Abstract
Copolymers from methacrylic acid (1) and trimethylsilyl methacrylate (2) have been synthesized by free radical copolymerisation and by controlled desilylation of poly(trimethylsilyl methacrylate) (3). The reactivity ratios were r~1~β=β2.75, r~2~β=β0.004. Differential scanning calorimetry showed a linear correlation between the peak temperature of the endotherm for the formation of cyclic anhydrides and the content of methacrylic acid in the copolymer. Obviously, the acid catalyses this reaction. The copolymers as well as poly(trimethylsilyl methacrylate) have a ceiling temperature. Sequence distributions were calculated and used to predict glass transition temperatures for comparison to the experimental results. The microstructure of the copolymers obtained by the different synthetic routes is different as shown from T~g~ and from their solubility. Those from desilylation are random with βreactivity ratiosβ of 1, those from copolymerisation seem to have longer sequences of methacrylic acid leading to formation of intermolecular aggregates.
Dependence of DSC peak temperature of anhydride formation on methacrylic acid content.
magnified imageDependence of DSC peak temperature of anhydride formation on methacrylic acid content.