Binary Mixtures Of Methyl Methacrylate Research Articles

Ultrasonic study of molecular interactions in binary mixtures of methyl methacrylate(MMA) with toluene and dimethylacetamide at 318 K

The ultrasonic velocity, density and viscosity at 318K have been measured in the binary systems of Methyl methacrylate + Toluene and Methyl methacrylate + Dimethylacetamide. In this work an attempt has been made for the first time to investigate the behavior of binary solutions of Methylmethacrylate(MMA) in Toluene and Dimethylacetamide(DMAC) with regard to acoustical parameters such as adiabatic compressibility(β), intermolecular free length(lf), free volume(Vf), Rao’s constant(R), Wada’s constant(W) and specific acoustical impedance(Z) from ultrasonic measurements at 318 K were calculated. The results are interpreted in terms of molecular interaction between the components of mixtures.

Densities, ultrasonic speeds, viscosities and excess properties of binary mixtures of methyl methacrylate with N,N-dimethylformamide and N,N-dimethylacetamide at different temperatures

The densities, ρ, ultrasonic speeds, u and viscosities, η of binary mixtures of methyl methacrylate (MMA) with N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA), including those of pure liquids, over the entire composition range were measured at temperatures (288.15, 293.15, 298.15, 303.15, 308.15, 313.15, and 318.15)K and atmospheric pressure. From the experimental results, the excess molar volume, VmE, and excess isentropic compressibility, κsE, excess isobaric coefficient of thermal expansion, αpE and excess molar isobaric expansion, Ep,mE were calculated. The excess partial molar volume, V¯m,1E and V¯m,2E and excess partial molar isentropic compressibility, K¯s,m,1E and K¯s,m,2E over the whole composition range; and partial molar volume, V¯m,1° and V¯m,2°, partial molar isentropic compressibility, K¯s,m,1° and K¯s,m,2°, excess partial molar volume, V¯m,1°E and V¯m,2°E, excess partial molar isentropic compressibility, K¯s,m,1°E and K¯s,m,2°E at infinite dilution, and excess partial molar isobaric expansion, E¯p,m,1E and E¯p,m,2E over the whole composition range have also been calculated. The variations of these parameters with composition and temperature of the mixtures are discussed in terms of molecular interaction in these mixtures. It is observed that the MMA-DMF/DMA interactions in these mixtures follow the order: DMF<DMA. Further, the viscosities of these binary mixtures were correlated theoretically by using various empirical and semi-empirical models and the results were compared with the experimental findings.

Prediction of Hildebrand solubility parameters of acrylate and methacrylate monomers and their mixtures by molecular simulation

AbstractHildebrand solubility parameters are predicted from molecular simulations using the transferable potentials for phase equilibrium‐united atom (TraPPE‐UA) and Dreiding force fields for the n‐alkyl acrylate and methacrylate esters (n ≤ 10), as well as the 2‐ethylhexyl acrylate, 2‐hydroxyethyl acrylate, isooctyl esters of acrylic acid, and the 2‐hydroxyethyl ester of methacrylic acid. The TraPPE‐UA force field yields very accurate solubility parameters (with a mean unsigned percent error of 2% or 0.2 Hildebrand units), whereas the Dreiding force field overpredicts the solubility parameter in every case examined. Correlations based on the normal boiling point or the refractive index do not yield satisfactory results for this monomer set with the former overestimating the magnitude and the latter yielding the incorrect sign for the decrease in the solubility parameter with chain length. Simulations with the TraPPE‐UA force field yield solubility parameters for binary mixtures of methyl methacrylate with 2‐ethylhexyl or isooctyl acrylate, which are very well described by a linear interpolation using the pure compound cohesive energies and molar volumes, whereas those for mixtures with 2‐hydroxyethyl acrylate or methacrylate small positive deviations due to structural microheterogeneity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Evaluation of Excess Free Volume and Internal Pressure in Binary Mixtures of Methyl Methacrylate(MMA) with Alcohols

Methyl methacrylate (MMA) is an important monomer attracting the attention of industrialists and scientists because of its various applications and reactivity. The knowledge of thermodynamic and transport properties of MMA in alcohols and other organic solvents is useful in industrial processes. Ultrasonic and viscometric parameters offer simple, easy and accurate ways for calculating several physical parameters which throw light on molecular interactions in solutions. In this paper, the interactions of two alcohols; tert‐butanol and iso‐butanol with MMA are reported for the first time. Comparison has been made on the interactive nature of the two alcohols. Computation of free volume, internal pressure and excess free volume has been made for the entire concentration range. Existence of mesomeric effects of MMA is clearly seen and the role of structure of alcohols is observed.

