Highly branched unsaturated polyethylenes achievable using strained imino-cyclopenta[b]pyridyl-nickel precatalysts
文献类型：期刊论文
| 作者 | Zhang, Youfu1,2,3; Huang, Chuanbing2,3,4; Wang, Xinxin2,3,4; Mahmood, Qaiser2,3,4; Hao, Xiang2,3; Hu, Xinquan1; Guo, Cun-Yue4; Solan, Gregory A.2,3,5; Sun, Wen-Hua2,3,4,6
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| 刊名 | POLYMER CHEMISTRY
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| 出版日期 | 2017-02-14 |
| 卷号 | 8期号:6页码:995-1005 |
| 英文摘要 | A new family of strained imino-cyclopenta[b] pyridines, 7-(ArN)-6-Me2C8H5N (Ar = 2,6-Me2Ph (L1), 2,6-Et2Ph (L2), 2,4,6-Me3Ph (L3), 2,6-Et-2-4-MePh (L4), 2,6-i-Pr2Ph (L5)), have been synthesized in reasonable yield by a sequence of reactions from 2-chloro-cyclopenta[b]pyridin-7-one. Treatment of L1 and L3 with NiCl2 center dot 6H(2)O generates mononuclear bis-ligated [7-(ArN)-6-Me2C8H5N](2)NiCl2 (Ar = 2,6-Me2Ph (Ni1), 2,4,6-Me3Ph (Ni3)), while with L2 and L4, the chloride-bridged binuclear complexes [7-(ArN)6- Me2C8H5N](2)Ni-2(mu-Cl)(2)Cl-2 (Ar = 2,6-Et2Ph (Ni2), 2,6-Et-2-4-MePh (Ni4)), have been isolated; no apparent reaction occurred with L5. On activation with either MAO or MMAO, Ni1-Ni4 exhibited high activities towards ethylene polymerization with Ni3 the most active (5.02 x 10(6) g PE per mol Ni per h at 20 degrees C); rapid regeneration of the active species (3096-5478 h(-1) at 20 degrees C) is a feature of their catalytic performance. A detailed microstructural analysis of the polyethylenes reveals the presence of vinyl and higher levels of internal vinylene groups indicative of high rates of chain isomerization, e.g., the ratio of (-CH=CH-) to (H2C=CH-) groups is 2.2 : 1 using Ni3/MAO at 60 degrees C. Agostic interactions involving gamma-, delta- and higher-hydrogens are inferred in addition to beta-hydrogen elimination to account for the vinylene groups and the longer chain alkyl branches. The molecular structures of Ni1 and Ni2 center dot 2MeOH are also reported. |
| 语种 | 英语 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/38249]  |
| 专题 | 化学研究所_工程塑料实验室 |
| 作者单位 | 1.Zhejiang Univ Technol, Coll Chem Engn, Hangzhou 310014, Zhejiang, Peoples R China 2.Chinese Acad Sci, Inst Chem, Key Lab Engn Plast, Beijing 100190, Peoples R China 3.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China 4.Univ Chinese Acad Sci, Sch Chem & Chem Engn, Beijing 100049, Peoples R China 5.Univ Leicester, Dept Chem, Univ Rd, Leicester LE1 7RH, Leics, England 6.Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China |
| 推荐引用方式 GB/T 7714 | Zhang, Youfu,Huang, Chuanbing,Wang, Xinxin,et al. Highly branched unsaturated polyethylenes achievable using strained imino-cyclopenta[b]pyridyl-nickel precatalysts[J]. POLYMER CHEMISTRY,2017,8(6):995-1005. |
| APA | Zhang, Youfu.,Huang, Chuanbing.,Wang, Xinxin.,Mahmood, Qaiser.,Hao, Xiang.,...&Sun, Wen-Hua.(2017).Highly branched unsaturated polyethylenes achievable using strained imino-cyclopenta[b]pyridyl-nickel precatalysts.POLYMER CHEMISTRY,8(6),995-1005. |
| MLA | Zhang, Youfu,et al."Highly branched unsaturated polyethylenes achievable using strained imino-cyclopenta[b]pyridyl-nickel precatalysts".POLYMER CHEMISTRY 8.6(2017):995-1005. |
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来源：化学研究所
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