Stereocomplexed Functional and Statistical Poly(lactide-carbonate)s via a Simple Organocatalytic System

Area of Science:

• Polymer Chemistry
• Materials Science
• Biomaterials

Background:

• Stereocomplexation of polylactide (PLA) enhances material properties but functionalized copolymers with high crystallinity are challenging.
• Developing sustainable and degradable materials with tunable properties is a key goal in polymer science.

Purpose of the Study:

• To synthesize functionalized polylactide copolymers via controlled ring-opening copolymerization (ROCOP) while maintaining crystallinity.
• To investigate the stereocomplexation ability of these novel copolymers.
• To demonstrate the utility of functional handles for post-polymerization modification.

Main Methods:

• Controlled ring-opening copolymerization (ROCOP) of lactide (LA) and functionalized cyclic carbonate monomers.
• Characterization of polymer crystallinity and thermal properties.
• Stereocomplexation studies with stereopure PLA and copolymers.
• Thiol-ene click chemistry for functionalization of alkene and alkyne pendent groups.

Main Results:

• Polymers remained crystalline up to 25 mol % carbonate content.
• Efficient stereocomplexation was achieved with homopolymer PLA and copolymers of opposite chirality.
• Polymers with alkene and alkyne handles were successfully derivatized using thiol-ene click chemistry.

Conclusions:

• Controlled ROCOP enables the synthesis of crystalline, functionalized PLA copolymers.
• These materials exhibit efficient stereocomplexation, offering a route to enhanced mechanical properties.
• The incorporated functional handles allow for versatile post-polymerization modification, including therapeutic conjugation and property tuning.