Unexpectedly rapid hydrosilation polymerization of the diallyl derivative of bisphenol A and 2,6-diallylphenol

Several members of a novel family of reactive oligomers and polymers have been synthesized using the hydrosilation polyaddition of 1,1,3,3- tetramethyldisiloxane and 1,1,3,3,5,5-hexamethyltrisiloxane with the 2,2'- diallyl derivative of bisphenol A (BPA) or 2,6-diallylphenol. Polymerization occurred much faster than that observed for any other hydrosilation reaction of which we are aware: while a typical hydrosilation takes minutes to hours to complete with catalytic amounts of various platinum catalysts, and most unprotected functional groups inhibit the addition, reactions of 2-allylphenol moieties occur virtually instantaneously. In fact, reactions of the diallyl monomers listed must be cooled to prevent explosive loss of reagents from the reaction vessel; even then, thermal loss of the silane monomers can disrupt stoichiometric balance. With cooling, good yields of polymers were obtained which possess excellent solubility in virtually all organic solvents and intrinsic viscosity values of 0.21-0.23 dL/g.