CN103694543A - 物理共混法制备的硅烷自交联电缆料 - Google Patents
物理共混法制备的硅烷自交联电缆料 Download PDFInfo
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Abstract
本发明公开了一种物理共混法制备的硅烷自交联电缆料;所述物理共混法包括如下步骤:将包括聚烯烃、引发剂、抗氧剂、硅烷偶联剂、高效吸水剂的硅烷自交联电缆A料、包括聚烯烃、抗氧剂、抗铜剂、高效催化剂、润滑剂的硅烷自交联电缆B料加入150~220℃往复式单螺杆进行混炼;混炼完毕后的混合物输送至150~180℃单螺杆挤出机进行挤出造粒,风冷切粒、鼓风干燥,即得所述硅烷自交联电缆颗粒料。本发明的产品与以往化学法制备的硅烷自交联料相比,减少了因产水不充分造成的交联速度过慢现象出现;且产品性能完全符合国家GB/T10437-2008《电线电缆用可交联聚乙烯绝缘料》的相关要求。
Description
技术领域
本发明涉及电缆及其制备领域,具体涉及一种物理共混法制备的硅烷自交联电缆料。
背景技术
硅烷接枝聚乙烯交联作为中低压电缆中最常用的一种交联方法,已被大范围使用在电缆行业中。但硅烷接枝聚乙烯交联要求电缆挤出后,用热水或者水蒸气热处理一定时间才能得到交联的聚乙烯制品,这种工艺存在着交联速度慢、不均匀且能耗高等缺点。从满足客户需求的角度出发,室温自交联聚乙烯为此被研发出来。通过对室温自交联低密度聚乙烯结晶动力学的研究发现,为了得到交联速度快、交联度均匀、能耗低的硅烷接枝聚乙烯,可采用使水在体系内部形成的方法来制备自交联聚乙烯料,而以往通过化学法分解成水制备的自交联聚乙烯料则存在着因反应不够充分而导致电缆交联度不够的现象。
发明内容
本发明的目的在于克服上述温水硅烷交联聚乙烯电缆料耗时、耗能的不足之处,并针对以往化学法制备的硅烷自交联电缆料交联度不足现象加以改进,提供了一种物理共混法制备的硅烷自交联电缆料。本发明的物理共混法自交联电缆料因添加物完全采用吸收空气中水蒸汽的方法,避免了上述耗时、耗能、交联度不足等现象的发生。
本发明的目的是通过以下技术方案来实现的:
本发明涉及一种物理共混法制备的硅烷自交联电缆料,所述物理共混法包括如下步骤:
A、将包括聚烯烃、引发剂、抗氧剂、硅烷偶联剂、高效吸水剂的硅烷自交联电缆A料、包括聚烯烃、抗氧剂、抗铜剂、高效催化剂、润滑剂的硅烷自交联电缆B料加入150~220℃往复式单螺杆进行混炼;
B、混炼完毕后的混合物输送至150~180℃单螺杆挤出机进行挤出造粒,风冷切粒、鼓风干燥,即得所述硅烷自交联电缆颗粒料。风冷切粒、鼓风干燥代替以往的水冷切粒,使得电缆料在完全干燥的情况下打包。
上述硅烷自交联电缆A料、硅烷自交联电缆B料是采用高精度的失重喂料***加入往复式单螺杆;鼓风干燥后的颗粒料是由自动称重包装***实现全自动包装。
优选地,所述混炼过程中的四个温度段为:加料段150~160℃,输送段160~170℃,熔融段170~190℃,机头200~220℃。
优选地,所述造粒过程中的四个温度段为:加料段150~160℃,输送段160~165℃,熔融段165~175℃,机头175~180℃。
优选地,所述硅烷自交联电缆A料包括如下重量份数的各组分:
优选地,所述聚烯烃为线性低密度聚乙烯、低密度聚乙烯、乙酸醋酸乙烯共聚物中的一种或几种的混合,所述聚烯烃中醋酸乙烯的重量百分比含量(VA%)为26%~40%,熔融指数为2~20g/10min。作为材料的基体树脂,聚烯烃决定了材料的机械性能我电气性能以及分子链接枝量的多少,流动速率的快慢。
优选地,所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂1050、抗氧剂300中的一种或几种。抗氧剂在加工和使用过程中起到保护高效吸水剂,防止高效吸水剂因温度过高分级,并有防止材料老化的作用。
优选地,所述引发剂为过氧化二异丙苯、特丁基过氧化物、过氧化月桂酸叔丁酯、过氧化苯甲酰中的一种或几种。引发剂的加入引起了基体树脂的接枝;其含量的多少决定了接枝速率的快慢。
