A library of new organofunctional silanes obtained by thiol-(meth)acrylate Michael addition reaction

Abstract

A simple and efficient method for the synthesis of organofunctional silanes by the thiol-(meth)acrylate addition reaction is presented. At first, systematic studies were carried out to select an optimum initiator/catalyst of the addition reaction for the model reaction involving 3-mercaptopropyltrimethoxysilane (MPTMS) and hexyl acrylate. Photoinitiators (in the presence of UV light energy), thermal initiators (such as aza compound and peroxide) as well as catalysts (primary and tertiary amines, phosphines and Lewis acid) were studied. After selecting an effective catalytic system and optimizing the reaction conditions, reactions between the thiol group (i.e. 3-mercaptopropyltrimethoxysilane) and (meth)acrylates containing various functional groups were carried out. All derivatives obtained were characterized by ¹H, ¹³C, ²⁹Si NMR and FT-IR analysis. In reactions carried out at room temperature, in an air atmosphere and in the presence of dimethylphenylphosphine (DMPP) as a catalyst, quantitative conversions of both substrates were obtained within a few minutes. The library of organofunctional silanes was expanded by compounds (containing various functional groups, i.e. alkenyl, epoxy, amino, ether, alkyl, aralkyl, fluoroalkyl) which were obtained in the thiol-Michael addition of 3-mercaptopropyltrimethoxysilane to a group of organofunctional (meth)acrylic acid esters.