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An array of highly fluorinated polymerizable phosphonium salts (HFPPS) were synthesized from PH3 gas via the radical addition to the corresponding olefin. The thermal properties of these new monomers were characterized and correlated to their chemical structure. The molecular design of the monomers had a pronounced effect on their thermal degradation profiles. Monomers utilizing the bis (trifluoromethylsulfonyl) imide ion displayed significantly higher thermal stability in comparison to their chloride analogues. Depending on rate of heating, the onset for degradation was altered dramatically. This has significant implications for the general analysis and discussion of quaternary phosphonium salts. 
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