Article(id=1193543217703518491, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193543214067056904, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.03.008, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1727366400000, receivedDateStr=2024-09-27, revisedDate=1730304000000, revisedDateStr=2024-10-31, acceptedDate=null, acceptedDateStr=null, onlineDate=1762492478060, onlineDateStr=2025-11-07, pubDate=1742400000000, pubDateStr=2025-03-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1762492478060, onlineIssueDateStr=2025-11-07, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1762492478060, creator=13701087609, updateTime=1762492478060, updator=13701087609, issue=Issue{id=1193543214067056904, tenantId=1146029695717560320, journalId=1149653034449285133, year='2025', volume='58', issue='3', pageStart='1', pageEnd='157', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1762492477194, creator=13701087609, updateTime=1762498203949, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1193567233872982429, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193543214067056904, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1193567233872982430, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193543214067056904, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=70, endPage=75, ext={EN=ArticleExt(id=1193543217934205212, articleId=1193543217703518491, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of anti-ager MB on thermal ageing resistance of crosslinked polyethylene, columnId=1193543215723806988, journalTitle=Insulating Materials, columnName=Special Issue on Advanced Cable Insulation, runingTitle=null, highlight=null, articleAbstract=

To improve the thermal ageing resistance of crosslinked polyethylene (XLPE), different contents of anti-ager 2-mercaptothiazole (MB) were blended with PE, and then MB/XLPE sheet samples were prepared through electron irradiation process. The effect of MB content on the crosslinking degree, thermal elongation performance, insulation properties, oxidation induction period, and carbonyl index of XLPE were studied. The results show that with the increase of MB content, the gel content and thermal elongation performance of MB/XLPE composites reduce, while the volume resistivity maintains stable. The addition of MB significantly extends the oxidation induction period and suppresses the carbonyl index growth of XLPE during thermal ageing. When the weight part of MB is 1, the oxidation induction period of MB/XLPE significantly increases from 0.9 min (for pure XLPE) to 80 min; after thermal ageing for 168 h at 165℃, and the carbonyl index of MB/XLPE only increases from 0.04 to 0.06, indicating marked improvement in thermal ageing resistance. Based on the Arrhenius equation, it is concluded that this MB/XLPE exhibits a service life of 76.2 years at 90℃ which is 2.5 times longer than that of conventional XLPE.

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为了提升交联聚乙烯(XLPE)的耐热老化性能,本文采用不同含量的防老剂2-硫醇基苯并咪唑(MB)与PE共混,通过电子辐照工艺制备了MB/XLPE板材样品,研究了MB含量对XLPE交联程度、热延伸性能、绝缘性能、氧化诱导期和羰基指数的影响。结果表明:随着MB含量的增加,MB/XLPE的凝胶含量进一步下降,热延伸性能恶化,但体积电阻率基本维持不变。MB的加入可显著提升XLPE氧化诱导期和降低XLPE热老化后的羰基指数增长量。当MB的添加量为1质量份时,MB/XLPE试样的氧化诱导期由XLPE的0.9 min显著提升至80 min;在165℃下热老化168 h后,MB/XLPE的羰基指数仅从XLPE的0.04增长到0.06,表明MB可显著提升XLPE的耐热老化性能;结合Arrhenius公式,推断出该MB/XLPE在90℃下的寿命可达76.2年,约为一般XLPE的2.5倍。

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王阳(1992-),男(汉族),安徽安庆人,工程师,主要从事电线电缆加工制造的研究;

张文华(1969-),男(汉族),江西永新人,高级工程师,主要从事电线电缆加工制造的研究。

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张文华(1969-),男(汉族),江西永新人,高级工程师,主要从事电线电缆加工制造的研究。

