ortho-Cycloalkyl substituted N, N'-diaryliminoacenaphthene- Ni(II) catalysts for polyethylene elastomers; exploring ring size and temperature effects

ortho-Cycloalkyl substituted N, N'-diaryliminoacenaphthene- Ni(II) catalysts for polyethylene elastomers; exploring ring size and temperature effects Full article

Journal

Dalton Transactions
ISSN: 1477-9226 , E-ISSN: 1477-9234

Output data

Year: 2017, Volume: 46, Number: 45, Pages: 15684-15697 Pages count : DOI: 10.1039/c7dt03362a

Authors

Suo Hongyi ^1,2 , Oleynik Irina V. ⁴ , Huang Chuanbing ^1,2,3 , Oleynik Ivan I. ^2,4 , Solan Gregory A. ^1,2,5 , Ma Yanping ^1,2 , Liang Tongling ^1,2 , Sun Wen-Hua ^1,2,3

Affiliations

1	(Данные Web of science) Chinese Acad Sci, Inst Chem, Key Lab Engn Plast, Beijing 100190, Peoples R China
2	(Данные Web of science) Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
3	(Данные Web of science) Univ Chinese Acad Sci, CAS Res Educ Ctr Excellence Mol Sci, Beijing 100049, Peoples R China
4	(Данные Web of science) NN Vorozhtsov Novosibirsk Inst Organ Chem, Pr Lavrentjeva 9, Novosibirsk 630090, Russia
5	(Данные Web of science) Univ Leicester, Dept Chem, Univ Rd, Leicester LE1 7RH, Leics, England

A family of six unsymmetrical N,N'-diiminoacenaphthene-nickel(II) bromide complexes, [1-{2,6-(Ph2CH)(2)-4- MeC6H2N}-2-(ArN)C2C10H6] NiBr2 (Ar = 2-(C6H11)-6-MeC6H2 Ni1, 2-(C5H9)-6-MeC6H2 Ni2, 2-(C8H15)-6- MeC6H2 Ni3, 2-(C6H11)-4,6-Me2C6H2 Ni4, 2-(C5H9)-4,6-Me2C6H2 Ni5, 2-(C8H15)-4,6-Me2C6H2 Ni6), each bearing one ring-size variable 4-R-2-methyl-6-cycloalkyl-substituted N-aryl group and one N'-4-methyl- 2,6-dibenzhydrylphenyl group, have been prepared and fully characterized. The molecular structures of Ni1, Ni2, Ni3 and Ni5 reveal distorted tetrahedral geometries with different degrees of steric protection imparted by the two inequivalent N-aryl groups. On activation with either EASC or MMAO, all the precatalysts are highly active (up to 17.45 x 10(6) g PE mol(-1) (Ni) h(-1)) for ethylene polymerization at 20-50 degrees C with their activities correlating with the type of cycloalkyl ortho-substituent: cyclooctyl (Ni6, Ni3) > the cyclopentyl (Ni5, Ni2) > cyclohexyl (Ni4, Ni1) for either R = H or Me. Moderately branched to hyperbranched polyethylenes (T-m's as low as 44.2 degrees C) can be obtained with molecular weights in the range 2.14-6.68 x 10(5) g mol(-1) with the branching content enhanced by the temperature of the polymerization. Dynamic mechanical analysis (DMA) and monotonic tensile stress-strain tests have been employed on the polyethylene samples and reveal the more branched materials to show good elastic recovery properties (up to 75.5%).

Suo H. , Oleynik I.V. , Huang C. , Oleynik I.I. , Solan G.A. , Ma Y. , Liang T. , Sun W-H.
ortho-Cycloalkyl substituted N, N'-diaryliminoacenaphthene- Ni(II) catalysts for polyethylene elastomers; exploring ring size and temperature effects

Dalton Transactions. 2017. V.46. N45. P.15684-15697. DOI: 10.1039/c7dt03362a WOS Scopus РИНЦ

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