Copolymerization of dienes with neodymium tricarboxylate-based catalysts andcis-polymerization mechanism of dienes
1998; Wiley; Volume: 36; Issue: 11 Linguagem: Inglês
10.1002/(sici)1099-0518(199808)36
ISSN1099-0518
AutoresEiichi Kobayashi, Nahoto Hayashi, Sadahito Aoshima, Junji Furukawa,
Tópico(s)Synthetic Organic Chemistry Methods
ResumoJournal of Polymer Science Part A: Polymer ChemistryVolume 36, Issue 11 p. 1707-1716 Article Copolymerization of dienes with neodymium tricarboxylate-based catalysts and cis-polymerization mechanism of dienes Eiichi Kobayashi, Corresponding Author Eiichi Kobayashi Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, Noda, Chiba 278, JapanDepartment of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, Noda, Chiba 278, JapanSearch for more papers by this authorNahoto Hayashi, Nahoto Hayashi Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, Noda, Chiba 278, JapanSearch for more papers by this authorSadahito Aoshima, Sadahito Aoshima Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, Noda, Chiba 278, JapanSearch for more papers by this authorJunji Furukawa, Junji Furukawa Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, Noda, Chiba 278, JapanSearch for more papers by this author Eiichi Kobayashi, Corresponding Author Eiichi Kobayashi Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, Noda, Chiba 278, JapanDepartment of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, Noda, Chiba 278, JapanSearch for more papers by this authorNahoto Hayashi, Nahoto Hayashi Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, Noda, Chiba 278, JapanSearch for more papers by this authorSadahito Aoshima, Sadahito Aoshima Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, Noda, Chiba 278, JapanSearch for more papers by this authorJunji Furukawa, Junji Furukawa Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, Noda, Chiba 278, JapanSearch for more papers by this author First published: 21 January 2000 https://doi.org/10.1002/(SICI)1099-0518(199808)36:11 3.0.CO;2-OCitations: 37AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat Abstract It was found that poly(butadiene), poly(isoprene), and poly(2,3-dimethylbutadiene) with high cis-1,4 content were obtained with Nd(OCOR)3–(i-Bu)3Al–Et2AlCl catalysts (R = CF3, CCl3, CHCl2, CH2Cl, CH3) in hexane at 50°C [cis-1,4 content: poly(BD), > 98%; poly(IP), ≥ 96%; poly(DMBD), ≥ 94%]. Copolymerization of IP and styrene (St) was carried out at various monomer feed ratios to evaluate the monomer reactivity ratio and cis-1,4 content of the diene unit and then to elucidate the cis-1,4 polymerization mechanism of IP. The cis-1,4 content of the IP unit in the copolymers decreased with increasing St content in the copolymers. The cis-1,4 polymerization was disturbed by incorporating St unit in the copolymers, since the penultimate St unit hardly coordinates to the neodymium metal, resulting in a decrease of the cis-1,4 content in the copolymers. That is, the cis-1,4 polymerization of IP is suggested to be controlled by a back-biting coordination of the penultimate diene unit. On the other hand, in the case of poly(BD-co-IP) and poly(BD-co-DMBD), the cis-1,4 content of the BD, IP, and DMBD units in the copolymers was almost constant (cis: 94–98%), irrespective of the monomer feed ratios and polymerization temperature. Consequently, the penultimate IP and DMBD units favorably control the terminal BD, IP, or DMBD unit to the cis-1,4 configuration through the back-biting coordination. For the monomer reactivity ratios, a clear difference was observed in each system: rBD = 1.22, rIP = 1.14; rBD = 40.9, rDMBD = 0.15. Low polymerizability of DMBD was mainly ascribed to the steric effect of the methyl substituents. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1707–1716, 1998 Citing Literature Volume36, Issue11August 1998Pages 1707-1716 RelatedInformation
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