Synthesis of helical aluminium catalysts for cyclic carbonate formation

Gaona, Miguel A.; Cruz-Martínez, Felipe de la; Fernández‐Baeza, Juan; Sánchez-Barba, Luis F.; Alonso‐Moreno, Carlos; Rodrı́guez, Ana; Rodríguez-Diéguez, Antonio; Castro‐Osma, José A.; Otero, Antonío; Lara‐Sánchez, Agustín

doi:10.1039/c9dt00323a

Cited by 34 publications

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“…55 The catalyst was able to carry out the ringopening copolymerization of epoxides and CO 2 and the reversible addition−fragmentation chain transfer polymerization of vinyl monomers, allowing the preparation of a broad range of CO 2 -based block copolymers. 55 Our research group has developed a number of scorpionate metal complexes as catalysts for the ROP of cyclic esters, 44,87−90 ROCOP of epoxides and CO 2 to prepare polycarbonates, 48 polyether−polycarbonates, 91 and ROCOP of epoxides and cyclic anhydrides to obtain polyesters. 44,46 Zinc complexes acted as catalysts for the ROCOP of cyclohexene oxide (CHO) with CO 2 to prepare PCHC with medium molecular weights and narrow polydispersities without the use of a cocatalyst.…”

Section: ■ Introductionmentioning

confidence: 99%

“…48 Later, helical aluminum catalysts were developed for the synthesis of polyether- polycarbonate materials derived from CHO and CO 2 in a ratio which could be modulated by changing the cocatalyst or the catalyst-to-cocatalyst ratio. 91 In this work we report the synthesis of a new family of bimetallic zinc complexes which have shown to be very efficient and versatile catalysts for the ROCOP of CHO with CO 2 and the terpolymerization of CHO, CO 2 , and phthalic anhydride (PA) to afford polycarbonate and polyesterpolycarbonate materials, respectively. Among the reported complexes, catalyst 3 showed to be highly versatile for the preparation of a range of biodegradable polymeric materials under the optimized reaction conditions.…”

Section: ■ Introductionmentioning

confidence: 99%

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Bimetallic Zinc Catalysts for Ring-Opening Copolymerization Processes

et al. 2020

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Novel bimetallic zinc acetate complexes supported by heteroscorpionate ligands have been developed for the ringopening copolymerization of cyclohexene oxide and CO 2 and the terpolymerization of cyclohexene oxide, phthalic anhydride, and CO 2 . Heteroscorpionate ligands precursors L 1 −L 3 were reacted with two equivalents of zinc acetate to afford the dinuclear zinc complexes [{Zn(κ 3 -bpzappe)}(μ-O 2 CCH 3 ) 3 -{Zn(HO 2 CCH 3 )}] (1), [{Zn(κ 3 -bpzbdmape)}(μ-O 2 CCH 3 ) 3 -{Zn(HO 2 CCH 3 )}] (2), and [{Zn(κ 3 -bpzbdeape)}(μ-O 2 CCH 3 ) 3 {Zn(HO 2 CCH 3 )}] (3) in excellent yields. The molecular structure of these compounds was determined spectroscopically and confirmed by X-ray diffraction analysis. Zinc acetate complexes 1−3 were screened as catalysts for the copolymerization of cyclohexene oxide and CO 2 to produce poly(cyclohexene)carbonate, and complex 3 was found to be the most active catalyst for this process in the absence of a cocatalyst. Furthermore, the terpolymerization of cyclohexene oxide, phthalic anhydride, and CO 2 was studied using the combination of complex 3 and 4-dimethylaminopyridine as catalyst system yielding the corresponding polyester-polycarbonate materials.

