Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts
The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO<sub>2</sub> as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyc...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-05-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/13/10/1651 |
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| author | Felipe de la Cruz-Martínez Marc Martínez de Sarasa Buchaca Almudena del Campo-Balguerías Juan Fernández-Baeza Luis F. Sánchez-Barba Andrés Garcés Carlos Alonso-Moreno José A. Castro-Osma Agustín Lara-Sánchez |
| author_facet | Felipe de la Cruz-Martínez Marc Martínez de Sarasa Buchaca Almudena del Campo-Balguerías Juan Fernández-Baeza Luis F. Sánchez-Barba Andrés Garcés Carlos Alonso-Moreno José A. Castro-Osma Agustín Lara-Sánchez |
| author_sort | Felipe de la Cruz-Martínez |
| collection | DOAJ |
| description | The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO<sub>2</sub> as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex <b>3</b> with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened. The catalytic system was capable of copolymerizing selectively and efficiently CHO with phthalic, maleic, succinic and naphthalic anhydrides to afford the corresponding polyester materials. The polyesters obtained were characterized by spectroscopic, spectrometric, and calorimetric techniques. Finally, the reaction mechanism of the catalytic system was proposed based on stoichiometric reactions. |
| first_indexed | 2024-03-10T11:15:00Z |
| format | Article |
| id | doaj.art-3436ebc47256432caf14c7871321dc65 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T11:15:00Z |
| publishDate | 2021-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-3436ebc47256432caf14c7871321dc652023-11-21T20:27:17ZengMDPI AGPolymers2073-43602021-05-011310165110.3390/polym13101651Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc CatalystsFelipe de la Cruz-Martínez0Marc Martínez de Sarasa Buchaca1Almudena del Campo-Balguerías2Juan Fernández-Baeza3Luis F. Sánchez-Barba4Andrés Garcés5Carlos Alonso-Moreno6José A. Castro-Osma7Agustín Lara-Sánchez8Universidad de Castilla-La Mancha, Departamento de Química Inorgánica, Orgánica y Bioquímica-Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias y Tecnologías Químicas, 13071 Ciudad Real, SpainUniversidad de Castilla-La Mancha, Departamento de Química Inorgánica, Orgánica y Bioquímica-Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias y Tecnologías Químicas, 13071 Ciudad Real, SpainUniversidad de Castilla-La Mancha, Departamento de Química Inorgánica, Orgánica y Bioquímica-Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Farmacia, 02071 Albacete, SpainUniversidad de Castilla-La Mancha, Departamento de Química Inorgánica, Orgánica y Bioquímica-Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias y Tecnologías Químicas, 13071 Ciudad Real, SpainUniversidad Rey Juan Carlos, Departamento de Biología y Geología, Física y Química Inorgánica, 28933 Móstoles, SpainUniversidad Rey Juan Carlos, Departamento de Biología y Geología, Física y Química Inorgánica, 28933 Móstoles, SpainUniversidad de Castilla-La Mancha, Departamento de Química Inorgánica, Orgánica y Bioquímica-Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Farmacia, 02071 Albacete, SpainUniversidad de Castilla-La Mancha, Departamento de Química Inorgánica, Orgánica y Bioquímica-Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Farmacia, 02071 Albacete, SpainUniversidad de Castilla-La Mancha, Departamento de Química Inorgánica, Orgánica y Bioquímica-Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias y Tecnologías Químicas, 13071 Ciudad Real, SpainThe catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO<sub>2</sub> as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex <b>3</b> with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened. The catalytic system was capable of copolymerizing selectively and efficiently CHO with phthalic, maleic, succinic and naphthalic anhydrides to afford the corresponding polyester materials. The polyesters obtained were characterized by spectroscopic, spectrometric, and calorimetric techniques. Finally, the reaction mechanism of the catalytic system was proposed based on stoichiometric reactions.https://www.mdpi.com/2073-4360/13/10/1651ring-opening copolymerizationepoxidescyclic anhydridespolymerszinc complexes |
| spellingShingle | Felipe de la Cruz-Martínez Marc Martínez de Sarasa Buchaca Almudena del Campo-Balguerías Juan Fernández-Baeza Luis F. Sánchez-Barba Andrés Garcés Carlos Alonso-Moreno José A. Castro-Osma Agustín Lara-Sánchez Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts Polymers ring-opening copolymerization epoxides cyclic anhydrides polymers zinc complexes |
| title | Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts |
| title_full | Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts |
| title_fullStr | Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts |
| title_full_unstemmed | Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts |
| title_short | Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts |
| title_sort | ring opening copolymerization of cyclohexene oxide and cyclic anhydrides catalyzed by bimetallic scorpionate zinc catalysts |
| topic | ring-opening copolymerization epoxides cyclic anhydrides polymers zinc complexes |
| url | https://www.mdpi.com/2073-4360/13/10/1651 |
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