Synthesis and Characterization of Spirocyclic Mid-Block Containing Triblock Copolymer

Polymers containing cyclic derivatives are a new class of macromolecular topologies with unique properties. Herein, we report the synthesis of a triblock copolymer containing a spirocyclic mid-block. To achieve this, a spirocyclic polystyrene (cPS) mid-block was first synthesized by atom transfer radical polymerization (ATRP) using a tetra-functional initiator, followed by end-group azidation and a copper (I)-catalyzed azide-alkyne cycloaddition reaction. The resulting functional cPS was purified using liquid chromatography techniques. Following the esterification of cPS, a macro-ATRP initiator was obtained and used to synthesize a poly (methyl methacrylate)-block-cPS-block-poly (methyl methacrylate) (PMMA-b-cPS-b-PMMA) triblock copolymer. This work provides a synthetic strategy for the preparation of a spirocyclic macroinitiator for the ATRP technique and as well as liquid chromatographic techniques for the purification of (spiro) cyclic polymers.

Automated summary

In this study, a synthetic strategy for the preparation of a triblock copolymer containing a spirocyclic mid-block is reported. A spirocyclic polystyrene (cPS) mid-block was synthesized by atom transfer radical polymerization (ATRP) and subsequent azidation and cycloaddition reactions. The resulting functional cPS was purified using liquid chromatography techniques. The cPS was then esterified to obtain a macro-ATRP initiator for the synthesis of a poly(methyl methacrylate)-block-cPS-block-poly(methyl methacrylate) (PMMA-b-cPS-b-PMMA) triblock copolymer. This work provides a synthetic strategy for the preparation of a spirocyclic macroinitiator for the ATRP technique and introduces liquid chromatographic techniques for the purification of (spiro) cyclic polymers.