Reactive Polymers Bearing Styrene Pendants through Selective Anionic Polymerization of 4-Vinylbenzyl Methacrylate

Selective anionic polymerization of 4-vinylbenzyl methacrylate at methacrylate site has been achieved using resonance stabilized anionic initiators such as 1,1-diphenylhexyllithium (DPHLi) and tritylpotassium (TritylK) in tetrahydrofuran (THF) at −78 °C. Polymerization proceeded selectively through methacrylate functionality of the monomer in a controlled manner and produced polymers and copolymers with narrow molecular weight distribution at low temperatures (≤−40 °C). ¹H NMR of the polymer showed the presence of styrene pendants in every monomeric repeating unit. The polymerization results confirm that the resonance stabilized carbanions with an optimum pK_a (30 ≤ pK_a ≤ 32) of their conjugate acids such as DPHLi and TritylK do not react with styrene functionality at −78 °C. The selective initiation without cross-linking is attributed to the differences in the electronegativity between polar methacrylate and styrene functionalities and an attenuation of initiator reactivity at low temperature. Poly­(4-vinylbenzyl methacrylate) and its copolymers with the vinyl pendant in close proximity with ester linkage are very reactive and unstable, readily undergoing cross-linking in solution or in solid state with or without a radical initiator.