Tributyl Methyl Ammonium Research Articles

PREPARATION AND CHARACTERIZATION OF PERFLUOROETHYLSUBSTITUTED ALKYLAMMONIUM OLIGOFLUOROPHOSPHATES

Mono-, di-, triperfluoroethyl substituted fluorophosphate anions are building blocks in the molecular design of salts with onium cations, and are used to increase hydrophobicity, modify surfactant properties and electrical conductivity. The work proposes methods for the synthesis of superacid H+[PF3(C2F5)3]- by the reaction of tri(pentafluoroethyl)difluorophosphorane with a solution of hydrofluoric acid, as well as superacids H+[PF4(C2F5)2]- and H+[PF5C2F5]- by step-by-step removal of the pentafluoroethyl substituent by hydrolysis with subsequent treatment with HF solution. Ionic compounds were synthesized by metathesis of anions at 0 °C from the corresponding quaternary ammonium chloride based on the obtained superacids. The article presents NR4FAP-class ionic compounds with the tributylmethylammonium (TBMA) cation of the general formula [(C4H9)3NCH3]+[PF6-n(C2F5)n]-, where n = 1, 2, 3. The square bipyramidal structure of the three studied anions was confirmed by nuclear magnetic resonance (NMR) spectroscopy and X-ray diffraction (XRD) data. The study shows, the synthesized compounds are characterized by extremely low vapor pressure up to 300 °C, a wide range of the liquid state with a width of up to 310 K by the methods of differential scanning calorimetry (DSC) and synchronous thermal analysis (STA). Melting temperatures and enthalpies were determined. The TBMA salts belong to ionic liquids (IL's), including one type liquid at room temperature (RT-IL). The general patterns of compounds decomposition were analyzed by the analysis of evolved gases (STA-EGA); it was shown that in all cases, the decomposition of the studied ionic liquids begins with the destruction of the anion. The electrical resistance of a pure ionic liquid at room temperature was studied. The described characteristics of perfluoroethylsubstituted alkyl ammonium oligofluorophosphates open up prospects for their use as electro conducting and antistatic additives for petrochemicals, fuels and polymers. For citation: Mokrushin I.G., Pinegina O.A., Krasnovskikh M.P., Dmitriev M.V., Markin I.V., Kozen A.L. Preparation and characterization of perfluoroethylsubstituted alkylammonium oligofluorophosphates. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 5. P. 54-61. DOI: 10.6060/ivkkt.20246705.6916.

A Graphite∥PTCDI Aqueous Dual-Ion Battery.

A full cell chemistry of aqueous dual-ion battery (DIB) was reported, comprising the graphite cathode and 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) as the anode. This DIB employed a mixture aqueous electrolyte: 5 m tributylmethylammonium (TBMA) chloride plus 5 m MgCl2 , where [MgCl3 ]- and TBMA+ serve as the charge carriers for cathode and anode of the DIB, respectively. This novel full cell exhibited a specific capacity of around 41 mAh g-1 based on the total active mass of both electrodes with an average operation voltage of 1.45 V and stable cycling for 400 cycles.

Effect of regenerated ionic liquid pretreatment on the thermogravimetric analysis of spent coffee ground

ABSTRACT Ionic liquids are regarded as green solvents and found very effective in the pretreatment of biomass and spent wastes. However, the high cost of ionic liquids is a major worry. In this concern, regeneration could be a feasible solution. In this study, the pretreatment performance of fresh and regenerated ionic liquid (tributyl methylammonium chloride) ([N1444] [Cl])) with respect to their thermal behavior was investigated. It was found that fresh and regenerated ionic liquids improved the volatility of Spent coffee ground from 8.53 to 10.69 and 10.62, respectively, and heating values from 17.53 MJ/kg to 17.62 MJ/Kg and 17.71 MJ/kg, respectively. The reactivity for untreated Spent coffee ground (0.024% min−1°C−1) was improved significantly after ionic liquid treatment (0.047% min−1°C−1). The results suggest that the regeneration of ionic liquids could favor the pretreatment of spent wastes that will ultimately lead to an economical industrial operation.

