Article(id=1304921526868923030, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921526004904728, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2026.03.003, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1751212800000, receivedDateStr=2025-06-30, revisedDate=1756137600000, revisedDateStr=2025-08-26, acceptedDate=null, acceptedDateStr=null, onlineDate=1789047136275, onlineDateStr=2026-09-10, pubDate=1773936000000, pubDateStr=2026-03-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1789047136275, onlineIssueDateStr=2026-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1789047136275, creator=13701087609, updateTime=1789047136275, updator=13701087609, issue=Issue{id=1304921526004904728, tenantId=1146029695717560320, journalId=1149653034449285133, year='2026', volume='59', issue='3', pageStart='1', pageEnd='154', issueExtLink='null', onlineDate='null', pubDate='1773936000000', pubDateStr='2026-03-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1789047136068, creator='13701087609', updateTime=1789118116024, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1305219237560217894, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921526004904728, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1305219237560217895, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921526004904728, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=19, endPage=30, ext={EN=ArticleExt(id=1304921527288353431, articleId=1304921526868923030, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Design and performance of polypropylene-based cable insulation materials containing a bimodal distribution of elastomers, columnId=1304921526780850970, journalTitle=Insulating Materials, columnName=Special Issue on Low-carbon Environmental Protection Advanced Insulation Materials, runingTitle=null, highlight=null, articleAbstract=

This study aims to prepare high-performance polypropylene (PP) insulation materials and investigate the enhancement mechanism of their properties. By combining in-reactor alloying and blending modification technologies, PP insulation materials with elastomer mass fractions of 20% to 30% for high-voltage cables were prepared. The interfacial compatibility between the elastomer and PP matrix and its impact on the performance of the PP insulation material were studied. The results show that the propylene-based elastomer can effectively improve the interfacial compatibility between elastomers and PP matrix, thereby reducing interfacial defects. The "bimodal" particle size distribution design of elastomers successfully balances the dual effects of the elastomer on mechanical toughness and electrical strength of PP insulaton materials, realizing the synergistic improvement in mechanical toughness, electric strength, and thermal stability, demonstrating excellent overall performance. Moreover, the prepared PP cable material possesses good processing adaptability.

, authors=Yunpeng ZHAN1, Shuai HOU1, Yajie CAO1, Mingli FU1, Yanfei LI2, Lingmeng FAN2, authorsList=Yunpeng ZHAN, Shuai HOU, Yajie CAO, Mingli FU, Yanfei LI, Lingmeng FAN, authorCompany=null, correspAuthors=null, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1304921529372922544, articleId=1304921526868923030, tenantId=1146029695717560320, journalId=1149653034449285133, language=CN, title=含“双峰”尺寸分布弹性体的聚丙烯电缆绝缘材料体系设计与性能研究, columnId=1304921527053480732, journalTitle=绝缘材料, columnName=低碳环保先进绝缘材料专题, runingTitle=null, highlight=null, articleAbstract=

本文旨在制备高性能的聚丙烯(PP)绝缘材料,并研究其性能提升机制。通过结合釜内合金技术和共混改性技术,制备了弹性体质量分数为20%~30%的高压电缆用PP绝缘材料,研究了弹性体与PP基体之间的界面相容性及其对PP绝缘材料性能的影响。结果表明:丙烯基弹性体能够有效提高弹性体与PP基体的界面相容性,减少界面缺陷;采用“双峰”分布的弹性体粒子尺寸设计,成功平衡了弹性体对PP绝缘材料力学韧性和耐电强度的双重影响,从而实现力学韧性、电气强度、热稳定性等性能参数的协同提升,展现了优异的综合性能。此外,所制备的PP电缆材料具有良好的加工适应性。

, authors=展云鹏1, 侯帅1, 曹亚杰1, 傅明利1, 李艳飞2, 樊灵孟2, authorsList=展云鹏, 侯帅, 曹亚杰, 傅明利, 李艳飞, 樊灵孟, authorCompany=null, correspAuthors=null, authorNote=

展云鹏(1994-),男(汉族),辽宁鞍山人,高级工程师,主要从事高压电缆及聚合物绝缘材料的研究

傅明利(1962-),男(汉族),陕西宝鸡人,正高级工程师,主要从事高电压设备安全运行及资产全生命周期管理、高电压交直流绝缘、绝缘系统故障诊断和新型绝缘材料的应用技术的研究。

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展云鹏(1994-),男(汉族),辽宁鞍山人,高级工程师,主要从事高压电缆及聚合物绝缘材料的研究

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展云鹏(1994-),男(汉族),辽宁鞍山人,高级工程师,主要从事高压电缆及聚合物绝缘材料的研究

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傅明利(1962-),男(汉族),陕西宝鸡人,正高级工程师,主要从事高电压设备安全运行及资产全生命周期管理、高电压交直流绝缘、绝缘系统故障诊断和新型绝缘材料的应用技术的研究。

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傅明利(1962-),男(汉族),陕西宝鸡人,正高级工程师,主要从事高电压设备安全运行及资产全生命周期管理、高电压交直流绝缘、绝缘系统故障诊断和新型绝缘材料的应用技术的研究。

