长支链化聚丙烯绝缘材料制备及其高温直流电性能研究

doi:10.19595/j.cnki.1000-6753.tces.251787

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摘要为提升抗冲共聚聚丙烯（IPC）的零切黏度与直流电性能,采用熔融接枝技术合成的马来酸酐（MAH）接枝改性聚丙烯（IPCgM）,配合双胺基小分子（二氨基二丙胺,DA）,通过酰亚胺化反应实现IPC分子链间的桥接,进而改变IPC的分子链长度与支化度,增强分子链间作用力与缠结作用,获得长支链化聚丙烯材料（IPCv）。通过傅里叶红外光谱（FTIR）、旋转流变、差示扫描量热（DSC）、动态热机械分析（DMA）、直流电性能测试及第一性原理计算,系统地探究了改性对材料分子结构、流变特性、力学性能及高温直流电性能的影响。结果表明,经酰亚胺化反应的IPCv在1 700 cm^-1出现马来酰亚胺基团中羰基的特征吸收峰,证实了反应的进行,0.5 phr DA添加量下MAH转化率达68.0%。经Carreau模型拟合,IPCv0.5的零切黏度达3 554 178.40 Pa·s,较未改性IPC提升965倍,熔体流动速率降至0.87 g/(10 min),有效地解决了挤出偏心问题。IPCv的拉伸强度与断裂伸长率大幅提高,材料柔软性得到小幅改善,20℃下IPCv0.5材料的储存模量约为486.67 MPa。在80℃下,IPCv0.5保持与IPC相近的电导电流,同时空间电荷分布特性得到大幅改善,试样内最大电场强度约为-44.8 kV/mm,较IPC的电场畸变率下降约18%。结合第一性原理计算,马来酰亚胺官能化IPCv材料具有丰富的局域态陷阱能力,并存在1.1 eV的空穴浅陷阱,有效地抑制了极板的空间电荷注入问题,表现出优异的直流电性能。该文通过分子链结构调控实现了材料加工性能与电气性能的协同优化,为热塑性聚丙烯电缆绝缘材料的工程应用提供了理论支撑与技术参考。

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关键词 ：聚丙烯, 接枝改性, 熔体黏度, 直流电性能

Abstract：Thermoplastic polypropylene (PP) insulated power cables are promising alternatives to cross-linked polyethylene (XLPE) due to their eco-friendly remoldability and recyclability. However, homopolypropylene’s high crystallinity-induced hardness and low zero-shear viscosity (causing extrusion eccentricity) limit its direct application. Thus, impact copolymer polypropylene (IPC), containing ethylene-propylene rubber segments, was selected as the base material, with its chain structure and local state traps regulated via maleic anhydride (MAH) graft modification and anhydride-amino imidization reaction to synergistically improve rheological and DC electrical properties.
Firstly, MAH-grafted IPC (IPCgM) was prepared via melt grafting with an optimized formulation (100 phr PP, 0.2 phr dicumyl peroxide, 1 phr MAH, 0.5 phr styrene). Then, 3,3′-diaminopropylamine (DA) was added at 0.2/0.5/1.0 phr and melt-blended at 200℃ for 10 minutes to form viscosity-modified IPCv. Fourier transform infrared (FTIR) spectroscopy confirmed successful imidization, with MAH conversion rates of 22.1%, 68.0%, and 82.4% for IPCv0.2, IPCv0.5, and IPCv1.0. Gel content tests (0±0.002% for all samples) verified no crosslinking, preserving PP’s thermoplasticity.
Melt flow rate (MFR) and rotational rheological tests (0.01~100 rad/s) showed IPCv’s viscosity first increased then decreased with DA content. Fitted via the Carreau model, IPCv0.5 exhibited the highest zero-shear viscosity (3 554 178.40 Pa·s), significantly higher than IPC (3 676.54 Pa·s) and IPCgM (236 015.16 Pa·s). It also had the lowest characteristic angular frequency (ω_c=5.01 rad/s) and longest relaxation time (τ_c=0.199 s), enhancing chain entanglement to suppress eccentricity. Mechanical testing results demonstrated that IPCv0.5 exhibited the maximum tensile strength (32.16 MPa), as well as the minimum elastic modulus (250 MPa) and yield strength (11.51 MPa). Dynamic mechanical analysis (DMA) in tensile mode revealed a reduced storage modulus (486.67 MPa at 25℃) and disappearance of the EPR phase’s -30℃ tanδ peak, indicating improved compatibility and flexibility.
Differential scanning calorimetry (DSC) tests showed modified IPC had higher crystallization temperature (improving processing efficiency) but unchanged melting temperature. IPCv’s crystallinity decreased with DA content, with IPCv0.5 at 29.93% (vs. 35.27% for IPC) and IPCv1.0 slightly recovering to 30.38% due to imidization competition. Reduced crystallinity enhanced flexibility by weakening chain constraints.
Furthermore, 80℃ DC conductivity and space charge tests showed IPCv0.5 maintained PP-comparable conductivity. Its space charge distribution was significantly improved, with a maximum electric field strength of ~-44.8 kV/mm and an 18% reduction in electric field distortion rate compared to IPC.

