Synthesis of thermoreactive polysiloxanes with cyclic fragments in the side chain

The synthesis of polysiloxanes with pendant unsaturated cyclic fragments have been successfully performed by hydrosilylation reactions of polymethylhydrosiloxane with 4‐vinyl‐1‐cyclohexene in the presence of platinum hydrochloric acid (0.1 M solution in THF), Karstedt's catalyst (Pt₂(VinSiMe₂)₂O]₃) and platinum on the charcoal (5%). Reactions were carried out at various temperatures with different ratios of initial compounds. It was shown, that not all active ≡Si? H groups take part in the hydrosilylation reaction. Some kinetic parameters of reactions were studied. The synthesized oligomers were characterized by FTIR, ¹H, ¹³C, H,H‐COSY, and C,H‐correlation NMR spectroscopy. Calculations using the quantum‐chemical semi empirical AM1 method for modeling reactions between methyldimethoxysilane Me(MeO)₂SiH] and 4‐vinyl‐1‐cyclohexene were performed to evaluate possible reaction paths. Synthesized oligomers were characterized by gel‐permeation chromatography, differential scanning calorimetric, thermogravimetric, and wide‐angle X‐ray analyses. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009