Ni(0)/NHC-Mediated Coordination Disproportionation Polymerization of Aromatic Dialdehydes to High-Performance...

Area of Science:

• Polymer Chemistry
• Organic Synthesis
• Materials Science

Background:

• Conventional polycondensation methods face challenges in synthesizing high-performance aromatic polyesters under mild conditions.
• Developing efficient and sustainable polymerization techniques is crucial for advanced materials.

Purpose of the Study:

• To report a novel Ni(0)/N-heterocyclic carbene (NHC)-catalyzed coordination disproportionation polymerization (CDP) for aromatic polyester synthesis.
• To enable the direct, byproduct-free synthesis of high-molar-mass polyesters from aromatic dialdehydes.
• To achieve polyesters with enhanced thermal stability, hydrolytic resistance, and recyclability.

Main Methods:

• Employed Ni(0)/N-heterocyclic carbene (NHC)-catalyzed coordination disproportionation polymerization (CDP).
• Utilized readily accessible aromatic dialdehydes as monomers.
• Tuned NHC ligand properties to control polymerization equilibrium and suppress side reactions like benzoin condensation.

Main Results:

• Achieved direct, byproduct-free synthesis of high-molar-mass polyesters from aromatic dialdehydes.
• Synthesized sequence-disordered polyesters with high thermal stability (T_d,5% up to 370 °C) and glass transition temperatures > 100 °C.
• Demonstrated exceptional hydrolytic stability (pH 0-14) and tunable degradability in alkaline organic solvents.

Conclusions:

• Coordination disproportionation polymerization (CDP) is a versatile platform for synthesizing high-performance aromatic polyesters.
• The developed method offers a sustainable route to polyesters with superior heat resistance and durability.
• Achieved an optimal balance between material durability and end-of-life recyclability.