The coupling of carbon dioxide (CO₂) with epoxides the formation cyclic carbonates is a highly attractive 100% atom economic reaction. It represents greener and safer alternative to conventional synthesis from diols toxic phosgene.

Novel linear polyurethanes were synthesized by bulk polyaddition of diamines with two vegetable-based biscarbonates produced from oleic acid methyl ester. Internal carbonated fatty diester (ICFAD) and terminal (TCFAD) obtained the reaction their epoxide precursors CO2. Terminal epoxy (TEFAD) was found to be more soluble reactive in CO2 than internal (IEFAD). Polyurethanes TCFAD ICFAD exhibit molecular weights up 13 500 g mol−1 glass transitions around −15 °C. Amide linkages not observed when...

Abstract Described is a robust platform for the synthesis of large diversity novel functional CO 2 ‐sourced polymers by exploiting regiocontrolled ring‐opening α‐alkylidene carbonates various nucleophiles. The reactivity dictated exocyclic olefinic group. polyaddition bis(α‐alkylidene carbonate)s (bis‐αCCs) with primary and secondary diamines provides regioregular poly(urethane)s. bis‐αCCs also exploited producing new poly(β‐oxo‐carbonate)s organocatalyzed diol. This variants world‐class...

The cycloaddition of carbon dioxide onto propylene oxide catalysed by ammonium and guanidinium salts has been investigated using density functional theory (DFT) in order to understand the catalytic mechanism role cation anion. Two different possible pathways were considered, but it found that one whereby activation epoxide onium salt occurs before addition CO2 was consistent with experimental findings. rate-determining step be ring opening results from nucleophilic attack anion catalyst on...

Abstract The addition of fluorinated alcohols to onium salts provides highly efficient organocatalysts for the chemical fixation CO 2 into epoxides under mild experimental conditions. combination online kinetic studies, NMR titrations and DFT calculations allows understanding this synergistic effect that an active organocatalyst /epoxides coupling.

A rational investigation of the cocatalytic activity a series commercially available hydrogen bond donors (HBDs) for synthesis cyclic carbonates from CO₂ and epoxides under mild conditions.

Novel fatty acid-based bis 5-membered carbonates for a non-isocyante route to polyurethanes.

Polyurethane (PU) foams are indisputably daily essential materials found in many applications, notably for comfort (for example, matrasses) or energy saving thermal insulation). Today, greener routes their production intensively searched to avoid the use of toxic isocyanates. An easily scalable process simple construction self-blown isocyanate-free PU by exploiting organocatalyzed chemo- and regioselective additions amines thiols accessible cyclic carbonates is described. These reactions...

Neutron diffraction experiments of heavy water at several supercritical states (380<T<500 °C and 200<P<900 bar) corresponding to densities ranging from 0.2 0.7 g/cm3 are performed. They allow the static structure factor pair correlation function be derived once absorption, multiple scattering, inelasticity corrections have been made. The experimental results compared with previous data obtained by Postorino et al. [Nature 366, 668 (1993)] new molecular dynamics...

A series of ionic salts have been investigated to catalyze the coupling reaction between epoxide and carbon dioxide at T = 80 °C P 8 MPa. Among them, we focused particularly on tetrabutylammonium, imidazolium guanidinium salts. The kinetics synthesis was monitored in situ using both FTIR Raman spectroscopy. For a given time, best yields were obtained with 1,5,7-triaza-bicyclo[4.4.0]dec-5-enium bromide (TBD·HBr) 1-methyl-3-methylimidazolium iodide (MMImI) not detail literature before. Thanks...

Optimal conditions deduced from <italic>in situ</italic> FTIR kinetic studies provide quantitative conversion of epoxidized linseed oil into carbonated using a bi-component organocatalyst.

In this article, we present an optimization study of the switchable solvent system DBU/CO2 for cellulose solubilization and derivatization via online Fourier transform infrared spectroscopy (FT-IR). By varying temperature, CO2 pressure, time, succeeded in achieving within 10–15 min at 30 °C. Compared to traditionally used ionic liquids, presented here is cheaper, easier recycle, enables a very fast under mild conditions. The efficiency our optimized conditions were further confirmed by X-ray...

