CN103980658A - 一种耐高温、防火绝缘加强型电力电缆及其制造方法 - Google Patents

一种耐高温、防火绝缘加强型电力电缆及其制造方法 Download PDF

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CN103980658A
CN103980658A CN201410183854.8A CN201410183854A CN103980658A CN 103980658 A CN103980658 A CN 103980658A CN 201410183854 A CN201410183854 A CN 201410183854A CN 103980658 A CN103980658 A CN 103980658A
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fire
power cable
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high temperature
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陈海波
陈桂兰
陈爱国
陈仁训
陈冰玲
刘桂春
陈春燕
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Guo Gao Building Materials Science And Technology Ltd Of Nan'an
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Abstract

一种耐高温、防火绝缘加强型电力电缆，其电缆料按质量百分比主要由以下原料组成：酚醛树脂 65-75份、高密度聚乙烯HDPE 20-30份、阻燃剂10-20份、改性丙烯酸树脂 5-10份、焙烧沸石粉10-15份、纳米碳酸钙粉10-15份、硅烷偶联剂1-2份、炭黑2-5份钛酸酯1-2份、抗氧剂1-1.5份、硬脂酸钡0.5-1份、树脂粘结剂 0.5-1份过氧化二烷烃 4-5份。

Description

一种耐高温、防火绝缘加强型电力电缆及其制造方法
技术领域
本发明涉及电缆领域，尤其涉及一种耐高温、防火绝缘加强型电力电缆及其制造方法。
背景技术
随着人类对保护生态环境及自身健康的日益重视，对电缆的环保性能提出了更高更全面的要求。目前，国内阻燃电线电缆通常分为一般阻燃电线电缆、低烟低卤阻燃电线电缆和低烟无卤阻燃电线电缆，这些阻燃电线电缆产品以含卤阻燃为主，这些阻燃电缆通常是在护套及绝缘层中添加含磷等阻燃剂，在高温下生成卤氢酸、磷酸等，进一步脱水生成的稳定的编磷酸覆盖在被燃电缆表面，以阻隔氧气，从而阻止燃烧进一步发展。但是，由于填充层不结实，使电缆的绝缘层与空气中氧气阻隔不够充分，燃烧时仍释放出有毒性的HCL气体，且有大量烟雾和腐蚀性卤化物产生，HCL气体刺激人体器官使人窒息，给人员造成伤害，也对高精密仪器及各种设备造成腐蚀，还给救护工作带来非常大的困难，并造成环境等危害，即所谓的“二次灾害”。
电力电缆从聚氯乙烯绝缘或聚乙烯绝缘、聚氯乙烯或聚乙烯护套非阻燃型电缆，发展到上世纪90年代开始的阻燃型聚氯乙烯绝缘或阻燃型聚乙烯绝缘、交联聚乙烯绝缘或硅橡胶及氟塑料绝缘(高温场合用)、阻燃型聚氯乙烯护套或阻燃型聚乙烯护套、阻燃型(主要分为A类、B类、C类)硅橡胶及氟塑料电缆，再发展到本世纪初开始的低烟无卤阻燃型电力电缆，可见对电缆的阻燃性能要求越来越高。 
低烟无卤阻燃电缆的绝缘基本采用低烟无卤聚烯烃绝缘，护套采用低烟无卤阻燃聚烯烃护套，而这类材料制造的电缆都不能达到无烟无卤不燃的性能要求。 
随着人们环保意识的提高和我国社会经济建设步伐的加快，低烟无卤阻燃电缆被广泛地应用在高层建筑、地铁、发电厂、核电站和轨道交通等重要部门及公共场所。当发生火灾时，电缆燃烧时不释放腐蚀性气体，并且透光性良好，对救援工作有很大的帮助，在很大程度上可以减少人员伤亡和财产损失。
当存在外部火源或因内部故障，电线电缆很容易燃烧，而一旦发生火灾，如果电线电缆不能及时自熄，火焰将会蔓延，造成人员人身伤害和财产损失，因此，电线电缆的绝缘或护套材料要求具有良好的阻燃性能，以及较小的发烟量和毒性指数，即无卤、低烟，就是现有市场上通常使用的低烟无卤阻燃聚烯烃电缆料。为减少火灾损失，保障人民生活生产安全，随着社会的发展，对电线电缆材料的阻燃要求越来越高，普通的低烟无卤阻燃聚烯烃电缆料已无法满足日益增长的阻燃要求了，如无法满足VW-1（垂直燃烧试验）的阻燃要求，或无法满足FT-4的阻燃要求，电线电缆市场亟需满足各种阻燃要求的聚烯烃电缆料。 
现有普通低烟无卤阻燃聚烯烃电缆料主要采用添加大量无机阻燃填料来达到阻燃的目的，然而大量添加无机阻燃填料后，电线电缆的抗开裂性能会劣化，机械性能变差，尤其是有钢带铠装的电缆在户外敷设时，电缆开裂问题更严重。另一方面，即使是这样添加大量无机阻燃填料，电缆料的阻燃性能也不是确定就能过关，产品质量不合格，又会给电缆厂造成很大的经济损失。
发明内容
本发明的目的是提供一种能克服上述缺陷、工作性能优良的具有良好耐高温、防火绝缘加强型电力电缆及其制造方法。
为了达到上述目的，本发明是通过以下技术方案实现的：
一种耐高温、防火绝缘加强型电力电缆，其特征在于电缆料按质量百分比主要由以下原料组成：
酚醛树脂                               65-75份
高密度聚乙烯HDPE            20-30份
阻燃剂                       10-20份
改性丙烯酸树脂                      5-10份
