Synthesis and characterization of star and brush grafted polysiloxanes, obtained by atom transfer radical polymerization

Abstract: Star- and brush-polysiloxanes were synthesized via living radical polymerization using two different catalytic systems. The new compounds were characterized by 1 H-NMR, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC) techniques. CuCl and 2,2’-bipyridyl proved to be the most efficient catalytic system. The type of catalytic system and the reaction conditions control the number of arms for star polymers or the grafted-chain density for brush polymers. The use of chloromethyl styrene as monomer or co-monomer yields homogeneous star- or brush-polysiloxanes, although chloromethyl styrene is an inimer system. The homogeneity of materials was verified by GPC and DSC (TOPEM) methods. For linear grafted polysiloxanes the molecular simulations reflect a tendency of chains to adopt globular conformation for high values of the branching density. The polysiloxanes grafted with styrene/chloromethyl styrene were modified with azobenzene in order to obtain systems able to react to the light stimuli. Rheological behavior of the polymer solutions were evaluated before and after irradiation with UV light. After the UV irradiation a significant viscosity increase was evidenced.