Stereocontrolled Phenol-Yne Click Polymerization Toward High-Performance Bioplastics with Closed-Loop Recyclability

Area of Science:

• Polymer Chemistry
• Organic Synthesis
• Materials Science

Background:

• Hydroxyl-yne click polymerization is effective for creating sequence-controlled polymers.
• Stereochemical control in this polymerization remains a significant challenge.
• Developing stereodivergent synthesis is crucial for advanced polymer applications.

Purpose of the Study:

• To develop organocatalyzed stereocontrolled phenol-yne click polymerization.
• To synthesize sequence- and stereocontrolled poly(vinyl ether ester)s.
• To enable tunable bulk properties and recyclability in polymers.

Main Methods:

• Organocatalyzed polymerization of bioderived diphenols and dipropiolates.
• Systematic variation of substrates, catalysts, and solvents.
• Characterization of polymer stereochemistry, thermal, mechanical, and transport properties.

Main Results:

• Achieved stereocontrolled synthesis of poly(vinyl ether ester)s with tunable trans content (46%-100%).
• Demonstrated broad tunability of thermal (Td: 329-362 °C, Tg: 48-92 °C), mechanical (strength: 41-89 MPa), and transport properties.
• Incorporated dynamic acetal moieties for enhanced degradability and recyclability.

Conclusions:

• Developed an efficient and sustainable strategy for stereoregulated biopolymer synthesis.
• Expanded the diversity of click polymers with controlled structures and tailored properties.
• Enabled closed-loop recyclability for advanced polymer materials.