Dimethyl Adipate Research Articles

Abraham solvation parameter model: experiment-based solute descriptors for (2-nitrophenyl)acetic acid

ABSTRACT Mole fraction solubilities are reported for (2-nitrophenyl)acetic acid dissolved in 1-pentanol, 1-heptanol, 1-octanol, 2-butanol, 3-methyl-1-butanol, 2-pentanol, 4-methyl-2-pentanol, cyclopentanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 1,4-dioxane, methyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, pentyl acetate, methyl butyrate, dimethyl adipate and propanenitrile at 298.15 K. Solubilities were determined using a spectrophotometric method of chemical analysis. Experiment-based Abraham model solute descriptors are calculated for the molecular, monomeric form of (2-nitrophenyl)acetic acid by combining our experimental values with the published solubility data obtained from the published paper by Zhou and co-workers. The calculated solute descriptors describe the observed solubility data to within an overall standard deviation of 0.10 log units.

High‐Efficiency Dimethyl Adipate Hydrogenation for 1,6‐Hexanediol Synthesis Over the Cu/SiO2 Nanoparticles with Reasonably Modulations of Pore Structure and Dispersion via Surface‐Assisted Method

AbstractSurfactant‐assisted co‐precipitation for catalyst preparation is an excellent potential preparation method for enhanced metal‐support interactions and abundant oxygen vacancy. Cu/SiO2 catalysts were prepared containing either glycolic acid ethoxylate lauryl ether (BRIJ35, B5), polyethylene oxide‐polypropylene oxide‐polyethylene oxide (P123 P3), or no surfactant. After further treatment with surfactants, the 1,6‐hexanediol selectivity was significantly increased, especially for P123 surfactant. The Cu/SiO2‐P3 catalyst showed good performance, which may be related to more surface basic amount, the larger dispersion of the Cu and abundant oxygen vacancy. Abundant Ovac may facilitate the hydrogenation of DMA by weakening the C=O bond. After the Cu/SiO2 catalyst was treated with surfactant, the micropores disappeared and SBET of the catalyst increased. Among them, Cu/SiO2‐P3 had the largest specific surface area (312.6 m2 g−1).

Palladium-catalyzed dicarbonylation of 1,3-butadiene with bidentate phosphine ligands: A density functional theory study

DFT calculations have been performed to discover the mechanism for the synthesis of dimethyl adipate (DMA) by 1,3-butadiene (BD) dicarbonylation catalyzed by a complex consisting of palladium and a bidentate diphosphine ligand. The computational results indicate that BD dicarbonylation involves two catalytic stages with the same reaction mechanism including terminal alkenyl insertion, CO migratory insertion, and methanolysis. Four different reaction routes have been explored, the pathway yielding linear DMA has the lowest alkenyl C-H insertion barrier with an overall barrier of 13.4 kcal·mol–1. The regioselectivity of the BD dicarbonylation depends mainly on the barrier of the alkenyl insertion into the palladium-hydrogen complex site. The computations well reproduced the experimentally observed linear selectivity.

Efficient synthesis of 1,6-Hexanediol via the hydrogenation of dimethyl adipate on CuZn nanoparticles with balanced Cu+-Cu0 sites

In this paper, Cu-based catalyst was prepared by co-precipitation method with DMA hydrogenation as a probe reaction. Compared to the binary Cu-ZnO catalyst, the Cu-ZnO-MxOy (M=Ce, Ti, Zr and Al) catalyst modified with the addition of a third component showed a significant increase in 1,6-Hexanediol (HDO) selectivity. Especially, the dimethyl adipate (DMA) conversion, HDO selectivity and yield of the CZZ catalyst were up to 75.7 %, 53.6 % and 40.6 %, respectively, higher than others. Combining the results of XPS and N2O titration, HDO selectivity was adjusted by varying the Cu+/(Cu0+Cu+) ratio via the third component. The addition of ZrO2 prevented further reduction of Cu+ due to the formation of Cu/ZrO2 or Cu/ZnO species, thus maintaining a constant Cu+/(Cu0+Cu+) ratio and realizing the efficient selectivity of HDO. Furthermore, higher alkaline site density on the CZZ catalyst facilitated CO bond activation further favored the formation of 1,6-hexanediol. In addition, CZZ catalyst had better hydrogen dissociation capacity and smaller catalyst particle size, which will further promote the hydrogen dissociation and thus the hydrogenation process of DMA.