焙烧沸石粉                   10-15份
纳米碳酸钙粉                 10-15份
硅烷偶联剂                   1-2份
炭黑                         2-5份
钛酸酯                       1-2份
抗氧剂                      1-1.5份
硬脂酸钡                     0.5-1份
树脂粘结剂                   0.5-1份
过氧化二烷烃                  4-5份。
所述的阻燃剂选自氢氧化铝和氢氧化镁中的一种或混合物。
所述的硅烷偶联剂用于对无机阻燃剂进行表面改性；所述硅烷偶联剂选自乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷中的一种或至少两种以任意比例混合的混合物。
所述的抗氧剂为受阻酚类抗氧剂和亚磷酸酯类抗氧剂按任意比例的混合物，其中，受阻酚类抗氧剂选择四[β-（3，5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯，或者N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺；亚磷酸酯类抗氧剂选择亚磷酸三壬基苯酯，或者三(2,4-二叔丁基苯基)亚磷酸酯。
一种耐高温、防火绝缘加强型电力电缆，其特征在于制备包括以下步骤：
（1）按组成原料的重量份称取各原料，将酚醛树脂、高密度聚乙烯HDPE、改性丙烯酸树脂和纳米碳酸钙粉混合均匀，得到混合料A；
（2）在上述步骤（1）中的混合料A中按重量份加入阻燃剂、焙烧沸石粉、纳米碳酸钙粉、硅烷偶联剂、炭黑、钛酸酯、抗氧剂、硬脂酸钡、树脂粘结剂 、过氧化二烷烃，常温下低速搅拌1-2分钟，使得混合均匀，得到混合料B；
（3）将上述步骤（2）得到的混合料B加入开炼机和密炼机或双螺杆挤出机混炼、造粒，控制温度140-170℃，得到成品。
所述的挤出机L/D＝20∶1～25∶1，转速50～70r/min；挤出温度：进料段120～140℃，压缩段160～180℃，均化段210～230℃，机头220～230℃。 
本发明与普通电缆料相比，提高了产品的耐温等级，耐温等级可达到150℃；提高了机械性能，消除了开裂问题；提高了阻燃性能，制成的材料可通过UL的VW-1和FT-4燃烧测试；另外，制造工艺简单，设备投资少，产品性能稳定。本发明的材料可广泛用于电力、建筑、通信、制造等众多国民经济领域。据有关统计，电线电缆行业是我国仅次于汽车行业的第二大行业，产品品种满足率和国内市场占有率均超过90％。在世界范围内，我国电线电缆总产值已超过美国，成为世界上第一大电线电缆生产国。这种优化改性后的低烟无卤阻燃抗静电耐老化电线电缆料使线缆更加优越、耐用，由此可见优化改性将给我国线缆材料市场带来巨大市场空间。
具体实施方式
实施例1
一种耐高温、防火绝缘加强型电力电缆，其特征在于电缆料按质量百分比主要由以下原料组成：
酚醛树脂                               65份
高密度聚乙烯HDPE            20份
阻燃剂                       10份
改性丙烯酸树脂                      5份
焙烧沸石粉                   10份
纳米碳酸钙粉                 10份
硅烷偶联剂                   1份
炭黑                         2份
钛酸酯                       1份
抗氧剂                      1份
硬脂酸钡                     0.5份
树脂粘结剂                   0.5份
过氧化二烷烃                  4份。
所述的阻燃剂选自氢氧化铝和氢氧化镁中的一种或混合物。
所述的硅烷偶联剂用于对无机阻燃剂进行表面改性；所述硅烷偶联剂选自乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷中的一种或至少两种以任意比例混合的混合物。
所述的抗氧剂为受阻酚类抗氧剂和亚磷酸酯类抗氧剂按任意比例的混合物，其中，受阻酚类抗氧剂选择四[β-（3，5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯，或者N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺；亚磷酸酯类抗氧剂选择亚磷酸三壬基苯酯，或者三(2,4-二叔丁基苯基)亚磷酸酯。
（1）按组成原料的重量份称取各原料，将酚醛树脂、高密度聚乙烯HDPE、改性丙烯酸树脂和纳米碳酸钙粉混合均匀，得到混合料A；
（2）在上述步骤（1）中的混合料A中按重量份加入阻燃剂、焙烧沸石粉、纳米碳酸钙粉、硅烷偶联剂、炭黑、钛酸酯、抗氧剂、硬脂酸钡、树脂粘结剂 、过氧化二烷烃，常温下低速搅拌1-2分钟，使得混合均匀，得到混合料B；
（3）将上述步骤（2）得到的混合料B加入开炼机和密炼机或双螺杆挤出机混炼、造粒，控制温度140-170℃，得到成品。
所述的挤出机L/D＝20∶1～25∶1，转速50～70r/min；挤出温度：进料段120～140℃，压缩段160～180℃，均化段210～230℃，机头220～230℃。 
电缆绝缘层性能：制成的电缆绝缘层燃烧产物pH加权值为6.2，燃烧时产生的烟尘透光率81.5％，单根燃烧、成束燃烧均满足GB/T18380要求；电缆绝缘层抗拉强度为18.5MPa，断裂伸长率为520％；该电缆绝缘层可耐受10kV高压。 
 
