• graft copolymers;
  • macromonomers;
  • polysiloxane;
  • radical polymerization


Poly(1,1-bis(ethoxycarbonyl)-2-vinyl cyclopropane (ECVP)-graft-dimethyl siloxane) copolymers were prepared using a macromonomer approach. Poly(dimethyl siloxane) (PDMS) macromonomers were prepared by living anionic polymerization of cyclosiloxanes followed by sequential chain-end capping with allyl chloroformate. These macromonomers were then copolymerized with ECVP. MALDI-ToF mass spectrometry and 1H NMR spectroscopy were used to show that the macromonomers had approximately 80% of the end groups functionalized with allyl carbonate groups. Gradient polymer elution chromatography showed that high yields of the graft copolymers were obtained, along with only small fractions of the PECVP and PDMS homopolymers. Differential scanning calorimetry showed that the low glass transition temperature (Tg) of the PDMS component could be maintained in the graft copolymers. However, the Tg was a function of polymer composition and the polymers produced had Tgs that ranged from −50 to −120 °C. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013