The polymerization of norbornadiene (NBD) initiated by the 2-chloro-2,4,4-trimethylpentane/titanium tetrachloride system was investigated. Efforts were made to develop conditions for the living polymerization of NBD by the use of proton trap and electron donor in the -35 to -60 degreesC range however this objective was only partially attained. The molecular weights increased linearly with conversion, and the rate was first-order in confirmed monomer concentration up to approximately 25%; however, chain transfer became operational beyond this range. The microstructure of polynorbornadiene (PNBD) was investigated by high-resolution H-1 and C-13 NMR spectroscopy According to these techniques, the chain consisted of About equal amounts of exo/exo and exo/endo connected tricyclic repeat units. The head and tail groups were identified and quantitated, and this led to absolute molecular weight determination by integration. Molecular weights obtained by this method and by gel permeation chromatography (relative to polyisobutylene standards) were in good agreement. NMR spectroscopy indicated the presence of small but still identifiable amounts of branching units and their structures. The plot of the glass-transition temperature against the reciprocal of the number-average molecular weight was linear and yielded a glass-transition temperature of 323 degreesC for the infinite molecular weight polymer. According to thermogravimetric analysis, PNBD was stable up to approximately 250 degreesC and showed a 5% weight loss at approximately 335 degreesC. (C) 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41:732-739,2003.