Polymerization of Cyclophosphazenes with Spriocyclic Methacrylate Containing Substituents

The radical addition polymerization and copolymerization of the cyclophosphazene monomers with spirocyclic methacrylate containing substituents, spiro(2,3-dioxypropylmethacryloyl)tetrachlorocyclotriphosphazene, N 3 P 3 Cl 4 [OCH 2 CH(OC(O)=CH 2 )O] ( 1 ) and spiro((2-methyl-3-oxy-2-(oxymethyl)propyl)methacryloyl)tetrachlorocyclotriphosphazene, N 3 P 3 Cl 4 [OCH 2 CMe(CH 2 OC(O)=CH 2 )CH 2 O] ( 2 ), has been investigated. In the case of 1 , homopolymerization using AIBN as the initiator yielded only cross-linked solids. Copolymerization of 1 with methyl methacrylate was accomplished using VAZO 52 under milder initiation temperature. GPC of copolymer suggested a significant amount of chain transfer. Homopolymerization of 2 gave low isolated yields of the homopolymer but copolymerization with methyl methacrylate yielded the expected copolymers. The reactive chlorine atoms in the copolymers of 2 can be replaced by trifluoroethoxide or methyl amine. Thermal properties of the copolymers were examined by DSC, TGA and pyrolysis mass spectrometry.