Cyclic ether and anhydride ring opening copolymerisation delivering new ABB sequences in poly(ester-alt-ethers)

Area of Science:

• Polymer Chemistry
• Materials Science

Background:

• Poly(ester-alt-ethers) combine rigid ester and flexible ether linkages, offering unique properties.
• Existing synthesis routes may lack versatility in monomer selection and structural control.

Purpose of the Study:

• To develop a generally applicable synthesis for poly(ester-alt-ethers) with variable compositions and structures.
• To explore the potential of these novel copolymers in various applications.

Main Methods:

• Ring-opening copolymerization of anhydrides, epoxides, and cyclic ethers catalyzed by Zr(IV).
• Utilized a range of commercial monomers including aromatic, unsaturated, and tricyclic anhydrides, and various alkylene oxides and cyclic ethers.
• Post-polymerization modification via thiol-ene reactions to introduce hydroxyl functionalities.

Main Results:

• Successfully synthesized ABB and ABC type poly(ester-alt-ethers) with controlled molecular weights (4-11 kg mol⁻¹) and narrow dispersity.
• Copolymers exhibited thermal decomposition between 270-344 °C and tunable glass transition temperatures (-50 to 48 °C).
• Hydroxyl-functionalized copolymers demonstrated moderated hydrophilicity, evidenced by water contact angle measurements.

Conclusions:

• A sequence-selective copolymerization catalysis is established for producing diverse poly(ester-alt-ethers).
• The developed method offers a versatile platform for creating novel polymeric materials.
• These copolymers show promise for applications in liquid formulations, electrolytes, surfactants, plasticizers, adhesives, coatings, elastomers, and foams.