Synthesis of Hydroxy-Functional PMMA Macromonomers by Anionic Polymerization

Living anionic polymerization has been utilized to synthesize hydroxy end-functionalized PMMA macromonomers with styryl or allyl functionalities as the polymerizable end-groups. Protected hydroxy-functionalized alkyl lithium initiators have been used to initiate anionic polymerization of MMA. Subsequently the living chains with protected hydroxyl function have been terminated using 4-vinylbenzyl chloride (4-VBC) or allyl methacrylate (ALMA) to form α-hydroxy-ω-styryl and α-hydroxy-ω-allyl PMMA, respectively. These protected hydroxy-functionalized PMMA macromonomers have been characterized by GPC and ¹H-NMR. Termination using 4-VBC led to 50% functionalization, whereas that using allyl methacrylate led to 100% functionalization of the hydroxy-PMMA.