Unveiling the hydroesterification of 1,3-butadiene with carbonyl cobalt ionic liquids: Facilitation of cationic protonic hydrogen for active species formation

The 1,3-butadiene hydroesterification products, such as methyl pentenoate and dimethyl adipate, play a significant role in the production of nylon, plasticizers, and pharmaceutical intermediates. However, due to its unique π-π conjugated system, slow reaction rate, and difficulties in controlling regioselectivity, butadiene presents itself as an incredibly challenging substrate. The development of efficient and low-cost catalysts has gained substantial attention in both theoretical studies and industrial applications due to the high cost or extremely high pressure requirements. In this study, carbonyl cobalt ionic liquids were innovatively employed as catalysts to facilitate the synthesis of monoesters from hydroesterification of butadiene under mild conditions. A series of carbonyl cobalt ionic liquids with different cations were prepared and characterized for their structural properties using IR, ESI, IC, and DFT calculations. The yield of methyl pentenoate was comparable to that of Co2CO8 at 400 bar, and the catalysts exhibited high selectivity to methyl 3-pentenoates (>95 %), establishing a stable, efficient, and low-cost catalytic system. The experiments revealed that the type of the cation in ionic liquids remarkably influence their catalytic performance. Electrostatic potential calculations further confirmed that this performance is tightly related to the dissociation and migration behaviors of protons, leading to the proposal of a screening method for ionic liquids. In this paper, we further calculated the qualitative reaction kinetics and proposed a reaction mechanism in conjunction with previous studies. The reaction is hypothesized to begin with the formation of the active species HCo(CO)4 by proton exchange of [HX]+[Co(CO)4]−, in line with our experimental findings and theoretical calculations. This study presents an innovative approach to overcome the challenges associated with butadiene hydroesterification and paves the way for the development of more efficient and cost-effective catalytic systems.

Controlled Enzymatic Synthesis of Polyesters Based on a Cellulose-Derived Triol Monomer: A Design of Experiment Approach.

Regioselective enzymatic polycondensation of the bio-based cellulose derived polyol, Triol-citro, and dimethyl adipate using Candida antarctica Lipase B (CaLB) was investigated. A Design of Experiment approach with MODDE® Pro 13 was used to determine important factors in the branching behavior of this polymer, and reactant ratio, temperature, reaction time and enzyme wt % were the studied factors. Multifunctional polyesters with pendant hydroxy groups were synthesized and fully characterized using 2D NMR techniques to determine degree of branching. Branching was minimal, with a maximum of 16 % observed, and monomer ratio, temperature and reaction time were all determined to be significant factors. In this work, Mn of up to 13 kDa were achieved, while maintaining degree of branching below 15 %, resulting in a linear polyester with the potential to be further functionalized.

Isobaric Vapor–Liquid Equilibrium of Binary Mixtures of 2-Methylpentanedioic Acid Dimethyl Ester and Dimethyl Adipate at 101.3, 50.0, 30.0, and 10.0 kPa

Isobaric Vapor–Liquid Equilibrium of Binary Mixtures of 2-Methylpentanedioic Acid Dimethyl Ester and Dimethyl Adipate at 101.3, 50.0, 30.0, and 10.0 kPa

Catalytic Conversion of Cyclopentanone into Dimethyl Adipate over Solid Basic Catalysts with Dimethyl Carbonate

The synthesis of dimethyl adipate (DAP), a stable configuration of adipic acid, from biomass-derived cyclopentanone (CPO) and dimethyl carbonate (DMC) constitutes an attractive greener route than petroleum-based industrial processes. Solid basic catalysts such as MgO, Mg5(CO3)4(OH)2·4H2O, KOCH3 and Ca(OCH3)2 have been used achieving a DAP yield up to 30% at 533 K. In addition to the type of catalyst, other operating conditions such as the substrate, reaction time, temperature and CPO concentration have been studied. The methylation of DAP and CPO and the self-aldol condensation of CPO to form dimers and oligomers are reactions that occur in parallel with the production of DAP. It has been established that the main challenge is the self-aldol condensation of CPO. It has been identified that at short reaction times, to prevent methylation, and at dilute concentrations, to avoid CPO self-condensation, the DAP formation rate is much higher than these other competitive reactions. Finally, it should be noted that a DAP productivity up to 3.45 g·gcat−1·h−1 has been achieved under mild conditions.

