧凑、致密、均匀的层状结构,有效抑制聚合物分子链的热运动,提高复合体系的粘度,该片层网结构起到减少挥发性可燃物溢出和外界氧气进入的功效,使得复合体系的氧指数提高,阻燃性能提高且环保无毒;
3)白石墨烯具有高热导率、高的机械强度及绝缘性能,大尺寸的白石墨烯在低含量添加下更容易出现搭桥形成导热通路,热流沿高导热填料通路传导更快,赋予ABS优异的导热性能和力学强度,同时不影响ABS的绝缘性能和加工性能。另外由于白石墨烯高的热导率,可以很好地将燃烧中产生的热量快速有效的传递出去,从而减缓燃烧速度,达到阻燃性能提高的作用。
4)白石墨烯为无色或透明的,不会影响ABS原有颜色。可用于对外观颜色有要求的汽车、电子电器、家用电器等领域。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将结合本发明实施例,对本发明的技术方案作进一步清楚、完整地描述。需要说明的是,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
步骤1)改性白石墨烯的制备:将5-10层的白石墨烯用0.1%的长链硼烷水溶液浸泡24h,得到长链硼烷改性的白石墨烯溶液。
步骤2)将100份ABS、0.1份改性白石墨烯、0.1份抗氧剂2912加入高速混合机内混合均匀;然后用双螺杆挤出机进行熔融共混,挤出造粒,切粒机切粒得到改性白石墨烯复合ABS材料。其中,双螺杆挤出机各区温度分别为:一区150℃、二区160℃、三区170℃、四区180℃、五区190℃、六区190℃、七区200℃、八区190℃、九区190℃、机头190℃。双螺杆挤出机主机转速为260rpm,喂料转速9Hz;切粒机速度7.5Hz。
实施例2
步骤1)改性白石墨烯的制备:将5-10层的白石墨烯用0.2%的油胺水溶液浸泡24h,得到油胺改性的白石墨烯溶液。
步骤2)将100份ABS、0.5份改性白石墨烯、0.2份抗氧剂1010、0.1份抗氧剂168加入高速混合机内混合均匀;然后用双螺杆挤出机进行熔融共混,挤出造粒,切粒机切粒,得到改性白石墨烯复合ABS材料。其中,双螺杆挤出机各区温度分别为:一区155℃、二区165℃、三区175℃、四区185℃、五区190℃、六区190℃、七区200℃、八区190℃、九区190℃、机头190℃。双螺杆挤出机主机转速为270rpm,喂料转速9.5Hz;切粒机速度8Hz。
实施例3
步骤1)改性白石墨烯的制备:将5-10层的白石墨烯用0.3%的烷基三甲基季铵盐水溶液浸泡24h,得到长链硼烷改性的白石墨烯溶液。
步骤2)将100份ABS、1.5份改性白石墨烯、0.2份抗氧剂1010加入高速混合机内混合均匀;然后用双螺杆挤出机进行熔融共混,挤出造粒,切粒机切粒,得到改性白石墨烯复合ABS材料。其中,双螺杆挤出机各区温度分别为:一区160℃、二区170℃、三区180℃、四区190℃、五区200℃、六区200℃、七区210℃、八区205℃、九区200℃、机头195℃。双螺杆挤出机主机转速为275rpm,喂料转速10Hz;切粒机速度9Hz。
实施例4
步骤1)改性白石墨烯的制备:将5-10层的白石墨烯用0.5%的十二烷基磺酸钠水溶液浸泡24h,得到油胺改性的白石墨烯溶液。
步骤2)将100份ABS、4.5份改性白石墨烯、0.3份抗氧剂1010加入高速混合机内混合均匀;然后用双螺杆挤出机进行熔融共混、挤出,切粒机切粒,得到改性白石墨烯复合ABS材料。其中,双螺杆挤出机各区温度分别为:一区160℃、二区165℃、三区175℃、四区195℃、五区200℃、六区205℃、七区210℃、八区205℃、九区200℃、机头195℃。双螺杆挤出机主机转速为280rpm,喂料转速10.5Hz;切粒机速度10Hz。
表1中为测定实施例1-4中所制备得到的改性白石墨烯复合ABS材料与对比例ABS(纯的ABS塑料)的性能参数:
表1实施例1-4和对比例的ABS性能测试结果
从上表可知,本发明的制备方法可以大幅度提高ABS的阻燃、导热性能和机械强度,同时不影响绝缘性能。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (10)
1.一种改性白石墨烯复合ABS材料,其特征在于,其原料组成按重量份包括:ABS 100份,改性白石墨烯0.1-5份,抗氧剂0.1-0.3份。
2.根据权利要求1所述的改性白石墨烯复合ABS材料,其特征在于,所述改性白石墨烯为单层或少层的改性白石墨烯,粒径5-10um,比表面积300-400m2/g。
3.根据权利要求1或2所述的改性白石墨烯复合ABS材料的制备,其特征在于,所述抗氧剂为抗氧剂1010、抗氧剂168、抗氧剂2912中的至少一种。
4.根据权利要求1或2所述的改性白石墨烯复合ABS材料,其特征在于,所述改性白石墨烯为石墨烯在质量浓度为0.1%-0.5%的表面活性剂水溶液中浸泡22-26h。
5.根据权利要求4所述的改性白石墨烯复合ABS材料,其特征在于,所述改性白石墨烯为石墨烯在质量浓度为0.3%的表面活性剂水溶液中浸泡24h。
6.根据权利要求4所述的改性白石墨烯复合ABS材料,其特征在于,所述表面活性剂包括长链路易斯碱、长链路易斯酸、季铵化物或磺酸化物。
7.根据权利要求6所述的改性白石墨烯复合ABS材料,其特征在于,所述长链路易斯碱为胺类;所述长链路易斯酸为硼烷类;所述季铵化物为烷基三甲基季铵盐、烷基二甲基苄基季铵盐、二烷基二甲基季铵盐中的一种;所述磺酸化物为十二烷基苯磺酸钠、十二烷基磺酸钠、木质素磺酸钠、甘胆酸钠中的一种。
8.一种改性白石墨烯复合ABS材料的制备方法,其特征在于,包括:
步骤1)改性白石墨烯的制备:选用5-10层的白石墨烯制备改性白石墨烯;
步骤2)按重量份称取ABS、改性白石墨烯、抗氧剂加入高速混合机内混合均匀;然后用挤出机进行熔融共混,挤出造粒,采用切粒机切粒得到改性白石墨烯复合ABS材料。
9.根据权利要求8所述的改性白石墨烯复合ABS材料的制备方法,其特征在于,所述挤出机各区温度分别为:一区150-160℃、二区160-170℃、三区170-180℃、四区180-195℃、五区190-200℃、六区190-205℃、七区200-210℃、八区190-205℃、九区190-200℃、机头190-195℃。
10.根据权利要求8所述的改性白石墨烯复合ABS材料的制备方法,其特征在于,所述挤出机主机转速为260-280rpm,喂料转速9-10.5Hz;切粒机速度7.5-10Hz。
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