Self-Assembly of Hydrogen-Bonding Gradient Copolymers: Sequence Control via Tandem Living Radical Polymerization with Transesterification

Abstract

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A Three‐Armed Polymer with Tunable Self‐Assembly and Self‐Healing Properties Based on Benzene‐1,3,5‐tricarboxamide and Metal–Ligand Interactions

“…Up to now, there is no relevant work that studied the assembly and self‐healing of three‐armed polymer based on BTA. Unlike the previous reports that BTA was located in the side chain of polymer, we designed a three‐armed polymer (star‐imidazole‐containing polymer (S‐ICP)) with BTA in the center (Figure A,D), which was polymerized by reversible addition–fragmentation chain transfer (RAFT) polymerization using a RAFT agent with BTA. Imidazole‐containing acrylate monomer (IMZa) and n ‐butyl acrylate (nBA) were chosen to endow the polymer chains with flexibility at room temperature and BTA content could be adjusted by the polymer chain length for their threefold H‐bonding assembly research (Figure B).…”

“…Previous study already shows that the pure polymer films contained fibrous structures after drying the polymer solution (Figure S10, Supporting Information), but the assembly capability of the polymer/metal complexes in the bulk state should be further investigated. And the condition of BTA assembly needed to be explored because heating was required to remove solvent during material preparation, which would destroy the H‐bonding that was formed in low temperature . Finally, materials were stored at 20 °C to give themselves enough time for assembling, producing the BTA based self‐healing materials with assembled structure.…”

Asymmetric Copolymers: Synthesis, Properties, and Applications of Gradient and Other Partially Segregated Copolymers

“…This constraint is met for methacrylate (co)polymerization, however the technique is less reliable for the synthesis of acrylate‐based gradients, due to the decreased steric bulk around the polymeric ester moieties and hence increased rate of transesterification. For methacrylates the technique appears general with primary alcohols bearing a range of functionalities, with aliphatic alcohols, poly(ethylene glycol), fluorinated alcohols, and alcohols bearing hydrogen‐bond motifs being exploited to date.…”

Sequence-controlled polymers via reversible-deactivation radical polymerization

“…The synchronized rate control is essential, and various functional groups can be incorporated by selecting different alcohols. [27][28][29][30] UNIQUE COPOLYMERS VIA CONCURRENT TRANSFORMATION OF ACTIVE SPECIES Different active species can be generated from identical dormant species according to the stimulus. For example, a carbon-halogen bond that is activated into a carbocationic species via Lewis acid catalysis for living cationic polymerization 31,32 is also available as the dormant species in conjunction with one-electron redox catalysis for metal-catalyzed living radical polymerization 4,5 or ATRP.…”