Tuning of Catalytic Dimethyl Adipate Hydrogenation by Changing Composition of Cu–ZnO–TiO2 Catalysts

Tuning of Catalytic Dimethyl Adipate Hydrogenation by Changing Composition of Cu–ZnO–TiO₂ Catalysts

Study on the stability of palladium complexes with Hemaraphos ligand and reaction kinetics in the bis-hydroalkoxycarbonylation of 1,3-butadiene

The bis-hydroalkoxycarbonylation of 1,3-butadine (BD) to synthesize dimethyl adipate offers an environmentally friendly alternative route for the production of adiponitrile. While through the study of the stability in different reaction systems proves that the nucleophilicity of “N” (pyridine group) in Hemaraphos ligand not only contributes to the stability of Pd complexes, but also promotes the formation of Pd-H active species. Moreover, based on the study of kinetics, this reaction was divided into two stages (Reaction 1: hydroalkoxycarbonylation of BD to methyl pentanoate, Reaction 2: hydroalkoxycarbonylation of methyl pentanoate to dimethyl adipate) and the qualitative kinetics for the two reaction stages was studied respectively. It was found that the reaction rate of Reaction 2 was much higher than that of Reaction 1. And even if the activation energy of the catalyst for Reaction 2 was lower than that of Reaction 1, the conversion of BD took priority when both BD and methyl pentanoate existed simultaneously in the system. Finally, the different reaction mechanisms for Hemaraphos and dtbpx was proposed and compared based on the different dynamic behaviors. The electron donor ability of “N” (pyridine group) is stronger than “O” (ester carbonyl group), which was found to be the possible reason for the two hydroalkoxycarbonylation reaction stages of Hemaraphos.

Ternary Cu-ZnO-ZrO2 Nanostructures Prepared by Surface-Assisted Coprecipitation for Catalytic Hydrogenation of Dimethyl Adipate to 1,6-Hexanediol

Ternary Cu-ZnO-ZrO₂ Nanostructures Prepared by Surface-Assisted Coprecipitation for Catalytic Hydrogenation of Dimethyl Adipate to 1,6-Hexanediol

HZSM‐5‐Catalyzed Vapor‐Phase Conversion of Dimethyl Adipate to Adiponitrile: The Influence of the SiO2/Al2O3 Ratio on Reactivity

AbstractThe vapor‐phase nitrilation of dimethyl adipate (DMA) with ammonia (NH3) is an environmentally benign route leading to adiponitrile (ADN) with great application value. In this study, the performance of HZSM‐5 zeolites, widely used in industry as the solid acid catalysts, was investigated. It exhibits a strong correlation between the SiO2/Al2O3 ratio (SAR) in HZSM‐5 zeolites and the reactivity (both activity and selectivity). The influence of Al density closely related to the value of SAR on the reactivity of HZSM‐5 was thus elucidated by mechanistic experiments. As a result, the introduction of Al element to the framework is beneficial to the activation of ester functionality, thus improving the activity, especially at a high liquid hourly space velocity (LHSV). However, a high Al density will lead to poor selectivity and deactivation due to too strong adsorption of esters and intermediates (e. g., amides). Herein, the balanced adsorption/desorption capability was reached on HZSM‐5 with SAR as 631 (i. e., HZSM‐5‐631), which provides the best selectivity to nitriles (SADN+MCP, 92.5 %) at a high single‐pass conversion of DMA (CDMA, 98.0 %).

