Acrylic Graft Copolymers Via Macromonomers

Comb-shaped poly(methyl methacrylate) (PMMA) and PMMA grafted with poly(nbutyl acrylate) (PnBuA) were prepared by radical copolymerisation of ω-methacryloyl-PMMA with MMA and nBuA, respectively. The comb-shaped PMMA is characterised with respect to radius of gyration by using GPC equipped with a multi-angle laser light scattering detector. The radical copolymerisation of the macromonomer with nBuA in toluene follows complex kinetics. The dependence of the relative reactivity of the macromonomer on absolute concentration and on the ratio of comonomers may be explained by preferential solvation of comonomers by segments of their own kind (“bootstrap effect”) or even micelle formation. However, there is no clear evidence for the formation of micelles in toluene. In contrast, NMR studies show micelle formation in the preferential solvent DMSO. The graft copolymers are transparent thermoplastic elastomers. Phase separation is demonstrated by DSC and morphological studies.