Key words： Polypropylene graft modification melt viscosity DC electrical performance

收稿日期: 2025-10-20

PACS:

TM215.1

基金资助:黑龙江省自然科学基金项目（TD2025E003）和南方电网科学研究院有限责任公司科技项目（SEPRI-K23B118）资助

通讯作者: 赵洪男,1955年生,教授,博士生导师,研究方向为极性化合物接枝改善聚烯烃直流电性和新型接枝方法。E-mail：hongzhao@hrbust.edu.cn

作者简介: 杨佳明男,1984年生,副教授,研究方向为介质理论及应用、聚丙烯电缆绝缘技术及应用、海缆技术。E-mail：jmyang@hrbust.edu.cn

引用本文:

杨佳明, 王凯, 赵洪, 杨旭, 赵新东, 展云鹏, 侯帅. 长支链化聚丙烯绝缘材料制备及其高温直流电性能研究[J]. 电工技术学报, 2026, 41(13): 4527-4537. Yang Jiaming, Wang Kai, Zhao Hong, Yang Xu, Zhao Xindong, Zhan Yunpeng, Hou Shuai. Preparation of Long-Chain Branched Polypropylene Insulation Material and Its High-Temperature DC Electrical Properties. Transactions of China Electrotechnical Society, 2026, 41(13): 4527-4537.

