The reaction of hydride polyaddition of methylhydridesiloxane and methylhydridesiloxane‐dimethylsiloxane oligomers to unsaturated carbocyclic compound ‐ tricyclodecadiene, at the various ratio of initial compounds, in the presence of platinum hydrochloric acid has been investigated. It was shown that hydrosilylation reaction proceeds both to 1.2 and 9.10 positions and by intermolecular with formation of branching systems. The polyorganosiloxanes with tricyclodecenyl fragment in the side chain, completely soluble in organic solvents were synthesized. For fully characterization of hydride addition of methylhydridesiloxane to tricyclodecadiene, by quantum‐chemical half empiric AM1 method, for all initial, intermediate and final products, in modelling reaction of hydrosilylation of methyldimethoxysilane to tricyclodecadiene, the heats of formations (ΔHf), change of energy (ΔH) of the system depending on the change of distance (RC‐Si) between C‐Si bonds, also the charges values (q) on the atoms, dipole moments (µ) and bonds orders (Pij) are calculated. It was concluded, that the course of hydride addition of modelling reaction of methyldimethoxysilane to tricyclodecadiene energetically is more favourable by 9.10‐addition. The hydride polyaddition reaction order, activation energies and rate constants were found. The synthesized oligomers were characterized by 1H and 13C NMR, FTIR, thermogravimetry, gel permeation chromatography, differential scanning calorimetry and wide angle X‐ray methods.
The reaction of hydride polyaddition of methylhydridesiloxanes to conjugated cyclohexa-1,3-diene, in the presence of catalytic amount of platinum hydrochloric acid, has been investigated at several temperatures. The polyorganosiloxanes with cyclohexenyl fragments in the side chain, completely soluble in organic solvents, were synthesized. The hydride polyaddition reaction order, activation energies, and rate constants were found. By quantum-chemical half-empirical method AM1, the electronic characteristics of cyclohexa-1,3-diene: the charges on the carbon atoms and bonds orders were calculated. For full characterization of hydrosilylation reaction, calculations for modeling reaction between methyldimethoxysilane and cyclohexa-1,3-diene were carried out using Gaussian 03 program package. The geometries of reactants, transition states, and products were optimized using PM3 semiempirical method followed by single-point calculations at B3LYP/6-31G(d) level of density functional theory. It was concluded that the course of hydride addition of modeling reaction of methyldimethoxysilane to cyclohexa-1,3-diene energetically is more favorable by 1,4-addition. The synthesized oligomers were characterized by FTIR, 1 H-and 13 C-NMR spectroscopy, thermogravimetry, gel permeation chromatography, differential scanning calorimetry, and wide-angle X-ray diffractometry.
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