Tailored Synthesis of Triblock Co- and Terpolymers Composed of Synthetically Difficult Sequence Orders by Combining Living Anionic Polymerization with Specially Designed Linking Reaction

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This study demonstrates the versatility and wider applicability of the recently developed methodology combining the living anionic polymerization with a specially designed linking reaction using the α-phenylacrylate (or benzyl bromide) function, allowing the synthesis of triblock co- and terpolymers, which are otherwise difficut to be obtained by sequential addition of monomers during a sequential polymerization approach. With this methodology using styrene and four para-substituted styrene derivatives with N-cyclohexylimine, 4-N,N-dimethyl-2-oxazoline, 2,6-di(tert-butyl)-4-methylphenyl ester, and nitrile, 12 polymers among the 16 possible triblock terpolymers and 6 triblock copolymers were successfully synthesized. Furthermore, the synthesis of two tetrablock quarterpolymers was achieved by the same linking methodology. The polymers synthesized in this study are all well-controlled in chain length, composition, which are difficult to be obtained by the sequential polymerization. In addition, they possess functional groups usable for the further modification and introduction of other functionalities.