Isobutene polymerization initiated by [CPTiMe2]+ in the presence of a series of novel, weakly coordinating counteranions

• Published in: Journal of polymer science. Part A, Polymer chemistry Polymer chemistry, 2002-10, Vol.40 (19), p.3302-3311
• Main Authors: Kumar, K. Rajesh, Hall, Chernoff, Penciu, Anca, Drewitt, Mark J., McInenly, Paula J., Baird, Michael C.
• Format: Article
• Language: English
• Subjects: Applied sciences; cationic polymerization; elastomers; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Polymerization; polyolefins; Preparation, kinetics, thermodynamics, mechanism and catalysts
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.10416

The highly electrophilic borane B(C6F5)3 reacts with n‐octadecanol (n‐C18H37OH) and n‐octadecanethiol (n‐C18H37SH) to form the 1:1 adducts (n‐C18H37EH)B(C6F5)3 (E = O or S). The latter are acidic and react with Cp*TiMe3 in methylene chloride and toluene to give methane and the complexes [Cp*TiMe2][(n‐C18H37E)B(C6F5)3], which are very good initiators for the carbocationic polymerization of isobutene (IB) from −40 to −20 °C. High conversions to high molecular weight polyisobutene (PIB) in methylene chloride and moderate conversions to high molecular weight PIB in toluene are observed and are consistent with the anions [(n‐C18H37E)B(C6F5)3]− being very weakly coordinating. Although polymerization in methylene chloride is too rapid for the temperature to be controlled, polymerization in toluene is slower, and the temperatures can be controlled so that Arrhenius‐type plots of the logarithm of the number‐average molecular weight versus T−1 = 1/T may be obtained. Activation energies for the degree of polymerization in these polymerization reactions and similar polymerizations carried out with n‐C18H37EH:borane ratios of 1:2 and with the activators [Ph3C][B(C6F5)4] and Al(C6F5)3 range from −11 to −27 kJ mol−1, values comparable to those for most conventional IB polymerization initiators. However, the values of the weight‐average and number‐average molecular weights are unusually high for the temperatures used, and this is consistent with current theories of the role of weakly coordinating anions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3302–3311, 2002 The complexes Cp*TiMe2(μ‐Me)B(C6F5)3 and [Cp*TiMe2][(n‐C18H37E)B(C6F5)3] (E = O, S) are excellent initiators in toluene for the controlled polymerization of isobutene in the studied temperature range.