anionic polymerization

ω-(p-Vinylphenyl)alkanols, including methanol, ethanol, propanol, pentanol, and hexanol, have been partially alkoxidated with potassium naphthalene to initiate anionic polymerization of ethylene oxide (EO) in order to directly prepare the corresponding α-p-vinylphenylalkyl-ω-hydroxy poly(ethylene oxide) (PEO) macromonomers. p-Vinylphenylmethanol, i.e. p-vinylbenzyl alcohol (VBA) afforded the expected well-defined macromonomer via living polymerization mechanism and the kinetics have been examined as a function of extent of potassium-alkoxidation.

Anionic polymerizations of 2-(4-vinylphenyl)ethoxy(trialkyl)silanes and 2-(4-vinylphenyl)ethoxy(t-butoxydimethyl)silane were investigated with oligo(α-methylstyryl)dilithium or -dipotassium as initiator in tetrahydrofuran at −78°C. These monomers readily polymerized to form ‘living polymers’. Subsequent deprotection of the silyl groups from the resulting polymers gave poly[2-(4-vinylphenyl)ethanol]s of the desired molecular weights with narrow molecular weight distributions ().