CN111825913A - 一种高压直流电缆用纳米改性绝缘料及其制备方法 - Google Patents
一种高压直流电缆用纳米改性绝缘料及其制备方法 Download PDFInfo
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Abstract
本发明提供一种高压直流电缆用纳米改性绝缘料及其制备方法,所述绝缘料包括以下重量份数的各组分:50~70份的乙烯‑醋酸乙烯共聚物、15~50份的线性低密度聚乙烯、0.5~3份的马来酸酐、0.5~3份的引发剂、1~5份的溶剂、0.1~1份的抗氧剂、1‑5份的无机纳米粉体、0.05‑0.1份的分散剂、0.1‑3份的助交联剂。制备方法包括以下步骤:配备原料;混合均匀,预塑化;双阶双螺杆挤出机进行挤出混炼造粒;冷却过筛,磁选,得到本发明的绝缘料。本发明可以显著抑制空间电荷的注入,大幅提高电缆绝缘料的介电强度,适用于高压直流电缆绝缘。
Description
技术领域
本发明具体涉及一种高压直流电缆用纳米改性绝缘料及其制备方法。
背景技术
挤包绝缘塑料电力电缆具有体积小、质量轻、铺设容易、易于维护等优势,被广泛用于输配电工程中。柔性直流输电由于具有可单极运行、功率控制简单、线路损耗小、传输距离长,特别适用于不同频率的交流系统之间的联网以及长距离大功率海底输电。高压直流电缆是柔性输电的重要装备之一。然而,目前所采用的挤包绝缘塑料电缆绝大多数是交联聚乙烯绝缘电缆,主要适用于用于交流输电。在直流电场下,交联聚乙烯内会发生空间电荷注入,导致绝缘内局部电场畸变严重,使得电缆服役寿命变得很短。在交联聚乙烯绝缘中加入无机纳米粒子可以抑制空间电荷注入,然而,由于大多数无机纳米粒子与交联聚乙烯基体不相容,极易在交联聚乙烯中发生团聚,造成绝缘料的击穿强度大幅降低、限制了交联聚乙烯绝缘料在高压直流电缆中的应用。
发明内容
为解决上述技术问题,本发明提供了一种高压直流电缆用纳米改性绝缘料及其制备方法,抑制空间电荷的注入,降低载流子迁移率,使材料具备较高的击穿强度和较低的电导率。
本发明采用如下技术方案:
一种高压直流电缆用纳米改性绝缘料,按重量配比包括以下原料组成:
优选的,所述乙烯-醋酸乙烯共聚物是乙烯单体和醋酸乙烯在反应器中聚合所得,即EVA,所述乙烯-醋酸乙烯共聚物要求为:熔融指数3~7g/10min,醋酸乙烯质量分数15~30%;测试标准依据GB/T3682-2000,测试条件为温度190℃,负荷2.16Kg;材料的流动性好,分子链长度适中,可以确保马来酸酐有稳定的接枝点。
优选的,所述线性低密度聚乙烯是乙烯与α-烯烃在催化剂作用下,经高压或低压聚合而成的共聚物,即LLDPE,所述线性低密度聚乙烯要求为:熔融指数2~6g/10min,测试标准依据GB/T3682-2000,测试条件为温度190℃,负荷2.16Kg,增加材料的熔体强度,易于造粒。
优选的,所述α-烯烃选自丁烯-1、己烯-1、辛烯-1、四甲基戊烯-1中的一种。
优选的,所述马来酸酐,即MAH,为无色针状晶体,活性高,接枝率稳定。
优选的,所述引发剂选自过氧化二异丙基苯、2,5-二甲基-2,5双(叔丁基过氧化)己烷中一种或二种的混合物,提供自由基引发熔融共聚反应。
优选的,所述溶剂为丙酮、丁酮中的一种或二者的混合物,均匀分散马来酸酐和引发剂。
优选的,所述抗氧剂选自四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、硫代二丙酸二月桂酯中一种或二者的混合物,其中,四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯为受阻酚抗氧剂,热稳定性高,持效性长,延长材料的使用期限;硫代二丙酸二月桂酯为辅助抗氧剂,和酚类抗氧剂并用可产生协同效应。
