New Functionalized Anionic Initiators Prepared from Substituted 1,1-Diphenylethylene Derivatives with Acetal-Protected Monosaccharides and Their Application to Chain-Multi-Functionalized Polymers with Glucose and Galactose Molecules

Abstract

Living anionic polymerizations of methyl methacrylate, tert-butyl methacrylate, 2-(perfluorobutyl)-ethyl methacrylate, tert-butyl acrylate, and ethylene oxide were carried out with functionalized initiators prepared from substituted 1,1-diphenylethylene (DPE) derivatives with two and four acetal-protected α-D-glucofuranose and α-D-galactopyranose residues and carbanionic species such as sec-butyllithium (sec-BuLi), cumylpotassium, lithium and potassium naphthalenides. In certain cases, either LiC1 or diethylzinc was used as an additive to control the polymerization. Several new well-defined chain-end- and in-chain-functionalized polymers with two and four glucose and two galactose molecules were successfully synthesed by these living polymerizations followed by deprotection. We have proposed a promising iterative methodology based on a convergent approach, with wich novel two denditric substitued DPE derivatives, with four and eight acetal-protected D-glucofuranose residues can successively by synthesized. With use of the functionalized anionic initiators prepared from such dendritic DPE derivatives and sec-BuLi in the polymerization of methyl methacrylate, well-defined chain-end-functionalized poly(methyl methacrylate)s with four and eight glucose molecules were synthesized.