CN103937234B - 一种应用改性碳材料的导热塑料及其制备方法 - Google Patents
一种应用改性碳材料的导热塑料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种应用改性碳材料的导热塑料及其制备方法,该导热塑料包括以下质量百分比组分:改性碳材料,氧化镁氮化硼,尼龙66,聚阴离子型高聚物,分散剂,偶联剂,其中改性碳材料由以下重量份组分组成:基碳料,表面活性剂,聚阳离子型高聚物,偶联剂。其中的改性碳材料将水:基碳料:氯化钠:表面活性剂:偶联剂按比例混合再进行超声,在超声过程中缓慢加入聚阳离子型高聚物,继续超声后再搅拌20-24h过滤烘干即可制备导热塑料。本发明可以有效解决塑料内部物料混合不均的问题,大大提高碳材料的相容性;可以增加整个物料混合物的分散性,在挤出过程中不易堵塞;合成工艺简单,不需要高温,强腐蚀环境等条件。
Description
【技术领域】
本发明涉及一种导热塑料及其制备方法,尤其涉及一种应用改性碳材料的导热塑料及其制备方法,属于无机非金属材料技术领域。
【背景技术】
高分子材料具有绝缘、质轻、耐腐蚀、抗疲劳和易成型等特点,现普遍应用于电子信息领域。不过单纯的高分子材料由于其比较低的导热性能,在一定程度上制约了在一些领域的广泛应用。尤其是日益发展的电子信息工业,越来越轻巧的电子产品造成了越来越紧密的内部结构,这就对其内部填充的高分子材料的散热性能提出了非常高的要求。
碳材料尤其是具有纳米结构的碳材料,因其特殊的结构所以不仅具有较高的导热系数而且还具有质轻、结构稳定等特点被广泛应用于航天、汽车、金属、陶瓷、纺织和化工领域。但是碳材料本身表面是惰性的、疏水的,所以它无法和其他诸如金属氧化物,金属氮化物,高分子塑料等充分均匀混合,这就导致了所挤出的导热塑料内部结构不均一,导热性能分布不均等,极大的影响了材料的导热效果。
一般处理碳材料表面的方法有物理分离法、液相氧化法、高分子修饰法等。其中物理分离法即把碳材料粗分散在水中,加入表面活性剂然后长时间超声,最后过滤、洗涤、层析。不过用这种方法无法去除碳材料表面的无定型碳和金属催化剂,而且长时间的超声也会对一些具有纳米性质的碳材料(如碳纳米管)的结构起到一定的破坏。
液相氧化法则是将碳材料在强氧化性溶液中加热、搅拌。通常是在浓酸中进行,这可以使碳材料表面富含一些含氧官能团,增加其亲水性,有助于包覆金属氧化物,不过在强氧化剂的作用下也会对一些纳米碳材料的结构造成破坏。
中国专利申请号:200710044603.1介绍了一种碳纤维改性塑料的方法,用其方法制作出的改性塑料在各项物理强度上都有明显的提高,但是因为只添加了偶联剂,所以改变碳纤维表面性能的效果不佳,导致了局部位置混合不均的情况。
中国专利申请号:200810010571.8介绍了一种新型的高分子导热塑料的合成方法,但是由于其中没有加入偶联剂,或者对碳材料表面进行修饰,所以合成效果不佳,内部碳材料聚积严重。
中国专利申请号:200810014694.9介绍了一种碳纤维的改性方法,具体是用电解表面来起到减少毛丝,增加力学性能的目的。不过经过实际测试,这种方式处理的碳纤维表面比较光滑不易包覆任何物质。
现今的大部分塑料的制作都是将各种物料充分混入挤出机内,利用挤出机内的螺旋送样通道进行加热共混的,不过纳米碳材料由于其特殊的纳米性能,普通的、未经处理的共混是不可能将纳米碳材料充分混匀,这往往会导致制作的塑料局部导热效果优异,局部导热效果差这一现象的出现。
【发明内容】
