Synthesis, characterization, and gamma radiation effects over well‐defined poly(vinylsiloxanes) copolymers

Anionic ring-opening polymerization (AROP) was employed for the controlled synthesis of linear model block copolymers of 1,3,5,7-tetrametil-1,3,5,7-tetravinyl(cyclotetrasiloxane) (V4) and 1,3,5-dimethyl(cyclotrisiloxane) (D3) monomers by using sec-butyl lithium (sec-Bu−Li+) as initiator, and high-vacuum anionic polymerization techniques. V4 copolymerization was promoted by employing D3 and sec-Bu−Li+ producing living silanolates that open the stable V4 ring. For this purpose, two strategies were applied: (a) sequential addition of monomers, and (b) one-step copolymerization at different reaction temperatures. According to the experimental results, higher levels of V4 incorporation (∼ 18.14 mol %) were obtained by mixing both co-monomers and performing the reaction at high temperature (80°C). This strategy allowed the control of the V4 incorporation into the copolymer structure, giving the opportunity of synthesizing model vinyl-siloxane polymers. The gamma radiation of these materials showed that lower doses are needed to achieve the same gel content as in a model poly(dimethylsiloxane) (PDMS). In such a sense, these results constitute one of the first reports regarding the effect of gamma radiation on vinyl-containing silicon polymers, and may be of fundamental importance if a biomedical cross-linked rubber-type PDMS is needed at earlier doses of sterilization. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012