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Modification Reactions of Methylhydrosiloxanes with Tricyclodecadiene
Author(s) -
Mukbaniani O.,
Zaikov G.,
Tatrishvili T.,
Mukbaniani N.,
Koberidze Kh.
Publication year - 2007
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.200750148
Subject(s) - hydrosilylation , hydride , chemistry , branching (polymer chemistry) , polymer chemistry , differential scanning calorimetry , thermogravimetry , gel permeation chromatography , activation energy , organic chemistry , inorganic chemistry , catalysis , hydrogen , polymer , physics , thermodynamics
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 (ΔH f ), change of energy (ΔH) of the system depending on the change of distance (R C‐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 1 H and 13 C NMR, FTIR, thermogravimetry, gel permeation chromatography, differential scanning calorimetry and wide angle X‐ray methods.