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Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Bimetallic Zinc Catalysts for Ring-Opening Copolymerization Processes

et al. 2020

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“…The zinc-based complexes displayed good catalytic activity and selectivity for the synthesis of medium molecular weight poly(cyclohexene carbonate) (PCHC) with narrow molecular weight distributions in the absence of a nucleophile as a cocatalyst [52,53]. The use of helical aluminum catalysts for the ROCOP of a range of epoxides and cyclic anhydrides or CHO and CO2 afforded the synthesis of polyester and polyether-polycarbonate materials respectively [36,51]. Furthermore, we have recently reported a new family of acetate Scorpionate aluminum and zinc complexes have been developed as efficient catalysts for the ROCOP of carbon dioxide and epoxides to afford polycarbonates and the terpolymerization reaction of epoxides, cyclic anhydrides and carbon dioxide [3,36,[51][52][53].…”

Section: Introductionmentioning

confidence: 99%

“…The use of helical aluminum catalysts for the ROCOP of a range of epoxides and cyclic anhydrides or CHO and CO2 afforded the synthesis of polyester and polyether-polycarbonate materials respectively [36,51]. Furthermore, we have recently reported a new family of acetate Scorpionate aluminum and zinc complexes have been developed as efficient catalysts for the ROCOP of carbon dioxide and epoxides to afford polycarbonates and the terpolymerization reaction of epoxides, cyclic anhydrides and carbon dioxide [3,36,[51][52][53]. The zinc-based complexes displayed good catalytic activity and selectivity for the synthesis of medium molecular weight poly(cyclohexene carbonate) (PCHC) with narrow molecular weight distributions in the absence of a nucleophile as a cocatalyst [52,53].…”

Section: Introductionmentioning

confidence: 99%

Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts

et al. 2021

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The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO2 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 3 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.

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“…The methods for synthesizing cyclic carbonates include epoxide–CO 2 or urea–polyol coupling reactions [ 8 , 9 , 10 , 11 , 12 ]. Catalysts used for the coupling reactions have been reviewed in many papers in recent years [ 13 , 14 , 15 , 16 , 17 , 18 ]. With respect to the homogeneous catalysts for the ring-opening polymerization of ε-caprolactone [ 19 , 20 , 21 , 22 ] and epoxide–CO 2 coupling reactions [ 23 , 24 ], common features of these catalysts include both of them being classified as Lewis acid metal complexes bearing varieties of organic ligands.…”

Section: Introductionmentioning

confidence: 99%

Ring-Opening Polymerization of ε-Caprolactone and Styrene Oxide–CO2 Coupling Reactions Catalyzed by Chelated Dehydroacetic Acid–Imine Aluminum Complexes

Wang

et al. 2021

Molecules

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A series of chelated dehydroacetic acid–imine-based ligands L1H~L4H was synthesized by reacting dehydroacetic acid with 2-t-butylaniline, (S)-1-phenyl-ethylamine, 4-methoxylbenzylamine, and 2-(aminoethyl)pyridine, respectively, in moderate yields. Ligands L1H~L4H reacted with AlMe3 in toluene to afford corresponding compounds AlMe2L1 (1), AlMe2L2 (2), AlMe2L3 (3), and AlMe2L4 (4). All the ligands and aluminum compounds were characterized by IR spectra, 1H and 13C NMR spectroscopy. Additionally, the ligands L1H~L4H and corresponding aluminum derivatives 1, 3, and 4 were characterized by single-crystal X-ray diffractometry. The catalytic activities using these aluminum compounds as catalysts for the ε-caprolactone ring-opening polymerization (ROP) and styrene oxide-CO2 coupling reactions were studied. The results show that increases in the reaction temperature and selective solvent intensify the conversions of ε-caprolactone to polycaprolactone. Regarding the coupling reactions of styrene oxide and CO2, the conversion rate is over 90% for a period of 12 h at 90 °C. This strategy dispenses the origination of cyclic styrene carbonates, which is an appealing concern because of the transformation of CO2 into an inexpensive, renewable and easy excess carbon feedstock.

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Synthesis of helical aluminium catalysts for cyclic carbonate formation

Abstract: Helical aluminium complexes have been prepared and used as catalysts for cyclic carbonate synthesis.

Cited by 34 publications

References 81 publications

Bimetallic Zinc Catalysts for Ring-Opening Copolymerization Processes

Bimetallic Zinc Catalysts for Ring-Opening Copolymerization Processes

Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts

Ring-Opening Polymerization of ε-Caprolactone and Styrene Oxide–CO2 Coupling Reactions Catalyzed by Chelated Dehydroacetic Acid–Imine Aluminum Complexes

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