实施例2
一种耐高温、防火绝缘加强型电力电缆，其特征在于电缆料按质量百分比主要由以下原料组成：
酚醛树脂                               75份
高密度聚乙烯HDPE            30份
阻燃剂                       20份
改性丙烯酸树脂                      10份
焙烧沸石粉                   15份
纳米碳酸钙粉                 15份
硅烷偶联剂                  2份
炭黑                         5份
钛酸酯                       2份
抗氧剂                      1.5份
硬脂酸钡                     1份
树脂粘结剂                  1份
过氧化二烷烃                  5份。
所述的阻燃剂选自氢氧化铝和氢氧化镁中的一种或混合物。
所述的硅烷偶联剂用于对无机阻燃剂进行表面改性；所述硅烷偶联剂选自乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷中的一种或至少两种以任意比例混合的混合物。
所述的抗氧剂为受阻酚类抗氧剂和亚磷酸酯类抗氧剂按任意比例的混合物，其中，受阻酚类抗氧剂选择四[β-（3，5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯，或者N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺；亚磷酸酯类抗氧剂选择亚磷酸三壬基苯酯，或者三(2,4-二叔丁基苯基)亚磷酸酯。
（1）按组成原料的重量份称取各原料，将酚醛树脂、高密度聚乙烯HDPE、改性丙烯酸树脂和纳米碳酸钙粉混合均匀，得到混合料A；
（2）在上述步骤（1）中的混合料A中按重量份加入阻燃剂、焙烧沸石粉、纳米碳酸钙粉、硅烷偶联剂、炭黑、钛酸酯、抗氧剂、硬脂酸钡、树脂粘结剂 、过氧化二烷烃，常温下低速搅拌1-2分钟，使得混合均匀，得到混合料B；
（3）将上述步骤（2）得到的混合料B加入开炼机和密炼机或双螺杆挤出机混炼、造粒，控制温度140-170℃，得到成品。
所述的挤出机L/D＝20∶1～25∶1，转速50～70r/min；挤出温度：进料段120～140℃，压缩段160～180℃，均化段210～230℃，机头220～230℃。 
电缆绝缘层性能：制成的电缆绝缘层燃烧产物PH加权值为4.5，燃烧时产生的烟尘透光率65％，单根燃烧满足GB/T18380要求、成束燃烧均不满足GB/T18380要求；电缆绝缘层抗拉强度为14.2MPa，断裂伸长率为400％；该电缆绝缘层可耐受3kV高压。
上述内容，仅为本发明的较佳实施例，并非用于限制本发明的实施方案，本领域普通技术人员根据本发明的主要构思和精神，可以十分方便地进行相应的变通或修改，故本发明的保护范围应以权利要求书所要求的保护范围为准。