优选地,所述硅烷偶联剂为乙烯基三甲氧基硅烷A-171、乙烯基三乙氧基硅烷A-151、Y-氨丙基三乙氧基硅烷(KH550)中的一种或几种。硅烷偶联剂在混炼过程中可和基体树脂进行接枝反应,并在催化剂作用下和水发生交联反应。
优选地,所述高效吸水剂为高分子吸水树脂(SAP)、聚乙烯醇、橡胶消泡剂中的一种或几种。高效吸水剂的加入增加了材料的吸水性能,并有一定的润滑作用。
优选地,所述硅烷自交联电缆B料包括如下重量份数的各组分:
优选地,所述聚烯烃为线性低密度聚乙烯、低密度聚乙烯、乙酸醋酸乙烯共聚物中的一种或几种的混合,所述聚烯烃中醋酸乙烯的重量百分比含量为26%~40%,熔融指数为2~20。作为材料的基体树脂,聚烯烃决定了材料的机械性能我电气性能以及分子链接枝量的多少,流动速率的快慢。
优选地,所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂1050、抗氧剂300中的一种或几种。抗氧剂在加工和使用过程中起到保护A料中高效吸水剂,防止高效吸水剂因温度过高分级,并有防止材料老化的作用。
优选地,所述润滑剂是聚乙烯蜡、聚对苯二酰对苯二胺、盐酸苯丙醇胺中的一种或几种。其主要起到润滑增塑的作用。
优选地,所述高效催化剂是二月桂酸二丁基锡、二月桂酸二辛基锡、十二烷基苯磺酸、二月桂酸二丁基衍生物中的一种或几种。其含量多少影响了与水交联的速率。
本发明具有的有益效果为:本发明提供的物理共混法制备的硅烷自交联电缆料,其性能完全符合国家GB/T10437—2008《电线电缆用可交联聚乙烯绝缘料二》的相关要求,并其性能优于化学法制备的硅烷自交联电缆料。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
因以往通过化学法分解成水制备的自交联聚乙烯料则存在着因反应不够充分而导致电缆交联度不够的现象。故本专利采用物理共混法制备自交联电缆料,其添加物完全采用吸收空气中水蒸汽的方法,避免了上述现象的发生。并且要求其性能要满足相关的国家标准,由此形成的技术方案及重量份数配方组成是:
硅烷自交联电缆A料:
硅烷自交联电缆B料:
本发明获得的样品在常温放置3天后,与经6h水煮和3天后的化学法制备的硅烷自交联电缆料进行比较经过测试,获得如下表1所示的数据:
表1
由表1可知,共混法制备的样品在放置3天后性能上已经十分接近水煮6h后的试样,并且其性能要优于采用化学法制备的自交联电缆料。
具体的物理共混法制备的硅烷自交联电缆料见以下各实施例:
实施例1
本实施例涉及一种的物理共混法制备的硅烷自交联电缆料,包含的原料成分及重量份如下:
硅烷自交联电缆A料:
硅烷自交联电缆B料:
按照上述原料配比,采用高精度的失重喂料***,在150~220℃往复式单螺杆上进行混炼(混炼过程中的四个温度段为:加料段150~160℃,输送段160~170℃,熔融段170~190℃,机头200~220℃),混炼完毕后在150~180℃单螺杆进行造粒(造粒过程中的四个温度段为:加料段150~160℃,输送段160~165℃,熔融段165~175℃,机头175~180℃),风冷切粒、沸腾干燥、由自动称重包装***实现全自动包装,得到颗粒料。
实施例2
本实施例涉及一种的物理共混法制备的硅烷自交联电缆料,包含的原料成分及重量份如下:
硅烷自交联电缆A料:
硅烷自交联电缆B料:
按照上述原料配比,采用高精度的失重喂料***,在150~220℃往复式单螺杆上进行混炼(混炼过程中的四个温度段为:加料段150~160℃,输送段160~170℃,熔融段170~190℃,机头200~220℃),混炼完毕后在150~180℃单螺杆进行造粒(造粒过程中的四个温度段为:加料段150~160℃,输送段160~165℃,熔融段165~175℃,机头175~180℃),风冷切粒、沸腾干燥、由自动称重包装***实现全自动包装,得到颗粒料。
实施例3
本实施例涉及一种的物理共混法制备的硅烷自交联电缆料,包含的原料成分及重量份如下:
硅烷自交联电缆A料:
硅烷自交联电缆B料:
按照上述原料配比,采用高精度的失重喂料***,在150~220℃往复式单螺杆上进行混炼(混炼过程中的四个温度段为:加料段150~160℃,输送段160~170℃,熔融段170~190℃,机头200~220℃),混炼完毕后在150~170℃单螺杆进行造粒(造粒过程中的四个温度段为:加料段150~160℃,输送段160~165℃,熔融段165~175℃,机头175~180℃),风冷切粒、沸腾干燥、由自动称重包装***实现全自动包装,得到颗粒料。
