Abstract
Solvent effects on free-radical copolymer composition and propagation kinetics of styrene (ST) with three methacrylates, 2-hydroxyethyl methacrylate (HEMA), glycidyl methacrylate (GMA), and n-butyl methacrylate (BMA), are investigated using pulsed-laser polymerization combined with size exclusion chromatography and proton NMR. Three representative solvents, n-butanol, toluene, and DMF (N,N-dimethylformamide), are selected based on their polarity and structure. It was found that all three solvents have an effect on ST/HEMA copolymer composition compared to bulk copolymerization, with a systematic variation in monomer reactivity ratios observed with solvent polarity. Only butanol affects ST/BMA copolymer composition, and solvent choice has no effect on composition for the ST/GMA system. Butanol increases the composition-averaged copolymerization propagation rate coefficient, kp,cop, only for the ST/BMA system, while DMF causes a uniform decrease of kp,cop for all three systems and toluene has no observable ...
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