Isobutene polymerization and isobutene-isoprene copolymerization catalyzed by cationic zirconocene hydride complexes

Garratt, Shaun, Carr, Andrew G., Langstein, Gerhard and Bochmann, Manfred ORCID: https://orcid.org/0000-0001-7736-5428 (2003) Isobutene polymerization and isobutene-isoprene copolymerization catalyzed by cationic zirconocene hydride complexes. Macromolecules, 36 (12). pp. 4276-4287. ISSN 0024-9297

Full text not available from this repository. (Request a copy)

Abstract

The cationic zirconocene trihydrides [Cp‘4Zr2H(µ-H)2]+X-, generated from [Cp‘2ZrH2]2 with various trityl salts of weakly coordinating anions, are powerful initiators for the polymerization of isobutene (IB) and its copolymerization with isoprene (IP) (Cp‘ = C5H4SiMe3). This study is concerned with the quantification of the effects of the counteranion and of trace moisture on IB/IP copolymers and the nature of the initiating species. Polymer molecular weights increase with decreasing anion nucleophilicity in the order X = [B(C6F5)4] ˜ [H2N{B(C6F5)3}2] > [CN{B(C6F5)3}2]. Using [Cp‘4Zr2H3]+ [CN{B(C6F5)3}2]-, high copolymer molecular weights are found (Mw ˜ 5 × 105 g/mol at -35 °C). There is little reduction in either rate or molecular weight on addition of isoprene. Polymer molecular weights are substantially higher than with the Et2AlCl/tBuCl initiator system under identical conditions. Water was shown to be an important chain-transfer agent; substoichiometric quantities of water reduced activity, and copolymer molecular weights decreased linearly with increasing [H2O]. Mechanistic studies suggest that [Cp‘4Zr2H(µ-H)2]+ does not itself act as a cationic initiator but is transformed into one or more other binuclear (polynuclear?) species, accompanied by alkene insertion into the Zr-H bond and a monomer hydrogenation step. Tentative structures for these reactive intermediates are suggested.

Item Type:	Article
Faculty \ School:	Faculty of Science > School of Chemistry
UEA Research Groups:	Faculty of Science > Research Groups > Synthetic Chemistry (former - to 2017) Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Chemistry of Materials and Catalysis
Depositing User:	Rachel Smith
Date Deposited:	02 Nov 2010 17:48
Last Modified:	13 Jan 2024 01:23
URI:	https://ueaeprints.uea.ac.uk/id/eprint/10491
DOI:	10.1021/ma034320p

Actions (login required)

View Item