Comb-type Organosilicon Compounds with Epoxy Groups in the Side Chain

Abstract

The reaction of hydride addition of a,w-bis(trimethylsiloxy)methylhydridesiloxanes with ally1 glycidyl ether in the presence of platinum chlorohydric acid and Pt/C at the I : 30 ratio of initial compounds has been studied. It was established that when the reaction proceeds without solvent, three-dimensional systems are obtained.The optimal condition of hydride addition reaction, concentration of the solution, the reaction temperature have been determined. The reaction order, activation energy and hydride addition rate constants were found. In the case of platinum chlorohydric acid hydride addition proceeds with inductive period, and faster than in the case of the catalyst platinum on the carbon Pt/C. The reactions of primary and secondary amines with epoxy groups containing organosiloxanes were carried out and comb-type organosiloxanes with aminohydroxy groups in the side chain have been obtained. After protonation of amino nitrogen groups in the side chain water soluble organosiloxane oligomers were obtained.The structure of all synthesized comb-type organosiloxanes were determined by IR, 'H and "C N M R spectra data.

Hydrosilylation and dehydrocondensation reactions of methylhydridesiloxane to acrylic and methacrylic acids

“…The hydrosilylation reactions of methylhydridesiloxanes to acrylic and methacrylic acids are distinguished from each other in the 1 H-and 13 C-NMR spectroscopy data and in the literature data. 1 With acrylic acid, hydrosilylation mainly proceeds by dehydrocondensation and hydrosilylation [Farmer rule (Scheme 11(1,3a)].…”

“…3) shows a signal for carbon in the residual acid carbonyl group with a chemical shift at d % 179.3 ppm, a signal with a chemical shift at d % 7.5 ppm in the BSiMe group, a signal with a chemical shift at d % 6.9 ppm in À ÀSiMe 3 , a signal with a chemical shift at d % 25.9 ppm characteristic of carbon in the BSiÀ ÀCH 2 À À group, and a signal with a chemical shift at d % 27.5 ppm characteristic of carbon in the methylene group in the À ÀCH 2 À ÀCOOH fragment. The reaction in the other direction by dehydrocondensation is proved by the presence in the 13 C-NMR spectrum of a signal with a chemical shift at d % 171.7 ppm, which is characteristic of free carbon from a proton carboxyl group (BSiÀ ÀOÀ ÀCOÀ À). The obtained crosslinked systems can be explained by intermolecular hydrosilylation and dehydrocondensation (Scheme 7).…”

“…Besides, there are no changes in the NMR spectra of the initial compounds. As known from the literature, 13 H 2 PtCI 6 , except for hydrosilylation, catalyzes the dehydrocondensation reaction. Therefore, for the complete characterization of the process during the reaction, the conversation of hydrogen has been observed.…”

“…The acquisition of three hydrosilylation products with methacrylic acid has been proved by 13 a Specific viscosity in a 1% solution of toluene at 258C.…”

“…9 On the other hand, H 2 PtCI 6 is a known catalyst of hydrosilylation. 12 The reaction capacity of the BSiÀ ÀH bond is determined by the nature and amount of the catalyst, the reaction temperature, the reactant concentration, the solvent character, and so forth. 7,8 We have shown that during the dehydrocondensation of hydride-containing organosiloxanes with hydroxylcontaining organosilanes and siloxanes in the presence of powderlike caustic potassium as a nucleophilic catalyst, the competing reaction of dialkylsiloxane elimination does not take place.…”