优选地,所述的无机纳米粉体为氮化硼、氧化铝、氧化锆、氧化镁、氧化硅、钛酸锶、钛酸钡中的至少一种。
优选的,所述分散剂是硬脂酸锌、硬脂酸钙中一种或二者的混合物。
优选的,所述助交联剂选自三烯丙基异氰脲酸酯、三羟甲基丙烷三甲基丙烯酸酯中一种或二者的混合物,在材料中提供交联活性点,可以确保材料的交联度。
本发明还提供了一种高压直流电缆用纳米改性绝缘料的制备方法,包括以下步骤:
S1、按重量份数称取如下原料:50~70份的乙烯-醋酸乙烯共聚物、15~50份的线性低密度聚乙烯、0.5~3份的马来酸酐、0.5~3份的引发剂、1~5份的溶剂、0.1~1份的抗氧剂、1-5份的无机纳米粉体、0.05-0.1份的分散剂、0.1-3份的助交联剂;
S2、首先将马来酸酐、引发剂加到溶剂中溶解均匀;
S3、将上述溶液与乙烯-醋酸乙烯共聚物投入高速捏合机,高速捏合3分钟后,加入线性低密度聚乙烯高速捏合2分钟,再将抗氧剂、分散剂投入高速捏合机,高速捏合3分钟,后将无机纳米粉体投入捏合机,高速捏合2分钟后快速加入助交联剂低速捏合3分钟,混合均匀,预塑化;
S4、双阶双螺杆挤出机进行挤出混炼造粒,挤出机温度设置范围160℃-220℃;
S5、冷却过筛,磁选,得到本发明的高压直流电缆绝缘料。
本发明的有益效果:本发明能够有效的抑制空间电荷的注入,降低载流子迁移率,使材料具备较高的击穿强度和较低的电导率,大幅提高电缆绝缘料的介电强度,可以用作高压直流电缆的绝缘料。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面进一步阐述本发明。
本发明的一种高压直流电缆用纳米改性绝缘料,各实施例的组分及重量份数组成见表1:
表1
表2是各实施例中具体使用的原料组分:
表2
本发明还提供了一种高压直流电缆用纳米改性绝缘料的制备方法,包括以下步骤:
步骤一:将所述原料按质量份数称取,
步骤二:首先将马来酸酐,引发剂加到溶剂中溶解均匀,
步骤三:将上述与乙烯-醋酸乙烯共聚物投入高速捏合机,高速捏合3分钟后,加入线性低密度聚乙烯高速捏合2分钟,再将抗氧剂、分散剂投入高速捏合机,高速捏合3分钟,后将无机纳米粉体投入捏合机,高速捏合2分钟后快速加入助交联剂低速捏合3分钟,混合均匀,预塑化;
步骤四:双阶双螺杆挤出机进行挤出混炼造粒,挤出机温度设置范围160℃-220℃;
步骤五:冷却过筛,磁选,得到本发明的高耐磨电缆料。
对比例1
称取如下重量份的原料:线性低密度聚乙烯40份、抗氧剂0.5份、助交联剂1.5份;将上述原料投入高速捏合机,高速捏合5分钟,混合均匀,预塑化;经过双阶双螺杆挤出机进行挤出混炼造粒,冷却过筛,磁选,得到对比例1的电缆料。
对比例2
称取如下重量份的原料:线性低密度聚乙烯40份、抗氧剂0.5份、助交联剂1.5份、无机纳米粉体2.5份;将上述原料投入高速捏合机,高速捏合5分钟,混合均匀,预塑化;经过双阶双螺杆挤出机进行挤出混炼造粒,冷却过筛,磁选,得到对比例2的电缆料。
测试过程:
取实施例1~6和比较例1~2所制备的电缆料,均经过平板硫化后制样测试。
利用PEA法对各试样进行空间电荷测试,先分别在10kV/mm,30kV/mm和50kV/mm场强下进行30min时长的加压测试。
按照上述测试标准,根据是否有明显的空间电荷积聚现象进行评价,测试结果见表3:
表3
