Orthogonal Radical and Cationic Single-Unit Monomer Insertions for Engineering Polymer Architectures

Ze Wei; Wei He; Zhihua Liu; Yating Lin; Maolin Wang; Liang Li; Chunxiao Wu; Sheng Yang; Guhuan Liu; Ronghua Yang

doi:10.1002/anie.202402265

Orthogonal Radical and Cationic Single-Unit Monomer Insertions for Engineering Polymer Architectures

Angew Chem Int Ed Engl. 2024 May 17:e202402265. doi: 10.1002/anie.202402265. Online ahead of print.

Authors

Ze Wei¹, Wei He², Zhihua Liu³, Yating Lin¹, Maolin Wang¹, Liang Li⁴, Chunxiao Wu¹, Sheng Yang¹, Guhuan Liu⁵, Ronghua Yang¹

Affiliations

¹ Hunan Normal University, Collage of Chemistry, CHINA.
² Hunan Normal University, College of Chemistry and Chemical Engineering, CHINA.
³ Hunan Normal University, Collage of chemistry, CHINA.
⁴ Hunan Normal University, collage of chemistry, CHINA.
⁵ Hunan Normal University, College of Chemistry and Chemical Engeering, 36 Lushan Road, 410081, Changsha, CHINA.

PMID: 38760991
DOI: 10.1002/anie.202402265

Abstract

The single-unit monomer insertion (SUMI), derived from living/controlled polymerization, can be directly functionalized at the end or within the chain of polymers prepared by living/controlled polymerization, offering potential applications in the preparation of polymers with complex architectures. Many scenarios demand the simultaneous incorporation of monomers suitable for different polymerization methods into complex polymers. Therefore, it becomes imperative to utilize SUMI technologies with diverse mechanisms, especially those that are compatible with each other. Here, we reported the orthogonal SUMI technique, seamlessly combining radical and cationic SUMI approaches. Through the careful optimization of monomer and chain transfer agent pairs and adjustments to reaction conditions, we can efficiently execute both radical and cationic SUMI processes in one pot without mutual interference. The utilization of orthogonal SUMI pairs facilitates the integration of radical and cationic reversible addition-fragmentation chain transfer (RAFT) polymerization in various configurations. This flexibility enables the synthesis of diblock, triblock, and star polymers that incorporate both cationically and radically polymerizable monomers. Moreover, we have successfully implemented a mixing mechanism of free radicals and cations in RAFT step-growth polymerization, resulting in the creation of a side-chain sequence-controlled polymer brushes.

Keywords: Single-Unit Monomer Insertions * Polymer Architectures * Orthogonal Reactions * Reversible Addition-Fragmentation Chain Transfer Polymerization.