Tris(trimethylsilyl)methyl functionalized 4‐chloromethyl styrene polymers: Effects of side chain modification on polymer structure and glass transition temperature

4‐Chloromethyl styrene was copolymerized with various molar ratio of methyl methacrylate or ethyl methacrylate by solution free radical polymerization method, at 70 ± 1°C using α,α′‐azobis(isobutyronitrile) as an initiator. Then, very highly sterically hindered tris(trimethylsilyl)methyl substituent was covalently linked to the obtained copolymers with liberation of chlorine atoms. The structure of all polymers was characterized and confirmed by FT‐IR, ¹H and ¹³C NMR spectroscopy techniques. The average molecular weight and glass transition temperature of polymers were determined using gel permeation chromatograph and differential scanning calorimeter instruments, respectively. Study of differential scanning calorimetry analyses showed that chemical modification of 4‐chloromethyl styrene copolymers with tris(trimethylsilyl)methyl substituents leads to an increase in the rigidity and glass transition temperature of polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 633–639, 2006