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试样编号 抗老化剂MB/份 抗氧剂1010/份 抗氧剂168/份 交联敏化剂TAIC/份
1 0 0 0 1
2 0 0.25 0.25 1
3 0.5 0.25 0.25 1
4 1.0 0.25 0.25 1
5 1.5 0.25 0.25 1
), ArticleFig(id=1195076429391077867, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193543217703518491, language=CN, label=表1, caption=

5种不同防老剂含量的MB/XLPE样品成分

, figureFileSmall=null, figureFileBig=null, tableContent=
试样编号 抗老化剂MB/份 抗氧剂1010/份 抗氧剂168/份 交联敏化剂TAIC/份
1 0 0 0 1
2 0 0.25 0.25 1
3 0.5 0.25 0.25 1
4 1.0 0.25 0.25 1
5 1.5 0.25 0.25 1
), ArticleFig(id=1195076429449798124, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193543217703518491, language=EN, label=Table 2, caption=Gel content, thermal extensibility and volume resistivity of MB/XLPE samples with different contents of anti-ager, figureFileSmall=null, figureFileBig=null, tableContent=
试样 凝胶含量/% 延伸性能(载荷下最大伸长率)/% 体积电阻率/(×1016 Ω∙cm)
1 85.68 35 9.696 50
2 76.44 90 3.613 55
3 74.22 100 3.365 20
4 73.87 120 3.286 10
5 73.40 125 3.159 20
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不同防老剂含量MB/XLPE样品的凝胶含量、热延伸性能和体积电阻率

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试样 凝胶含量/% 延伸性能(载荷下最大伸长率)/% 体积电阻率/(×1016 Ω∙cm)
1 85.68 35 9.696 50
2 76.44 90 3.613 55
3 74.22 100 3.365 20
4 73.87 120 3.286 10
5 73.40 125 3.159 20
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防老剂MB对交联聚乙烯耐热老化性能的影响
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王阳 1, 2 , 张文华 2
绝缘材料 | 先进电缆绝缘专题 2025,58(3): 70-75
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绝缘材料 | 先进电缆绝缘专题 2025, 58(3): 70-75
防老剂MB对交联聚乙烯耐热老化性能的影响
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王阳1, 2, 张文华2
作者信息
  • 1 江西铜业技术研究院有限公司,江西 南昌 330096
  • 2 江西电缆有限责任公司,江西 吉安 343008
  • 王阳(1992-),男(汉族),安徽安庆人,工程师,主要从事电线电缆加工制造的研究;

    张文华(1969-),男(汉族),江西永新人,高级工程师,主要从事电线电缆加工制造的研究。

Effect of anti-ager MB on thermal ageing resistance of crosslinked polyethylene
Yang WANG1, 2, Wenhua ZHANG2
Affiliations
  • 1 Jiangxi Copper Technology Research Institute Co., Ltd., Nanchang 330096, China
  • 2 Jiangxi Cable Co., Ltd., Ji′an 343008, China
出版时间: 2025-03-20 doi: 10.16790/j.cnki.1009-9239.im.2025.03.008
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为了提升交联聚乙烯(XLPE)的耐热老化性能,本文采用不同含量的防老剂2-硫醇基苯并咪唑(MB)与PE共混,通过电子辐照工艺制备了MB/XLPE板材样品,研究了MB含量对XLPE交联程度、热延伸性能、绝缘性能、氧化诱导期和羰基指数的影响。结果表明:随着MB含量的增加,MB/XLPE的凝胶含量进一步下降,热延伸性能恶化,但体积电阻率基本维持不变。MB的加入可显著提升XLPE氧化诱导期和降低XLPE热老化后的羰基指数增长量。当MB的添加量为1质量份时,MB/XLPE试样的氧化诱导期由XLPE的0.9 min显著提升至80 min;在165℃下热老化168 h后,MB/XLPE的羰基指数仅从XLPE的0.04增长到0.06,表明MB可显著提升XLPE的耐热老化性能;结合Arrhenius公式,推断出该MB/XLPE在90℃下的寿命可达76.2年,约为一般XLPE的2.5倍。

