The integration of sulfur atoms into polymer backbones to synthesize S-containing polymers, such as aliphatic polysulfones, renders many unique properties of the materials. Conventional methods are facing great challenges to achieve sequence-controlled aliphatic polysulfones with high molecular weight (MW), significantly restricting the use of these polymers. We devise a novel approach for the preparation of aliphatic polysulfones via sulfonyl radical-mediated group transfer radical polymerization (GTRP). The polymerization proceeds through a practical SO2-free pathway, producing a series of ABC sequence-defined high-MW polymers (up to 199 kg/mol). DFT calculations are conducted, which support the radical Smiles rearrangement pathway involved in the GTRP process.

中文翻译：

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基团转移自由基聚合制备序列控制的脂肪族聚砜


将硫原子整合到聚合物主链中以合成含 S 的聚合物，例如脂肪族聚砜，使材料具有许多独特的性能。传统方法在获得高分子量 （MW） 的序列控制脂肪族聚砜方面面临着巨大挑战，这极大地限制了这些聚合物的使用。我们设计了一种通过磺酰基自由基介导的基团转移自由基聚合 （GTRP） 制备脂肪族多砜的新方法。聚合通过实际的无 SO2 途径进行，产生一系列 ABC 序列定义的高分子量聚合物（高达 199 kg/mol）。进行 DFT 计算，这支持 GTRP 过程中涉及的自由基 Smiles 重排通路。