Streamlined access to end-functionalized thermoresponsive polymers via a combination of bulk RAFT polymerization and quasi solvent-free Passerini three-component reaction

This research achieves a streamlined synthesis of end-functionalized thermoresponsive polymers via the combination of bulk reversible addition-fragmentation chain-transfer (RAFT) polymerization and quasi solvent-free Passerini three-component reaction (3CR) for the modification of chain-end groups. The RAFT polymerization of poly(ethylene glycol) methyl ether acrylate (mPEGA) and di(ethylene glycol)ethyl ether acrylate (DEGA) initiated by aldehydes featuring chain transfer agents proceeded under solvent-free conditions to afford aldehyde end-functionalized P(mPEGA-co-DEGA)s with the target molecular weight and moderate polydispersity index (D) value of similar to 1.4. Furthermore, the obtained aldehyde end-functionalized P(mPEGA-co-DEGA) was subjected to Passerini-3CR under quasi solvent-free conditions, which proceeded with >80% aldehyde conversion to afford P(mPEGA-co-DEGA) end-functionalized with alpha-acyloxy amides. The resulting alpha-acyloxy amide end-functionalized P(mPEGA-co-DEGA) showed critical solution temperature behaviors in water different from the parental polymer. In addition, the bulk RAFT polymerization and Passerini chain-end functionalization processes were combined in a one-pot process to provide a streamlined protocol that enables easy access to end-functionalized thermoresponsive polymers within 72 h with minimal use of solvents and reactants. A streamlined access to end-functionalized thermoresponsive polymers

Automated summary

This research demonstrates a streamlined synthesis of end-functionalized thermoresponsive polymers through the combination of RAFT polymerization and Passerini three-component reaction. The one-pot process allows for the easy access to end-functionalized polymers within 72 hours with minimal use of solvents and reactants.