Aggregation and emulsifying properties of soybean protein isolate pretreated by combination of dual-frequency ultrasound and ionic liquids

The objectives of this study were to investigate the changes in the aggregation and emulsifying properties of soy protein isolate (SPI) pretreated with dual-frequency ultrasound and three different ionic liquids (ILs), tributyl methyl ammonium chloride ([TBMA]Cl), 1-butyl-3-methyl imidazolium chloride ([BMIM]Cl) and 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM]BF4). Results showed that dual-frequency ultrasound and ILs could not change the primary structure of SPI. The changes in UV–vis spectra indicated the unfolding of SPI as pretreated by [TBMA]Cl and [BMIM]Cl combined with dual-frequency ultrasound, followed by formation of soluble aggregates. The thermal stability analysis of the regenerated SPI suggested that [BMIM]BF4 presumably broke most of the hydrogen bonds within adjacent SPI molecules, leading to the decrease of thermal stability. Transmission electron microscopy showed major changes in protein morphology upon protein–protein interactions. SPI emulsion pretreated with dual-frequency ultrasound and [BMIM]BF4 had a higher emulsion stability index than the other samples (P < 0.05). Furthermore, as compared to untreated protein, all ultrasound and ILs pretreatments decreased the creaming index of SPI emulsion. These results indicated that combination of dual-frequency ultrasound and ionic liquids could be a potential method to change the aggregation and emulsifying properties of SPI.

Effect of ionic liquids as additives for improving the performance of plasticized PVC gel actuators

Dielectric gels are low-density materials that exhibit a mechanical reaction to electric stimuli. They have recently attracted attention for their potential applications in actuators for wearable robotics. In order to lower the driving voltages of actuators consisting of polyvinyl chloride (PVC) gels (PVC gels with a plasticizer), we studied the generated strain of PVC gel actuators with four types of ionic liquids (ILs) additives: trihexyltetradecyl phosphonium chloride (THTDPCl), tetradodecylammonium chloride (TDACl ), tributylmethyl ammonium chloride (TBMACl), and 1-Butyl-3-mthylimidazolium hexafluorophosphate (BMIMPF6). We found that the actuator responses for PVC gels with additives of 0.01 wt% THTDPCl and TDACl were almost two times larger than those for PVC gels without ILs at low applied voltages ranging from 200 to 600 V. Conversely, the displacement responses of PVC gels with the same IL content but of TBMACl and BMIMPF6 were lower than those of gels without ILs. We studied the electrochemical properties of PVC gels with ILs and proposed an improved electromechanical model based on one proposed in a previous study. Based on the proposed electromechanical model, the effect of the IL additives for lowering the driving voltage can be clearly described.

Separation of adjacent rare earth elements enhanced by “external push-pull” extraction system: An example for the separation of Pr and Nd

Separation of adjacent rare-earth elements, such as Pr and Nd, is extremely difficult due to the similarity in their physicochemical properties. Enhanced separation of adjacent rare-earth elements based on the “push-pull effect” by addition of water-soluble complexing agents was an effective strategy in traditional organic-aqueous two-phase extraction. However, environmental pollution is serious due to the residual of complexing agent in the extraction raffinates. In present work, a novel “external push-pull” extraction system, composed of three coexisting liquid phases, P507 organic phase, ionic liquid (tributyl-methyl ammonium nitrate, N4441NO3)-rich phase and NaNO3 aqueous solutions, is suggested to improve the separation between Pr and Nd. It is revealed that Nd and Pr can be enriched respectively into the P507 organic top phase and N4441NO3-rich ionic liquid middle phase in the external push-pull extraction system, owing to a so-called “external push-pull effect” from a reversed extraction selectivity of P507 organic phase and N4441NO3 ionic liquid-rich phase towards Nd and Pr, respectively. Compared to traditional organic-water two-phase systems, the separation factor of Pr to Nd in the suggested external push-pull extraction system could increase obviously to 3.5 or even more. Various effects from the aqueous pH, NaNO3 concentration, the initial concentration ratios of Pr to Nd in feed aqueous solutions, and the addition amount of N4441NO3, the volume of P507 organic phase on the separation between Pr and Nd are discussed. In addition, reversal extraction of rare earth ions in the ionic liquid-rich phase is found to be closely related to the complexation behavior of rare earth ions with NO3− ions by using molecular dynamic simulations. Based on this work, a possibility for extraction and separation of 14 rare-earth element ions from their coexisting aqueous solutions using the suggested external push-pull extraction system is also explored. The present work highlights a novel green strategy for improving the separation of adjacent rare-earth elements.

