CN103804779A - 一种用于自限温电伴热带电缆的耐高温ptc复合材料及其制备方法 - Google Patents
一种用于自限温电伴热带电缆的耐高温ptc复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种自限温电伴热带电缆的耐高温复合材料及其制备方法,由热塑性聚合物、导电填料和助剂构成。炭黑经偶联剂表面处理成导电填料,增大了炭黑在复合材料中的分散性,提高复合材料的导电性能与PTC强度,并使其PTC复合材料具有较高的工作温度。
Description
技术领域
本发明属于高分子复合材料技术领域,具体涉及一种用于自限温电伴热带电缆的耐高温PTC复合材料及其制备方法。
技术背景
自限温电伴热带电缆由导电高分子复合材料和两根平行金属导线及绝缘护套构成的扁形带状电缆,具有PTC特性,其在低温状态快速启动,温度均匀,每一局部皆可因其被伴热处的温度变化;并能随被加热体系的温度变化自动调节输出功率,自动限制加热的温度。所以该电缆可以被任意截短或在一定范围内接长使用,并允许多次交叉重叠而无高温热点及烧毁之虑,因此被广泛地应用于化工、电、制糖等行业用于自动调节温度要求高的领域。
目前用于自限温电伴热带电缆PTC复合材料主要以聚乙烯(PE)、乙烯一醋酸乙烯酷共聚物(EVA)、聚偏氟乙烯(PVDF)等单组分结晶或半结晶聚合物为基体材料,以性价比高的导电炭黑(CB)为导电填料。由于聚乙烯(PE)、乙烯一醋酸乙烯酷共聚物(EVA)、聚偏氟乙烯(PVDF)这类结晶性聚合物的熔点一般都在150℃以下,致使得到的PTC复合材料的PTC转变温度较低(<150℃),不能满足高温场合的应用需求。
随着现代科技的日新月异,高分子PTC材料应用领域不断拓展,单一结构的聚合物基PTC材料已经难以满足社会的需要,综合性能更加优良的聚合物共混物及复合材料,通过共混可使两种或多种聚合物组成一个稳定体系,在性能上优势互补,其价格又可大幅降低。其中CB填充双组份聚合物基PTC复合材料由于较以往单一聚合物基PTC复合材料具有更低的渗流闽值和更优良的机械加工性能,在聚合物基PTC材料的研究和开发中越来越受到人们的关注。
发明内容
本发明针对现有技术中存在的问题,提供一种耐高温PTC复合材料,该导电聚合材料具有低室温电阻率、高PTC强度。本发明的另一个目的是提供制备上述耐高温PTC复合材料方法。
为了达到上述目的,本发明是通过下列技术方案来实现的:
一种用于自限温电伴热带电缆的耐高温PTC复合材料,所述PTC复合材料包括热塑性聚合物、导电填料和助剂,其各组份的质量百分比为:
热塑性聚合物:80-95%;
导电填料:1-16%;
助剂:2-5%。
所述热塑性聚合物为组份A与组份B组成,所述组份A为聚丙烯,组份B为高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯或聚偏氟乙烯;所述组份A与组份B质量比为1:4-4:1。
所述导电填料是指炭黑放入偶联剂的异丙醇溶液中经过表面处理得到的导电填料,所述炭黑与偶联剂的质量比为100:1。
所述助剂为抗氧剂、润滑剂。
进一步方案,所述偶联剂为钛酸酯类偶联剂,所述钛酸酯类偶联剂为NDZ-101或NDZ-40。
所述抗氧剂为四(β-(3, 5-二叔丁基-4-羟基苯基)丙酸)季戊四醇酯(1010)、三(2,4-二叔丁基苯基)亚磷酸酯(168)、硫代二丙酸双十八醇酯(DSTDP)中的至少一种。
所述润滑剂为有机硅树脂、聚乙烯蜡、氧化聚乙烯蜡、聚硬脂酸乙烯醋、脂肪酸醋。
一种制备如上述的PTC复合材料的方法,包括如下步骤:
(1)炭黑的表面处理:
按质量比为100:1,将炭黑放入偶联剂的异丙醇溶液中,经球磨2-3小时后于烘箱中蒸发溶剂,再于真空烘箱中反应得到炭黑导电填料;
