A simple route to synthesize polyhedral silsesquioxanes, (RSiO1.5)
n
, by the hydrolytic
condensation of modified aminosilanes, is reported. The starting material was N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, a trifunctional aminosilane. It was reacted with a stoichiometric amount
of phenylglycidyl ether in sealed ampules at 50 °C for 24 h, leading to the trisubstituted product plus a
series of oligomers arising from the intermolecular reaction between methoxysilane groups and the
secondary hydroxyls generated by the epoxy−amine reaction. When this product was subjected to
hydrolytic condensation using a variety of catalysts (HCl, NaOH, HCOOH) and a thermal cycle attaining
150 °C, polyhedral silsesquioxanes (SSQO) were obtained. Their molar mass was independent of reaction
conditions as revealed by size exclusion chromatography. Characterization by 1H, 13C, and 29Si NMR
suggested that the main product was a mixture of polyhedral SSQO with n = 8 and 10; i.e., T8 and T10.
Due to the high OH functionality, i.e., 24 OH groups in T8 and 30 OH groups in T10 polyhedra, the
synthesized product may be used as a cross-linking unit of very high functionality or as a modifier for
several polymeric materials.
High resolution PVC and PVC reduced with Bu,SnH. The reduction is never complete and CHzCl groups preferentially remain. It causes almost complete formation of cyclopentane structures from both internal and chain end unsaturation. as chain end unsaturation except if there are interferences with initiator residues : in that case, its combination with chain end unsaturation. By the last method short branches and long ends are determined. Residual primary chlorine in all kinds of branches (methyl, ethyl, butyl, long ends) is taken into account. Long end contents are to be corrected (factor around 1.5), due to incomplete relaxation in standard analysis conditions. 'H NMR of reduced PVC can be used to get the total non-reduced structures, both -CH,Cl and -CHCl-. PVC was prepared by suspension or solution (trichlorobenzene) polymerization at 55' C,using dicetyl peroxydicarbonate as an initiator. The initiator residue content is higher in suspension PVC at very low conversion, and then levels off at a low value : in solution polymerization, it chiefly depends on the monomer/initiator ratio. At low conversion, more chain end and less short branches are present in suspension polymerization. Otherwise, only the butyl branch content shows a definite trend to increase with conversion. In solution polymerization, the number of defects is chiefly dependent on the initial monomer concentration : it is generally much higher than in suspension, except for the chloromethyl branches where both processes give about the same results.'H and 13C NMR data were obtained on 'H NMR gives total unsaturation as well 13C NMR of reduced PVC gives the
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