Electrosynthesis of coordination polymers containing magnesium(II) and benzene 1,3,5-tricarboxylate: the influence of solvents and electrolytes toward the dimensionality

The synthesis of coordination polymers (CPs) and metal-organic frameworks (MOFs) through electrochemical method has become an interesting preference due to ease of handling, time and cost-efficient, and abundant results with high crystallinity. In this research one- and two-dimensions of CPs containing magnesium (II) and benzene 1,3,5-tricarboxylic acid (H3BTC) were successfully electro-synthesized at 15 V for 1.5 h. Reaction parameters such as solvents and electrolytes were variated and produced white crystalline materials. X-Ray diffractogram revealed that the use of 0.1 M tetrabutyl ammonium tetra-fluoroborate (TBATFB) as an electrolyte in both ethanol and ethanol: water (1:1, mol/mol) lead to the formation of 2-dimensional CP [Mg2 (BTC)(OH)(H2O)4] 2H2O (NICS-5) (NICS: National Institute of Chemistry Slovenia) . The use of 0.1 M tributyl methyl ammonium methyl sulfate (MTBS) in both ethanol and ethanol: water (1: 1) indicates conformity with the simulated pattern of [Mg3 (BTC)2(H2O)12] (NICS-4) which has a one-dimensional structure. The formation of these two compounds is further confirmed by FTIR analysis. Nitrogen sorption isotherm indicates the both compounds are non-porous materials. Compound NICS-5 synthesized in ethanol: water (1: 1) has a BET surface area of 44.243 m2/g with a total pore volume of 0.16 cc/g and an average pore diameter of 16.81Å, larger than the compound NICS-5 synthesized only in ethanol. SEM image shows that compound NICS-5 has a bigger average crystallite size than compound NICS-4. Compound NICS-5 and NICS-4 are thermally stable up to 490°C and 455°C, respectively, according to thermogravimetric measurement.

Ether bond effects in quaternary ammonium and phosphonium ionic liquid-propanol solutions

The liquid-liquid equilibria (LLE) of quaternary ammonium and phosphonium ionic liquid (IL)-propanol solutions were examined. The ILs contained cations with or without ether bonds; the anion in all the ILs was bis(trifluoromethanesulfonyl)imide (TFSI−). The cations without ether groups are tributylmethyl ammonium (N4441+), triethylpentyl phosphonium (P2225+), triethyloctyl phosphonium (P2228+), and tributylmethyl phosphonium (P4441+). The cations containing ether groups are N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium, (N122(2O1)+), triethyl(methoxymethyl) phosphonium (P222(1O1)+), and triethyl(2-methoxyethyl) phosphonium, (P222(2O1)+). Propanol isomer effect was observed to affect the LLEs, reflecting the geometrical factors and hydrophobicities of 1-propanol and 2-propanol. According to Raman spectroscopy, the TFSI− anion conformers in the mixtures were altered in the presence of ether bonds in the cations. The universal quasichemical (UNIQUAC) interaction parameters are consistent with significant factors affecting IL-propanol solutions, such as the type of cation (ammonium or phosphonium), ether bonds, TFSI− conformers, and propanol isomer effects.

Enhancement of enzymatic digestibility of oil palm empty fruit bunch by ionic-liquid pretreatment

In this study, 4-methylmorpholine N-oxide (NMMO) and four ionic liquids were compared to determine the most suitable type for use in pretreatment of oil palm empty fruit bunch (EFB) to enhance enzymatic digestibility and obtain maximal fermentable sugar (glucose). Four types of ionic liquids, namely, 1-ethyl-3-methyl imidazolium acetate ([Emim]OAc), 1-butyl-3-methyl imidazolium chloride ([Bmim]Cl), tributyl methyl ammonium methylsulfate (MTBS), and 1-ethyl-3-methyl imidazolium diethylphosphate ([Emim]DEP), were used. The effects of pretreatment temperature and time on the enzymatic digestibility of EFB were examined. Among NMMO and four ionic liquids, NMMO and [Emim]OAc, showing high enzymatic digestibility, were found to be most effective for EFB pretreatment. The enzymatic digestibility of NMMO-pretreated EFB increased as pretreatment temperature and time increased. After [Emim]OAc pretreatment, the crystallinity index of EFB decreased, due to the conversion of crystalline cellulose to amorphous cellulose, and the enzymatic digestibility thereby was increased to 96.6% at 110 °C for 2 h.

ChemInform Abstract: Radical‐Mediated Intramolecular C—C Bond Formation and the Deoxygenation of Alcohols under Solvent‐Free Conditions with Tributyl Methyl Ammonium Hypophosphite.

AbstractThe use of AHP as hydrogen donor under radical conditions allows the cyclization of iodoacetals (I).

