Living anionic polymerizations of methyl methacrylate, tert-butyl methacrylate, 2-(perfluorobutyl)-ethyl methacrylate, tert-buty acrylate, and ethylene oxide were carried out with functionalized initiators prepared from substituted 1,1-diphenylethylene (DPE) derivatives with two and four acetal-protected alpha-D-glucofuranose and alpha-D-galactopyranose residues and carbanionic species such as sec-butyllithium (sec-BuLi), cumylpotassium, lithium and potassium naphthalenides. In certain cases, either LiCl 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 synthesized by these living polymerizations followed by deprotection. We have proposed a promising iterative methodology based on a convergent approach, with which novel two dendritic substituted DPE derivatives with four and eight acetal-protected D-glucofuranose residues can successively be synthesized. With use of the functionalized anionic initiators prepared from such dendrite 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.