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Polymer,2020,202:122674., articleTitle=Insulative ethylene-propylene copolymer-nanostructured polypropylene for high-voltage cable insulation applications, refAbstract=null), Reference(id=1304921539829322540, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, doi=null, pmid=null, pmcid=null, year=2023, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=19, rfOrder=29, authorNames=鲍国栋, journalName=null, refType=null, unstructuredReference=鲍国栋.聚丙烯接枝改性直流电缆空间电荷特性研究[D].北京:华北电力大学,2023., articleTitle=聚丙烯接枝改性直流电缆空间电荷特性研究, refAbstract=null), Reference(id=1304921539892237102, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, doi=null, pmid=null, pmcid=null, year=2023, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=19, rfOrder=30, authorNames=BAO Guodong, journalName=null, refType=null, unstructuredReference=BAO Guodong. Study on space charge characteristics of grafted polypropylene DC cable[D]. Beijing: North China Electric Power University,2023., articleTitle=Study on space charge characteristics of grafted polypropylene DC cable, refAbstract=null), Reference(id=1304921540185838383, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, doi=null, pmid=null, pmcid=null, year=2017, volume=33, issue=4, pageStart=27, pageEnd=33, url=null, language=null, rfNumber=20, rfOrder=31, authorNames=ANDRISCH T, VAUGHAN A, STEVENS G C, journalName=IEEE Electrical Insulation Magazine, refType=null, unstructuredReference=ANDRISCH T, VAUGHAN A, STEVENS G C. Novel insulation materials for high voltage cable systems[J]. 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Exploration on loca-lization application of environmentally friendly polypropylene insulated power cable[J]. 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ArticleFig(id=1304921533714027253, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=EN, label=Fig.9, caption=Rheological test results and variation in die-exit expansion rate during extrusion process of sample 3-3, figureFileSmall=yfgXX+YZa3Kca2K/i/fygQ==, figureFileBig=rGR08Bh7lsv6sBh0eTNgtw==, tableContent=null), ArticleFig(id=1304921533785330422, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=CN, label=图9, caption=优选3-3样品的流变测试结果及挤出加工过程中离模膨胀率变化, figureFileSmall=yfgXX+YZa3Kca2K/i/fygQ==, figureFileBig=rGR08Bh7lsv6sBh0eTNgtw==, tableContent=null), ArticleFig(id=1304921533953102584, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=EN, label=Table 1, caption=

The physical property parameters of raw materials

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产品牌号共聚弹性体质量分数/%密度/(g/cm3)熔体流动速率/(g/10 min)重均分子量/(×105)
PP-1#280.902.53.80
PP-2#400.911.33.45
), ArticleFig(id=1304921534322201337, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=CN, label=表1, caption=

原材料的相关物性参数

, figureFileSmall=null, figureFileBig=null, tableContent=
产品牌号共聚弹性体质量分数/%密度/(g/cm3)熔体流动速率/(g/10 min)重均分子量/(×105)
PP-1#280.902.53.80
PP-2#400.911.33.45
), ArticleFig(id=1304921534414476027, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=EN, label=Table 2, caption=

The component of polypropylene insulation materials with different elastomer content

, figureFileSmall=null, figureFileBig=null, tableContent=
样品编号质量分数/%
PP-1#PP-2#E1
1-18020
1-27030
2-18020
2-27030
), ArticleFig(id=1304921534754214652, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=CN, label=表2, caption=

不同弹性体含量聚丙烯绝缘材料的组成

, figureFileSmall=null, figureFileBig=null, tableContent=
样品编号质量分数/%
PP-1#PP-2#E1
1-18020
1-27030
2-18020
2-27030
), ArticleFig(id=1304921534825517821, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=EN, label=Table 3, caption=

The thermal elongation properties of samples with different elastomer content

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样品编号初始长度/cm热变形后长度/cm负荷形变率/%永久形变率/%
1-12.002.021.01.0
1-22.002.021.51.0
2-12.002.3620.018.0
2-22.002.4826.024.0
), ArticleFig(id=1304921535156867839, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=CN, label=表3, caption=

不同弹性体含量样品热延伸性能

, figureFileSmall=null, figureFileBig=null, tableContent=
样品编号初始长度/cm热变形后长度/cm负荷形变率/%永久形变率/%
1-12.002.021.01.0
1-22.002.021.51.0
2-12.002.3620.018.0
2-22.002.4826.024.0
), ArticleFig(id=1304921535249142528, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=EN, label=Table 4, caption=

The component of polypropylene insulation materials compounded with different PP-based resins

, figureFileSmall=null, figureFileBig=null, tableContent=
样品编号质量分数/%
PP-1#PP-2#E1
3-1155530
3-2205030
3-3254530
3-4304030
3-5353530
), ArticleFig(id=1304921535328834305, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=CN, label=表4, caption=

不同PP基础树脂复配的聚丙烯绝缘材料组成

, figureFileSmall=null, figureFileBig=null, tableContent=
样品编号质量分数/%
PP-1#PP-2#E1
3-1155530
3-2205030
3-3254530
3-4304030
3-5353530
), ArticleFig(id=1304921535576298243, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=EN, label=Table 5, caption=

Thermal elongation performance of insulation materials with different PP-based resins

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样品编号初始长度/cm热变形后长度/cm负荷伸长率/%永久形变率/%
3-12.002.2815.014.0
3-22.002.2413.012.0
3-32.002.105.55.0
3-42.002.064.03.0
3-52.002.042.02.0
), ArticleFig(id=1304921535643407108, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=CN, label=表5, caption=

