Synthesis of well-defined chain-end- and in-chain-functionalized polystyrenes with a definite number of benzyl chloride moieties and D-glucose residues

Novel well-defined chain-end- and in-chain-functionalized polystyrenes with six, eight, twelve, and sixteen benzyl chloride moieties and with four and eight D-glucose residues have been successfully synthesized by developing the methodology based on living anionic polymerization of using new functionalized agents derived from functionalized 1,1-diphenylethylene (DPE) derivatives. They are 1,10-dichloro-4,4-7,7-tetra(3-methoxymethylphenyl)decane, its iodide derivative, the dianion prepared from 1,1-bis(3-methoxymethylphenyl)ethylene and potassium naphthalenide, and 1,1-bis[3′,5′-bis(1,2:5,6-di-O-isopropylidene-α-D-glucofuranose-3-oxymethyl)phenyl]ethylene. The developed methodology involves diverse modes of reactions of polystyryllithium with new functionalized agents and either the subsequent transformation reaction with BCl₃ into benzyl chloride moieties or acid-hydrolysis to regenerate D-glucose residues. The resulting chain-multi-functionalized polystyrenes were precisely controlled with respect to chain length and quantitatively functionalized within experimental errors.