Claims (6)

1.一种耐高温、防火绝缘加强型电力电缆，其特征在于电缆料按份数主要由以下原料组成：
酚醛树脂                               65-75份
高密度聚乙烯HDPE            20-30份
阻燃剂                       10-20份
改性丙烯酸树脂                      5-10份
焙烧沸石粉                   10-15份
纳米碳酸钙粉                 10-15份
硅烷偶联剂                   1-2份
炭黑                         2-5份
钛酸酯                       1-2份
抗氧剂                      1-1.5份
硬脂酸钡                     0.5-1份
树脂粘结剂                   0.5-1份
过氧化二烷烃                  4-5份。
2.根据权利要求1所述的耐高温、防火绝缘加强型电力电缆，其特征在于：所述的阻燃剂选自氢氧化铝和氢氧化镁中的一种或混合物。
3.根据权利要求1所述的耐高温、防火绝缘加强型电力电缆，其特征在于：硅烷偶联剂用于对无机阻燃剂进行表面改性；所述硅烷偶联剂选自乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷中的一种或至少两种以任意比例混合的混合物。
4.根据权利要求1所述的耐高温、防火绝缘加强型电力电缆，其特征在于：抗氧剂为受阻酚类抗氧剂和亚磷酸酯类抗氧剂按任意比例的混合物，其中，受阻酚类抗氧剂选择四[β-（3，5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯，或者N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺；亚磷酸酯类抗氧剂选择亚磷酸三壬基苯酯，或者三(2,4-二叔丁基苯基)亚磷酸酯。
5.一种如权利要求1所述的耐高温、防火绝缘加强型电力电缆，其特征在于制备包括以下步骤：
（1）按组成原料的重量份称取各原料，将酚醛树脂、高密度聚乙烯HDPE、改性丙烯酸树脂和纳米碳酸钙粉混合均匀，得到混合料A；
（2）在上述步骤（1）中的混合料A中按重量份加入阻燃剂、焙烧沸石粉、纳米碳酸钙粉、硅烷偶联剂、炭黑、钛酸酯、抗氧剂、硬脂酸钡、树脂粘结剂 、过氧化二烷烃，常温下低速搅拌1-2分钟，使得混合均匀，得到混合料B；
（3）将上述步骤（2）得到的混合料B加入开炼机和密炼机或双螺杆挤出机混炼、造粒，控制温度140-170℃，得到成品。
6.根据权利要求5所述的制备方法，其特征在于：所述的挤出机L/D＝20∶1～25∶1，转速50～70r/min；挤出温度：进料段120～140℃，压缩段160～180℃，均化段210～230℃，机头220～230℃。
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