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., Ax + By 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.