Radical-mediated intramolecular C–C bond formation and the deoxygenation of alcohols under solvent-free conditions with tributyl methyl ammonium hypophosphite

A green, solvent-free protocol was developed for the radical-mediated intramolecular cyclization of haloacetals and the deoxygenation of S-methyl dithiocarbonates and cyclic thionocarbonate. This process uses tributyl methyl ammonium hypophosphite as a H-donor in the presence of triethylborane or t-butyl peroxide. This methodology provides eco-friendly reaction conditions.

MULTI-SITE PHASE TRANSFER CATALYZED RADICAL POLYMERIZATION OF n-BUTYL METHACRYLATE: A KINETIC STUDY

The kinetics and mechanism of radical polymerization of n-butyl methacrylate (n-BMA) using potassium peroxydisulfate (PDS) as a water-soluble initiator in the presence of 1,4-bis(tributyl methyl ammonium) benzene dichloride (TBMABDC) as a multi-site phase transfer catalyst (MPTC) were studied. The polymerization reactions were carried out under oxygen-free, unstirred conditions at a constant temperature of 60° ± 1°C in cyclohexane-water two-phase systems. The dependence of rate of polymerization (Rp) on concentrations of monomer, initiator, and catalyst, volume fraction of aqueous phase, solvent polarity, and temperature was determined. The reaction order with respect to monomer, initiator, and multi-site phase transfer catalyst was found to be 0.50, 1.0, and 0.52 respectively. Based on the experimental results, an appropriate reaction mechanism has been proposed and its significance discussed. The prepared polymer was characterized with spectral analysis.

Study of the ethanolic tributylmethylammonium aluminosilicate solutions using 27Al NMR

Alkaline solutions containing both silicate and aluminate ions are of considerable research interest inter alia because of their involvement in the synthesis of zeolites. In the present work, we use 27Al NMR to characterize alkaline aqueous and ethanolic tributylmethylammonium aluminosilicate solutions with different Al/Si ratios. Tributylmethylammonium (TBMA) used as a cation template and no alkaline metals are used for preparation of aluminosilicate solutions. Aluminum-27 NMR spectra of TBMA aluminosilicate solutions indicate that considerable changes occurred by changing the Si/Al ratio. The distribution of aluminosilicate species was affected by the presence of the methanol and the method of mixing the silicate and aluminosilicate solutions. To understand the reaction between silicate and aluminate ions in this system, the evolutions of 27Al NMR spectra with time are investigated.

Silicon-29 NMR Study of Alkaline Aqueous and Alcoholic Tri-butylmethyl Ammonium (TBMA) Silicate Solutions

ABSTRACT Silicon-29 NMR spectroscopy was used to characterize aqueous and alcoholic alkaline solutions of tri-butylmethyl ammonium (TBMA) silicates. The effect of TBMA cation on the equilibrium of silicate oligomers in aqueous alkaline silicate solutions was investigated using 29Si NMR spectra. It was found that TBMA cation has a structure directing role and directs the silicate species to form minor amounts of silicate anion in the presence of high concentration of silicon. Silicon-29 NMR spectra of TBMA silicate solutions indicate that considerable changes occurred by changing the Si/TBMA ratio. The distribution of silicate species was affected by the presence of the alcohols, specifically methanol.

Kinetics and Mechanism of Multi-site Phase Transfer Catalyzed Radical Polymerization of Ethyl Methacrylate

The application of multi-site phase transfer catalyst (denoted herein as QX2) with water-soluble initiator for the radical polymerization of ethyl methacrylate (EMA) was explored. The radical polymerization of water-insoluble vinyl monomer (EMA), with water – soluble initiator (potassium peroxydisulphate PDS) and a multi-site phase transfer catalyst (1,4-bis tributyl methyl ammonium) benzene dichloride TBMABDC) were carried out in a water/cyclohexane two-phase system at constant temperature 60±1°C under nitrogen circumstances. The rate of polymerization (Rp) was determined as a function of various reaction parameters such as the concentration of monomer, initiator, catalyst and variation of the aqueous phase and organic solvents and temperature. Based on the experimental results, a suitable kinetic scheme and mechanism has been proposed for the polymerization reaction.

Free radical polymerisation of methyl methacrylate initiated by multi-site phase transfer catalyst—a kinetic study

The kinetics of multi-site phase transfer catalysed (MPTC) radical polymerisation of methyl methacrylate (MMA) using potassium peroxydisulphate (PDS) and synthesised 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst was investigated in cyclohexane–water two-phase system at constant temperature 60 ± 1 °C under nitrogen circumstances. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer, initiator and phase transfer catalyst were found to be 0.80, 1.0 and 0.5, respectively. A suitable kinetic scheme has been proposed to account for the experimental observations and its significance is discussed. The prepared polymer was characterised by spectral analysis.