防老剂MB  /  交联聚乙烯  /  热氧老化  /  耐热老化性能  /  寿命

To improve the thermal ageing resistance of crosslinked polyethylene (XLPE), different contents of anti-ager 2-mercaptothiazole (MB) were blended with PE, and then MB/XLPE sheet samples were prepared through electron irradiation process. The effect of MB content on the crosslinking degree, thermal elongation performance, insulation properties, oxidation induction period, and carbonyl index of XLPE were studied. The results show that with the increase of MB content, the gel content and thermal elongation performance of MB/XLPE composites reduce, while the volume resistivity maintains stable. The addition of MB significantly extends the oxidation induction period and suppresses the carbonyl index growth of XLPE during thermal ageing. When the weight part of MB is 1, the oxidation induction period of MB/XLPE significantly increases from 0.9 min (for pure XLPE) to 80 min; after thermal ageing for 168 h at 165℃, and the carbonyl index of MB/XLPE only increases from 0.04 to 0.06, indicating marked improvement in thermal ageing resistance. Based on the Arrhenius equation, it is concluded that this MB/XLPE exhibits a service life of 76.2 years at 90℃ which is 2.5 times longer than that of conventional XLPE.

anti-ager MB  /  crosslinked polyethylene  /  thermal-oxidative ageing  /  thermal ageing resistance  /  life
王阳, 张文华. 防老剂MB对交联聚乙烯耐热老化性能的影响. 绝缘材料, 2025 , 58 (3) : 70 -75 . DOI: 10.16790/j.cnki.1009-9239.im.2025.03.008
Yang WANG, Wenhua ZHANG. Effect of anti-ager MB on thermal ageing resistance of crosslinked polyethylene[J]. Insulating Materials, 2025 , 58 (3) : 70 -75 . DOI: 10.16790/j.cnki.1009-9239.im.2025.03.008
聚乙烯(PE)通过物理/化学交联后,二维线型结构转变为三维网状结构,多项性能显著提升,尤其是热延伸性能。交联聚乙烯(XLPE)因具有优异的热延伸性能和绝缘性能,已广泛应用于电缆绝缘材料[1-2]。然而电缆在长期工作后,由于热量的不断积累,交联聚乙烯绝缘层在热、氧的作用下发生热老化,导致性能大幅度下降[3]。孙建宇等[4]详细分析了XLPE在热老化过程中依次发生链引发、链传递、链增长和链终止4个阶段,明确了热老化本质是氧化反应。章彬等[5]研究了XLPE在90℃和135℃加速老化温度下电学性能和力学性能的演变规律,结果表明在加速老化过程中XLPE的力学性能、电气强度、体积电导率均发生了显著恶化。
