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RAFT Step-Growth Polymerization of Diacrylates
ACS Macro Letters ( IF 5.1 ) Pub Date : 2022-08-19 , DOI: 10.1021/acsmacrolett.2c00476
Noel E Archer 1 , Parker T Boeck 1 , Yasmin Ajirniar 1 , Joji Tanaka 1 , Wei You 1
Affiliation  

RAFT step-growth polymerization was previously demonstrated with monomers that bear low rate of homopropagation to favor the chain transfer process; by contrast, acrylates are known to be fast homopropagating monomers, thereby posing serious challenges for RAFT step-growth. Here, we identified a chain transfer agent (CTA) that rapidly yields single unit monomer inserted (SUMI) CTA adducts with a model acrylate monomer. Using a bifunctional reagent of this CTA, we successfully demonstrated RAFT step-growth polymerization with diacrylates, yielding linear polymer backbones. Furthermore, we achieved inclusion of functionality (i.e., disulfide) into RAFT step-growth polymer via a disulfide incorporated bifunctional CTA. Grafting from this backbone resulted in molecular brush polymers with cleavable functionality in each repeat unit of the backbone, allowing selective degradation to afford well-defined unimolecular species of two polymeric side chains. Given the wide selection of commercially available diacrylates, RAFT step-growth polymerization of diacrylates will further enable facile synthesis of complex architectures with modular backbones.

中文翻译:

二丙烯酸酯的 RAFT 步长聚合

RAFT 逐步增长聚合先前已证明使用具有低同质增殖率的单体有利于链转移过程;相比之下,已知丙烯酸酯是快速均相增殖的单体,因此对 RAFT 逐步增长提出了严峻挑战。在这里,我们确定了一种链转移剂 (CTA),它与模型丙烯酸酯单体快速产生单单元单体插入 (SUMI) CTA 加合物。使用这种 CTA 的双功能试剂,我们成功地证明了 RAFT 逐步增长聚合与二丙烯酸酯,产生线性聚合物主链。此外,我们通过结合二硫化物的双功能 CTA 实现了将功能性(即二硫化物)包含到 RAFT 逐步生长聚合物中。从这个主链接枝得到分子刷聚合物,在主链的每个重复单元中都具有可裂解的官能团,允许选择性降解以提供两个聚合物侧链的明确定义的单分子种类。鉴于市售二丙烯酸酯的广泛选择,二丙烯酸酯的 RAFT 逐步增长聚合将进一步使具有模块化骨架的复杂结构的轻松合成成为可能。
更新日期:2022-08-19
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