A scale-up procedure to dialkyl carbonates; evaluation of their properties, biodegradability, and toxicity

Trapasso, Giacomo; Salaris, Claudio; Reich, Marco; Logunova, Evgenia; Salata, Cristiano; Kümmerer, Klaus; Figoli, Alberto; Aricò, Fabio

doi:10.1016/j.scp.2022.100639

Cited by 5 publications

(12 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…According to the data collected, it is evident that the family of DACs allowed to produce a wide variety of membranes. These compounds were easily synthesizable in large scale in a sustainable way . Despite the chemical similarities between the selected DACs, the nascent membranes displayed different proprieties, as highlighted by the characterization analyses carried out in the previous paragraphs.…”

Section: Resultsmentioning

confidence: 99%

“…Symmetrical and asymmetrical DACs were synthesized in large scale according to the procedure previously reported in the literature …”

Section: Methodsmentioning

confidence: 99%

“…The majority of DACs obtained was demonstrated to partially or completely biodegrade in the environment, and� except for amino and thio-based carbonates�they did not display any cytotoxicity in animal cells. 49 Starting from these premises, the present work focuses on the use of both custom-made and commercially available DACs as non-toxic and biodegradable solvents for the preparation of polymeric membranes with dense and porous morphologies. Preliminary theoretical thermodynamic studies were conducted to predict the solubilities of different polymers in DACs.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Symmetrical and asymmetrical DACs were synthesized in large scale according to the procedure previously reported in the literature. 49 Membrane Preparation Using PVDF Solef 21510. A dope solution (10 or 14 wt %) of PVDF Solef 21510 in each of the selected DACs was prepared and heated at a temperature between 40 and 130 °C until complete dissolution was achieved.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Compared to chlorine-based compounds, organic carbonates offer different benefits, among which are (i) low toxicity, (ii) non-persistence in the environment, and (iii) absence of dangerous wastes and side products . Due to these characteristics, these compounds can be securely used and handled without any particular safety precautions for the operator . Nevertheless, because of their lower reactivity compared to chlorinated compounds, reactions involving DACs usually require higher temperatures (60–200 °C) and longer reaction times.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Dialkyl Carbonates as Green Solvents for Polyvinylidene Difluoride Membrane Preparation

Trapasso

Russo

Galiano

et al. 2023

ACS Sustainable Chem. Eng.

Self Cite

View full text Add to dashboard Cite

Membrane processes are employed in a wide variety of industrial applications such as separation of complex mixtures, hydrogen isolation, CO2 removal, wastewater treatment, etc. Their use allows energy savings on the production cost compared to other traditional separation technologies. Nevertheless, the preparation of membranes not always fulfills sustainability obligations, especially when considering the commonly employed solvents, i.e., N-methyl-2-pyrrolidone and N,N-dimethylformamide, to mention just a few. Dialkyl carbonates (DACs) are well-known green solvents and reagents that have been extensively investigated as safe alternatives to chlorine-based compounds and media such as alkyl halides, phosgene, and chlorinated solvents. Following our recent study on a scale-up procedure to non-commercially available or expensive DACs, herein we report for the first time the application of organic carbonates as green media for membrane preparation. Theoretical thermodynamic studies were first carried out to predict the solubilities in DACs of different polymers commonly employed for membranes preparation. As a result, the use of selected organic carbonates as media for polyvinylidene difluoride membrane preparation was investigated by nonsolvent-induced phase separation (NIPS) and a combination of vapor-induced phase separation (VIPS)-NIPS techniques. Membranes obtained with custom-made DACs displayed greater structural resistances and smaller pore sizes compared to the ones achieved using commercially available cyclic organic carbonates. Data collected showed that it was possible to achieve a wide variety of dense and porous membranes by using a single family of compounds, highlighting once again the great versatility of DACs as green solvents.

show abstract

Section: Resultsmentioning

confidence: 99%

“…Symmetrical and asymmetrical DACs were synthesized in large scale according to the procedure previously reported in the literature …”

Section: Methodsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Dialkyl Carbonates as Green Solvents for Polyvinylidene Difluoride Membrane Preparation

Trapasso

Russo

Galiano

et al. 2023

ACS Sustainable Chem. Eng.

