CN103642108A - 柔软透明硅烷交联聚乙烯绝缘料及其制备方法 - Google Patents

柔软透明硅烷交联聚乙烯绝缘料及其制备方法 Download PDF

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CN103642108A
CN103642108A CN201310539551.0A CN201310539551A CN103642108A CN 103642108 A CN103642108 A CN 103642108A CN 201310539551 A CN201310539551 A CN 201310539551A CN 103642108 A CN103642108 A CN 103642108A
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徐晓辉
嵇建忠
钟伟勤
徐永卫
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Abstract

本发明提供了一种柔软透明硅烷交联聚乙烯绝缘料及其制备方法，所述绝缘料由A料和B料组成；A料由如下重量份的组分组成：超低密度聚乙烯50-70份，低密度聚乙烯30-50份，硅烷交联剂2～5份，引发剂0.1～0.2份，成核剂0.1～0.5份，B料由如下重量份的组分组成：超低密度聚乙烯100份，有机锡2～5份，抗氧剂2～5份，铜抑制剂2～5份。本发明透明度大幅提升，雾度大为降低，同时又保持了电性能和力学性能的高标准，有效拓展了硅烷交联聚乙烯电缆料的应用领域，满足了新型工业日益增长的个性化需求。

Description

柔软透明硅烷交联聚乙烯绝缘料及其制备方法
技术领域
本发明涉及一种可应用于中低压电缆绝缘层的硅烷交联聚乙烯绝缘料及其制备方法。
背景技术
硅烷交联聚乙烯具有电性能优异、耐应力开裂性能优异、耐热氧老化、易加工、价格低廉等特点，是一种非常优异的中低压电线电缆用绝缘材料。
目前，市面上的硅烷交联聚乙烯电缆料主要采用低密度聚乙烯（LDPE）和线性低密度聚乙烯（LLDPE）为基料，由于低密度聚乙烯为半结晶性高分子材料，在成缆的过程中由于结晶而导致不透明。此外，低密度聚乙烯硬度较大，导致电线电缆较硬而限制了弯曲半径。不透明和硬度较大虽然对于硅烷交联聚乙烯电缆料而言并非大的缺陷，但是如果能对其配方和工艺进行改进从而获得一种柔软、透明的硅烷交联聚乙烯绝缘料，使其在保持自身优异电性能和力学性能的同时又具有类似聚氯乙烯（PVC）电缆料的柔软性和可透明性，将使得硅烷交联聚乙烯电缆料的应用拓展到一个新的领域。
发明内容
本发明的目的旨在提供一种柔软透明硅烷交联聚乙烯绝缘料及其制备方法，以满足人们对硅烷交联聚乙烯新应用领域的个性化需要。
本发明所述的柔软透明硅烷交联聚乙烯绝缘料，由A料和B料组成，两者重量比为：A料∶B料=90～95∶10～5，优选95∶5，
所述A料由如下重量份的组分组成：
Figure BDA0000407566230000011
Figure BDA0000407566230000021
所述B料由如下重量份的组分组成：
Figure BDA0000407566230000022
优选的，所述A料由如下重量份的组分组成：
Figure BDA0000407566230000023
所述B料由如下重量份的组分组成：
Figure BDA0000407566230000024
所述超低密度聚乙烯(ULDPE)的密度为0.880～0.902g/cm3；
所述低密度聚乙烯（LDPE）的密度为0.918～0.922g/cm3，熔体流动指数为1～2g/10min，不含开口剂和爽滑剂；
所述硅烷交联剂为乙烯基三甲氧基硅烷（A171）或乙烯基三乙氧基硅烷（A151）中的一种；
所述的引发剂过氧化二异丙苯（DCP）、过氧化二叔丁基（DTBP）、2，5-二甲基-2，5-二（叔丁基过氧基）己烷（DPBMH）中的一种或几种；
所述的成核剂为山梨醇类、对羟基苯甲酸类、硬脂酸盐类中的一种或几种；
所述的有机锡为二月桂酸二丁基锡、二月桂酸二辛基锡、二(十二烷基硫)二丁基锡中的一种或几种；
所述的抗氧剂为四[甲基-β-（3，5-二叔丁基-4-羟基苯基）丙酸酯]季戊四醇酯（商品名抗氧剂1010）、三［2.4-二叔丁基苯基］亚磷酸酯（商品名抗氧剂168）、4,4'-硫代双(6-叔丁基-3-甲基苯酚)（商品名抗氧剂300）、β-（3,5-二叔丁基-4-羟基苯基）丙酸正十八碳醇酯（商品名抗氧剂1076）中的一种或几种；
所述的铜抑制剂为水杨酰胺基邻苯二甲酰亚胺、双（3,5-二叔丁基-4-羟基苯基丙酰）肼中的一种或几种。
本发明所述的柔软透明硅烷交联聚乙烯绝缘料的制备方法，包括以下步骤：
（1）将A料的各个组分通过超长长径比（L/D=60）的双螺杆挤出机反应挤出，温度为180～230℃，造粒，干燥，即得到A料；
（2）将B料的各个组分通过双螺杆挤出机共混造粒，温度为110～150℃，干燥，即得到B料；
（3）按照A料和B料混合，即得到柔软透明硅烷交联聚乙烯绝缘料。
本发明制备的绝缘料具有以下特点：1、采用超低密度聚乙烯（ULDPE）和高压低密度聚乙烯（LDPE）为主要原料，既保证了优异的电性能和机械力学性能，又利用ULDPE较多的支链以及ULDPE和LDPE良好的相容性大大降低了LDPE的分子链结晶能力，进而降低了结晶度，提高了透光率；2、成核剂的加入使得LDPE/ULDPE的球晶细小化至可见光波长级别，使得光线透过率大为增加，透明度大为改善；3、超长长径比双螺杆（L/D=60）挤出机的反应挤出工艺，使得硅烷交联剂更加有效充分的接枝到熔融态的LDPE/ULDPE分子链中，大量体积庞大的硅烷支链的引入破坏了LDPE/ULDPE分子链的可堆砌性，使得LDPE/ULDPE混合物在冷却过程中难以有效形成结晶，因此透明度提高；4、柔软性优异的ULDPE的使用，使得混合料保持了很好的柔韧性。
本发明与现有技术的硅烷交联聚乙烯电缆料相比，透明度大幅提升，雾度大为降低，同时又保持了电性能和力学性能的高标准，有效拓展了硅烷交联聚乙烯电缆料的应用领域，满足了新型工业日益增长的个性化需求。
具体实施方式
实施例1
A料：
Figure BDA0000407566230000041
通过超长长径比（L/D=60）的双螺杆挤出机反应挤出造粒，温度为210℃，冷却后进行干燥，即得到A料；
B料：
Figure BDA0000407566230000042
通过双螺杆挤出机共混造粒，温度为130℃，风冷后进行干燥，即得到B料。
按照A料:B料=95:5的比例混合，即得到柔软透明硅烷交联聚乙烯绝缘料。采用JB/T10437-2004标准进行检测，结果见表1。
实施例2
A料：
Figure BDA0000407566230000051
通过超长长径比（L/D=60）的双螺杆挤出机反应挤出造粒，温度为230℃，冷却后
进行干燥，即得到A料；
B料：
Figure BDA0000407566230000052
通过双螺杆挤出机共混造粒，温度为140℃，风冷后进行干燥，即得到B料。
按照A料:B料=90:10的比例混合，即得到柔软透明硅烷交联聚乙烯电缆料。采用JB/T10437-2004标准进行检测，结果见表1。
实施例3
A料：
Figure BDA0000407566230000053
Figure BDA0000407566230000061
通过超长长径比（L/D=60）的双螺杆挤出机反应挤出造粒，温度为220℃，冷却后进行干燥处理，即得到A料；
B料：
通过双螺杆挤出机共混造粒，温度为150℃，风冷后进行干燥，即得到B料。
按照A料:B料=95:5的比例混合，即得到柔软透明硅烷交联聚乙烯电缆料。采用JB/T10437-2004标准进行检测，结果见表1。
以上三个实例制备而成的柔软透明硅烷交联聚乙烯绝缘料，力学性能、电学性能优良，柔软性好，透明度高，特点明显。
表1实例性能测试结果
Figure BDA0000407566230000063
Figure BDA0000407566230000071
注：*厚度为2mm。