Effect of ion-pair formation with bile salts on the in vitro cellular transport of berberine

The objective of this study was to examine the effect of ion-pair complexation with endogenous bile salts on the transport of a quarternary ammonium organic cationic (OC) drug, berberine, across the Caco-2 and LLC-PK1 cell monolayers. The basolateral-to-apical (BL-AP) transport of berberine in Caco-2 cells was temperature dependent and 10-fold higher than that of the apical-to-basolateral (AP-BL) transport. Similar results were observed for the transport of berberine across the LLC-PK1 cells. Moreover, the BL-AP transport in the Caco-2 cells was significantly reduced by the cis-presence of P-glycoprotein (P-gp) inhibitors such as cyclosporine A, verapamil, and digoxin. These results suggest that an efflux transporter, probably P-gp, is involved in the Caco-2 cell transport. The Km and Vmax values for the carrier-mediated transport were estimated to be 83.4 mM and 7640 pmole/h/cm2, respectively. The apparent partition coefficient (APC) of berberine between n-octanol and a phosphate buffer (pH 7.4) was increased by the presence of an organic anion (OA), taurodeoxycholate (TDC, a bile salt), suggesting the formation of a lipophilic ion-pair complex between an OC (berberine) and an OA (TDC). Despite the ion-pair complexation, however, the BL-AP transport of berberine across the Caco-2 and LLC-PK1 cells was not altered by the cis-presence of bile salts or the rat bile juice. This is consistent with the reportedly unaltered secretory transport of a quarternary ammonium compound, tributylmethylammonium (TBuMA), across the Caco-2 cell monolayers in the cis-presence of bile salts or the rat bile juice, but not with our previous report in which the secretory transport of TBuMA across the LLC-PK1 cell was increased in the cis-presence of TDC. Therefore, the effect of ion-pair formation with the bile components or bile salts on the secretory transport of OCs appears to depend on the molecular properties of OCs (e.g., molecular weight, lipophilicity and affinity to relevant transporters) and the characteristics of cell strains (e.g., expression and contribution of responsible transporters to the transport).

Multi-site phase transfer catalyst assisted radical polymerisation of glycidyl methacrylate using potassium peroxydisulphate as initiator – a kinetic study

In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate (PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has been proposed to account for the experimental observations and its significance discussed.

Decreased biliary excretion of tributylmethyl ammonium in cholestyramine pretreated rats due to reduced formation of ion‐pair complexes with hepatic bile salts

The hypothesis that higher molecular weight (MW) quaternary ammoniums (QAs) form lipophilic ion-pair complexes with bile salts in the liver, and are subsequently excreted into bile via a canalicular transporter, P-gp, was re-examined in the present study for its validity. The biliary excretion of tributylmethyl ammonium (TBuMA), a QA with a MW of 200, in bile salt-depleted rats was determined. Depletion was induced by a daily oral administration of a resin, cholestyramine, at a dose of 0.5 g/kg for 2 consecutive weeks, which decreased the concentration of total bile salts in the liver by 38%. When TBuMA was administered intravenously (12 micromol/kg) to these rats, the plasma level, area under the plasma concentration-time curve (AUC), systemic clearance (CL) and volume of distribution (V(ss)) of the compound remained unchanged, whereas bile flow (23.03 vs 16.94 microl/min, p<0.05) and biliary clearance (CL(bile), 12.75 vs 5.34 ml/min/kg, p<0.01) were decreased significantly. These results implied the biliary clearance of TBuMA in rats with bile salt depletion was significantly decreased as a result of decreased ion-pair complexation of TBuMA. The above results are consistent with our hypothesis and the existence of a MW threshold (i.e. 200+/-50 for rats) for the biliary excretion of QAs.

Synthesis and characterization of multi-site phase transfer catalyst: application in radical polymerisation of acrylonitrile – a kinetic study

The multi-sited phase transfer radical polymerisation of acrylonitrile (AN) with newly synthesized and characterized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (MPTC) was investigated in K2S2O8 aqueous-organic two phase system at 60 ± 1 °C under nitrogen atmosphere. The role of concentrations of monomer, initiator, catalyst, temperature, acid and ionic strength on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer, initiator and multi-site phase transfer catalyst were found to be 0.5, 1.0 and 0.5, respectively. A suitable kinetic scheme has been proposed to account for experimental observations and its significance. The prepared polymer was characterized by FT-IR and XRD analysis.