Chemical modification of polysiloxanes with polar pendant groups by co-hydrosilylation

Abstract

New polymers with tuneable dielectric properties were prepared by modifying trimethylsilyl end-terminated poly(methylhydro)siloxane with polar γ-cyanopropyl groups. The amount of polar groups was tuned by adjusting the allyl cyanide/n-hexene ratio in poly(methylhydro)siloxane co-hydrosilylation. The copolymers were characterized by FTIR and NMR spectroscopy. The distribution of the polar groups along the chain was evaluated based on ¹H NMR spectroscopy. The influence of the amount of polar γ-cyanopropyl on the glass transition temperature (T_g) and on the dielectric properties was investigated by DSC and impedance spectrometry. All polymers showed T_gs well below room temperature. A linear increase in permittivity (ε′) with increasing amount of γ-cyanopropyl groups was observed. A maximum ε′ value of 15.9 for the copolymer containing 89 mol% polar groups was achieved, which is 6-fold higher than polydimethylsiloxane. The incomplete conversion of Si–H groups observed in all hydrosilylation reactions with allyl cyanide opened up the possibility of using the prepared copolymers as cross-linkers.