Self Cite

View full text Add to dashboard Cite

show abstract

Comparative Study between 2‐Furonitrile and 2‐Cyanopyridine as Dehydrants in Direct Synthesis of Dialkyl Carbonates from CO₂ and Alcohols over Cerium Oxide Catalyst

Sun,

Li,

Yabushita

et al. 2023

ChemSusChem

View full text Add to dashboard Cite

The shift of equilibrium by removing water with nitrile dehydrants is crucial for CeO2‐catalyzed synthesis of dialkyl carbonates from CO2 and alcohols. Two nitriles – 2‐cyanopyridine and 2‐furonitrile – were previously found as effective dehydrants, yet their detailed comparison as well as exploration of potential of 2‐furonitrile remain insufficient. Herein, the performance of 2‐cyanopyridine and 2‐furonitrile was compared in the synthesis of various dialkyl carbonates. 2‐furonitrile was found to be superior to 2‐cyanopyridine in the synthesis of dialkyl carbonates from CO2 and bulky or long‐chain (≥C3) alcohols. Namely, the yield of diisopropyl carbonate (up to 50 %) achieved using CeO2 and 2‐furonitrile is comparable to or even higher than previously reported ones. Meanwhile, 2‐cyanopyridine acted as a better dehydrant than 2‐furonitrile in the synthesis of dimethyl carbonate and diethyl carbonate. The adsorption experiments and density functional theory calculations have indicated that the better performance of 2‐furonitrile compared to 2‐cyanopyridine in the synthesis of dialkyl carbonates from bulky or long‐chain alcohols is due to the weaker interaction of 2‐furonitrile with the CeO2 surface. Such weak interaction of 2‐furonitrile offers a larger reaction field on the catalyst surface for both CO2 and alcohols.

show abstract

Nitrile Furanics via Copper‐Catalyzed Dehydration of Aldoximes and Knoevenagel Condensation

Annatelli,

Sadraoui,

Trapasso

et al. 2024

Eur J Org Chem

Self Cite

View full text Add to dashboard Cite

In this work two synthetic approaches to introduce nitrile moieties into bio‐based derived furanic compounds were investigated, i.e., dehydration of aldoximes and Knoevenagel condensation. Both methodologies have been first tested and optimized on furfural and thus exploited on 5‐hydroxymethyl‐2‐furfural (HMF) and 5,5’‐oxy(bismethylene)‐2‐furaldehyde (OBMF). The syntheses of furfural, HMF and OBMF aldoximes were efficiently conducted (also in large scale) under mild reaction conditions and short reaction time. The subsequent dehydration to nitrile furanic compounds was carried out in the presence of catalytic amount of copper acetate monohydrate. Furthermore, Knoevenagel condensations were performed on furfural, HMF and OBMF with different Activated Methylene Group compounds, using for the first‐time dimethyl carbonate as the reaction media. Most of the resulting products were isolated as pure via simple liquid‐liquid extraction in good to excellent yields. Future applications of these compounds might include aldoxime reduction into amine furanics ‐ herein also preliminary investigated ‐ and hydrolysis of the nitrile derivatives in the related carboxylic acid (or ester) furanics. All these products are interesting monomers for the preparation of bio‐based polymers.

show abstract

A scale-up procedure to dialkyl carbonates; evaluation of their properties, biodegradability, and toxicity

Cited by 5 publications

References 54 publications

Dialkyl Carbonates as Green Solvents for Polyvinylidene Difluoride Membrane Preparation

Dialkyl Carbonates as Green Solvents for Polyvinylidene Difluoride Membrane Preparation

Comparative Study between 2‐Furonitrile and 2‐Cyanopyridine as Dehydrants in Direct Synthesis of Dialkyl Carbonates from CO₂ and Alcohols over Cerium Oxide Catalyst

Nitrile Furanics via Copper‐Catalyzed Dehydration of Aldoximes and Knoevenagel Condensation

Contact Info

Product

Resources

About

A scale-up procedure to dialkyl carbonates; evaluation of their properties, biodegradability, and toxicity

Cited by 5 publications

References 54 publications

Dialkyl Carbonates as Green Solvents for Polyvinylidene Difluoride Membrane Preparation

Dialkyl Carbonates as Green Solvents for Polyvinylidene Difluoride Membrane Preparation

Comparative Study between 2‐Furonitrile and 2‐Cyanopyridine as Dehydrants in Direct Synthesis of Dialkyl Carbonates from CO2 and Alcohols over Cerium Oxide Catalyst

Nitrile Furanics via Copper‐Catalyzed Dehydration of Aldoximes and Knoevenagel Condensation

Contact Info

Product

Resources

About

Comparative Study between 2‐Furonitrile and 2‐Cyanopyridine as Dehydrants in Direct Synthesis of Dialkyl Carbonates from CO₂ and Alcohols over Cerium Oxide Catalyst