Acrylic thermoplastic elastomers and comb‐shaped poly(methyl methacrylate) via the macromonomer technique

Comb-shaped poly(methyl methacrylate) (PMMA) and poly(butyl acrylate) (PnBuA) grafted with PMMA were prepared by radical copolymerization of ω-methacryloyl-PMMA with MMA and nBuA, respectively. The comb-shaped PMMA is characterized with respect to radius of gyration by using gel permeation chromatography equipped with a multi-angle laser light scattering detector. The radical copolymerization 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 dimethyl sulfoxide. The graft copolymers are transparent thermoplastic elastomers. Phase separation is demonstrated by differential scanning calorimetry and morphological studies.