场强 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 对比例1 | 对比例2 |
10kV/mm | 无 | 无 | 无 | 无 | 无 | 无 | 少量 | 无 |
30kV/mm | 无 | 无 | 无 | 无 | 无 | 无 | 明显 | 少量 |
50kV/mm | 无 | 少量 | 无 | 无 | 少量 | 少量 | 明显 | 明显 |
从表3中可以看出,在10kV/mm场强下,只有对比例1出现少量的空间电荷积聚现象;在30kV/mm场强下,对比例2开始出现少量空间电荷积聚现象,而比较例1已经出现明显的空间电荷积聚现象;在50kV/mm场强下,比较例1和2均已经出现明显的空间电荷积聚现象,实施例2、5、6也开始出现少量空间电荷积聚现象,而实施例1、3、4仍然未检测到空间电荷积聚现象。此结果说明,相较于纯线性低密度聚乙烯,本发明实现了对材料内部空间电荷积聚现象的有效抑制,可以用作高压直流电缆的绝缘料。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (9)
2.根据权利要求1所述的一种高压直流电缆用纳米改性绝缘料,其特征在于,所述线性低密度聚乙烯是乙烯与α-烯烃在催化剂作用下,经高压或低压聚合而成的共聚物,所述α-烯烃选自丁烯-1、己烯-1、辛烯-1、四甲基戊烯-1中的一种。
3.根据权利要求1所述的一种高压直流电缆用纳米改性绝缘料,其特征在于,所述引发剂选自过氧化二异丙基苯、2,5-二甲基-2,5双(叔丁基过氧化)己烷中一种或二种的混合物。
4.根据权利要求1所述的一种高压直流电缆用纳米改性绝缘料,其特征在于,所述溶剂为丙酮、丁酮中的一种或二者的混合物。
5.根据权利要求1所述的一种高压直流电缆用纳米改性绝缘料,其特征在于,所述抗氧剂选自四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、硫代二丙酸二月桂酯中一种或二者的混合物。
6.根据权利要求1所述的一种高压直流电缆用纳米改性绝缘料,其特征在于,所述的无机纳米粉体为氮化硼、氧化铝、氧化锆、氧化镁、氧化硅、钛酸锶、钛酸钡中的至少一种。
7.根据权利要求1所述的一种高压直流电缆用纳米改性绝缘料,其特征在于,所述分散剂是硬脂酸锌、硬脂酸钙中一种或二者的混合物。
8.根据权利要求1所述的一种高压直流电缆用纳米改性绝缘料,其特征在于,所述助交联剂选自三烯丙基异氰脲酸酯、三羟甲基丙烷三甲基丙烯酸酯中一种或二者的混合物。
9.一种高压直流电缆用纳米改性绝缘料的制备方法,其特征在于,包括以下步骤:
S1、按重量份数称取如下原料:50~70份的乙烯-醋酸乙烯共聚物、15~50份的线性低密度聚乙烯、0.5~3份的马来酸酐、0.5~3份的引发剂、1~5份的溶剂、0.1~1份的抗氧剂、1-5份的无机纳米粉体、0.05-0.1份的分散剂、0.1-3份的助交联剂;
S2、首先将马来酸酐、引发剂加到溶剂中溶解均匀;
S3、将上述溶液与乙烯-醋酸乙烯共聚物投入高速捏合机,高速捏合3分钟后,加入线性低密度聚乙烯高速捏合2分钟,再将抗氧剂、分散剂投入高速捏合机,高速捏合3分钟,后将无机纳米粉体投入捏合机,高速捏合2分钟后快速加入助交联剂低速捏合3分钟,混合均匀,预塑化;
S4、双阶双螺杆挤出机进行挤出混炼造粒,挤出机温度设置范围160℃-220℃;
S5、冷却过筛,磁选,得到本发明的高压直流电缆绝缘料。
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