Ring opening reactions of glycidyl methacrylate copolymers to introduce bulky organosilicon side chain substituents

Glycidyl methacrylate (GMA) random copolymers with methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (BA), methyl methacrylate (MMA), ethyl methacrylate (EMA) and n-butyl methacrylate (BMA) were synthesized by solution free radical polymerizations, at 70 +/- 1 degrees C using alpha,alpha'-azobis(isobutyronitrile) as an initiator to give the copolymers I - VI in good yields. The copolymer compositions were obtained using related H-1 NMR spectra and the polydispersity indices of the copolymers determined using gel permeation chromatography (GPC). Tris(trimethylsilyl)methyl (Tsi=trisyl) groups were then covalently attached to the obtained copolymers as side chains by ring opening reaction between excess of TsiLi and expoxide groups of GMA units to give the copolymers I-Tsi - VITsi in good yields. In the coupling reaction, the TsiLi reacted selectively with the epoxy groups of the backbone polymer rather than with the carbonyl groups of the backbone. This method of preparing functionalized silanes is limited by the readiness with which TsiLi abstracts a proton, if one is available, rather than attacks at carbon. In addition in the reaction with epoxides, the product alkoxide can transfer a silyl group from carbon to oxygen or ring opening polymerization. However these were shown not to occur at the conditions of interest here. The epoxy group possesses a higher reactivity for the TsiLi than the ester and chloromethyl groups. The ring opening reaction between the epoxy group and the TsiLi is simple and fast. All the resulted polymers were characterized by FT-IR and H-1 NMR spectroscopic techniques. The glass transition temperature (Tg) of all copolymers was determined by differential scanning calorimetry (DSC) apparatus. All the polymers containing trisyl groups showed a high glass transition temperature in comparison with unmodified copolymers (I - VI). Attaching the tris(trimethylsilyl)methyl group to macromolecular chain should lead to important modifications of polymer properties such as gas permeability and perm selectivity parameters.