XLPE热老化的本质是发生了氧化反应,因此可通过添加抗氧剂提升XLPE的耐热老化性能。侯帅等[6]研究了抗氧剂300、1010和1035对XLPE耐热老化性能、交联特性、介电性能的影响,结果表明,添加抗氧剂可明显提升XLPE的耐热老化性能,但同时会降低XLPE的交联度和热延伸性能;对于提升XLPE介电性能和耐老化性能,复配添加抗氧剂1010和1035明显优于单独添加抗氧剂300。闫可新等[7]研究了协同添加抗氧剂HP-136和300对XLPE加工流变性能、氧化诱导期(OIT)和介电性能的影响,结果表明,抗氧剂的添加虽然可以提升XLPE的抗焦烧性、耐热老化性能和氧化诱导期,但降低了介电性能。因此,需严格调控抗氧剂的种类和添加量。
防老剂2-硫醇基苯并咪唑(简称MB,分子式为C7H6N2S)属于杂环类有机化合物[8]。防老剂MB价格便宜,属于广谱抗氧剂,可分解橡胶老化过程中形成的氢过氧化物,因此已广泛应用于橡胶的防老化。本文通过熔融共混制备出不同防老剂MB含量的XLPE板材,研究防老剂MB含量对XLPE交联程度、热延伸性能、绝缘性能、氧化诱导期和碳基指数的影响,进而探究防老剂MB对XLPE耐热老化性能的影响机制。最后,根据老化寿命理论模型对制备出的耐热老化性能优异的MB/XLPE样品进行耐热老化寿命评估。
低密度聚乙烯(LDPE)基料,上海石化股份有限公司;抗氧剂1010、168,扬子巴斯夫有限责任公司;防老剂2-硫醇基苯并咪唑(MB),宁波艾克姆新材料有限公司;交联敏化剂三烯丙基异三聚氰酸酯(TAIC)为市售。
利用哈克转矩流变仪(HAAKE PolyLab OS型,赛默飞世尔科技公司)在140℃下以50 rad/min的转速混炼基料和添加剂10 min得到5种不同防老剂含量的MB/XLPE共混物,具体组成如表1所示。随后利用平板硫化仪(TY-7006A型,江苏天源试验设备有限公司)在150℃、15 MPa条件下,将5种共混物热压10 min,得到尺寸为200 mm×200 mm×2 mm的MB/XLPE板材状样品。再采用电子加速器(GJ-2型,上海先锋电机厂)对5种MB/XLPE板材样进行辐照交联,辐照剂量为250 kGy。最后按照GB/T 2951.12—2008,将辐照后的板材样品裁剪成Ⅱ型哑铃片(长度为50 mm,标距长度为20 mm,宽度为 4 mm),悬挂于鼓风老化试验箱中在不同温度下进行加速热氧老化试验。
采用场发射扫描电镜(Apreo 2型,赛默飞世尔科技公司)进行微观形貌表征,测试前将样品在液氮温度下脆断后进行表面喷金。采用傅里叶变换红外光谱仪(Nicolet iN10型,赛默飞世尔科技公司)进行红外光谱测试。按照JB/T 10437—2024进行凝胶含量测试,萃取溶液为二甲苯,萃取时间为12 h。采用电子万能试验机(UTM 6104型,深圳三思试验设备有限公司)按照GB/T 1040.3—2006测试试样的力学性能,将样品加工成Ⅱ型哑铃片,拉伸速率为200 mm/min。按照GB/T 2951.11—2008测试试样在载荷下的最大伸长率,试验条件为200℃、0.2 MPa、10 min,样品为Ⅱ型哑铃片。采用高阻计(SM7120型,日置HIOKI公司)测试试样的体积电阻率,每间隔10 min测试一次。采用差示扫描量热仪(DSC200F3型,德国耐驰公司)按照GB/T 19466.6—2009测定试样的氧化诱导期,采用40 mL/min空气气泵、200℃恒温条件。
表2为5种不同防老剂含量的MB/XLPE板材样的凝胶含量和热延伸性能(载荷下最大伸长率)测试结果。从表2可以看出,未加抗氧剂和防老剂的XLPE(试样1)凝胶含量为85.68%、载荷下的最大伸长率为35%。随着抗氧剂1010和168的加入(试样2),XLPE凝胶含量下降至76.44%,载荷下最大伸长率增至90%。出现该现象的原因是,交联反应会使PE分子从线型或支链型结构转变为三维网状结构。XLPE分子间的交联连接点越多,交联程度越高,凝胶含量就越高[2,6];XLPE分子链之间的交联点越多,分子链的移动性就越低,热延伸性能会得到改善(载荷下最大伸长率降低)[2,6]。因此,随着XLPE交联程度的增加,凝胶含量值增加,热延伸性能得到提升。根据文献[9-10],在交联过程中,抗氧剂会捕捉自由基,可有效抑制XLPE交联。因此抗氧剂1010和168的加入降低了XLPE的交联程度,从而不利于热延伸性能的提升。