Boosted nitrilation of dimethyl adipate with NH3 to adiponitrile over bimetallic oxide: Synergetic effect between Nb and W

To reach highly active and selective gas-phase nitrilation of dimethyl adipate (DMA) with NH3, a series of NbxW10-x (x = 10, 9, 7, 5 and 0) composite were fabricated by a sol–gel method to approach the homogeneous combination of NbOx and WOx. As a result, the single-pass yield of adiponitrile (ADN) reached 85.2% over Nb9W1 under lower reaction temperature and lower NH3/DMA molar ratio. Consequently, the space–time yield (STY) of ADN over Nb9W1 was 1.7 ∼ 30 times higher than that of previous catalysts. Mechanistic experiments demonstrated the activity strongly correlates the interaction between the carbonyl functionality and the composite. Further, a significant synergistic effect between W and Nb was disclosed, wherein the Nb-based domains account for activating DMA while the W-based domains mainly adsorb and activate NH3 feedstock.

Fabrication and characterization of microencapsulated dimethyl adipate phase change material with melamine-formaldehyde shell for cold thermal energy storage in coating

Abstract Microencapsulated phase change material (MPCM) was synthesized by using the in-situ polymerization technique. Dimethyl adipate (DMA) and melamine-formaldehyde were used as core and shell material for polymerization respectively. Sodium laureate sulphate (SLS) is used as a surfactant. The thermal properties were characterized by using a differential scanning calorimeter (DSC) and thermogravimetry analysis (TGA). Fourier transform infrared spectroscopy (FT-IR) was used to confirm the chemical structure. The morphology of microcapsules was studied by using, scanning electron microscopy. DSC result of MPCM has been observed to melt at 10.09 °C with melting latent enthalpy 88 J/g and crystallizes at 4.69 °C with crystallization latent heat 89.50 J/g. TGA analysis confirms increases in the thermal stability of MPCM. The decorative coating was prepared with 0, 5, 10, 15, and 20 % MPCM loading, and the prepared paint was tested for pencil hardness, gloss, and stain resistances. The thermal energy transfer rate was used to measure how much time coated panel took to reach the equilibrium temperature of 25 °C. Coating with 20 % MPCM loading revealed good thermal storage capacity but other general coating properties deteriorate.

Development of Abraham model correlations for dimethyl adipate from measured solubility data of nonelectrolyte organic compounds

ABSTRACT Mole fraction solubilities are reported for acenaphthene, o-acetoacetanisidide, anthracene, benzil, benzoic acid, benzoin, 4-tert-butylbenzoic acid, 1-chloroanthraquinone, 4-chlorobenzoic acid, 2-chloro-5-nitrobenzoic acid, 4-chloro-3-nitrobenzoic acid, 3,4-dichlorobenzoic acid, 3,4-dimethoxybenzoic acid, 3,5-dinitrobenzoic acid, diphenyl sulphone, 2-ethylanthraquinone, 2-naphthoxyacetic acid, 2-hydroxybenzoic acid, N-hydroxyphthalimide, 2-methoxybenzoic acid, 4-methoxybenzoic acid, 3-methylbenzoic acid, 2-methyl-3-nitrobenzoic acid, 3-methyl-4-nitrobenzoic acid, 4-methyl-3-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, salicylamide, 3,4,5-trimethoxybenzoic acid, trans-stilbene, thioxanthen-9-one and xanthene dissolved in dimethyl adipate at 298.15 K. Results of these measurements, combined with published literature data for adipic acid, glutaric acid and succinic acid, are used to derive predictive Abraham model correlations. The derived correlations back-calculate the observed solubility data to within ±0.12 log units.

Searching for a "Green" Hydrogenolysis Catalyst

This paper is an overview of the scientific results that have been achieved during the development of a sustainable hydrogenolysis catalyst. The paper describes the effects of various synthesis methods and their parameters, as well as the effect of diverse promoters and supports on the catalyst structure, activity and selectivity in the hydrogenolysis of dimethyl adipate. From the green chemistry point of view, a suitable alternative to the Adkins catalyst was found on the laboratory scale.

