Polymerization of Isobutylene and the Copolymerization of Isobutylene and Isoprene Initiated by the Metallocene Derivative Cp*TiMe2(μ-Me)B(C6F5)3

Isobutylene polymerization is initiated by Cp*TiMe 2 (μ-Me)B(C 6 F 5 ) 3, formed by combining Cp*TiMe 3 and B(C 6 F 5 ) 3 in a 1:1 ratio. The polymerization process exhibits the signature of a carbocationic mechanism, as molecular weights generally increase with decreasing temperature, polydispersities are ∼2, and polymers contain vinylidene end groups. Initiation probably occurs via η 1 -coordination of a molecule of monomer to the cationic species [Cp*TiMe 2 ] +, while propagation and chain transfer proceed as with conventional Lewis acid initiators. Although addition of the proton trap 2,6-di- tert -butylpyridine does have an adverse effect on polymerization, this is not because traces of possible protic initiators are being scavenged but rather because the 2,6-di- tert -butylpyridine coordinates to the titanium cation and inhibits activation of monomer. Further evidence that [Cp*TiMe 2 ] + behaves as a carbocationic initiator is that the system induces dimerization of 1,1-diphenylethylene to 1,3,3-triphenyl-3-methylindan and also the formation of isobutylene−isoprene copolymers (butyl rubber) in which the isoprene is incorporated via trans-1,4-addition, again typical of conventional initiators. This initiator system is the first metallocene-based carbocationic initiator system to be discovered, and it also appears to be one of the more active.