不同PP基础树脂复配绝缘材料的热延伸性能

, figureFileSmall=null, figureFileBig=null, tableContent=
样品编号初始长度/cm热变形后长度/cm负荷伸长率/%永久形变率/%
3-12.002.2815.014.0
3-22.002.2413.012.0
3-32.002.105.55.0
3-42.002.064.03.0
3-52.002.042.02.0
), ArticleFig(id=1304921535714710277, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=EN, label=Table 6, caption=

Grain size of sample 3-3 and the compounded matrix resins

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样品晶面2θ/(°)半峰宽/radL/nm
3-3(110)14.20.6312.1
PP-1#(110)14.20.6212.2
PP-2#(110)14.20.6312.1
), ArticleFig(id=1304921535987340038, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921526868923030, language=CN, label=表6, caption=

样品3-3与复配基体树脂的晶粒尺寸

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样品晶面2θ/(°)半峰宽/radL/nm
3-3(110)14.20.6312.1
PP-1#(110)14.20.6212.2
PP-2#(110)14.20.6312.1
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含“双峰”尺寸分布弹性体的聚丙烯电缆绝缘材料体系设计与性能研究
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展云鹏 1 , 侯帅 1 , 曹亚杰 1 , 傅明利 1 , 李艳飞 2 , 樊灵孟 2
绝缘材料 | 低碳环保先进绝缘材料专题 2026,59(3): 19-30
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绝缘材料 |低碳环保先进绝缘材料专题 2026 , 59 (3) : 19 -30
含“双峰”尺寸分布弹性体的聚丙烯电缆绝缘材料体系设计与性能研究
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傅明利(1962-),男(汉族),陕西宝鸡人,正高级工程师,主要从事高电压设备安全运行及资产全生命周期管理、高电压交直流绝缘、绝缘系统故障诊断和新型绝缘材料的应用技术的研究。

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展云鹏1, 侯帅1, 曹亚杰1, 傅明利1, 李艳飞2, 樊灵孟2
作者信息
  • 1南方电网科学研究院有限责任公司,广东 广州 510663
  • 2中国南方电网有限责任公司,广东 广州 510663
作者简介:

展云鹏(1994-),男(汉族),辽宁鞍山人,高级工程师,主要从事高压电缆及聚合物绝缘材料的研究

傅明利(1962-),男(汉族),陕西宝鸡人,正高级工程师,主要从事高电压设备安全运行及资产全生命周期管理、高电压交直流绝缘、绝缘系统故障诊断和新型绝缘材料的应用技术的研究。

Design and performance of polypropylene-based cable insulation materials containing a bimodal distribution of elastomers
Yunpeng ZHAN1, Shuai HOU1, Yajie CAO1, Mingli FU1, Yanfei LI2, Lingmeng FAN2
Affiliations
  • 1Electric Power Research Institute, China Southern Power Grid, Guangzhou 510663, China
  • 2China Southern Power Grid Company Limited, Guangzhou 510663, China
出版时间: 2026-03-20 doi: 10.16790/j.cnki.1009-9239.im.2026.03.003
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本文旨在制备高性能的聚丙烯(PP)绝缘材料,并研究其性能提升机制。通过结合釜内合金技术和共混改性技术,制备了弹性体质量分数为20%~30%的高压电缆用PP绝缘材料,研究了弹性体与PP基体之间的界面相容性及其对PP绝缘材料性能的影响。结果表明:丙烯基弹性体能够有效提高弹性体与PP基体的界面相容性,减少界面缺陷;采用“双峰”分布的弹性体粒子尺寸设计,成功平衡了弹性体对PP绝缘材料力学韧性和耐电强度的双重影响,从而实现力学韧性、电气强度、热稳定性等性能参数的协同提升,展现了优异的综合性能。此外,所制备的PP电缆材料具有良好的加工适应性。

聚丙烯  /  本征型弹性体  /  共混改性  /  力学性能  /  电气性能

This study aims to prepare high-performance polypropylene (PP) insulation materials and investigate the enhancement mechanism of their properties. By combining in-reactor alloying and blending modification technologies, PP insulation materials with elastomer mass fractions of 20% to 30% for high-voltage cables were prepared. The interfacial compatibility between the elastomer and PP matrix and its impact on the performance of the PP insulation material were studied. The results show that the propylene-based elastomer can effectively improve the interfacial compatibility between elastomers and PP matrix, thereby reducing interfacial defects. The "bimodal" particle size distribution design of elastomers successfully balances the dual effects of the elastomer on mechanical toughness and electrical strength of PP insulaton materials, realizing the synergistic improvement in mechanical toughness, electric strength, and thermal stability, demonstrating excellent overall performance. Moreover, the prepared PP cable material possesses good processing adaptability.

