Polydimethylsiloxane–vinyl block polymers. I. The synthesis of polydimethylsiloxane macroinitiators containing thermolyzable bis(silyl pinacolate) groups in their backbones

This first paper on the topic of polydimethylsiloxane–vinyl block polymers describes the development of a unique class of vinyl functional silicon containing free–radical initiators which can be used in the synthesis of block polymers. Details of the synthesis and characterization of these initiators are described together with the kinetics of their thermolysis. Specific conditions are described under which these initiators can be condensed with α,ω‐hydrogen functional polydimethylsiloxane oligomers by a platinum‐catalyzed hydrosilylation reaction to yield macroinitiators.