Synthesis and characterization of new polymer systems containing very bulky tris(trimethylsilyl)methyl substituents as side chains

The 4-chloromethyl styrene (CMS) was copolymerized with different styrenic monomers such as methyl styrene, 4-methoxy styrene and alpha-methyl styrene by free radical polymerization method at 70 +/- 1 degreesC using alpha,alpha'-azobis(isobutyronitrile) (AIBN) as an initiator and the copolymers I, II and III collected respectively. The very bulky tris(trimethylsilyl)methyl {trisyl} substituents were covalently attached to the obtained copolymers with replacement of all the chlorine atoms in CMS units. The polymers, obtained in quantitative yields, were characterized by FT-IR, H-1 NMR and C-13 NMR spectroscopy; differential scanning calorimetry (DSC) and GPC studies. All the polymers containing trisyl groups showed a high glass transition temperature (in the range 150-190 degreesC) in comparison with copolymers I-III (in the range 90-95 degreesC). The increase of the glass transition temperature reflects the substantial increase in rigidity of new polymers bearing very bulky substituents in side chains. (C) 2003 Elsevier Ltd. All rights reserved.