polypropylene  /  intrinsic elastomers  /  blending modification  /  mechanical properties  /  electrical properties
展云鹏, 侯帅, 曹亚杰, 傅明利, 李艳飞, 樊灵孟. 含“双峰”尺寸分布弹性体的聚丙烯电缆绝缘材料体系设计与性能研究. 绝缘材料, 2026 , 59 (3) : 19 -30 . DOI: 10.16790/j.cnki.1009-9239.im.2026.03.003
Yunpeng ZHAN, Shuai HOU, Yajie CAO, Mingli FU, Yanfei LI, Lingmeng FAN. Design and performance of polypropylene-based cable insulation materials containing a bimodal distribution of elastomers[J]. Insulating Materials, 2026 , 59 (3) : 19 -30 . DOI: 10.16790/j.cnki.1009-9239.im.2026.03.003
电缆是电力传输系统的核心组成部分,在高压和超高压输电线路中,电缆绝缘材料的性能决定了其耐受高电场强度和极端环境的能力。优异的电缆绝缘材料不仅能够延长电缆的使用寿命,还能降低电力传输过程中的能量损失,从而提高整体电力系统的效率和稳定性。随着电力传输和电力分配系统的快速发展,对高性能电缆绝缘材料的需求愈发迫切。目前,交联聚乙烯(XLPE)由于其优异的电气性能、机械强度和耐热性能,已成为中高压电缆绝缘材料的主流选择。通过化学手段,在聚乙烯(PE)中引入交联结构,可提升聚乙烯的耐热和耐老化性能,使其能够在更高的工作温度下保持稳定的理化特性和电气性能。然而,XLPE也存在一些不可忽视的缺点:在生产过程中需要进行脱气、交联处理,生产能耗大,工艺复杂;交联副产物易在绝缘层中形成杂质,进而积聚电荷,导致电击穿;不可逆的交联结构限制其回收再利用,造成了资源浪费和环境污染;在高温条件下的热老化和应力裂化问题限制了其长期使用寿命[1]
相比之下,聚丙烯(PP)作为一种具有潜力的电缆绝缘材料,因其独特的材料特性和环保优势而引起广泛关注。作为热塑性材料,PP拥有可熔融再加工的特性,可进行回收和再利用,有效减少废弃物的产生,符合全球对绿色环保和可持续发展的要求。PP的熔点较高,约为160~170℃,比XLPE更具耐热性,更契合当今社会对大容量输电的要求。PP的生产过程不需要复杂的交联工艺,可显著降低能耗,简化生产流程,从而提高生产效率,减少潜在的杂质含量,提高材料的纯净度和电气性能。但是,PP较高的刚度和较差的机械韧性限制了其在电缆绝缘材料中的广泛应用[2-3]。针对这一瓶颈问题,研究人员提出了弹性体增韧改性策略,实现方式主要包括共混改性和共聚改性。共混改性是通过将PP与弹性体进行物理混合,改善其韧性和耐低温性能。常用的弹性体包括乙丙橡胶(EPR)、三元乙丙橡胶(EPDM)或苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物(SEBS)。该方法通过引入弹性体相,在PP基体中形成分散相,从而产生界面银纹或剪切带,提高力学韧性。共聚改性是通过在PP的聚合过程中引入其他单体(如乙烯),破坏分子链的规整性,降低材料的结晶能力,形成无规共聚物或嵌段共聚物,从而提高力学韧性和低温下的力学性能。釜内合金技术是共聚改性中常用的一种技术,在聚合反应釜内,通过控制不同单体的加入顺序和比例、催化剂类型及反应条件,实现PP与其他单体(如乙烯、丁烯等)的原位共聚,制备出结构均匀、性能可调的PP釜内合金树脂。
弹性体增韧改性PP材料通常需要添加较高含量的弹性体,才能有效改善力学韧性。而且低熔点、低结晶度的弹性体不仅会降低材料的耐热性能,还会与PP产生相界面缺陷,引发局部电场畸变,降低绝缘材料的电气强度和体积电阻率等电气性能参数。因此,PP电缆用绝缘材料开发的关键技术问题之一就是实现PP绝缘材料的力学韧性、电气性能和耐热性能的协同提升。
本文结合釜内合金技术和物理共混改性技术,在PP基体中构筑呈现“双峰”分布的增韧弹性体形貌,由PP釜内合金中的本征型弹性体贡献小尺寸部分,由外加弹性体贡献大尺寸部分,从而优化增韧弹性体的尺寸与分散形态,得到界面相容性良好的相态结构,实现在较低弹性体含量下PP绝缘材料力学韧性、电气性能以及耐热性能的平衡,为研发具有优异性能的PP绝缘材料提供参考。
本文选用的PP树脂原料为中国石化生产的含本征型弹性体(乙烯-丙烯共聚弹性体)的PP釜内合金,相关物性参数如表1所示,其中乙烯含量越高,弹性体相的质量分数越高。丙烯基弹性体E1为美国埃克森美孚公司生产,其密度为0.874 g/cm³,乙烯质量分数为11%,熔体流动速率为2.5 g/10 min。
采用转矩共混制备测试样品,将PP釜内合金(质量分数为70%~80%)和弹性体原料(质量分数为20%~30%)同时放入转矩腔中熔融塑化,转矩温度设置为180℃,转子速度为60 r/min,共混10 min后取出。将转矩共混后样品采用模压成型制备测试样品。首先将共混样品在180℃下预热10 min,然后在180℃、10 MPa条件下热压5 min,最后在10 MPa压力下经过循环水冷却3 min得到片状样品。