表2还可以看出,随着防老剂MB的继续加入,MB/XLPE凝胶含量进一步下降,热延伸性能恶化,表明防老剂MB的加入同样会抑制交联,降低XLPE的交联程度,不利于热延伸性能的提升。但一般XLPE绝缘电缆要求绝缘层热延伸性能(载荷下最大伸长率)≤175%,本研究制备的不同防老剂含量的MB/XLPE样品热延伸性能仍满足要求。
表2中还列出了5种MB/XLPE样品的体积电阻率。从表2可以看出,试样1的体积电阻率为9.696 50×1016 Ω·cm,随着抗氧剂1010和168的加入,试样的体积电阻率降至3.613 55×1016 Ω·cm。根据文献[11],添加极性较大的抗氧剂使得XLPE在电场下容易电离出导电粒子,从而使得绝缘性能下降。因此,复配抗氧剂1010和168后,试样2体积电阻率发生了明显下降。然而,相较于抗氧剂1010和168,防老剂MB分子量小和含氧基团少,相对极性小。因此,随着防老剂MB的继续加入,MB/XLPE的体积电阻率基本维持不变。一般XLPE绝缘电缆要求绝缘层体积电阻率≥1016 Ω·cm,因此本研究制备的MB/XLPE样品体积电阻率均满足要求。
图1(a)为不同防老剂含量的MB/XLPE板材样氧化诱导期测试结果。
图1(a)可以看出,试样1的氧化诱导期为0.9 min,基本可以忽略不计,表明在DSC测试中(200℃热氧条件)XLPE分子链容易断裂产生自由基,引发XLPE发生热氧老化反应。反应产生的自由基被O2氧化生成过氧化自由基和氢过氧化物,氢过氧化物再分解为自由基,这些自由基继续捕捉XLPE分子链上的氢原子,从而不断促进XLPE热氧老化[4,12-13]。因此在热氧条件下,XLPE抗热氧老化降解能力差,从而导致耐热老化性能差。根据文献[14],抗氧剂1010为受阻酚类,可以捕捉XLPE分子链断链形成的自由基;抗氧168为亚磷酸酯类,可以消耗氢过氧化物。因此,随着抗氧剂1010和168的加入,试样2的氧化诱导期提升至35 min。
图1(a)还可以看出,随着防老剂MB的继续加入,MB/XLPE氧化诱导期先增后减。当添加1质量份防老剂MB时,试样4的氧化诱导期显著提升至80 min。根据文献[8],防老剂MB作为一种带有巯基基团的咪唑类物质,可以分解XLPE老化过程中形成的氢过氧化物,从而抑制氢过氧化物分解形成自由基,提升XLPE抗热氧老化性能。然而,当添加1.5质量份防老剂MB时,试样5的氧化诱导期反而下降至62 min。下降的主要原因在于较高含量防老剂MB存在部分团聚现象,没有完全均匀分散在基体中(其断口SEM图如图1(b)所示),与XLPE老化过程中形成的氢过氧化物接触不够,导致无法有效发挥作用。然而,MB/XLPE的氧化诱导期相较XLPE均得到进一步提升,表明添加防老剂MB可提升XLPE耐热老化性能。
发生热氧老化后,XLPE分子链断裂形成羰基化合物,因此可以用羰基指数(I c)来评价XLPE热氧老化行为[15]图2(a)(b)为5种MB/XLPE试样经165℃热老化168 h前后的红外光谱图。谱图中,2 916 cm-1处为甲基振动吸收峰,其吸收峰强度(A)不随着抗氧剂1010或168、防老剂MB的添加和热氧老化的发生而变化,可用于I c计算的基准。1 712 cm-1处为羰基吸收峰,I c=A 1712/A 2916,计算结果如图2(c)所示。
图2(c)可以看出,在165℃下热老化168 h后,试样1的羰基指数从0.06显著增加到2.12。随着抗氧剂1010和168的加入,试样的羰基指数增长量大幅度下降。随着防老剂MB继续添加到1质量份时,试样4的羰基指数增长幅度进一步降低,仅从0.04增长到0.06,表明1质量份防老剂MB的加入,提升了XLPE在热老化过程分解氢过氧化物的效率,减慢了氧化速率,从而提升了XLPE耐热老化性能。
综上分析,随着1质量份防老剂MB的加入,试样氧化诱导期显著增加,热老化后试样羰基指数增长幅度显著下降,表明1质量份防老剂MB的加入可以显著提升XLPE试样的耐热老化性能。参考GB/T 11026.1—2016和IEC 60216-1:2013,选择3个不同温度点,对材料进行人工加速老化试验。然后结合Arrhenius公式,引入寿命t和温度T,评估试样4的耐热老化寿命。根据文献[16-17],Arrhenius公式中的E/R为常数,可以进一步简化为式(1)
