Investigation of homopolymerization rate of perfluoro-4,5-substituted-2- methylene-1,3-dioxolane derivatives and properties of the polymers

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).