CN103980600A - 一种超净纳米改性聚烯烃高压直流电缆料的制备方法 - Google Patents

一种超净纳米改性聚烯烃高压直流电缆料的制备方法 Download PDF

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CN103980600A
CN103980600A CN201410251465.4A CN201410251465A CN103980600A CN 103980600 A CN103980600 A CN 103980600A CN 201410251465 A CN201410251465 A CN 201410251465A CN 103980600 A CN103980600 A CN 103980600A
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党智敏
巫运辉
张翀
查俊伟
王思蛟
林祥
于凡
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Smart Grid Research Institute of SGCC
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Abstract

一种超净纳米改性聚烯烃高压直流电缆料的制备方法，属于电缆绝缘材料加工技术领域。其特征在于使用一种低沸点、易挥发的液体作为纳米粒子载体，将纳米粒子均匀粘附在聚烯烃颗粒表面，同时载体在纳米粒子均匀粘附于聚烯烃颗粒表面的过程中挥发，最后将表面均匀粘附纳米粒子的聚烯烃颗粒通过双螺杆挤出、造粒。通过该方法制备的超净纳米改性聚烯烃高压直流电缆料的绝缘性能优异。添加1wt％MgO纳米粒子的LDPE的直流击穿场强比纯LDPE提高接近一倍,纯LDPE的直流击穿场强为275.3kV/mm,添加1wt％MgO的LDPE的击穿场强为455.6kV/mm。添加1wt％MgO的LDPE抑制空间电荷能力得到明显提高。

Description

一种超净纳米改性聚烯烃高压直流电缆料的制备方法
技术领域
本发明涉及一种超净纳米改性聚烯烃高压直流电缆料的制备方法。属于电缆绝缘材料加工技术领域。
背景技术
近十年来，纳米改性聚烯烃用于制备高压绝缘材料被世界各大电气公司及研究机构所重视。2000年至今，J.K.Nelson等人的研究表明，纳米改性聚烯烃复合材料在树枝老化、空间电荷、局部放电、介电强度、介质损耗、电导等多方面都具有优异的性能，已成为高性能绝缘材料的发展方向。目前，塑料绝缘高压和超高压直流电缆的应用越来越受到国家相关部门的重视，市场需求几乎是指数式增长。国际上有瑞典ABB和日本J-PowerSystems Corporation等公司能够提供超高压塑料绝缘直流电缆；日本采用纳米MgO复合XLPE的技术成功研制出500kV高压直流塑料电缆，还在试验中，尚未推向市场。
制备超净纳米改性聚烯烃高压直流电缆料已经成为世界各国争相突破的技术难题。其中的难题之一：如何使纳米粒子均匀分散在聚烯烃中，而不引入任何杂质，从而制备性能优良的超净纳米改性聚烯烃高压直流电缆料。
纳米粒子由于具有表面效应，量子尺寸效应，小尺寸效应，宏观量子效应等特性，极易发生团聚，以致纳米粒子很难均匀分散在聚烯烃中。此外，如果采用加工助剂使纳米粒子均匀分散在聚烯烃中又会引入杂质。最终，导致制备的纳米改性聚烯烃高压直流电缆料性能远不及预期理论值。
发明内容
本发明的目的在于解决现有技术的难题，提供一种制备超净纳米改性聚烯烃高压直流电缆料的方法。该方法具有如下特点：设备要求低，工艺简单，易推广，实用性强，不引入杂质的情况下使纳米粒子较均匀地分散在聚烯烃基体中。
本发明的发明人在生产中发现，直接将纳米粒子与聚烯烃颗粒共混，因纳米粒子粒径小，在混料/加料的过程中直接从聚烯烃颗粒之间的缝隙沉入底部，导致纳米粒子在聚烯烃中局部积聚。其次，业界普遍采用加工助剂(如液体石蜡等)，通过高速搅拌使纳米粒子粘附在聚烯烃颗粒表面，挤出、造粒，制备纳米改性聚烯烃电缆料，但引入了杂质液体石蜡，这样会大大降低电缆料的电气性能。基于上述遇到的难题，本发明的构思方案是通过一种易挥发性的载体，将纳米粒子通过本身具有较高表面能粘附在聚烯烃颗粒表面，将载体通过升温挥发而不引入杂质，再通过熔融挤出造粒，最后得到超净纳米改性聚烯烃高压直流电缆料。
超净纳米改性聚烯烃高压直流电缆料的制备方法，是通过以下技术方案实现的：
1)将一定质量的纳米粒子与低沸点载体混合，形成悬浮液。纳米粒子所用载体为低沸点无水乙醇、无水甲醇、无水丙酮等具有较好挥发性液体，与聚烯烃无副作用，且不能溶解纳米粒子；纳米粒子为三氧化二铝Al2O3、氧化镁MgO、碳化硅SiC、二氧化硅SiO2等。
2)将1)得到的悬浮液超声分散一定时间，使纳米粒子解团聚，均匀分散在载体中。
3)将2)制备的纳米粒子悬浮液与聚烯烃颗粒在低于载体沸点下复合，搅拌，混合均匀。然后烘干，除去载体。
4)将3)中制备的纳米粒子/聚烯烃混合物，采用双螺杆挤出、造粒，最后制备出超净纳米改性聚烯烃高压直流电缆料。
本发明的关键在于选择一种不改变纳米粒子化学成份及结构的液态载体，载体必须是易挥发，不含水分。通过载体挥发使纳米粒子通过本身具有较高的表面能均匀粘附在聚烯烃颗粒表面，最后挤出造粒，制备出超净纳米改性聚烯烃高压直流电缆料。
本发明具有以下效果：
1)本发明所制备的超净纳米改性聚烯烃高压直流电缆料具有优良的电气性能，包括：优异的抑制空间电荷特性，较大地提高电缆料的直流击穿性能。
2)本发明所提供的制备超净纳米改性聚烯烃高压直流电缆料的方法具有设备成本低，工艺简单，适合工业化生产，不引入杂质，纳米改性后的电气性能提高显著。
附图说明
图1、纯净的聚乙烯颗粒形貌。
图2、用低沸点挥发性液体作为载体将4.5wt％无机纳米粒子粘附在聚乙烯颗粒表面。
图3、使用本发明方法制备的4.5wt％无机纳米粒子均匀分散在聚乙烯基体中的断面电镜图。
图4、直接将1wt％无机纳米粒子与聚烯烃共混制备的无机纳米粒子/LDPE绝缘电缆料在30kV/mm下的空间电荷分布。
图5、使用本法明方法制备的1％wt无机纳米粒子与聚烯烃制备的超净无机纳米粒子/LDPE绝缘电缆料在30kV/mm下的空间电荷分布。
图6、使用本发明方法制备的不同质量百分数的超净无机纳米粒子/LDPE的直流击穿场强。
具体实施方式
实施例1
1)选用低沸点挥发性液体为载体，纳米粒子为粒径50～80nm氧化镁，聚烯烃为低密度聚乙烯LDPE。
2)载体：纳米氧化镁：LDPE的质量之比为12:1:100。向1g纳米氧化镁中加入12g无水乙醇，用玻璃棒搅拌均匀，然后超声1.5h，制备出纳米氧化镁粒子分散液。
3)将制得的纳米氧化镁分散液与LDPE颗粒混合，搅拌均匀，制备出表面均匀粘附纳米氧化镁粒子的低密度LDPE颗粒，烘干，再通过双螺杆挤出、造粒，最后挤出得到混合均匀的超净纳米氧化镁改性低密度LDPE高压直流电缆料。
实施例2
1)选用低沸点挥发性液体为载体，纳米粒子为粒径100nm氧化铝，聚烯烃为低密度聚乙烯LDPE。
2)载体：纳米氧化铝：LDPE的质量之比为20:1:100。向1g纳米氧化铝中加入20g无水乙醇，用玻璃棒搅拌均匀，然后超声2h～3h，制备出纳米氧化铝颗粒分散液。
3)将制得纳米氧化铝分散液与LDPE颗粒粉料共混，搅拌均匀，烘干，制备出表面均匀粘附纳米氧化铝粒子的低密度LDPE颗粒。在60～70℃下干燥30～40min，再通过哈克MINILAB共混，最后挤出得到混合均匀的超净纳米氧化铝改性低密度LDPE高压直流电缆料。
实施例3
1)选用低沸点挥发性液体为载体，纳米粒子为粒径80nm二氧化硅，聚烯烃为聚丙烯PP。
2)载体：SiO2：PP的质量之比为15:1:100。向1g纳米SiO2加入15g丙酮，搅拌均匀，超声1～2h，制备得到纳米SiO2分散液。
3)将制得纳米SiO2分散液与PP颗粒混合均匀，50～60℃干燥40～60min，再最后通过哈克MINILAB，最后挤出得到混合均匀的超净纳米二氧化硅改性低密度LDPE高压直流电缆料。