l n   t = A / T + B
式(1)中:AB为常数;t为达到性能临界值所需要的时间,h;T为绝对温度,K。
选择3个温度点145、160、175℃,按照GB/T 11026.1—2016进行常规加速热老化实验,得到不同老化时间下的断裂伸长率,老化时间与断裂伸长率保留率的曲线如图3(a)所示。选取断裂伸长率为50%作为老化寿命终点标准,得到3个温度下对应的老化时间如图3(a)中所示,再将3个温度和断裂伸长率为50%时的老化时间代入式(1),通过线性拟合可以得到寿命与温度的线性关系,如图3(b)所示。对于XLPE绝缘电缆,一般导体长期工作温度为90℃,XLPE寿命约为30年[18]。由图3(b)可知,试样4在90℃下寿命可达76.2年,约为普通XLPE寿命的2.5倍,表明1%防老剂MB的添加可显著提升XLPE的使用寿命。
(1)随着抗氧剂1010和168的加入,XLPE凝胶含量从85.68%下降至76.44%,热延伸性能从35%恶化至90%,体积电阻率从9.696 50×1016 Ω·cm下降至3.613 55×1016 Ω·cm。随着防老剂MB的继续加入,MB/XLPE凝胶含量和热延伸性能进一步下降,然而体积电阻率基本维持不变。
(2)防老剂MB的加入可显著提升XLPE的氧化诱导期。当添加1质量份MB时,MB/XLPE氧化诱导期显著提升至80 min,表明防老剂MB可显著提升XLPE耐热老化性能。然而,当添加1.5质量份MB时,大量防老剂MB没有均匀分散在基体中,存在部分团聚现象,导致MB/XLPE氧化诱导期反而下降至62 min,但仍比未添加MB的试样高。
(3)防老剂MB的加入可显著降低XLPE热老化后羰基指数的增长幅度。当添加1质量份MB时,MB/XLPE在165℃下热老化168 h后羰基指数仅从0.04增长到0.06,表明防老剂MB可显著降低XLPE在热老化过程中的氧化速率,从而改善其耐热老化性能。
(4)通过145、160、175℃人工加速老化试验,结合Arrhenius公式,推断出添加1质量份MB时的MB/XLPE试样在90℃下寿命可达76.2年,表明1质量份MB的添加可显著提升XLPE的使用寿命。
  • 2023年吉安市科技计划“百博百企”专项(20233-127595)
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2025年第58卷第3期
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doi: 10.16790/j.cnki.1009-9239.im.2025.03.008
  • 接收时间:2024-09-27
  • 首发时间:2025-11-07
  • 出版时间:2025-03-20
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  • 收稿日期:2024-09-27
  • 修回日期:2024-10-31
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2023年吉安市科技计划“百博百企”专项(20233-127595)
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    1 江西铜业技术研究院有限公司,江西 南昌 330096
    2 江西电缆有限责任公司,江西 吉安 343008
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2种不同金属材料的力学参数

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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
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红菇属 Russula 17 8.13
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