This paper aims at exploring the scCO2 impregnation of three commonly implanted polymer sutures made poly-l-lactide (PLLA), poly(ethylene terephthalate) (PET) and polypropylene (PP) with two anti-inflammatory drugs namely ketoprofen aspirin. For all investigated polymer/drug systems, drug loading increases temperature pressure. It appears that main criteria must be fulfilled by to achieve high loading: (i) a good affinity between (ii) chain mobility favor diffusion into matrix. As PLLA...

The novel monomer, vinyl trifluorobutyrate (VTFBu), when polymerized in a controlled fashion by RAFT/MADIX polymerization with xanthate transfer agent, yields poly(vinyl ester)s improved solubility supercritical carbon dioxide. thermodynamic parameters controlling the of VTFBu/vinyl acetate statistical copolymers are discussed based on ab initio calculations, glass transition temperatures copolymers, and surface tension measurements. enhanced this new class CO2-philic polymer combined its...

The bifunctional activity (base/H-bond donor) of TBD allows understanding its higher efficiency compared to methyl counterpart (MTBD) for the aminolysis cyclic carbonates by amines.

Abstract The organocatalytic coupling of CO 2 with oxetanes is investigated under solvent‐free conditions. influence the main reaction parameters (type system, pressure, and temperature) on yield, product formed, selectivity are discussed. An onium salt combined a fluorinated alcohol promotes efficient selective synthesis α,ω‐hydroxyl oligocarbonates by at 130 °C pressure as low MPa. NMR characterizations were correlated matrix‐assisted laser desorption/ionization time‐of‐flight mass...

Hydrogenation of sugar monomers to sugars alcohols was performed in the presence a commercial Ru/Al2O3 catalyst. It shown that glucose (10 wt %) selectively converted sorbitol with yield around 97% under optimized conditions (100 °C, 30 bar, 150 min reaction and 5 % catalyst). The pathway determined by analysis intermediate compounds. This catalyst stable up 10 cycles due alumina phases support Ru particle sizes. Moreover, it during is reactivate hydrogen explaining its stability, helping...

This review is dedicated to the state-of-the art routes used for synthesis of CO2-based (a)cyclic carbonates and polycarbonates from alcohol substrates, with an emphasis on their respective main advantages limitations. The first section reviews organic such as dialkyl or cyclic carbonation alcohols. Many different synthetic strategies have been reported (dehydrative condensation, alkylation route, “leaving group” strategy, carbodiimide protected alcohols etc.) various substrates...

The interaction between water and hexafluorobenzene is discussed in light of an ab initio study. It found that a dimer formed with binding energy about −2 kcal/mol, geometry such the oxygen above molecule, both hydrogen atoms pointing out ring, C2 axis collinear main symmetry aromatic compound. In addition, intermolecular potential surface (IPS) has been fully characterized. comes rotational motion molecule around its nearly "free", whereas two other bending motions are to be strongly...

Infrared spectroscopic measurements of the νOD stretching vibration dilute deuterated ethanol in supercritical CO2 have been performed and analyzed, via a theoretical model ab initio calculations, to better understand ethanol−CO2 interaction. It was found that strongly attractive interactions, predominantly due dispersion, dominate stabilization energy between CO2. Differences observed theoretically predicted spectral shifts indicate presence local density enhancements. The continued...

In this paper, we investigated the 1:1 EDA complexes of CO2 formed with alcohols, namely, methanol and ethanol (sp3 O-donating atom), acetone (sp2 atom) in light ab initio calculations. The interaction energy geometry have been evaluated Moller−Plesset perturbation theory at second-order level (MP2) using Dunning's basis sets. predicted structures are found to be rather similar compared calculations SCF/3-21G* reported by Jamroz et al. (Jamroz, M. H.; Dobrowolski, J. C.; Bajdor, K.;...