实施例4
本实施例涉及一种的物理共混法制备的硅烷自交联电缆料,包含的原料成分及重量份如下:
硅烷自交联电缆A料:
硅烷自交联电缆B料:
按照上述原料配比,采用高精度的失重喂料***,在150~220℃往复式单螺杆上进行混炼(混炼过程中的四个温度段为:加料段150~160℃,输送段160~170℃,熔融段170~190℃,机头200~220℃),混炼完毕后在150~170℃单螺杆进行造粒(造粒过程中的四个温度段为:加料段150~160℃,输送段160~165℃,熔融段165~175℃,机头175~180℃),风冷切粒、沸腾干燥、由自动称重包装***实现全自动包装,得到颗粒料。
对比例1
本对比例涉及一种物理共混法制备的硅烷自交联电缆料,包含的原料成分及重量份同实施例3,所不同之处在于,所述硅烷自交联电缆A料不包含高效吸水剂。其制备方法同实施例3。
对比例2
本对比例涉及一种物理共混法制备的硅烷自交联电缆料,包含的原料成分及重量份同实施例4,所不同之处在于,所述硅烷自交联电缆B料不包含高效催化剂。其制备方法同实施例4。
以上实施例1~4以及对比例1、2采用JB/T10437-2004标准进行检测,结果见下表2。
表2 实施例性能测试结果
由表2可知,实施例3与实施例4在凝胶含量和热延伸上都高于未加入高效吸水剂的对比例1与未加入高效催化剂的对比例2。说明高效吸水剂、高效催化剂对电缆料的整体性能产生了协同提高作用。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。
Claims (11)
1.一种物理共混法制备的硅烷自交联电缆料,其特征在于,所述物理共混法包括如下步骤:
A、将包括聚烯烃、引发剂、抗氧剂、硅烷偶联剂、高效吸水剂的硅烷自交联电缆A料、包括聚烯烃、抗氧剂、抗铜剂、高效催化剂、润滑剂的硅烷自交联电缆B料加入150~220℃往复式单螺杆挤出机进行混炼;
B、混炼完毕后的混合物输送至150~180℃单螺杆挤出机进行挤出造粒,风冷切粒、鼓风干燥,即得所述硅烷自交联电缆颗粒料。
2.如权利要求1所述的物理共混法制备的硅烷自交联电缆料,其特征在于,所述混炼过程中的四个温度段为:加料段150~160℃,输送段160~170℃,熔融段170~190℃,机头200~220℃。
3.如权利要求1所述的物理共混法制备的硅烷自交联电缆料,其特征在于,所述造粒过程中的四个温度段为:加料段150~160℃,输送段160~165℃,熔融段165~175℃,机头175~180℃。
5.如权利要求4所述的物理共混法制备的硅烷自交联电缆料,其特征在于,所述聚烯烃为线性低密度聚乙烯、低密度聚乙烯、乙酸醋酸乙烯共聚物中的一种或几种的混合,所述聚烯烃中醋酸乙烯的重量百分比含量为26%~40%,熔融指数为2~20g/lOmin;所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂1050、抗氧剂300中的一种或几种。
6.如权利要求4所述的物理共混法制备的硅烷自交联电缆料,其特征在于,所述引发剂为过氧化二异丙苯、特丁基过氧化物、过氧化月桂酸叔丁酯、过氧化苯甲酰中的一种或几种。
7.如权利要求4所述的物理共混法制备的硅烷自交联电缆料,其特征在于,所述硅烷偶联剂为乙烯基三甲氧基硅烷A-171、乙烯基三乙氧基硅烷A-151、Y-氨丙基三乙氧基硅烷中的一种或几种。
8.如权利要求4所述的物理共混法制备的硅烷自交联电缆料,其特征在于,所述高效吸水剂为高分子吸水树脂、聚乙烯醇、橡胶消泡剂中的一种或几种。
10.如权利要求9所述的物理共混法制备的硅烷自交联电缆料,其特征在于,所述润滑剂是聚乙烯蜡、聚对苯二酰对苯二胺、盐酸苯丙醇胺中的一种或几种。
11.如权利要求9所述的物理共混法制备的硅烷自交联电缆料,其特征在于,所述高效催化剂是二月桂酸二丁基锡、二月桂酸二辛基锡、十二烷基苯磺酸、二月桂酸二丁基衍生物中的一种或几种。
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