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<p>Although radical polymerization has been well established for incorporating C2 (vinyl) and C4 (diene) backbone units (also known as C2 and C4 polymerization), the development of efficient radical C3 polymerizations remains an important and unresolved challenge. Here we report a strategy for C3 alternating copolymerization by synergistically combining 1,2-boryl migration with radical polarity matching. Our design uses boryl-substituted α-olefin monomers that, when attacked by electrophilic radicals, undergo 1,2-boryl migration to form more stable nucleophilic carbon radicals. These intermediates selectively react with electron-deficient comonomers, regenerating electrophilic radicals and establishing a polarity-matching propagation cycle that ensures strict alternating sequence control. Mechanistic investigations demonstrate that this process is governed by both the thermodynamic driving force of 1,2-boryl migration and the kinetic preference for nucleophilic radical addition to electron-deficient monomers. This approach provides a versatile platform for synthesizing precisely alternating C3-structured copolymers, expanding the toolbox of polymerization reactions and the accessible diversity of polymer structures with promising material properties.</p><p></p>

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Radical C3 alternating polymerization driven by 1,2-boryl migration via radical polarity matching

  • 期刊论文

  • 发表日期：

    2026年3月23日

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  • Chaoran Xu,
  • Yu Kong,
  • Asja A. Kroeger,
  • Michelle L. Coote,
  • Xiangcheng Pan

摘要

Although radical polymerization has been well established for incorporating C2 (vinyl) and C4 (diene) backbone units (also known as C2 and C4 polymerization), the development of efficient radical C3 polymerizations remains an important and unresolved challenge. Here we report a strategy for C3 alternating copolymerization by synergistically combining 1,2-boryl migration with radical polarity matching. Our design uses boryl-substituted α-olefin monomers that, when attacked by electrophilic radicals, undergo 1,2-boryl migration to form more stable nucleophilic carbon radicals. These intermediates selectively react with electron-deficient comonomers, regenerating electrophilic radicals and establishing a polarity-matching propagation cycle that ensures strict alternating sequence control. Mechanistic investigations demonstrate that this process is governed by both the thermodynamic driving force of 1,2-boryl migration and the kinetic preference for nucleophilic radical addition to electron-deficient monomers. This approach provides a versatile platform for synthesizing precisely alternating C3-structured copolymers, expanding the toolbox of polymerization reactions and the accessible diversity of polymer structures with promising material properties.