CN107383578A - 一种高阻燃耐漏电起痕伞裙套管及其生产方法 - Google Patents

一种高阻燃耐漏电起痕伞裙套管及其生产方法 Download PDF

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CN107383578A
CN107383578A CN201710701876.2A CN201710701876A CN107383578A CN 107383578 A CN107383578 A CN 107383578A CN 201710701876 A CN201710701876 A CN 201710701876A CN 107383578 A CN107383578 A CN 107383578A
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full skirt
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张龙
饶喜梅
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Shenzhen Woer Heat Shrinkable Material Co Ltd
Changzhou Woer Heat Shrinkable Material Co Ltd
Huizhou LTK Electronic Cable Co Ltd
LTK Electric Wire Huizhou Co Ltd
Shenzhen Woer Special Cable Co Ltd
Changzhou Woer Nuclear Material Co Ltd
Shenzhen Woer New Energy Electric Technology Co Ltd
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Shenzhen Woer Heat Shrinkable Material Co Ltd
Huizhou LTK Electronic Cable Co Ltd
LTK Electric Wire Huizhou Co Ltd
Shenzhen Woer Special Cable Co Ltd
Changzhou Woer Nuclear Material Co Ltd
Shenzhen Woer New Energy Electric Technology Co Ltd
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Abstract

本发明公开一种高阻燃耐漏电起痕伞裙套管，以重量计，包括以下原料组份：聚烯烃树脂100份；增容树脂5‑15份；阻燃耐漏电起痕添加剂30‑45份；加工助剂1‑5份，抗氧剂0.5‑3份。套管力学性能满足常规热缩材料的要求，达到UL94 V0阻燃的同时，耐漏电起痕性能可达到1A3.5kV等级，能够满足注塑及扩张生产要求。

