Hyperbranched polycarbosiloxanes and polycarbosilanes via bimolecular non-linear hydrosilylation polymerization

The syntheses and selected structure–property relationships of two series of polycarbosiloxanes (HB-PCSOX) and polycarbosilanes (HB-PCS) prepared by the platinum-catalyzed bimolecular non-linear hydrosilylation polymerizations of commercially available 1,3-diallyl- or 1,3-divinyl- disiloxanes or disilanes and tri- or tetra-functional siloxysilanes or silanes (i.e., A_x + B_y polymerization systems where x = 2 and y = 3 or 4) are described. The polymerizations were controlled to avoid gelation and ensure preparation of non-crosslinked soluble polymer products by adjusting the molar ratios of the reacting A (allylsilyl, Si–CH₂–CHCH₂, or vinylsilyl, Si–CHCH₂) and B (silyl, Si–H) reactive functional groups such that r ≤ 1/[(x ? 1)(y ? 1)] or r ≥ (x ? 1)(y ? 1) where r = [A]/[B]. The polymers were characterized by IR, ¹H, ¹³C and ²⁹Si NMR, SEC, DSC and TGA. Their molecular weights were found to increase in the following order of the side-group substitution in the 1,3-divinyldisiloxane monomer used: EtO > Me > MePh > Ph₂, consistent with the increased electron-donation to the vinyl groups causing their increased reactivity in hydrosilylation. These polymers represent unique yet easily and economically available multifunctional nanoscopic dendritic building blocks for more complex 3D nano-structured materials for a variety of applications in electronics, photonics, lithography, specialty coatings, etc.