利用扫描电子显微镜(SEM,Inspect F型,FEI公司)观察样品的微观形貌,测试加速电压为5 kV。测试前,将厚度为1 mm的PP绝缘样品在液氮中低温脆断,随后置于60℃的正庚烷中刻蚀12 h,洗涤干燥后,对刻蚀脆断面进行喷金处理,通过SEM观测样品断面的形貌,并使用Nano Measure软件对SEM图像中的橡胶粒子进行粒径统计。
将模压PP片状样品裁成尺寸为15 mm×15 mm的方形薄片,利用X射线衍射仪(UltimaIV型,Rigaku公司)表征其晶体结构,靶材为CuKα,波长λ=0.154 nm,测试范围2θ为2°~80°,步长为0.02°,检测不同晶面的衍射信号。采用Scherrer公式计算样品的平均晶粒尺寸(L),如式(1)所示。
L=kλBcosθ
式(1)中:k=0.89;B为PP特征晶面衍射峰的半高峰宽。
使用差示扫描量热仪(DSC250型,TA Instruments)表征样品的晶体结构。取5~10 mg样品,在N2氛围下,以5℃/min的升温速率将样品由40℃加热至200℃,观测晶体熔融行为,记录升温过程中的热流信号。利用升温曲线计算结晶度(χc),如式(2)所示。
χc=ΔHmωΔHm0×100%
式(2)中:Hm0为100%结晶PP的熔融焓,其值为209 J/g;ΔHm为DSC测试样品熔融焓;ω为共混样品中PP釜内合金的质量分数。
根据GB/T 2951.11—2008,将样品裁制成尺寸为75 mm×4 mm的哑铃型标准试样,使用电子万能试验机(Model 5967型,Instron Instrument)在室温下进行拉伸测试。拉伸速率为250 mm/min,夹头间距为50 mm。每组样品至少测5次,结果取平均值。
按照GB/T 9341—2008使用电子万能试验机进行弯曲性能测定,试样尺寸为80 mm×10 mm×4 mm,测试标距设定为64 mm,弯曲速度为2 mm/min,在3.5%应变(对应规定的挠度)下测试。每组样品至少测试5次,结果取平均值。
使用计算机控制电压击穿试验仪(ZJC-100 kV型,北京航天纵横检测仪器有限公司)测试样品的交流击穿电压(U),升压速率为0.5 kV/s,每个样品取10个点进行测试,利用U和样品厚度d(本研究中d=1 mm)计算电气强度,如式(3)所示。采用双参数Weibull分布对电气强度进行分析,如式(4)所示。
E=Ud
PE=1-exp-EE0β
式(4)中:P(E)为累计失效概率;E为实际测试电气强度;E0为累计失效概率达63.2%时的特征电气强度;β为形状参数,表征击穿数据的分散程度。
使用空间电荷测试装置(HY-PEA-DPT01型,上海荷仪电气有限公司)通过电声脉冲法(PEA)研究PP绝缘样品的空间电荷特性。对厚度为200 μm、直径为8 cm的样品在30 kV/mm电场强度下进行3 600 s的极化,试验温度为25℃。由于空间电荷的积累,样品内部的电场可能会失真,极化过程中的电场畸变率ΔE由式(5)计算。
ΔE=Emax-EavEav
式(5)中:Emax为极化过程中样品内部电场的最大绝对值;Eav为施加的理想电场。
使用高阻计(ZC36型,日置(上海)测量技术有限公司)测试样品的电阻,测试电压为 1 kV,极化时间为1 min。每种样品测试3次,取平均值为最终结果。其中样品厚度为1 mm,由测厚仪(CHY-C2A型,济南兰光机电技术有限公司,精度为0.001 mm)测得,再由式(6)计算体积电阻率。
ρv=RxAh
式(6)中:ρv为体积电阻率;Rx为测试电阻;A为样品的有效面积;h为样品厚度。
取与拉伸性能测试相同的试样,按照GB/T 2951.12—2008要求将试样放置在温度为150℃的热延伸试验箱中维持15 min,载荷为0.2 N/mm2,待试样冷却后,测试试样长度并换算试样永久形变率,由此检验共混材料的耐高温性能。
使用精密LCR数字电桥(2830型,常州同惠电子股份有限公司)测试样品(厚度为1 mm)的介电常数和介质损耗因数,测试电压为1 kV,测试频率为50 Hz。每种样品测试3次,取平均值为最终结果。
将双螺杆挤出后的共混粒料从固定尺寸为10 cm×0.1 cm的扁平口模挤出,待样品冷却后,测定样品的横截面积,沿横截面积的宽度方向测试10次,结果取平均值。将测试结果与口模面积作比较,记为挤出过程的离模膨胀率,计算式如式(7)所示。
B=As-AmAm
式(7)中:As为样品的横截面积;Am为模口截面积;B为离模膨胀率。
使用旋转流变仪(MCR302e型,奥地利安东帕有限公司)进行测试,选用平行板夹具,其直径为25 mm,板间距为1 mm,采用频率扫描振荡测试,频率范围为0.1~100 rad/s,测试温度为200℃。
一般而言,聚丙烯物理共混改性研究中,弹性体的引入能有效改善PP的断裂伸长率、弯曲模量等。但当弹性体质量分数较大(>30%)时,常造成PP绝缘材料绝缘性能下降、耐热性不足、成本增加等问题。本文基于前期的研究[4-5],以PP-1#和PP-2#为优选的PP基础树脂,丙烯基弹性体E1为增韧材料,控制物理共混体系中弹性体质量分数低于30%,设计了表2所示配方。
