RAFT Step-Growth Polymerization of Diacrylates
RAFT Step-Growth Polymerization of Diacrylates
复制标题
二丙烯酸酯的 RAFT 逐步聚合
DOI：
10.1021/acsmacrolett.2c00476
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发表时间：
2022
影响因子：
7.015
通讯作者：
You, Wei
中科院分区：
文献类型：
--
作者：
Archer, Noel E.;Boeck, Parker T.;Ajirniar, Yasmin;Tanaka, Joji;You, Wei
RAFT逐步增长聚合先前被证明具有低同相增长速率的单体有利于链转移过程;相比之下，丙烯酸酯已知是快速同相增长单体，从而对RAFT逐步增长构成严重挑战。在这里，我们确定了一种链转移剂（CTA），快速产生单单元单体插入（SUMI）CTA加合物与模型丙烯酸酯单体。使用双官能试剂的CTA，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，我们实现了功能的包含（即，二硫化物）通过二硫化物掺入的双官能CTA进入RAFT逐步生长聚合物。从该主链接枝导致在主链的每个重复单元中具有可裂解官能团的分子刷聚合物，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物质。考虑到可商购的二丙烯酸酯的广泛选择，二丙烯酸酯的RAFT逐步生长聚合将进一步使得能够容易地合成具有模块化主链的复杂结构。
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.