Mechanism of urethane formation from cyclocarbonates and amines: a quantum chemical study

Zabalov, M. V.; Тигер, Р. П.; Берлин, А. А.

doi:10.1007/s11172-012-0076-8

Cited by 39 publications

(20 citation statements)

References 6 publications

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“…The reaction mechanism of this process has been analyzed from different standpoints, so that, according to Tomita et al [193], this reaction is controlled by differences in electron densities giving rise to the appearance or breaking of chemical linkages, while to Zabalov et al [194] it is based on a single-or several-step procedure in which a second amine molecule acts as catalyst. Anyhow, it was disclosed the second-order character of this reaction [193], besides the fact that primary amines and polar solvents seem to promote the addition reaction [195].…”

Section: Non-isocyanate Polyurethanesmentioning

confidence: 99%

A Review of the Sustainable Approaches in the Production of Bio-based Polyurethanes and Their Applications in the Adhesive Field

2020

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On account of the irreversible environmental damage caused by the utilization of non-renewable raw materials in industrial production, since the end of the twentieth century, the interest in replacing the traditionally applied petroleum-based starting compounds in the polyurethane production by more sustainable feedstocks has grown enormously. Such pursuit of Green Chemistry has been fostered by the implementation of a set of national and international initiatives and stricter regulations, especially in the field of adhesives. In this respect, the latest advances in the production of bio-based polyurethanes are collected in this review. Thus, after a brief introduction to this subject and main tendencies towards the production of more sustainable polyurethanes, the first section reviews the feasibility of manufacturing polyurethanes from a range of natural platforms, including lignocellulosic biomass and vegetable oils, whether modified or in their original form, along with some industrial wastes. Afterwards, the hitherto considered synthetic routes for the preparation of greener polyurethanes are assessed, encompassing waterborne, radiation-curable and non-isocyanate polyurethane techniques. Finally, the last section focuses on the research advancement on the synthesis, properties and different uses of bio-based polyurethanes specifically implemented in the field of adhesives.

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Section: Non-isocyanate Polyurethanesmentioning

confidence: 99%

A Review of the Sustainable Approaches in the Production of Bio-based Polyurethanes and Their Applications in the Adhesive Field

2020

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“…So far, mechanistic studies on metal complex catalyzed PU reaction have been performed mainly for organotin catalysts, 58,[60][61][62][63][64][65] leaving critical questions still unanswered. It remains for example unclear what factors determine the selectivity and speed of the isocyanate-hydroxyl reaction when catalyzed by tin, zirconium, bismuth, or zinc catalysts.…”

Section: Mechanistic Investigation and Density Functional Theory Calcmentioning

confidence: 99%

Heterobimetallic complexes composed of bismuth and lithium carboxylates as polyurethane catalysts – alternatives to organotin compounds

et al. 2021

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“…The 4 regio-isomers of hydroxyurethane are "cyclic" due to a H-bond between the alcohol and the O atom of the carbonyl group. 36 Thus, the differences in term of barrier heights and reaction's Gibbs free energy are so closed that the choice to consider the reaction leading to only one regio-isomer (i.e. the S product of the secondary alcohol) appears to be sufficiently representative of the reactivity of the cyclic carbonate with an amine.…”

Section: Cyclic Carbonate -Amine Coupling Without Catalystmentioning

confidence: 99%

“…33 The mechanism of the uncatalysed hydroxyurethane formation by aminolysis of carbonate was previously investigated in detail by Zabalov et al [34][35][36] using DFT calculations. They established that the reaction might progress notably throughout a six-centre ring intermediate based on the 5-membered cyclic carbonate and two amine molecules, one playing a catalytic role.…”

mentioning

confidence: 99%

DFT investigation of the reaction mechanism for the guanidine catalysed ring-opening of cyclic carbonates by aromatic and alkyl-amines

et al. 2017

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The guanidine catalysed aminolysis of propylene carbonate has been investigated using density functional theory (DFT) and highlights that different reaction pathways are involved, depending on the aromatic or aliphatic nature of the amine. The structural ability of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) to simultaneously give and receive protons was demonstrated by a detailed mechanistic investigation. The bifunctional activity (base/H-bond donor) of TBD significantly reduces the Gibbs energy of the reaction and allows understanding of its higher efficiency compared to its methyl counterpart (MTBD).

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Mechanism of urethane formation from cyclocarbonates and amines: a quantum chemical study

Cited by 39 publications

References 6 publications

A Review of the Sustainable Approaches in the Production of Bio-based Polyurethanes and Their Applications in the Adhesive Field

A Review of the Sustainable Approaches in the Production of Bio-based Polyurethanes and Their Applications in the Adhesive Field

Heterobimetallic complexes composed of bismuth and lithium carboxylates as polyurethane catalysts – alternatives to organotin compounds

DFT investigation of the reaction mechanism for the guanidine catalysed ring-opening of cyclic carbonates by aromatic and alkyl-amines

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