(2)混炼:按配方称取热塑性聚合物、助剂和(1)处理后的导电填料,在150-200℃下进行混炼8-15分钟;
(3)成型:将(2)中混炼后的物质放入双螺杆挤出机造粒、挤出,经冷却得到PTC复合材料。
本发明相比于现有技术具有以下有益效果:
1、炭黑经偶联剂表面处理成导电填料,增大了炭黑在复合材料中的分散性,提高复合材料的导电性能;
2、双组份热塑性聚合物组成一个稳定体系,在性能上优势互补,又可大幅降低价格;
3、这种复合材料有着优异的导电性能及PTC性能,在导电填料含量很低的情况下,就可以明显提高复合材料的导电性,而且能够在较低导电填料含量时出现渗流现象,进一步提高复合材料的PTC强度。
4、本PTC复合材料可以通过调节复合材料中导电填料的含量改变复合材料的导电性,而且由于电导率随着填料变化进行相应的连续的稳定变化,因此可以较为精确的控制复合材料的室温电导率;
5、采用熔融共混的方法进行复合,可以使得两相聚合物均匀混合及导电填料能够较为均匀的在基体中分散,从而得到较低的电阻率及稳定的PTC性能;
6、复合后的材料具有较高的工作温度。
具体实施方式:
下面给出实施例以对本发明进行具体的描述,有必要在此指出的是以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,该领域的技术熟练人员根据本发明内容对本发明做出的一些非本质的改进和调整仍属于本发明的保护范围。
本发明中所用的原料均是市售产品,各厂家生产的基本类似,在此不一一指出。下面对本发明的原料配方与制备方法进行举例说明。
实施例1
(1)按质量比为100:1,将炭黑放入偶联剂NDZ-101的异丙醇溶液中,经球磨2小时后于烘箱中蒸发溶剂,再于真空烘箱中反应得到炭黑导电填料;
(2)按配方称取聚丙烯18%、高密度聚乙烯72%、抗1010为1%、抗168为1%、有机硅树脂3%和经(1)处理得到的导电填料5%,在180℃下进行混炼10分钟;
(3)将(2)中混炼后的物质放入双螺杆挤出机造粒、挤出,经冷却得到PTC复合材料。
实施例2
(1)按质量比为100:1,将炭黑放入偶联剂NDZ-40的异丙醇溶液中,经球磨2.5小时后于烘箱中蒸发溶剂,再于真空烘箱中反应得到炭黑导电填料;
(2)按配方称取聚丙烯22%、低密度聚乙烯66%、抗168为2%、聚乙烯蜡3%和经(1)处理得到的导电填料7%,在200℃下进行混炼8分钟;
(3)将(2)中混炼后的物质放入双螺杆挤出机造粒、挤出,经冷却得到PTC复合材料。
实施例3
(1)按质量比为100:1,将炭黑放入偶联剂NDZ-101的异丙醇溶液中,经球磨2小时后于烘箱中蒸发溶剂,再于真空烘箱中反应得到炭黑导电填料;
(2)按配方称取聚丙烯30%、高密度聚乙烯60%、抗1010为1%、有机硅树脂1%和经(1)处理得到的导电填料8%,在180℃下进行混炼10分钟;
(3)将(2)中混炼后的物质放入双螺杆挤出机造粒、挤出,经冷却得到PTC复合材料。
实施例4
(1)按质量比为100:1,将炭黑放入偶联剂NDZ-101的异丙醇溶液中,经球磨3小时后于烘箱中蒸发溶剂,再于真空烘箱中反应得到炭黑导电填料;
(2)按配方称取聚丙烯45%、线性低密度聚乙烯45%、抗1010为1%、氧化聚乙烯蜡2%和经(1)处理得到的导电填料7%,在180℃下进行混炼15分钟;
(3)将(2)中混炼后的物质放入双螺杆挤出机造粒、挤出,经冷却得到PTC复合材料。
实施例5
(1)按质量比为100:1,将炭黑放入偶联剂NDZ-40的异丙醇溶液中,经球磨2.5小时后于烘箱中蒸发溶剂,再于真空烘箱中反应得到炭黑导电填料;
(2)按配方称取聚丙烯64%、聚偏氟乙烯16%、抗DSTDP为2%、聚硬脂酸乙烯醋2%和经(1)处理得到的导电填料16%,在200℃下进行混炼8分钟;
(3)将(2)中混炼后的物质放入双螺杆挤出机造粒、挤出,经冷却得到PTC复合材料。
实施例6