Claims (5)

1.柔软透明硅烷交联聚乙烯绝缘料，其特征在于，由A料和B料组成； 
所述A料由如下重量份的组分组成： 
Figure FDA0000407566220000011
所述B料由如下重量份的组分组成： 
Figure FDA0000407566220000012
2.根据权利要求1所述的柔软透明硅烷交联聚乙烯绝缘料，其特征在于，所述A料由如下重量份的组分组成： 
Figure FDA0000407566220000013
所述B料由如下重量份的组分组成： 
Figure FDA0000407566220000014
3.根据权利要求1或2所述的柔软透明硅烷交联聚乙烯绝缘料，其特征在于，A料和B料重量比为：A料∶B料=90～95∶10～5，优选95∶5。 
所述超低密度聚乙烯(ULDPE)的密度为0.880～0.902g/cm3。 
4.根据权利要求3所述的柔软透明硅烷交联聚乙烯绝缘料，其特征在于，所述硅烷交联剂为乙烯基三甲氧基硅烷（A171）或乙烯基三乙氧基硅烷（A151）中的一种； 
所述的引发剂过氧化二异丙苯（DCP）、过氧化二叔丁基（DTBP）、2，5-二甲基-2，5-二（叔丁基过氧基）己烷（DPBMH）中的一种或几种； 
所述的成核剂为山梨醇类、对羟基苯甲酸类、硬脂酸盐类中的一种或几种； 
所述的有机锡为二月桂酸二丁基锡、二月桂酸二辛基锡、二(十二烷基硫)二丁基锡中的一种或几种； 
所述的抗氧剂为四[甲基-β-（3，5-二叔丁基-4-羟基苯基）丙酸酯]季戊四醇酯、三［2.4-二叔丁基苯基］亚磷酸酯、4,4'-硫代双(6-叔丁基-3-甲基苯酚)、β-（3,5-二叔丁基-4-羟基苯基）丙酸正十八碳醇酯中的一种或几种； 
所述的铜抑制剂为水杨酰胺基邻苯二甲酰亚胺、双（3,5-二叔丁基-4-羟基苯基丙酰）肼中的一种或几种。 
5.制备权利要求1～4任一项所述的柔软透明硅烷交联聚乙烯绝缘料的方法，其特征在于，包括以下步骤： 
（1）将A料的各个组分通过超长长径比（L/D=60）的双螺杆挤出机反应挤出，温度为180-230℃，造粒，干燥，即得到A料； 
（2）将B料的各个组分通过双螺杆挤出机共混造粒，温度为110～150℃，干燥，即得到B料； 
（3）按照A料和B料混合，即得到柔软透明硅烷交联聚乙烯绝缘料。 
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CN112375284A (zh) * 2020-11-16 2021-02-19 苏州亨利通信材料有限公司 大小线通用3kv及以下交联聚乙烯绝缘料及制备方法
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* Cited by examiner, † Cited by third party
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CN104829901A (zh) * 2015-04-10 2015-08-12 中山市鸿程科研技术服务有限公司 一种电缆料的制备工艺
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