Liquid-liquid equilibria of the ternary systems water + C1 – C3 alcohols + dimethyl adipate at 298.15 K and atmospheric pressure: Experimental data and modeling

The aim of this study was to examine the possibility of using a green organic solvent, dimethyl adipate (DMA), as a separation agent in the extraction of different alcohols from aqueous solutions. For that purpose, the liquid–liquid equilibria (LLE) of four ternary systems were analytically determined at 298.15 K and atmospheric pressure using stirred and thermo-regulated cells: {water + methanol + dimethyl adipate (DMA)}, {water + ethanol + DMA}, {water + 1-propanol + DMA}, {water + 2-propanol + DMA}. Phase diagrams for these four ternary systems were obtained by determining a binodal curve and tie-lines data using a visual cloud-point method, but also gas chromatography. Distribution coefficients and separation factors were calculated for the immiscibility region. Hand and Othmer-Tobias correlations were used to examine the reliability of the tie-line data. In addition, the experimental ternary LLE data were correlated with the UNIversal QUAsiChemical (UNIQUAC) activity coefficient models. The obtained results showed that DMA is a suitable candidate for the extraction of methanol, ethanol, 1-propanol, and 2-propanol from water. With some alcohols, this potential is more noticeable than with others. The potential of DMA as a separation agent is increasing in the following sequence: methanol < ethanol < 2-propanol < 1-propanol, and that also could be noticed from the selectivity values that also increase in this sequence. The UNIQUAC model proved as successful in correlating the LLE data.

Vapor-liquid equilibrium phase behavior of binary systems of carbon dioxide with dimethyl adipate or monomethyl adipate

The vapor–liquid equilibria (VLE) phase boundary data were measured for the binary systems of carbon dioxide + dimethyl adipate (DMA) and carbon dioxide + monomethyl adipate (MMA) at 313.15 K, 333.15 K, 353.15 K, and 373.15 K and pressures up to 29 MPa. A visual and variable-volume phase equilibrium analyzer (PEA) was employed to observe the phase transition over the whole composition range. The vapor-liquid equilibrium ratios (K-values) and the critical points have been estimated from the VLE phase boundary data. The new VLE data obtained from this work were correlated with the Soave-Redlich-Kwong (SRK) and the Peng-Robinson (PR) equations of state incorporating with the two-parameter van der Waals one-fluid mixing rules (vdW2). The PR equation of state yields better results and the average absolute pressure deviations are lower than 4 %.

Adjustment of W-O-Zr Boundaries Boosts Efficient Nitrilation of Dimethyl Adipate with Ammonia on WOx/ZrO2 Catalysts.

In this study, a tungstated zirconia (WOx/ZrO2) catalyst was developed for the continuous synthesis of adiponitrile (ADN) by gas-phase nitrilation of dimethyl adipate (DMA) with NH3. The highest TOFADN could be reached on WOx/ZrO2 bearing ∼1D WOx species (highly dispersed and discontinuous status) at the surface, which, however, delivered the poorest selectivity toward nitrilation (SADN+MCP). In comparison, both efficient and selective transformation of DMA to ADN was achieved by fabricating WOx/ZrO2 with continuously distributed oligomeric WOx species (∼2D) at the surface, either by varying the dosage of the W-reagent in the preparation of WOx(m)/ZrO2 or by doping a proper amount of the Mn element into WOx(5.0)/ZrO2, bearing WO3 NPs. Furthermore, the in situ diffuse reflectance infrared Fourier transform spectroscopy investigations of both independent and competitive adsorptions of ester functionality and NH3 over W-O-Zr, W-O-W, and Zr-O-Zr boundaries at the surface clarified the synergistic effect of these species in the activation of DMA/NH3 and thereby nitrilation.

Modification of Cu–ZnO–ZrO2 catalysts with La2O3 to quantitatively tune Cu+–Cu0 dual sites for hydrogenation of dimethyl adipate to produce 1,6-hexanediol

The strong electron donor–acceptor interaction between lanthanum and copper species retards the aggregation of the copper species, and inhibits the transformation of Cu2O to metallic Cu, thus maintaining a constant ratio of Cu+/(Cu0 + Cu+).