L'utilizzo di carbonati come reagenti per la sintesi "green" di derivati fenolici: l'esempio del 2-fenossi-1-etanolo

2-Phenoxyethanol (ethylene glycol monophenyl ether) is used as solvent for cellulose acetate, dyes, inks, and resins; it is a synthetic intermediate in the production of plasticizers, pharmaceuticals, and fragrances. Phenoxyethanol is obtained industrially by reaction of phenol with ethylene oxide, in the presence of an homogeneous alkaline catalyst, typically sodium hydroxide. The yield is not higher than 95-96%, because of the formation of polyethoxylated compounds. However, the product obtained may not be acceptable for use in cosmetic preparations and fragrance formulations, due to presence of a pungent “metallic” odor which masks the pleasant odor of the ether, deriving from residual traces of the metallic catalyst. Here we report a study aimed at using ethylene carbonate in place of ethylene oxide as the reactant for phenoxyethanol synthesis; the use of carbonates as green nucleophilic reactants is an important issue in the context of a modern and sustainable chemical industry. Moreover, in the aim of developing a process which might adhere the principles of Green Chemistry, we avoided the use of solvents, and used heterogeneous basic catalysts. We carried out the reaction by using various molar ratios between phenol and ethylene carbonate, at temperatures ranging between 180 and 240°C, with a Na-mordenite catalyst. Under specific conditions, it was possible to obtain total phenol conversion with >99% yield to phenoxyethanol in few hours reaction time, using a moderate excess of ethylene carbonate. Similar results, but with longer reaction times, were obtained using a stoichiometric feed ratio of reactants. One important issue of the research was finding conditions under which the leaching of Na was avoided, and the catalyst could be separated and reused for several reaction batches.

An experimental and modelling study of the capture of CO2 from gas mixtures with different techniques, with focus on multicomponent effects.

In the present work, the deviations in the solubility of CO2, CH4, and N2 at 30 °c in the mixed gases (CO2/CH4) and (CO2/N2) from the pure gas behavior were studied using the dual-mode model over a wide range of equilibrium composition and pressure values in two glassy polymers. The first of which was PI-DAR which is the polyimide formed by the reaction between 4, 6-diaminoresorcinol dihydrochloride (DAR-Cl) and 2, 2’-bis-(3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA). The other glassy polymer was TR-DAR which is the corresponding thermally rearranged polymer of PI-DAR. Also, mixed gas sorption experiments for the gas mixture (CO2/CH4) in TR-DAR at 30°c took place in order to assess the degree of accuracy of the dual-mode model in predicting the true mixed gas behavior. The experiments were conducted on a pressure decay apparatus coupled with a gas chromatography column. On the other hand, the solubility of CO2 and CH4 in two rubbery polymers at 30⁰c in the mixed gas (CO2/CH4) was modelled using the Lacombe and Sanchez equation of state at various values of equilibrium composition and pressure. These two rubbery polymers were cross-linked poly (ethylene oxide) (XLPEO) and poly (dimethylsiloxane) (PDMS). Moreover, data about the sorption of CO2 and CH4 in liquid methyl dietahnolamine MDEA that was collected from literature65-67 was used to determine the deviations in the sorption behavior in the mixed gas from that in the pure gases. It was observed that the competition effects between the penetrants were prevailing in the glassy polymers while swelling effects were predominant in the rubbery polymers above a certain value of the fugacity of CO2. Also, it was found that the dual-mode model showed a good prediction of the sorption of CH4 in the mixed gas for small pressure values but in general, it failed to predict the actual sorption of the penetrants in the mixed gas.