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Living Regioselective Copolymerization of Ethylene with Nonconjugated Bicyclic Dienes Using (Salicylaldiminato)(beta-enaminoketonato) Titanium Catalysts
Long, Ying-Yun2; Wang, Yong-Xia2; Liu, Jing-Yu2; Li, Xiao-Fang1; Li, Yue-Sheng2
2011-11-01
Source PublicationJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
ISSN0887-624X
Volume49Issue:21Pages:4626-4638
AbstractA series of heteroligated (salicylaldiminato)(beta-enaminoketonato) titanium complexes [3-(t)Bu-2-OC(6)H(3)CH N(C(6)F(5))] [PhN=C(CF(3))CHCRO]TiCl(2) [3a: R Ph, 3b: R C(6)H(4)Cl(p), 3c: R = C(6)H(4)OMe(p), 3d: R = C(6)H(4)Me(p), 3e: R = C(6)H(4)Me(o)] were synthesized and characterized. Molecular structures of 3b and 3c were further confirmed by X-ray crystallographic analyses. In the presence of modified methylaluminoxane as a cocatalyst, these unsymmetric catalysts displayed favorable ability to incorporate 5-vinyl-2-norbornene (VNB) and 5-ethylidene-2-norbornene (ENB) into the polymer chains, affording high-molecular weight copolymers with high-comonomer incorporations and alternating sequence under the mild conditions. The comonomer concentration in the polymerization medium had a profound influence on the molecular weight distribution of the resultant copolymer. At initial comonomer concentration of higher than 0.4 mol/L, the titanium complexes with electron-donating groups in the beta-enaminoketonato moiety mediated room-temperature living ethylene/VNB or ENB copolymerizations. Polymerization results coupled with density functional theory calculations suggested that the highly controlled living copolymerization is probably a consequence of the difficulty in chain transfer of VNB (or ENB)-last-inserted species and some characteristics of living ethylene polymerization under limited conditions. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 4626-4638, 2011
KeywordHeteroligated Catalyst Living Polymerization Poly-olefins Ziegler-natta Polymerization
DOI10.1002/pola.24906
Indexed BySCI
Language英语
WOS IDWOS:000296255200014
PublisherWILEY-BLACKWELL
Citation statistics
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/73260
Collection中国科学院化学研究所
Corresponding AuthorLi, Xiao-Fang
Affiliation1.Beijing Inst Technol, Key Lab Cluster Sci, Minist Educ, Beijing 100081, Peoples R China
2.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China
Recommended Citation
GB/T 7714
Long, Ying-Yun,Wang, Yong-Xia,Liu, Jing-Yu,et al. Living Regioselective Copolymerization of Ethylene with Nonconjugated Bicyclic Dienes Using (Salicylaldiminato)(beta-enaminoketonato) Titanium Catalysts[J]. JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY,2011,49(21):4626-4638.
APA Long, Ying-Yun,Wang, Yong-Xia,Liu, Jing-Yu,Li, Xiao-Fang,&Li, Yue-Sheng.(2011).Living Regioselective Copolymerization of Ethylene with Nonconjugated Bicyclic Dienes Using (Salicylaldiminato)(beta-enaminoketonato) Titanium Catalysts.JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY,49(21),4626-4638.
MLA Long, Ying-Yun,et al."Living Regioselective Copolymerization of Ethylene with Nonconjugated Bicyclic Dienes Using (Salicylaldiminato)(beta-enaminoketonato) Titanium Catalysts".JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49.21(2011):4626-4638.
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