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[1] 舒印彪, 汤涌, 张正陵, 等. 新型配电网构建及其关键技术[J]. 中国电机工程学报, 2024, 44(17): 6721-6732.
Shu Yinbiao, Tang Yong, Zhang Zhengling, et al.Construction of new distribution network and its key technologies[J]. Proceedings of the CSEE, 2024, 44(17): 6721-6732.
[2] 黄晟, 凌吉莉, 魏娟, 等. 大规模风电机群服役质量调控方法研究综述[J]. 电工技术学报, 2025, 40(10): 3274-3300.
Huang Sheng, Ling Jili, Wei Juan, et al.A review of regulation method of service quality of large-scale wind farm[J]. Transactions of China Electrotechnical Society, 2025, 40(10): 3274-3300.
[3] 陈曦. 交联聚乙烯高压直流电缆的研究现状与发展[J]. 电线电缆, 2015, 58(2): 1-5.
Chen Xi.Research status and trend of XLPE HVDC cable[J]. Electric Wire & Cable, 2015, 58(2): 1-5.
[4] 张雯嘉, 王伟, 袁浩, 等. 接枝聚丙烯电缆绝缘材料的电树枝特性及机理[J]. 电工技术学报, 2024, 39(1): 88-98.
Zhang Wenjia, Wang Wei, Yuan Hao, et al.Electrical tree characteristics and mechanism of grafted polypropylene cable insulation[J]. Transactions of China Electrotechnical Society, 2024, 39(1): 88-98.
[5] 李盛涛, 王诗航, 李建英. 高压直流电缆料的研发进展与路径分析[J]. 高电压技术, 2018, 44(5): 1399-1411.
Li Shengtao, Wang Shihang, Li Jianying.Research progress and path analysis of insulating materials used in HVDC cable[J]. High Voltage Engineering, 2018, 44(5): 1399-1411.
[6] 何金良, 彭琳, 周垚. 环保型高压直流电缆绝缘材料研究进展[J]. 高电压技术, 2017, 43(2): 337-343.
He Jinliang, Peng Lin, Zhou Yao.Research progress of environment-friendly HVDC power cable insulation materials[J]. High Voltage Engineering, 2017, 43(2): 337-343.
[7] 黄兴溢, 张军, 江平开. 热塑性电力电缆绝缘材料: 历史与发展[J]. 高电压技术, 2018, 44(5): 1377-1398.
Huang Xingyi, Zhang Jun, Jiang Pingkai.Thermoplastic insulation materials for power cables: history and progress[J]. High Voltage Engineering, 2018, 44(5): 1377-1398.
[8] 李加才, 尚恺, 司志成, 等. 高压电缆绝缘低密度聚乙烯交联过程中级数和自催化反应的逆向调控[J]. 电工技术学报, 2024, 39(1): 13-22.
Li Jiacai, Shang Kai, Si Zhicheng, et al.Reverse regulation of order and autocatalysis reactions during the cross-linking process of low-density polyethylene used in high-voltage cable insulation[J]. Transactions of China Electrotechnical Society, 2024, 39(1): 13-22.
[9] 尚恺, 李加才, 王诗航, 等. 高压电缆交联聚乙烯绝缘料黏度参数对挤出特性影响的仿真研究[J]. 电工技术学报, 2024, 39(3): 810-819.
Shang Kai, Li Jiacai, Wang Shihang, et al.Simulation study on the extrusion performances based on the viscosity parameters of cross-linked polyethylene insulating materials for high-voltage cables[J]. Transactions of China Electrotechnical Society, 2024, 39(3): 810-819.
[10] 张耀东, 任想. 液体添加剂对高压电缆绝缘材料加工特性和物理性能的影响[J]. 绝缘材料, 2025, 58(3): 35-41.
Zhang Yaodong, Ren Xiang.Effects of liquid additives on processing characteristics and physical properties of high-voltage cable insulation materials[J]. Insulating Materials, 2025, 58(3): 35-41.
[11] 董新华, 王伟, 袁浩, 等. 基于乙烯共聚的高压抗冲共聚聚丙烯电缆绝缘材料机械和电气性能的协同优化[J]. 电工技术学报, 2025, 40(23): 7763-7775.
Dong Xinhua, Wang Wei, Yuan Hao, et al.Synergistic optimization of the mechanical and electrical properties of high voltage impact polypropylene copolymer cable insulation materials based on ethylene copolymerization[J]. Transactions of China Electrotechnical Society, 2025, 40(23): 7763-7775.
[12] 杜伯学, 李忠磊, 周硕凡, 等. 聚丙烯高压直流电缆绝缘研究进展与展望[J]. 电气工程学报, 2021, 16(2): 2-11.
Du Boxue, Li Zhonglei, Zhou Shuofan, et al.Research progress and perspective of polypropylene- based insulation for HVDC cables[J]. Journal of Electrical Engineering, 2021, 16(2): 2-11.
[13] 赵鹏, 欧阳本红, 黄凯文, 等. 不同改性聚丙烯电缆绝缘料热氧老化特性和选型[J]. 高电压技术, 2022, 48(7): 2642-2649.
Zhao Peng, Ouyang Benhong, Huang Kaiwen, et al.Thermal aging characteristics and selection of different modified polypropylene cable insulating materials[J]. High Voltage Engineering, 2022, 48(7): 2642-2649.
[14] 张伟, 徐曼, 陈光辉, 等. 等规和嵌段聚丙烯的结构和性能[J]. 高电压技术, 2017, 43(11): 3634-3644.
Zhang Wei, Xu Man, Chen Guanghui, et al.Structure and properties of isotactic polypropylene and ethylene-propylene copolymer[J]. High Voltage Engineering, 2017, 43(11): 3634-3644.
[15] 赵鹏, 欧阳本红, 宁昕, 等. 乙烯共聚改性聚丙烯电缆绝缘料的结构-性能分析[J]. 高电压技术, 2025, 51(6): 2662-2671.
Zhao Peng, Ouyang Benhong, Ning Xin, et al.Structural and performance analysis of ethylene copolymer modified polypropylene cable insulation material[J]. High Voltage Engineering, 2025, 51(6): 2662-2671.