图1为不同弹性体含量PP绝缘材料的力学性能统计结果。从图1(a)可以看出,4种配方都呈现经典的韧性材料应力-应变曲线,即经历弹性形变、屈服、应变软化、应变硬化、断裂的过程。从图1(b)~(d)可以看出,在相同的PP基体种类下,共混弹性体的含量会显著影响共混PP样品的力学性能。以PP-1#为例,当共混弹性体质量分数从20%增加到30%时,断裂伸长率从465%增加至479%,拉伸强度从25.8 MPa降低至24.2 MPa,弯曲模量从630.5 MPa降低至417.7 MPa,呈现出典型的共混弹性体增韧现象,即力学韧性的提高会带来力学性能一定程度的下降。PP-2#的共混样品也表现出类似的现象。在共混弹性体含量相同的情况下,PP基体类型也显著影响力学性能。与PP-1#改性样品相比,PP-2#改性样品的断裂伸长率较高,拉伸强度较低,弯曲模量较低,说明PP-2#的力学韧性较好。这主要源于PP-2#中较高的本征型弹性体含量。增韧弹性体的分子结构通常具有较强的柔性,能够有效地吸收和分散外力,防止裂纹的形成和扩展,从而提高材料的力学韧性[7]。本征弹性体通过共聚的方式一方面破坏PP的结晶能力,降低结晶度,另一方面原位生成乙烯-丙烯共聚弹性体,从而增强材料的延展性和韧性。
根据GB/T 11017.2—2024[6],110 kV电缆绝缘料的断裂伸长率需要大于500%,拉伸强度需要大于17 MPa。虽然没有对弯曲模量作出具体要求,但是过高的弯曲模量会导致电缆在运输过程中难以卷曲,易在外力作用下产生裂纹,进而增加材料损耗和人力成本,而弯曲模量过低会导致材料在实际使用中出现强度不足和蠕变现象。参照行业要求,PP绝缘材料的弯曲模量为300 MPa比较合适。PP-1#改性样品的断裂伸长率和弯曲模量均较高,力学韧性达不到使用要求;PP-2#改性样品的力学韧性优异,但弯曲模量过低,存在耐蠕变性能不足的问题。
图2展示了不同弹性体含量样品的交流电气强度Weibull分布图及其统计结果。从图2可以看出,以击穿概率为63.2%时的特征电气强度衡量,两个系列样品之间的差异并不显著,都位于30~32 kV/mm。以PP-1#改性样品为例,电气强度随着共混弹性体含量的增加而略微下降。这是因为共混弹性体本身电气强度较低,导致材料整体的电气强度下降[8]。但本文采用了较低质量分数的弹性体(20%~30%)设计策略,以电气性能优异的PP树脂为主体,维持了整体的电气强度,从而表现出共混弹性体含量对电气强度的影响相对较小的现象。值得注意的是,样品1-2的形状因子明显降低,可能是由于在PP-1#中添加30%质量分数的弹性体后,材料内部形成了较弱的相界面。这些相界面可能成为电场集中的区域,导致耐击穿稳定性下降。形状因子的降低通常意味着材料在外电场作用下的电气强度和稳定性较差,更容易发生击穿。因此,尽管共混弹性体的添加对电气强度的影响较小,但其在材料中的分布不均和相界面弱化也会影响材料的耐 击穿稳定性[9]
PP材料在高温下会发生热软化和蠕变。热延伸测试能检测PP绝缘材料在150℃高温下的热形变率,从而评估PP绝缘材料在高温下的稳定性和可靠性。根据GB/T 11017.2—2024,110 kV电缆绝缘料的永久形变率应小于10%。表3为不同弹性体含量样品的热延伸性能统计结果。从表3可以看出,PP-1#改性样品永久形变率很低,仅有1%~2%,而PP-2#改性样品永久形变率达到了18%~24%,远高于国标对电缆绝缘料的热稳定性要求。这是由于PP-2#中本征弹性体含量高,破坏了PP原本的结晶结构,使材料在高温下的分子链活动性增加,材料容易发生延伸和形变[10]。因此,还需对PP-2#基体的耐热性能进行改性。
综上,对比分析单相PP基体树脂共混弹性体后的力学、电学和热学等核心性能,以PP-1#为基体的样品拉伸强度较高,热稳定性好,但力学延展性不足且弯曲模量较高,会增大电缆的铺设难度;以PP-2#为基体的样品虽然力学韧性达到使用要求,但是弯曲模量低,热稳定性差,难以满足电缆工作时对尺寸稳定性的要求。因此,下面进一步探究两种基体树脂进行复配对PP绝缘材料综合性能的影响,以实现力-电-热性能的平衡。
通过上述不同弹性体含量样品的力学、电学和热学性能研究,将弹性体E1的质量分数设定为30%,将PP-1#和PP-2#为PP基础树脂进行复配,探究复配后基础树脂对PP绝缘材料综合性能的影响,设计了表4所示配方体系。
图3为不同PP基础树脂复配的PP绝缘材料力学性能统计结果。从图3(a)可以看出,所有配方样品均表现为经典韧性材料的应力-应变曲线。从图3(b)~(d)可以看出,当PP-1#与PP-2#的复配比从3∶11(样品3-1)增加至1∶1(样品3-5)时,断裂伸长率从560%降低至518%,拉伸强度从22.9 MPa提高至24.5 MPa,弯曲模量从228.5 MPa增加至287.3 MPa。与样品1-2相比,样品3-3断裂伸长率提高14.2%,弯曲模量降低39.1%。这是由于PP-1#本征弹性体含量低于PP-2#,PP-1#组分的增多会导致材料中整体弹性体含量减少,从而降低材料的形变能力,进而降低了力学韧性。特别是当PP-1#含量达到30%~35%时,样品3-4、3-5的断裂伸长率已经接近500%的指标下限。因此,尽管在力学韧性方面存在一定程度的下降,但PP-1#和PP-2#复配后仍具备较好的综合性能,符合电缆材料力学性能的要求,而PP-1#含量过高会限制材料的延展性,需要合理调控PP-1#和PP-2#的组分比,探索合适的本征型弹性体含量。
