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<p>We report a reversible addition-fragmentation chain transfer (RAFT) dispersion self-condensing vinyl polymerization (SCVP) platform using a chain-transfer monomer (CTM) and macro-RAFT agent for the one-pot synthesis of monodisperse microspheres composed of well-defined branched (multi)block copolymers. Under RAFT dispersion polymerization conditions, the CTM functions as both a comonomer and branching RAFT site, affording polymer microspheres containing branched polymers while maintaining narrow particle size distributions. The preserved RAFT end-groups on the branches enabled seeded chain extension to give branched diblock and multiblock copolymer microspheres with methyl methacrylate (MMA) and a range of second monomers, while retaining microsphere monodispersity. Using styrene (St) as the second monomer yielded nanostructured branched PMMA-<i>b</i>-PSt microspheres, whose internal morphologies underwent a sphere-to-cylinder transition as the branching degree in the PMMA block was decreased at a fixed composition. These results establish the branching degree in the branched block as an effective parameter to manipulate intraparticle phase behavior and demonstrate RAFT dispersion SCVP as a scalable route to sequence-controlled, topologically complex polymer microspheres with tunable internal nanostructures.</p>

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Uniform Branched Polymer Microspheres via Reversible Addition-fragmentation Chain Transfer Dispersion Self-condensing Vinyl Polymerization

  • 期刊论文

  • 发表日期：

    2026年5月9日

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  • Chao-Jian Luo,
  • Li Zhang,
  • Jian-Bo Tan

摘要

We report a reversible addition-fragmentation chain transfer (RAFT) dispersion self-condensing vinyl polymerization (SCVP) platform using a chain-transfer monomer (CTM) and macro-RAFT agent for the one-pot synthesis of monodisperse microspheres composed of well-defined branched (multi)block copolymers. Under RAFT dispersion polymerization conditions, the CTM functions as both a comonomer and branching RAFT site, affording polymer microspheres containing branched polymers while maintaining narrow particle size distributions. The preserved RAFT end-groups on the branches enabled seeded chain extension to give branched diblock and multiblock copolymer microspheres with methyl methacrylate (MMA) and a range of second monomers, while retaining microsphere monodispersity. Using styrene (St) as the second monomer yielded nanostructured branched PMMA-b-PSt microspheres, whose internal morphologies underwent a sphere-to-cylinder transition as the branching degree in the PMMA block was decreased at a fixed composition. These results establish the branching degree in the branched block as an effective parameter to manipulate intraparticle phase behavior and demonstrate RAFT dispersion SCVP as a scalable route to sequence-controlled, topologically complex polymer microspheres with tunable internal nanostructures.