Linear PCHD and polyisoprenes with different microstructures and molecular weights are synthesized and chemically modifi ed to improve their thermal and chemical stability by forming a three-membered ring structure containing two C Ϫ F bonds. Pyrolysis of these fl uorinated polydienes proceeds through a two-stage decomposition involving chain scission, crosslinking, dehydrogenation, and dehalogenation. The pyrolysis leads to graphite-like residues, whereas their polydiene precursors decompose completely under the same conditions. The fl uorination of PCHD enhances its thermal stability. The stronger C Ϫ F bond along with high strain of the three-membered ring structure and formation of relatively stable free radicals play an important role in the thermal stability of fl uorinated polydienes.
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