Five perfluoro-4,5-substituted-2-methylene-1,3-dioxolane monomers were synthesized. These monomers were found to readily polymerized by a free radical initiator in bulk and/or in solutions. Homopolymerization rates were determined using in situ 19F NMR measurements and found to be 0.25 to 1.66 × 10-4 mol L-1 s-1 in 1,1,2-trichlorotrifluoroethane at 41°C using the perfluorodibenzoyl peroxide as an initiator. The rates depend on the substituents on the 4 and 5 positions of the dioxolane. The purified polymers were thermally stable (up to 350°C). They show low refractive indexes (1.33-1.36 at 532 nm). They are transparent from UV to near IR region and have high glass transition temperatures (100-170°C).
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