Enhanced aminolysis of cyclic carbonates by β-hydroxylamines for the production of fully biobased polyhydroxyurethanes

Abstract

The aminolysis of five-membered cyclic carbonates which results in polyhydroxyurethanes (PHUs) is one of the most promising synthetic pathway to achieve isocyanate-free polyurethanes (NIPUs), one of the main industrial challenges...

Taking advantage of β-hydroxy amine enhanced reactivity and functionality for the synthesis of dual covalent adaptable networks

“…This effect was observed for the addition of amine on both epoxy 50 and cyclocarbonate. 51 Moreover, β-hydroxy amines can easily be obtained from biobased epoxy monomers. Here, inspired by the work of Du Prez et al , 45 β-hydroxy amines were used to prepare CANs containing β-amino esters as they represent an innovative way to bring hydroxyl group in a transesterification material.…”

Understanding the Reshaping of Fluorinated Polyester Vitrimers by Kinetic and DFT Studies of the Transesterification Reaction

“…The transesterification of 5 ‐F by n ‐hexanol (data in Table S10, pseudo‐first order plot in Figure S14) revealed an interesting rate enhancement relative to the ethyl ester 2 ‐F, see Table 2 ( k 5‐F / k 2‐F =4.3). This modest but sensible accelerating effect is most likely due to an electrophilic activation of the ester thanks to an intramolecular hydrogen bond between the carbonyl function and the β‐hydroxy group, as also recently evidenced for the cyclic carbonate aminolysis [23] …”

“…This modest but sensible accelerating effect is most likely due to an electrophilic activation of the ester thanks to an intramolecular hydrogen bond between the carbonyl function and the β-hydroxy group, as also recently evidenced for the cyclic carbonate aminolysis. [23] Influence of the competing alcohol Finally, the influence of the steric hindrance of the alcohol nucleophile was also examined using 4-heptanol as the competing nucleophile for the transesterification of 2-F (data in Table S11). As explained above, the vitrimer material was prepared by the opening of a monosubstituted epoxide (benzyl glycidyl ether) with an α,α-difluorinated acid (2,2-difluorophenylacetic acid), giving rise to the privileged, but not exclusive, formation of secondary alcohols such as in 5-F.…”

Synthesis of porous poly(ionic liquid)s for chemical CO2fixation with epoxides

“…[18][19][20] The products cyclic carbonates have been widely used in the dyeing and printing industry, textile, polymer synthesis, electrochemistry, pharmaceuticals, fine chemical intermediates and other industries. [21][22][23] However, the reaction does not occur spontaneously, encouraging the development of efficient catalysts to allow smooth transformation under mild conditions.…”