Synthesis and characterization of trifluoromethyl substituted styrene polymers and copolymers with methacrylates: Effects of trifluoromethyl substituent on styrene

2-Trifluoromethyl styrene (2TFMS), 2,5-bis(trifluoromethyl) styrene (25BTFMS), and 3,5-bis(trifluoromethyl) styrene (35BTFMS) were synthesized. These styrenes were readily polymerized in bulk and also in solution using AIBN as a free radical initiator. The polymerization rate of these trifluoromethyl substituted styrenes and other monomers such as styrene (St), pentafluorostyrene (PFS) and 4-trifluoromethyl-tetrafluorostyrene (TFMTFS) were measured in benzene and dioxane by monitoring the ¹H NMR spectra of the double bond hydrogen. The order of polymerization rates was TFMTFS > 35BTFMS > 25BTFMS > PFS > 2TFMS > St. T_gs of styrene polymers with CF₃ substituted on the ortho position of the phenyl ring were much higher than those of the meta and para substituted styrenes due to the steric hindrance of the bulky CF₃ group close to the polymer main chain, which resulted in a decrease in the segment mobility of the polymer chains and an increasing T_g of the polymers. The copolymers of 2TFMS with methyl methacrylate (MMA) and also 25BTFMS with trifluoroethyl methacrylate (TFEMA) were prepared. T_gs of the copolymers were in the range of 120-145 °C and the copolymers were transparent and thermally stable. The copolymer films were flexible and exhibited high transmittance as the homopolymers of MMA and TFEMA. Thus, these copolymers may be utilized as novel optical materials.