Claims (2)

1.一种超净纳米改性聚烯烃高压直流电缆料的制备方法，其特征在于，使用一种低沸点、易挥发的液体作为纳米粒子载体，将纳米粒子均匀粘附在聚烯烃颗粒表面，同时载体在纳米粒子均匀粘附聚烯烃颗粒表面过程中挥发，最后将表面均匀粘附纳米粒子的聚烯烃颗粒通过双螺杆挤出造粒；
所述的低沸点、易挥发的载体为无水乙醇、无水甲醇、无水丙酮；其中载体必须是不改变纳米粒子的化学成份及结构，沸点低于80℃，不含有水分；纳米粒子为三氧化二铝Al2O3、氧化镁MgO、碳化硅SiC、二氧化硅SiO2。
2.根据权利要求1所述的一种超净纳米改性聚烯烃高压直流电缆料的制备方法，其特征在于，包括以下步骤：
1)将载体与纳米粒子按质量比为10～20：1混合后超声振荡分散大于1h，纳米粒子在超声过程中解团聚，分散均匀，得到分散性较好的悬浮液；
2)将1)得到的悬浮液与聚烯烃颗粒混合，搅拌均匀，烘干，制得表面均匀粘附纳米粒子的聚烯烃颗粒；
3)将粘附纳米粒子的聚烯烃颗粒挤出、造粒，制备出超净纳米改性聚烯烃高压直流电缆料。
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CN108485027A (zh) * 2018-03-16 2018-09-04 安徽滁州德威新材料有限公司 一种高压电缆绝缘超洁净直流母料及制备方法

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CN106867078A (zh) * 2017-03-06 2017-06-20 哈尔滨理工大学 一种纳米二氧化硅/低密度聚乙烯复合材料及其制备方法
CN107383538A (zh) * 2017-08-10 2017-11-24 全球能源互联网研究院 高压直流电缆用高分散纳米复合超净绝缘料及其制备方法
CN108485027A (zh) * 2018-03-16 2018-09-04 安徽滁州德威新材料有限公司 一种高压电缆绝缘超洁净直流母料及制备方法

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