Polyglycidamides: from Backbone-Promoted Amidation to Degradable Polyether with Wide-Range LCST

Area of Science:

• Polymer Chemistry
• Organic Synthesis

Background:

• Amide groups are crucial in both natural and synthetic polymers.
• Developing efficient synthesis routes for functional polymers is essential.

Purpose of the Study:

• To establish a controlled pathway for synthesizing amide-functionalized polyethers.
• To investigate the properties and degradability of the synthesized polyglycidamides (PGAms).

Main Methods:

• Ring-opening polymerization (ROP) of ethyl glycidate using a two-component organocatalyst.
• Post-polymerization amidation of pendant ester groups.
• Characterization of polymer properties, including thermoresponsiveness and degradation.

Main Results:

• Efficient and controlled synthesis of PGAms was achieved, inhibiting transesterification during ROP.
• Amidation proceeded efficiently even at 0°C without a catalyst, attributed to backbone effects and hydrogen bonding.
• PGAms displayed aqueous thermoresponsive behavior, with tunable cloud points.
• PGAms demonstrated degradability via retro-oxa-Michael addition under basic conditions.

Conclusions:

• A novel, efficient method for synthesizing amide-functionalized polyethers (PGAms) was developed.
• PGAms exhibit unique properties like tunable thermoresponsiveness and base-catalyzed degradability.
• These findings offer new possibilities for designing functional and degradable polymers.