Thermally reversible polymer systems by cyclopentadienylation. I. A model for termination by cyclopentadienylation of olefin polymerization

The reaction between tert-butylchloride (t-BuCl) and dimethylcyclopentadienylaluminum (Me₂AlCPD) was studied as a model for initiation by the tert-butyl cation (t-Bu^⊕) and termination by cyclopentadienylation by the Me₂Al(CPD)Cl^? counteranion of isobutylene polymerization. All reaction products formed in this model system have been identified and quantitatively determined. A comprehensive scheme that indicates pathways to these products was developed (scheme III). It is proposed that the predominant product, tert-butylcyclopentadiene (t-BuCPD), arises in the collapse of the t-Bu^⊕-Me₂Al(CPD)Cl^? ion pair, mainly by CPD^? transfer to the tert-butyl cation. The minor products are neopentane (t-BuMe) and isobutylene (i-C₄H₈), which are probably formed, respectively, by Me^? transfer to and proton loss from the t-butyl cation. Cyclopentadienylation selectivity increases by lowering the temperature and extrapolation of results suggests 100% cyclopentadienylation at ?55°C. The t-BuCl/Me₂AlCPD ratio strongly influences the overall reaction pathway. The reaction is first order in t-BuCl with ΔE_a of ca. 7 kcal/mole (1,2-dichloroethane or chlorobenzene solvents, +24 to ?29°C). Indirect evidence indicates that the kinetic product of cyclopentadienylation is 5-t-BuCPD and that this isomer cannot be tert-butylated; that is, the initiation of 5-t-BuCPD polymerization by t-Bu^⊕ is sterically unfavorable. Detailed analysis of the chemistry and kinetics of the t-BuCl/Me₂AlCPD model system holds important clues to the controlled polymerization of olefins leading to macromolecules with cyclopentadiene (CPD) termini.