Aluminium complexes bearing N,O-aminophenol ligands as efficient catalysts for the ring opening polymerization of lactide

Roymuhury, Sagnik K.; Chakraborty, Debashis; Ramkumar, V.

doi:10.1016/j.eurpolymj.2015.07.025

Cited by 22 publications

(7 citation statements)

References 78 publications

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“…In conclusion, we should like to emphasize that some aspects of the molecular structure of ROP precatalysts have been refined by DFT modeling [148,152,153,154,155,156,157]. However, the results of such modeling do not reflect fully the catalytic behavior of these complexes and therefore were irrelevant for our review.…”

Section: Coordination Polymerization Of Lactides and Glycolidementioning

confidence: 99%

Coordination Ring-Opening Polymerization of Cyclic Esters: A Critical Overview of DFT Modeling and Visualization of the Reaction Mechanisms

Nifant’ev

Ivchenko

2019

Molecules

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Ring-opening polymerization (ROP) of cyclic esters (lactones, lactides, cyclic carbonates and phosphates) is an effective tool to synthesize biocompatible and biodegradable polymers. Metal complexes effectively catalyze ROP, a remarkable diversity of the ROP mechanisms prompted the use of density functional theory (DFT) methods for simulation and visualization of the ROP pathways. Optimization of the molecular structures of the key reaction intermediates and transition states has allowed to explain the values of catalytic activities and stereocontrol events. DFT computation data sets might be viewed as a sound basis for the design of novel ROP catalysts and cyclic substrates, for the creation of new types of homo- and copolymers with promising properties. In this review, we summarized the results of DFT modeling of coordination ROP of cyclic esters. The importance to understand the difference between initiation and propagation stages, to consider the possibility of polymer–catalyst coordination, to figure out the key transition states, and other aspects of DFT simulation and visualization of ROP have been also discussed in our review.

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Section: Coordination Polymerization Of Lactides and Glycolidementioning

confidence: 99%

Coordination Ring-Opening Polymerization of Cyclic Esters: A Critical Overview of DFT Modeling and Visualization of the Reaction Mechanisms

Nifant’ev

Ivchenko

2019

Molecules

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“…The ligands used for this purpose were prepared by a mechanochemical technique which formed coordination bonds with silver (I) using nitrogen atoms in imine and pyridinyl [132]. Roymuhury et al used novel complexes of dimethyl aluminium containing bidentate aminophenolate ligands as a catalyst to polymerize Llactide and rac-lactide via ring opening polymerization [133]. Rosen synthesized hexablocks of poly(lactic acid) of defined lengths through ROP using a novel magnesium based catalyst.…”

Section: Other Developments In Functionalizedmentioning

confidence: 99%

Recent Advances in Biodegradable Polymers

Dhamaniya¹,

Gupta²,

Kakatkar³

2018

J. Res. Updates Polym. Sci.

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Biodegradable polymers are important as an alternative to conventional non-degradable polymers for sustainable eco-system. The recent trends indicate that the new developments in biodegradable polymers focus on novel polymer systems that can cater the need of biomedical and packaging applications in-terms of performance and economics. The new interest is rapidly moving toward reducing carbon footprint through utilization of carbon dioxide and developing new methods of manufacturing such as 3D printing for specific purposes. This review focus on the present state-of-art and recent developments in biodegradable polymers covering their sources, synthetic methodologies, salient properties, degradation patterns, polymer blends and nanocomposites. As well as biodegradable polymers as a 3D printing material and the use of carbon dioxide as a renewable raw material for biomedical and packaging applications.

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“…Metal alkoxy complexes are effective catalysts of ring-opening polymerization (ROP); the mechanistic paradigm for ROP initiated by metal alkoxides bases on “coordination-insertion” concept [13,14,15,16,17,18,19,20] (Scheme 1b). The density functional theory (DFT) modeling was successfully applied in the mechanistic study of coordination homopolymerization of lactones [21,22,23,24,25,26,27,28,29,30,31,32,33], lactides [31,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48], cyclic carbonates [30,42,49,50] and phosphates [51].…”

Section: Introductionmentioning

confidence: 99%

DFT Visualization and Experimental Evidence of BHT-Mg-Catalyzed Copolymerization of Lactides, Lactones and Ethylene Phosphates

et al. 2019

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Catalytic ring-opening polymerization (ROP) of cyclic esters (lactides, lactones) and cyclic ethylene phosphates is an effective way to process materials with regulated hydrophilicity and controlled biodegradability. Random copolymers of cyclic monomers of different chemical nature are highly attractive due to their high variability of characteristics. Aryloxy-alkoxy complexes of non-toxic metals such as derivatives of 2,6-di-tert-butyl-4-methylphenoxy magnesium (BHT-Mg) complexes are effective coordination catalysts for homopolymerization of all types of traditional ROP monomers. In the present paper, we report the results of density functional theory (DFT) modeling of BHT-Mg-catalyzed copolymerization for lactone/lactide, lactone/ethylene phosphate and lactide/ethylene phosphate mixtures. ε-Caprolactone (ε-CL), l-lactide (l-LA) and methyl ethylene phosphate (MeOEP) were used as examples of monomers in DFT simulations by the Gaussian-09 program package with the B3PW91/DGTZVP basis set. Both binuclear and mononuclear reaction mechanistic concepts have been applied for the calculations of the reaction profiles. The results of calculations predict the possibility of the formation of random copolymers based on l-LA/MeOEP, and substantial hindrance of copolymerization for ε-CL/l-LA and ε-CL/MeOEP pairs. From the mechanistic point of view, the formation of highly stable five-membered chelate by the products of l-LA ring-opening and high donor properties of phosphates are the key factors that rule the reactions. The results of DFT modeling have been confirmed by copolymerization experiments.

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Aluminium complexes bearing N,O-aminophenol ligands as efficient catalysts for the ring opening polymerization of lactide

Cited by 22 publications

References 78 publications

Coordination Ring-Opening Polymerization of Cyclic Esters: A Critical Overview of DFT Modeling and Visualization of the Reaction Mechanisms

Coordination Ring-Opening Polymerization of Cyclic Esters: A Critical Overview of DFT Modeling and Visualization of the Reaction Mechanisms

Recent Advances in Biodegradable Polymers

DFT Visualization and Experimental Evidence of BHT-Mg-Catalyzed Copolymerization of Lactides, Lactones and Ethylene Phosphates

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