Phenyl-rich silicone polymers are used for their excellent thermal properties and high refractive indices. Traditional syntheses of these polymers utilize cationic or anionic equilibration, which limits the molecular weights that can be achieved due, in part, to the coproduction of cyclic monomers that must be removed. Kinetically controlled processes may reduce the impact of these limitations, but require high temperatures, alkyllithium initiators and an inert atmosphere; precise structures are difficult to access. The Piers-Rubinsztajn reaction, combined with hydrolysis, allows the synthesis of highly ordered, Si-H terminated, phenyl-rich silicone homo-and copolymers comprised of phenylmethyl, diphenyl and, dimethylsilicone monomers. The processes are mild and permit a high level of structural control, including alternating copolymers with different levels of phenyl content (Ph/Si = 0.3-1.5) with molecular weights up to 100 kDa. Yet higher molecular weights could be achieved-M n up to 300 kDa-when phenyl-rich siloxanes were incorporated into block copolymers with dimethylsilicones (Ph/Si = 0.4). Unlike kinetic processes in which cyclic byproducts are formed by redistribution or backbiting (particularly at high conversion), in this process cyclics form near the onset of the reaction and only with low molecular weight starting materials (< 4 siloxane units).

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