(1)按质量比为100:1,将炭黑放入偶联剂NDZ-40的异丙醇溶液中,经球磨2小时后于烘箱中蒸发溶剂,再于真空烘箱中反应得到炭黑导电填料;
(2)按配方称取聚丙烯50%、聚偏氟乙烯45%、抗DSTDP为2%、聚硬脂酸乙烯醋2%和经(1)处理得到的导电填料1%,在190℃下进行混炼12分钟;
(3)将(2)中混炼后的物质放入双螺杆挤出机造粒、挤出,经冷却得到PTC复合材料。
对比试验:
将上述实施例1-6中制得的PTC复合材料按照统一工艺注塑成长为5mm、宽为5mm、厚为0.5 mm的样品,采用微欧计测量样品的电阻,根据面积和厚度换算得到各聚合材料的常温电阻R1。再把制成的样品放入150度恒温箱中30分钟后测量样品的电阻R2,用电阻R2除以样品的常温电阻R1,得到PTC强度数据。
表1:聚合材料的PTC性能测试比较
编号 | 温度/℃ | 电阻/欧姆·厘米 | PTC强度/ Rmax/R0 |
实施例1 | 320 | 0.345 | 1.1*108 |
实施例2 | 350 | 0.165 | 9.78*107 |
实施例3 | 420 | 0.019 | 5.2*108 |
实施例4 | 340 | 0.215 | 5.44*107 |
实施例5 | 402 | 0.034 | 3.58*108 |
实施例6 | 360 | 0.264 | 6.89*107 |
通过以上具体实施例1-6,可以看出采用本发明的配方制备的耐高温PTC复合材料耐高温均在320℃以上,电阻率在0.019-0.345欧姆·厘米之间,PTC强度在5.44*107 Rmax/R0以上。因此本发明的低电阻率正温度系数型导电聚合物复合材料的室温电阻率得到了大大降低,PTC强度提高。
Claims (8)
1. 一种用于自限温电伴热带电缆的耐高温PTC复合材料,其特征在于:所述PTC复合材料包括热塑性聚合物、导电填料和助剂,其各组份的质量百分比为:
热塑性聚合物:80-95%;
导电填料:1-16%;
助剂:2-5%。
2. 根据权利要求1所述的PTC复合材料,其特征在于:所述热塑性聚合物为组份A与组份B组成,所述组份A为聚丙烯,组份B为高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯或聚偏氟乙烯;所述组份A与组份B质量比为1:4-4:1。
3. 根据权利要求1所述的PTC复合材料,其特征在于:所述导电填料是指炭黑放入偶联剂的异丙醇溶液中经过表面处理得到的导电填料,所述炭黑与偶联剂的质量比为100:1。
4. 根据权利要求1所述的PTC复合材料,其特征在于:所述助剂为抗氧剂、润滑剂。
5.根据权利要求3所述的PTC复合材料,其特征在于:所述偶联剂为钛酸酯类偶联剂,所述钛酸酯类偶联剂为NDZ-101或NDZ-40。
6. 根据权利要求4所述的PTC复合材料,其特征在于:所述抗氧剂为四(β-(3, 5-二叔丁基-4-羟基苯基)丙酸)季戊四醇酯(1010)、三(2,4-二叔丁基苯基)亚磷酸酯(168)、硫代二丙酸双十八醇酯(DSTDP)中的至少一种。
7. 根据权利要求4所述的PTC复合材料,其特征在于:所述润滑剂为有机硅树脂、聚乙烯蜡、氧化聚乙烯蜡、聚硬脂酸乙烯醋、脂肪酸醋。
8.一种制备如权利要求1所述的PTC复合材料的方法,其特征在于:包括如下步骤:
(1)炭黑的表面处理:
按质量比为100:1,将炭黑放入偶联剂的异丙醇溶液中,经球磨2-3小时后于烘箱中蒸发溶剂,再于真空烘箱中反应得到炭黑导电填料;
(2)混炼:按配方称取热塑性聚合物、助剂和(1)处理后的导电填料,在150-200℃下进行混炼8-15分钟;
(3)成型:将(2)中混炼后的物质放入双螺杆挤出机造粒、挤出,经冷却得到PTC复合材料。
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