Description

一种高阻燃耐漏电起痕伞裙套管及其生产方法
技术领域
本发明涉及电力系统电缆附件用高分子材料领域，特别涉及电力机车或高铁动车组的高压箱用的车顶高压电缆刚性终端中，用作该电缆终端中的一体式伞裙套管，起到防污闪、抗风阻、耐漏电起痕的作用。
背景技术
目前在电力机车、动车组或者高铁机车的使用过程中，电力机车或者动车组高压箱的应用越来越普遍，现有技术中与高压箱连接的高压电缆都是采用热缩终端，该终端主要由金属法兰、高压电缆、电应力控制组件、热缩一体式伞裙套管、热缩增硬套管等组成。其中热缩一体式伞裙套管以聚烯烃为基体，具有良好的机械强度、电绝缘性和化学稳定性，并且质量轻，硬度高，可在机车运行的时候抵抗住风阻，伞裙不会变形，目前在电力机车车顶终端中得到广泛应用。
然而，不可避免的是，伞裙套管在长期使用过程中会受到污秽、潮气、盐露以及其它化学品的污染，在外界强电场的作用下，产生沿面泄漏电流及电弧反复放电，促使材料表面水分蒸发、炭化并形成导电通路( 即漏电起痕破坏)，致使伞裙套管失效甚至燃烧。近年来，随着环境问题( 如雾霾、酸雨、沙尘暴等) 的日益恶化，以及电力系统中电压等级的逐步提高，伞裙套管面临着严酷工作环境和高电压等级的双重考验。
因此，提高伞裙套管的阻燃性能和耐漏电起痕能力是非常重要的，可以有效地提高车顶电缆终端的运行寿命，减少因为伞裙套管的失效导致的故障问题。
目前，提高高聚物的耐漏电起痕性能普遍采用的方法是添加耐漏电起痕助剂。通过检索发现，目前关于提高硅橡胶材质的耐漏电起痕性能研究的较多，而关于普通热缩聚烯烃材质的耐漏电性能改善的文章极少。
常用的硅橡胶耐漏电起痕助剂主要有氢氧化铝、氧化铝、二氧化钛、钛酸钡、碳酸锌和碱式碳酸锌等。中国发明专利申请CN104130580A 采用氢氧化铝、硼酸锌以及三氧化二铝等多种无机填料复配填充，制备了一种耐漏电起痕的硅橡胶，但由于填料添加量大、相容性差，劣化了加工性能和力学性能。Lars E.Schmidt 报道三聚氰胺氰尿酸盐和白炭黑复配填充也可以显著提高硅橡胶耐漏电起痕性能和阻燃性能，但同样存在相容性差、力学性能恶化的问题(Tracking and erosion resistance of high temperaturevulcanizingATH-free silicone rubber,IEEE Transactions on Dielectric andElectrical Insulation,2010,17(2):533-540)。
美国专利US Patent4426549指出，在硅橡胶中添加的耐漏电添加剂如氢氧化铝，在聚烯烃材质并不适用，即使添加量超过50%时，其耐漏电起痕性能也无明显改善。而一般作为阻燃协效剂的硼酸锌对聚烯烃材质的耐漏电起痕性能改善明显，但硼酸锌即使加入到50wt％，阻燃性也达不到UL94V0的要求，且添加量(>50wt％ )时严重损害了聚烯烃加工性能和力学性能，大大限制了该聚烯烃材质的应用范围，影响制品在长期运行中的防护性能，存在一定的安全隐患。
因此，研究高效阻燃、耐漏电起痕添加剂，制备具有良好耐漏电起痕性能及阻燃性能的聚烯烃制品具有重要的意义。
发明内容
本发明的目的在于针对现有热缩一体式伞裙套管的阻燃及导耐漏电起痕能力方面存在的缺陷，提供一种具有耐漏电起痕能力且阻燃达到UL94 V0级别的聚烯烃材质热缩伞裙套管。
为达成上述目的，本发明提供一种高阻燃耐漏电起痕伞裙套管，以重量计，包括以下原料组份：
聚烯烃树脂 100份；
增容树脂 5-15份；
阻燃耐漏电起痕添加剂30-45份；
加工助剂1-5份；
抗氧剂0.5-3份。
所述聚烯烃树脂为乙烯-醋酸乙烯酯、低密度聚乙烯、高密度聚乙烯、乙烯-辛烯共聚物、聚丙、乙烯丙烯酸酯共聚物中的两种或多种，优选乙烯-醋酸乙烯酯和低密度聚乙烯复配。
所述增容树脂为低密度聚乙烯、乙烯-辛烯共聚物、乙烯-醋酸乙烯酯共聚物接枝马来酸酐的一种或多种。
所述阻燃耐漏电起痕添加剂由三部分组成，分别为：红磷、聚磷酸铵、苯氧基聚磷腈；硼酸锌、三聚氰胺氰尿酸盐、三聚氰胺焦磷酸盐；三氧化二铁、聚四氟乙烯粉、钼系阻燃剂。三部分的比例为5-15份：10-30份：2-5份。
所述润滑助剂为低分子量硅酮和硬脂酸锌的一种或两种复配。
所述抗氧剂为抗氧剂1010、抗氧剂1035、抗氧剂1076、抗氧剂300中的一种或并用体。
本发明还提供一种高阻燃耐漏电起痕伞裙套管的生产方法，包括如下步骤：
(1)将聚烯烃树脂100份、增容树脂5-15份、阻燃耐漏电起痕添加剂30-45份、加工助剂、抗氧剂0.5-3份等投入密炼机中，密炼至130-160℃出锅，然后通过双螺杆挤出机完成造粒，造粒温度为140-170℃。
(2) 使用注塑机对造粒料进行注塑成型，得到热缩一体式散裙套管半成品，将半成品送往电子辐照加速器或钴源进行辐照交联。
(3)将交联后的伞裙套管于烘箱中加热至140-170℃，使用模具进行扩张，冷却后即得到伞裙套管成品。
本发明的有益技术效果：
1.本发明克服了常用高分子绝缘材料达到高阻燃高耐漏电性能需要高填充量的缺点，通过添加少量的阻燃耐漏电起痕添加剂，在总体质量分数小于50%的情况下，达到了阻燃UL94V0级和耐漏电起痕性能1A3.5 级。
2.本发明添加的阻燃耐漏电起痕添加剂较少，因此在达到阻燃耐漏电性能的同时，材料具备较优良的力学及加工性能，可满足注塑生产要求，这能克服因填料加入过量带来的注塑困难的缺点。
3.本发明阻燃耐漏电起痕材料的原料易得，制备工艺简单，易于实现工业化生产，具有良好的应用前景。
具体实施方式
为详细说明本发明的技术内容、构造特征、所实现目的及效果，以下结合实施方式详予说明。
本发明高阻燃耐漏电起痕伞裙套管，以重量计，包括以下原料组份：
聚烯烃树脂 100份；
增容树脂 5-15份；
阻燃耐漏电起痕添加剂30-45份；
加工助剂1-5份；
抗氧剂0.5-3份；
所述聚烯烃树脂为乙烯-醋酸乙烯酯、低密度聚乙烯、高密度聚乙烯、乙烯-辛烯共聚物、聚丙、乙烯丙烯酸酯共聚物中的两种或多种，优选乙烯-醋酸乙烯酯和低密度聚乙烯复配。
所述增容树脂为低密度聚乙烯、乙烯-辛烯共聚物、乙烯-醋酸乙烯酯共聚物接枝马来酸酐的一种或多种。
所述阻燃耐漏电起痕添加剂由三部分组成，分别为：红磷、聚磷酸铵、苯氧基聚磷腈；硼酸锌、三聚氰胺氰尿酸盐、三聚氰胺焦磷酸盐；三氧化二铁、聚四氟乙烯粉、钼系阻燃剂。三部分的比例为5-15份：10-30份：2-5份。
所述润滑助剂为低分子量硅酮和硬脂酸锌的一种或两种复配。
所述抗氧剂为抗氧剂1010、抗氧剂1035、抗氧剂1076、抗氧剂300中的一种或并用体。
本发明还提供一种高阻燃耐漏电起痕伞裙套管的生产方法，包括如下步骤：
(1)将聚烯烃树脂100份、增容树脂5-15份、阻燃耐漏电起痕添加剂30-45份、加工助剂、抗氧剂0.5-3份等投入密炼机中，密炼至130-160℃出锅，然后通过双螺杆挤出机完成造粒，造粒温度为140-170℃。
(2) 使用注塑机对造粒料进行注塑成型，得到热缩一体式散裙套管半成品，将半成品送往电子辐照加速器或钴源进行辐照交联。
(3)将交联后的伞裙套管于烘箱中加热至140-170℃，使用模具进行扩张，冷却后即得到伞裙套管成品。
以下实施例套管的制备原料和方法均采用上述高阻燃耐漏电起痕伞裙套管原料组份范围和生产方法。
实施例1
一种具有优良耐漏电起痕能力和高阻燃性的热缩一体式伞裙套管的配比为：乙烯-醋酸乙烯酯100份，乙烯醋酸乙烯酯接枝马来酸酐10份，红磷10份，三聚氰胺氰尿酸盐30份，三氧化二铁5份，硬脂酸锌1份，抗氧剂1010 1.5份。
实施例2
一种电力机车车顶用无卤阻燃高耐漏电起痕性的热缩一体式伞裙材料的制备配比是：乙烯-醋酸乙烯酯90份，乙烯辛烯共聚物10份，乙烯-辛烯接枝马来酸酐15份，红磷2份，苯氧基聚磷腈8份，三聚氰胺氰尿酸盐25份，三氧化二铁1份，聚四氟乙烯粉4份，硬脂酸锌1份，抗氧剂1010 1.5份。
实施例3
一种电力机车车顶用无卤阻燃高耐漏电起痕性的热缩一体式伞裙材料的制备配比是：乙烯-醋酸乙烯酯80份，高密度聚乙烯10份，乙烯辛烯共聚物10份，乙烯-辛烯接枝马来酸酐10份，聚磷酸铵10份，红磷5份，苯氧基聚磷腈10份，三聚氰胺焦磷酸盐15份，三氧化二铁5份，硬脂酸锌1份，抗氧剂1010 1份。
下表为实施例1至实施例3中热熔胶的介电常数和介质损耗
以实施例1为例，将材料制成6mm的片材分别进行漏电起痕性能测试和电力机车防火性能测试。其中漏电起痕性能按GB/T6553-2003要求进行测量，防火试验按DIN5510-2-2009进行测试。耐漏电起痕3.5kV通过，未出现伞络击穿现象。防火等级通过S2的要求。
本发明并不局限于上述具体实施方式，熟悉本技术领域的人员还可据此做出多种变化，但任何与本发明等同或相类似的变化都应涵盖在本发明权利要求的范围内。

