Amine-reactive polymers synthesized by RAFT polymerization using an azlactone functional trithiocarbonate RAFT agent

Area of Science:

• Polymer Chemistry
• Organic Synthesis

Background:

• Reversible-addition-fragmentation chain-transfer (RAFT) polymerization is a powerful technique for synthesizing polymers with controlled architectures.
• Azlactone functionalities offer versatile handles for post-polymerization modification.

Purpose of the Study:

• To synthesize a new azlactone-derived trithiocarbonate chain-transfer agent (CTA).
• To utilize this CTA for mediating RAFT polymerization of various monomers.
• To demonstrate the utility of the resulting end-functionalized polymers.

Main Methods:

• Synthesis of a novel azlactone-derived trithiocarbonate.
• Mediation of RAFT polymerization of styrene, ethyl acrylate, and N-isopropyl acrylamide.
• Characterization of polymer molecular weights and molecular weight distributions (PDIs).
• Post-polymerization modification via reaction with primary amines.

Main Results:

• Successful preparation of a new azlactone-derived trithiocarbonate CTA.
• Controlled RAFT polymerization yielding well-defined polymers (M(n) = 1000-7000 g mol(-1), PDI = 1.05-1.10).
• Azlactone functionality was successfully retained at the polymer chain end.
• Quantitative reaction of end-functionalized polymers with amino groups at room temperature, preserving the thiocarbonylthio moiety.

Conclusions:

• The developed azlactone-derived trithiocarbonate is an effective CTA for RAFT polymerization.
• This method provides access to end-functionalized polymers with controlled properties.
• The retained azlactone group allows for facile and quantitative post-polymerization modification.