本发明的目的是为了克服现有技术的不足,提供一种应用改性碳材料的导热塑料,该改性碳材料易于和主体塑料相容,使得挤出的塑料内部结构均一,性能稳定。
本发明的另一目的是为了提供上述导热塑料的制备方法。
本发明为了实现上述目的,采用以下技术方案:
一种应用改性碳材料的导热塑料,其特征在于包括以下质量百分比组分:
上述各组的重量百分比之和为100%;
其中所述改性碳材料由以下重量份组分组成:
本发明中的基碳料为石墨、炭黑、碳纤维其中的一种。
本发明中的表面活性剂为阴离子表面活性剂,可以为十二烷基苯磺酸钠或硬脂酸等。
本发明中的氧化镁与氮化硼的粒径均为微米级。
本发明中的主体塑料为尼龙66。
本发明导热塑料中的偶联剂与改性碳材料中的偶联剂均选自硅烷偶联剂。
本发明中的分散剂为聚乙烯基吡咯烷酮。
一种上述应用改性碳材料的导热塑料的制备方法,其特征在于包括以下步骤:
a、制备改性碳材料:
将水:基碳料:氯化钠:表面活性剂:偶联剂按质量比100:1:1:0.5:1于常温下混合均匀为预混合物,再放入超声清洗器内于200-300W的超声频率范围内进行超声,在超声过程中缓慢加入聚阳离子型高聚物,继续超声30-60min后再搅拌20-24h,然后过滤烘干,即得改性碳材料;
b、制备应用改性碳材料的导热塑料:
将步骤a制得的改性碳材料与氧化镁,氮化硼,尼龙66,聚阴离子型高聚物和分散剂与偶联剂共混后用双螺杆挤出机挤出造粒即可。
其中双螺杆挤出机的挤出温度为200-270℃,熔体加工扭矩30-70N·m。
本发明中制备改性碳材料的过程中,超声可以加快溶液内物料的分散,防止团聚和混合不均,功率小于200W的话分散力度不够,无法达到分散的效果,功率大于300W的话虽然分散效果更好但是噪音比较大而且更加耗费电量,所以优选200W-300W,水为反应介质,氯化钠不参与反应,主要作用是防止加入聚阳离子高聚物时产生团聚。
制备改性碳材料时在基碳材料中加入聚阳离子高聚物可以使得碳材料表面带有正电荷,在和混有聚阴离子型高聚物的塑料混合后由于电荷自组装作用使得二者可以充分相容,提高碳材料和塑料的相容性。
本发明相对于现有技术,有以下优点:
本发明应用的改性碳材料之间由于斥力作用不会发生团聚,而且由于电荷自组装作用会在碳材料表面均匀的包覆一层金属的氧化物或氮化物,使得改性后的碳材料在具有良好导热性质的同时,易于并且充分地和其他塑料材料相容,使得挤出的塑料内部结构均一,提高塑料的导热系数,各项物理参数不会随着区域的不同而发生太大变化,性能稳定。
本发明可以有效解决塑料内部物料混合不均的问题,大大提高碳材料的相容性;可以增加整个物料混合物的分散性,在挤出过程中不易堵塞;合成工艺简单,不需要高温,强腐蚀环境等条件。
本发明制备简易,成本低,适于工业化生产。
【具体实施方式】
下面结合具体实施例对本发明作进一步描述,其中的百分比均为质量百分比:
实施例1:
a、制备改性碳材料:将水:石墨:氯化钠:表面活性剂:硅烷偶联剂按质量比100:1:1:0.5:1于常温下混合均匀为预混合物,再放入超声清洗器内于250W的超声频率范围内进行超声,在超声过程中缓慢加入聚阳离子型高聚物,继续超声45min后再搅拌20h,然后过滤烘干,即得改性碳材料;
b、制备应用改性碳材料的导热塑料:将步骤a制得的改性碳材料30%与氧化镁20%,氮化硼15%,主体塑料30%,聚阴离子型高聚物1%,分散剂2%与硅烷偶联剂2%共混后用双螺杆挤出机于挤出温度为200-210℃,熔体加工扭矩70N·m的条件下挤出造粒即可。
实施例2:
a、制备改性碳材料:将水:炭黑:氯化钠:表面活性剂:硅烷偶联剂按质量比100:1:1:0.5:1于常温下混合均匀为预混合物,再放入超声清洗器内于300W的超声频率范围内进行超声,在超声过程中缓慢加入聚阳离子型高聚物,继续超声30min后再搅拌24h,然后过滤烘干,即得改性碳材料;
b、制备应用改性碳材料的导热塑料:将步骤a制得的改性碳材料20%与氧化镁15%,氮化硼20%,主体塑料39%,聚阴离子型高聚物2%,分散剂3%与硅烷偶联剂1%共混后用双螺杆挤出机于挤出温度为220-230℃,熔体加工扭矩60N·m的条件下挤出造粒即可。
实施例3:
a、制备改性碳材料:将水:碳纤维:氯化钠:表面活性剂:硅烷偶联剂按质量比100:1:1:0.5:1于常温下混合均匀为预混合物,再放入超声清洗器内于200W的超声频率范围内进行超声,在超声过程中缓慢加入聚阳离子型高聚物,继续超声60min后再搅拌22h,然后过滤烘干,即得改性碳材料;
b、制备应用改性碳材料的导热塑料:将步骤a制得的改性碳材料20%与氧化镁25%,氮化硼15%,主体塑料30%,聚阴离子型高聚物3%,分散剂5%与硅烷偶联剂2%共混后用双螺杆挤出机于挤出温度为240-250℃,熔体加工扭矩50N·m的条件下挤出造粒即可。
实施例4:
a、制备改性碳材料:将水:石墨:氯化钠:表面活性剂:硅烷偶联剂按质量比100:1:1:0.5:1于常温下混合均匀为预混合物,再放入超声清洗器内于250W的超声频率范围内进行超声,在超声过程中缓慢加入聚阳离子型高聚物,继续超声45min后再搅拌22h,然后过滤烘干,即得改性碳材料;
b、制备应用改性碳材料的导热塑料:将步骤a制得的改性碳材料20%与氧化镁15%,氮化硼15%,主体塑料46%,聚阴离子型高聚物1%,分散剂2%与硅烷偶联剂1%共混后用双螺杆挤出机于挤出温度为250-270℃,熔体加工扭矩30N·m的条件下挤出造粒即可。
对实施例1-4进行热物性检测,检测方法为ASTME1461激光法,测试仪器为导热系数仪FL4010,测试结果如表1所示。
表1:
由表1中的测试数据可知,本发明应用改性碳材料的的导热塑料导热系统稳定在1.40W/m.K左右。
Claims (2)
1.一种应用改性碳材料的导热塑料的制备方法,其特征在于:应用改性碳材料的导热塑料包括以下质量百分比组分:
上述各组分的重量百分比之和为100%;
其中所述改性碳材料由以下质量份组分组成:
,
所述的基碳料为石墨、炭黑、碳纤维其中的一种,所述的表面活性剂为阴离子表面活性剂,所述的氧化镁与氮化硼的粒径均为微米级,所述的主体塑料为尼龙66,所述的导热塑料中的偶联剂与改性碳材料中的偶联剂均选自硅烷偶联剂,所述的分散剂为聚乙烯基吡咯烷酮;
应用改性碳材料的导热塑料制备方法包括以下步骤:
a、制备改性碳材料:
将水:基碳料:氯化钠:表面活性剂:偶联剂按质量比100:1:1:0.5:1于常温下混合均匀为预混合物,再放入超声清洗器内于200-300W的超声频率范围内进行超声,在超声过程中缓慢加入聚阳离子型高聚物,继续超声30-60min后再搅拌20-24h,然后过滤烘干,即得改性碳材料;
b、制备应用改性碳材料的导热塑料:
将步骤a制得的改性碳材料与氧化镁,氮化硼,尼龙66,聚阴离子型高聚物和分散剂与偶联剂共混后用双螺杆挤出机挤出造粒即可。
2.根据权利要求1所述的一种应用改性碳材料的导热塑料的制备方法,其特征在于所述双螺杆挤出机的挤出温度为200-270℃,熔体加工扭矩30-70N·m。
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