Claims (8)

1.一种高阻燃耐漏电起痕伞裙套管，以重量计，包括以下原料组份：
聚烯烃树脂 100份；
增容树脂 5-5份；
阻燃耐漏电起痕添加剂30-45份；
加工助剂1-5份；
抗氧剂0.5-3份。
2.根据权利要求1所述的高阻燃耐漏电起痕伞裙套管，其特征在于，所述聚烯烃树脂为乙烯-醋酸乙烯酯、低密度聚乙烯、高密度聚乙烯、乙烯-辛烯共聚物、聚丙、乙烯丙烯酸酯共聚物中的两种或多种，优选乙烯-醋酸乙烯酯和低密度聚乙烯复配。
3.根据权利要求1所述的高阻燃耐漏电起痕伞裙套管，其特征在于，所述增容树脂为低密度聚乙烯、乙烯-辛烯共聚物、乙烯-醋酸乙烯酯共聚物接枝马来酸酐的一种或多种。
4.根据权利要求1所述的高阻燃耐漏电起痕伞裙套管，其特征在于，所述阻燃耐漏电起痕添加剂由三部分组成，分别为：红磷、聚磷酸铵、苯氧基聚磷腈；硼酸锌、三聚氰胺氰尿酸盐、三聚氰胺焦磷酸盐；三氧化二铁、聚四氟乙烯粉、钼系阻燃剂。
5.三部分的比例为5-15份：10-30份：2-5份。
6.根据权利要求1所述的高阻燃耐漏电起痕伞裙套管，其特征在于，所述润滑助剂为低分子量硅酮和硬脂酸锌的一种或两种复配。
7.根据权利要求1所述的高阻燃耐漏电起痕伞裙套管，其特征在于，所述抗氧剂为抗氧剂1010、抗氧剂1035、抗氧剂1076、抗氧剂300中的一种或并用体。
8.一种高阻燃耐漏电起痕伞裙套管的生产方法，包括如下步骤：
(1)将聚烯烃树脂100份、增容树脂5-15份、阻燃耐漏电起痕添加剂30-45份、加工助剂、抗氧剂0.5-3份等投入密炼机中，密炼至130-160℃出锅，然后通过双螺杆挤出机完成造粒，造粒温度为140-170℃；
(2) 使用注塑机对造粒料进行注塑成型，得到热缩一体式散裙套管半成品，将半成品送往电子辐照加速器或钴源进行辐照交联；
(3)将交联后的伞裙套管于烘箱中加热至140℃-170，使用模具进行扩张，冷却后即得到伞裙套管成品。
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