图4为不同PP基础树脂复配绝缘材料的交流电气强度Weibull分布和统计结果。从图4可以看出,PP-1#和PP-2#的复配比例对特征电气强度没有显著的影响,集中分布在31~33 kV/mm。其中样品3-3的形状因子最高,达到70,反映了PP基体和共混弹性体在材料中的均匀分散,宏观表现为结构上的均匀性。当PP基体和共混弹性体能够均匀分布时,共同形成了一个相对均匀的电性能结构,有助于电场在材料中的均匀分布[11],减少了局部电场集中现象,使电气强度的表现更加稳定。
表5为不同PP基础树脂复配PP绝缘材料的热延伸性能。从表5可以看出,随着PP-1#含量增加,PP-2#含量减少,样品的永久形变率呈现降低趋势。以样品3-1为例,PP-2#含量较高,材料体系在150℃下的热延伸永久形变率达到14%,不满足使用标准要求。一般来说,弹性体为非晶结构,耐热性较差,无论是本征型弹性体还是共混弹性体,引入过多都会导致材料的耐热性能劣化。同时在共聚体系中,共聚单体的引入打乱了PP分子链的规整性,降低了结晶度[13-14]。而当本征弹性体含量下降时,材料中刚性结晶相的比例增加,PP的晶态结构在高温下会表现出较高的热稳定性,不易软化,从而提高了材料体系的耐热性。
综上所述,样品3-3在力学性能、交流电气强度、耐热性能等方面表现出较为平衡的综合性能,在PP电缆绝缘材料领域的应用潜力较大。接下来将以样品3-3为研究对象,进一步剖析其微观结构与综合性能之间的关系。
图5为PP釜内合金PP-1#及优选样品3-3经过正庚烷刻蚀后的微观形貌及粒径统计。从图5可以看出,刻蚀处理后,两种样品表面出现了大量孔洞[14]。这是本征弹性体相和共混弹性体相被正庚烷溶出后留下的孔洞。两种类型的弹性体在PP基体中的分布呈现典型的“海岛结构”,即弹性体相在基体中分布形成岛屿状结构,而PP基体充当海洋部分,作为连续的骨架,为材料体系的长期耐热稳定性提供基础[15-16]。对粒径分布采用高斯非线性曲线拟合(正态分布),拟合至曲线收敛。由于单独的粒径分布符合正态分布,使用该方法可以直观地看出弹性体粒径的集中分布。从图5(a)可以看出,粒径较小的结构(0.4~0.6 μm)是由釜内合金技术原位生成的本征弹性体,图5(c)中粒径较大的结构(约为1.0 μm)是以共混改性分散在PP基体中的共混弹性体E1。从图5(b)可以看出,釜内合金PP-1#的粒径呈现正态分布,平均粒径为0.45 μm;从图5(d)可以看出,在优选样品中存在两种粒径集中分散的弹性体粒子,尺寸呈现双峰分布。结合样品3-3的性能提升可知,粒径小的弹性体通常具有更大的比表面积,能够更好地分散在PP基体中,通过精细化的粒子分散可以改善材料的微观结构,减少内部孔洞和缺陷,从而有效减少电荷积聚,降低弹性体引入对PP绝缘性能的影响。但由于粒径小,其对PP材料的增韧效果有限。大粒径弹性体具有较高的弹性模量和韧性,能够在外力作用下发生塑性变形。当材料受到外部拉伸或冲击时,大粒径弹性体能够通过自身形变来吸收部分能量,减缓材料的断裂过程。相对于小粒径弹性体,大粒径粒子的塑性形变能力更强,能够延缓断裂的发生,减少PP材料在外力作用下的脆性断裂。此外,适当的大粒径粒子共混含量可使耐热性能增强。因此,采用双峰分布的弹性体粒子尺寸设计,能够实现对PP力学、电学和热学性能的协同优化。
图6为样品3-3与复配基体树脂的结构表征。从图6(a)可以看出,样品3-3在14.2°、17.0°、18.6°、21.4°、21.9°处分别显示出聚丙烯明显α晶的(110)、(040)、(130)、(041)、(131)晶面的特征衍射峰,未检测到β晶信号,与PP-1#、PP-2#的晶体衍射信号基本一致。通过Scherrer公式,计算了样品的平均晶粒尺寸(L),结果如表6所示。从表6可以看出,样品3-3的晶粒尺寸为12.1 nm,与PP-1#和PP-2#基本无差别,说明弹性体含量对PP晶粒尺寸影响不大[17]。从图6(b)可以看出,PP-1#的结晶度为33.4%,熔点为164.7℃,而PP-2#的结晶度为20.4%,熔点为151.4℃。这主要是PP-2#在合成过程中,引入了更多的乙烯单体,增加了本征弹性体的含量,降低了结晶度,且破坏了PP分子链的规整性,降低了PP晶体结构的完善程度。经过基础树脂的复配,优选样品3-3表现出适中的结晶度(23.9%)和较高的熔点(161.7℃),为PP绝缘材料在更高的运行温度下工作提供保障,提高高温下的服役稳定性。
参照500 kV及以下直流电缆绝缘材料测试标准,对优选样品进行空间电荷测试,结果如图7所示。图7(a)的电荷密度色度图记录了加压3 600 s期间优选样品内部的电荷密度变化情况,可以发现在这一过程中并没有明显的电荷注入现象。即使长时间施加外部电场,样品内部依然未明显发生电荷注入现象。从图7(b)可以看出,样品3-3在加压3 s时,阴极附近的电荷量便已经达到饱和,并且在持续极化3 600 s的过程中,样品内部的电荷密度仍然接近0。这表明在30 kV/mm的外加电场下,空间电荷难以注入优选样品3-3的内部,该材料在较高电场作用下表现出较强的电荷隔离能力,减少了电荷积聚和电场畸变的现象。从图7(c)可以看出,由于样品两侧接触电极,电场强度在两极处较高,但在样品内部厚度为50~300 μm处,电场畸变率保持在6%以下,说明在电场作用下,样品内部的电场分布相对均匀,电场畸变程度较低[18]
