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High-Glass-Transition Polyesters Produced with Phthalic Anhydride and Epoxides by Ring-Opening Copolymerization
Selena Silvano1,2, Matteo Proverbio1, Adriano Vignali1
1Institute of Chemical Science and Technologies-"G. Natta", National Research Council, Via A. Corti 12, 20133 Milan, Italy.
Polymers
|July 14, 2023
Summary
High glass transition temperature polyesters were synthesized using limonene oxide or vinylcyclohexene oxide and phthalic anhydride via ring-opening copolymerization. These novel materials exhibit excellent thermal properties and potential for biodegradation and functionalization.
Area of Science:
- Polymer Chemistry
- Materials Science
- Organic Synthesis
Background:
- Development of high-performance polyesters with enhanced thermal stability is crucial for advanced material applications.
- Ring-opening copolymerization (ROCOP) offers a versatile route to synthesize well-defined polymer architectures.
- Exploring bio-based monomers like limonene oxide (LO) and vinylcyclohexene oxide (VCHO) is key for sustainable polymer development.
Purpose of the Study:
- To synthesize high glass transition temperature (Tg) polyesters using limonene oxide (LO) or vinylcyclohexene oxide (VCHO) and phthalic anhydride (PA).
- To investigate the influence of catalyst/cocatalyst systems and reaction conditions on polymerization outcomes.
- To evaluate the thermal properties, biodegradability, and functionalization potential of the resulting copolymers.
Main Methods:
- Alternating ring-opening copolymerization (ROCOP) of LO or VCHO with PA using salen-type metal complexes (Cr, Al, Mn) and cocatalysts (DMAP, PPNCl, PPNN3).
- Optimization of precontact time and polymerization duration to control molecular weight and Tg.
- Characterization using GPC, DSC, TGA, and biodegradation tests (ISO 14851); functionalization via thiol-ene click chemistry.
Main Results:
- Polyesters with Tg up to 136 °C and molecular weights up to 14.0 kg/mol were successfully synthesized.
- Low polyether units (<3 mol%) were observed, indicating efficient alternating copolymerization.
- Poly(LO-alt-PA) demonstrated biodegradability and the vinyl group allowed for facile thiol modification.
Conclusions:
- Salen-type catalysts enable efficient ROCOP of cyclic epoxides and phthalic anhydride, yielding high Tg polyesters.
- The synthesized polyesters possess tunable thermal properties and potential for further modification and sustainable applications.
- This study highlights a promising pathway for creating advanced, functional polyesters from renewable resources.
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