[16] 展云鹏, 侯帅, 傅明利, 等. 直流电缆绝缘用国产抗冲共聚聚丙烯材料结构与性能[J]. 高电压技术, 2025, 51(12): 5845-5858.
Zhan Yunpeng, Hou Shuai, Fu Mingli, et al.Structure and properties of domestic impact-resistant poly-propylene for DC cable insulation material[J]. High Voltage Engineering, 2025, 51(12): 5845-5858.
[17] Ouyang Yingwei, Pourrahimi A M, Lund A, et al.High-temperature creep resistant ternary blends based on polyethylene and polypropylene for thermoplastic power cable insulation[J]. Journal of Polymer Science, 2021, 59(11): 1084-1094.
[18] Mohammady S Z, Khairou K S.Impact of filler on the soft phase molecular dynamics of PP/EPDM/SiO₂ thermoplastic elastomeric nano-composites[J]. Egyptian Journal of Petroleum, 2021, 30(2): 23-27.
[19] Kochetov R, Andritsch T, Morshuis P H F, et al. Anomalous behaviour of the dielectric spectroscopy response of nanocomposites[J]. IEEE Transactions on Dielectrics and Electrical Insulation, 2012, 19(1): 107-117.
[20] 程璐, 刘宏博, 刘标, 等. 三元复合聚丙烯电介质材料性能调控研究进展[J]. 高电压技术, 2024, 50(6): 2332-2343.
Cheng Lu, Liu Hongbo, Liu Biao, et al.Recent research improvements in ternary polypropylene dielectric materials[J]. High Voltage Engineering, 2024, 50(6): 2332-2343.
[21] 陈铮铮, 赵鹏, 李震宇, 等. 评价直流电缆绝缘材料电性能的有效方法[J]. 高电压技术, 2021, 47(10): 3558-3565.
Chen Zhengzheng, Zhao Peng, Li Zhenyu, et al.Effective method for evaluating the electrical properties of DC cable insulation materials[J]. High Voltage Engineering, 2021, 47(10): 3558-3565.
[22] 欧阳本红, 赵鹏, 黄凯文, 等. 热塑性聚丙烯电缆料研究进展评述[J]. 高电压技术, 2023, 49(3): 907-919.
Ouyang Benhong, Zhao Peng, Huang Kaiwen, et al.Review on progress of thermoplastic polypropylene cable materials[J]. High Voltage Engineering, 2023, 49(3): 907-919.
[23] 陈鸿, 赵健康, 黄凯文, 等. 不同改性聚丙烯电缆绝缘料的结构与性能对比分析[J]. 电力工程技术, 2022, 41(5): 233-239.
Chen Hong, Zhao Jiankang, Huang Kaiwen, et al.Comparative analysis of atructure and properties of different modified polypropylene cable insulation materials[J]. Jiangsu Electrical Engineering, 2022, 41(5): 233-239.
[24] 蒋毅恺, 徐曼, 王若霏, 等. 电缆绝缘用聚丙烯/弹性体复合材料的高温介电性能[J]. 电工技术学报, 2024, 39(1): 99-109.
Jiang Yikai, Xu Man, Wang Ruofei, et al.High temperature dielectric properties of polypropylene and elastomer blends for cable insulation[J]. Transactions of China Electrotechnical Society, 2024, 39(1): 99-109.
[25] 胡世勋, 张雅茹, 邵清, 等. 不同改性技术路线的聚丙烯基高压直流电缆绝缘材料综合性能比较[J]. 中国电机工程学报, 2022, 42(4): 1243-1251.
Hu Shixun, Zhang Yaru, Shao Qing, et al.Comprehensive performance comparisons of poly-propylene-based HVDC cable insulating materials adopting different modification technical routes[J]. Proceedings of the CSEE, 2022, 42(4): 1243-1251.
[26] Sui Haoran, Wu Kangning, Zhao Ge, et al.Greatly enhanced temperature stability of eco-friendly polypropylene for cable insulation by multifold long-chain branched structures[J]. Chemical Engineering Journal, 2024, 485: 149811.
[27] Zhang Zhijian, Yang Kai, Li Jianying, et al.Simultaneous promotion of the mechanical flexibility and dielectric strength of impact polypropylene copolymers containing multifold H-shape long-chain- branching structures for recyclable power cable insulation application[J]. ACS Applied Polymer Materials, 2024, 6(4): 2210-2222.
[28] Fu Zhe, Yang Jiaming, Yang Xu, et al.Modeling for short-circuit process in polypropylene-based cable insulation considering phase change and melt flow[J]. IEEE Transactions on Dielectrics and Electrical Insulation, 2025, 32(5): 2858-2867.
[29] 王凯, 赵新东, 郑海峰, 等. 极性分子的结构异同性对接枝改性交联聚乙烯材料直流电性能的影响[J]. 电工技术学报, 2024, 39(1): 34-44.
Wang Kai, Zhao Xindong, Zheng Haifeng, et al.Influence of the structural similarities of polar molecules on DC properties of grafted modified cross-linked polyethylene materials[J]. Transactions of China Electrotechnical Society, 2024, 39(1): 34-44.
[30] Yang Xu, Zhao Hong, Li Chunyang, et al.Improved wide-temperature-range insulation properties of block polypropylene by UV-irradiated cografting of maleic anhydride and 4-tert-butylstyrene[J]. ACS Applied Polymer Materials, 2023, 5(1): 247-258.