图8是优选样品3-3的电学综合性能图。
图8可以看出,样品3-3在5项关键电气性能上均优于GB/T 11017.2—2014要求,展现出卓越的电气特性。其中电气强度为31 kV/mm,显著高于标准要求的22 kV/mm,表明材料具备优异的耐电击穿能力;介质损耗因数仅为1.9×10-4,体积电阻率为1×1014 Ω·m,显示出优异的电气绝缘性能;电场畸变率仅为6%,远低于标准要求的20%,保证了良好的电气稳定性且减少了电场畸变;相对介电常数为2.35,满足标准要求,确保了可靠的绝缘性。这些优异性能归因于“双峰分布”的本征弹性体与外加丙烯基弹性体的协同作用,优化了界面相容性,在分子结构上形成更均匀的耐电结构,而弹性体与基体之间的界面会表现出一定的电荷陷阱效应,可以作为电荷捕捉和隔离的有效位置,有效阻止电荷的自由流动,减少电荷迁移对电气性能的负面影响,提升电气绝缘性和电气稳定性并降低电场畸变率。通过优化共混比例,优选样品3-3在高压绝缘应用中展现出良好的应用潜力,尤其在耐电性、低电场畸变率和高体积电阻率等方面符合高压电缆等领域的要求[19]
图9(a)~(b)为优选样品3-3的旋转流变测试结果。从图9(a)可以看出,储能模量和损耗模量的交点在频率约为4 Hz处,对应实际生产中加工设备的低速生产。从图9(b)可以看出,样品3-3的零切黏度达到10 000 Pa·s,且复数黏度随着频率的增加而减小,表现出典型的剪切变稀行为。为了探究电缆实际挤出生产工艺[20-21]对挤出尺寸稳定性的影响,图9(c)~(d)中统计了不同螺杆转速和不同加工温度下的离模膨胀率。从图9(c)可以看出,螺杆转速对离模膨胀率的影响非常明显。在温度为200℃下,当转速为10 r/min时,离模膨胀率仅为5%;而当转速超过20 r/min时,离模膨胀率迅速升高,达到40%~50%。从图9(d)可以看出,随着加工温度的变化,PP的离模膨胀率在200℃时达到最低值,当温度在200℃附近波动时离模膨胀率会增大。分析认为,高螺杆转速下,PP材料在挤出过程中受到更大的剪切力,导致熔体流动性增强,分子链发生取向,剪切变稀现象明显。离开挤出口模后,高弹形变恢复,造成膨胀。而在较低的转速下,剪切速率较小,分子链取向相对较弱,膨胀率较低。加工温度对离模膨胀率的影响主要由两个方面来相互制约。加工温度越高,熔体黏度降低,分子链取向更加容易,从而产生更多的高弹形变。但温度越高,分子链运动更加剧烈,高弹形变的恢复也会更加容易,最终温度为200℃时离模膨胀率最低。综上,在保证生产效率的前提下,可以选择200℃的加工温度,并选择较小且适合生产效率的加工速率。
(1)弹性体的分布及设计会直接影响高压电缆用聚丙烯绝缘材料的力学、电气等性能。本文耦合釜内合金技术和共混改性技术,复配两种PP釜内合金,制备了低弹性体含量(30%)的高压电缆用PP绝缘材料,与单一PP和弹性体共混相比,其断裂伸长率提高14.2%,弯曲模量降低39.1%,并具有较高的电气强度和热稳定性。
(2)通过PP釜内合金工艺引入较小粒径的增韧粒子,并在此基础上加入一定质量分数的较大粒径弹性体,从而形成了双峰粒径分布。这种设计通过小粒径弹性体的加入有效改善了弹性体与PP基体的界面相容性,同时小粒径弹性体的均匀分布减少了材料内部缺陷,提高了材料的电气性能。大粒径粒子的塑性变形能力更强,能够延缓断裂的发生,减少PP材料在外力作用下的脆性断裂。通过合理调控小粒径和大粒径弹性体的比例,在力学韧性与电气性能之间实现了平衡,从而提高了PP绝缘材料的综合性能,满足了实际应用中的需求。
(3)通过系统分析PP绝缘材料的微观结构与宏观性能,阐明了PP绝缘材料综合性能协同提升的机理。在探究PP绝缘材料的成型加工性能时,发现在200℃常规挤出成型加工温度下,PP材料更适合进行低转速加工生产,可降低离模膨胀率至5%左右,且能维持电缆形状。

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2026年第59卷第3期
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doi: 10.16790/j.cnki.1009-9239.im.2026.03.003
  • 接收时间:2025-06-30
  • 首发时间:2026-09-10
  • 出版时间:2026-03-20
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  • 收稿日期:2025-06-30
  • 修回日期:2025-08-26
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    1南方电网科学研究院有限责任公司,广东 广州 510663
    2中国南方电网有限责任公司,广东 广州 510663
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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