{"title":"用二苯并亚胺吡啶镍催化剂合成高MFI聚烯烃弹性体","authors":"Jun Gan and Shengyu Dai","doi":"10.1039/D5PY00083A","DOIUrl":null,"url":null,"abstract":"<p >Recently, nickel-based α-diimine catalysts have been widely used in the preparation of polyolefin elastomer materials. However, the polyolefin materials obtained from this system often exhibit high molecular weights, leading to a low melt flow index (MFI) and difficulties in film processing. Herein, we first report the synthesis and characterization of a class of nickel dibenzosuberyl iminopyridyl catalysts, featuring backbones and arylamine substituents with varying electronic effects. These catalysts demonstrate high activity (10<small><sup>6</sup></small> g mol<small><sup>−1</sup></small> h<small><sup>−1</sup></small>) in ethylene polymerization and enable the synthesis of polyethylene elastomers with moderate molecular weights (53.8–156.9 kg mol<small><sup>−1</sup></small>) and branching densities (55–87/1000 C). The electronic properties of the catalyst backbone and the arylamine substituents have a general influence on ethylene polymerization and the properties of the resulting products. However, increasing the polymerization temperature significantly reduced the polymerization activity and altered the molecular weight and branching density of the obtained polyethylene elastomers. Mechanical property tests of these polyethylene elastomers reveal excellent elongation at break (1617%–1729%) and moderate tensile strength at break (5.46–10.58 MPa) and elastic recovery ratios (30%–45%). MFI tests, as well as transmittance and volume resistivity measurements, indicate that the obtained polyethylene elastomer materials possess high MFR (16–22 g per 10 min), high transmittance (84–89%), and high volume resistivity (151–321 × 10<small><sup>15</sup></small> Ω m), making them suitable for use as photovoltaic encapsulant films.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 27","pages":" 3172-3178"},"PeriodicalIF":3.9000,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis of high MFI polyolefin elastomers using dibenzosuberyl iminopyridyl Ni(ii) catalysts†\",\"authors\":\"Jun Gan and Shengyu Dai\",\"doi\":\"10.1039/D5PY00083A\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Recently, nickel-based α-diimine catalysts have been widely used in the preparation of polyolefin elastomer materials. However, the polyolefin materials obtained from this system often exhibit high molecular weights, leading to a low melt flow index (MFI) and difficulties in film processing. Herein, we first report the synthesis and characterization of a class of nickel dibenzosuberyl iminopyridyl catalysts, featuring backbones and arylamine substituents with varying electronic effects. These catalysts demonstrate high activity (10<small><sup>6</sup></small> g mol<small><sup>−1</sup></small> h<small><sup>−1</sup></small>) in ethylene polymerization and enable the synthesis of polyethylene elastomers with moderate molecular weights (53.8–156.9 kg mol<small><sup>−1</sup></small>) and branching densities (55–87/1000 C). The electronic properties of the catalyst backbone and the arylamine substituents have a general influence on ethylene polymerization and the properties of the resulting products. However, increasing the polymerization temperature significantly reduced the polymerization activity and altered the molecular weight and branching density of the obtained polyethylene elastomers. Mechanical property tests of these polyethylene elastomers reveal excellent elongation at break (1617%–1729%) and moderate tensile strength at break (5.46–10.58 MPa) and elastic recovery ratios (30%–45%). MFI tests, as well as transmittance and volume resistivity measurements, indicate that the obtained polyethylene elastomer materials possess high MFR (16–22 g per 10 min), high transmittance (84–89%), and high volume resistivity (151–321 × 10<small><sup>15</sup></small> Ω m), making them suitable for use as photovoltaic encapsulant films.</p>\",\"PeriodicalId\":100,\"journal\":{\"name\":\"Polymer Chemistry\",\"volume\":\" 27\",\"pages\":\" 3172-3178\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2025-06-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/py/d5py00083a\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/py/d5py00083a","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
摘要
近年来,镍基α-二亚胺催化剂在制备聚烯烃弹性体材料中得到了广泛的应用。然而,从该体系中获得的聚烯烃材料通常具有高分子量,导致低熔体流动指数(MFI)和薄膜加工困难。在此,我们首次报道了一类具有不同电子效应的骨架和芳胺取代基的二苯并亚氨基吡啶镍催化剂的合成和表征。这些催化剂在乙烯聚合中表现出高活性(106 g mol-1 h-1),能够合成中等分子量(53.8-156.9 kg mol-1)和分支密度(55-87/1000℃)的聚乙烯弹性体。催化剂主链和芳胺取代基的电子性质对乙烯聚合和产物的性质有普遍的影响。而提高聚合温度会显著降低聚合活性,并改变所得聚乙烯弹性体的分子量和分支密度。力学性能测试表明,聚乙烯弹性体具有优异的断裂伸长率(1617% ~ 1729%)、中等的断裂抗拉强度(5.46 ~ 10.58 MPa)和弹性回复率(30% ~ 45%)。MFI测试以及透光率和体积电阻率测量表明,所得聚乙烯弹性体材料具有高MFI (16-22 g/10 min)、高透光率(84-89%)和高体积电阻率(151-321 × 1015 Ω·m),适合用作光伏封装膜。
Synthesis of high MFI polyolefin elastomers using dibenzosuberyl iminopyridyl Ni(ii) catalysts†
Recently, nickel-based α-diimine catalysts have been widely used in the preparation of polyolefin elastomer materials. However, the polyolefin materials obtained from this system often exhibit high molecular weights, leading to a low melt flow index (MFI) and difficulties in film processing. Herein, we first report the synthesis and characterization of a class of nickel dibenzosuberyl iminopyridyl catalysts, featuring backbones and arylamine substituents with varying electronic effects. These catalysts demonstrate high activity (106 g mol−1 h−1) in ethylene polymerization and enable the synthesis of polyethylene elastomers with moderate molecular weights (53.8–156.9 kg mol−1) and branching densities (55–87/1000 C). The electronic properties of the catalyst backbone and the arylamine substituents have a general influence on ethylene polymerization and the properties of the resulting products. However, increasing the polymerization temperature significantly reduced the polymerization activity and altered the molecular weight and branching density of the obtained polyethylene elastomers. Mechanical property tests of these polyethylene elastomers reveal excellent elongation at break (1617%–1729%) and moderate tensile strength at break (5.46–10.58 MPa) and elastic recovery ratios (30%–45%). MFI tests, as well as transmittance and volume resistivity measurements, indicate that the obtained polyethylene elastomer materials possess high MFR (16–22 g per 10 min), high transmittance (84–89%), and high volume resistivity (151–321 × 1015 Ω m), making them suitable for use as photovoltaic encapsulant films.
期刊介绍:
Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.