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新合成的乙烯/1-己烯/4-乙烯基环己烯三元共聚物的介电和绝缘性能评估

Evaluation of the Dielectric and Insulating Properties of Newly Synthesized Ethylene/1-Hexene/4-Vinylcyclohexene Terpolymers.

作者信息

Ali Amjad, Alabbosh Khulood Fahad Saud, Naveed Ahmad, Uddin Azim, Chen Yanlin, Aziz Tariq, Moradian Jamile Mohammadi, Imran Muhammad, Yin Lu, Hassan Mobashar, Qureshi Waqar Ahamad, Ullah Muhammad Wajid, Fan Zhiqiang, Guo Li

机构信息

Research School of Polymeric Materials, School of Materials Science & Engineering, Jiangsu University, Zhenjiang 212013, P. R. China.

MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, P. R. China.

出版信息

ACS Omega. 2022 Aug 25;7(35):31509-31519. doi: 10.1021/acsomega.2c04123. eCollection 2022 Sep 6.

Abstract

Terpolymerizations of newly synthesized ethylene (E), vinylcyclohexene (VCH), and 1-hexene were carried out with symmetrical metallocene catalysts -MeSi(2-Me-4-Ph-Ind)ZrCl (catalyst A) and -Et(Ind)ZrCl (catalyst B). X-ray diffractometry (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), high-temperature gel permeation chromatography (GPC), and nuclear magnetic resonance (NMR) spectroscopy were used to evaluate the behavior and microstructure of the polymers. The activity of catalyst B was 1.49 × 10 gm/mmol·h), with a of 73.45 (°C) and Δ of 43.19 (J/g), while catalyst A produced first higher 1-hexene, 19.6 mol %, and VCH contents with a narrow molecular weight distribution (MWD). In previous reports, ethylene propylene monomer dienes (EPDM) had a low content and were used for dielectric and insulating properties with nanomaterials. Second, this paper presents a kind of elastomeric polymers based on E/1-hexene and VCH with a high dielectric constant ( = 6-4) and mechanical properties. In addition, low dielectric loss suggests the suitable application potential of these polymeric materials for the fabrications of capacitors. Also, this work reveals that these polymers can be a better candidate for high-voltage electrical insulation due to their enhanced dielectric, mechanical, and thermal characteristics. To examine the insulating property, the interface characteristics of the polymer were evaluated using electrochemical impedance spectroscopy (EIS) with a frequency range of 1 × 10-0.01 Hz and an amplitude of 5.0 mV. EIS is an effective method to investigate the polymers' interfacial electron transfer characteristics. The EIS Nyquist plot showed high Warburg impedance features in the low-frequency domain with straight lines without a semicircle, suggesting that the property of the polymer owing to the high electrical resistance and poor conductivity for ionic kinetics in the electrolyte may have surpassed that of the semicircle. Although the slope of low frequencies in polymers holding potent exoelectrogenic bacteria ( MR-1) as a charge carrier in the electrolyte could significantly reduce the Warburg resistance, it still could not improve the conductivity, which demonstrated that the external charge supply could not alter the insulating property in the used polymers.

摘要

采用对称茂金属催化剂 -MeSi(2-Me-4-Ph-Ind)ZrCl(催化剂 A)和 -Et(Ind)ZrCl(催化剂 B)进行新合成的乙烯(E)、乙烯基环己烯(VCH)和 1-己烯的三元聚合反应。利用 X 射线衍射仪(XRD)、扫描电子显微镜(SEM)、差示扫描量热法(DSC)、高温凝胶渗透色谱法(GPC)和核磁共振(NMR)光谱来评估聚合物的行为和微观结构。催化剂 B 的活性为 1.49×10 gm/mmol·h,熔点为 73.45(°C),熔融热为 43.19(J/g),而催化剂 A 首先生成较高含量的 1-己烯(19.6 摩尔%)和 VCH,且分子量分布较窄(MWD)。在先前的报道中,乙烯-丙烯-二烯烃单体(EPDM)含量较低,与纳米材料一起用于介电和绝缘性能。其次,本文提出了一种基于 E/1-己烯和 VCH 的具有高介电常数(= 6 - 4)和机械性能的弹性体聚合物。此外,低介电损耗表明这些聚合物材料在制造电容器方面具有合适的应用潜力。而且,这项工作表明,由于其增强的介电、机械和热特性,这些聚合物可以成为高压电绝缘的更好候选材料。为了研究绝缘性能,使用频率范围为 1×10 - 0.01 Hz、幅度为 5.0 mV 的电化学阻抗谱(EIS)来评估聚合物的界面特性。EIS 是研究聚合物界面电子转移特性的有效方法。EIS 奈奎斯特图在低频域显示出高 Warburg 阻抗特征,为无半圆的直线,这表明聚合物的性能由于电解质中高电阻和离子动力学导电性差可能超过了半圆的情况。尽管在电解质中以强效产电细菌(MR - 1)作为电荷载体的聚合物中低频斜率可显著降低 Warburg 电阻,但仍无法提高导电性,这表明外部电荷供应无法改变所用聚合物的绝缘性能。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c59/9453979/a2eb7438674b/ao2c04123_0002.jpg

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