Dielectric study of methyl methacrylate-alcohol mixtures by Time Domain Reflectometry at 293 K

Using picosecond Time Domain Reflectometry (TDR), dielectric relaxation studies have been carried out on binary mixtures of methyl methacrylate with 1-propanol, 1-butanol, 1-heptanol and 1-octanol for various concentrations over the frequency range from 10 MHz to 10 GHz at 293 K. The Kirkwood correlation factor and excess inverse relaxation times were determined and discussed to yield information on the molecular structure and dynamics of the mixture. The static permittivity and relaxation time decrease with an increase in the percentage of methyl methacrylate.

Thermophysical Properties of Binary Mixtures of Methyl Methacrylate+Di-Ethers (Ethyl, Isopropyl, and Butyl) at 298.15 and 308.15 K

Experimental data for the densities, dynamic viscosities, sound speeds, and relative permittivities and for three binary systems of methyl methacrylate (MMA)+di-ethers (ethyl, isopropyl, and butyl) at 298.15 and 308.15 K and at atmospheric pressure are reported. The mixture viscosities are correlated by Grunberg–Nissan, McAllister, and Auslander equations over the complete composition range. The sound speeds for the mixtures are also calculated by using free length and collision factor theories, and Nomoto and Junjie equations. From the measured primary properties, deviation functions such as deviations in viscosities, sound speeds, relative permittivities, molar polarizations, excess isentropic compressibilities, and molar electrical susceptibilities were calculated, and the compositional dependence of each of the functions was expressed with a Redlich–Kister type equation. The variation of the Kirkwood correlation factor was determined over the complete composition range.

Densities, speeds of sound, isentropic compressibilities, and refractive indices of binary mixtures of methyl methacrylate with hydrocarbons, haloalkanes and alkyl amines

Isentropic compressibilities K S, and thermal expansion coefficients α for methyl methacrylate, 1,2-dichloroethane (DCE), 1,1,2,2-tetrachloroethane (TCE), 1-chlorohexane, and 1-bromohexane in the temperature range 298.15–333.15 K and isentropic compressibilities K S, excess isentropic compressibilities K S E, and excess molar volumes V E for 14 binary mixtures of methyl methacrylate (MMA) with hexane, cyclohexane, benzene, toluene, chlorobenzene, tetrachloromethane, trichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1-chlorohexane, 1-bromohexane, n-propylamine, n-butylamine, and tri- n-butylamine over the entire range of composition at 303.15 K, derived from experimental densities ρ and speeds of sound u have been reported. The values of K S E and V E for 14 binary mixtures indicate varying extent of molecular interactions and interstitial accommodation between unlike components. The experimental speeds of sound have been analyzed in terms of collision factor theory (CFT) and free length theory (FLT).

Thermophysical Properties of Nonelectrolyte Mixtures. Densities, Viscosities, and Sound Speeds of Binary Mixtures of Methyl Methacrylate+Branched Alcohols (Propan-2-ol, 2-Methylpropan-1-ol, Butan-2-ol, and 2-Methylpropan-2-ol) at T=298.15 and 308.15 K

Measurements of the densities, viscosities, and sound speeds at T=298.15 and 308.15 K for the binary mixtures of methyl methacrylate+propan-2-ol, +2-methylpropan-1-ol, +butan-2-ol, and +2-methylpropan-2-ol are made over the complete composition range. From the measured data, excess isentropic compressibilities have been calculated. The mixture viscosities have been correlated by the Grunberg–Nissan, McAllister, and Auslander equations, while the sound speed in binary mixtures has been analyzed using free length and collision factor theories, and Junjie and Nomoto equations. The excess isentropic compressibilities, κEs are fitted to a third degree polynomial equation. The qualitative analysis of κEs have been made in terms of bulk molecular interactions. The conclusions drawn were supplemented by examining the variation of relative association and solvation numbers over the complete composition range.

A molecular simulations study of the miscibility in binary mixtures of polymers and low molecular weight molecules

The miscibility behavior of binary mixtures of polymeric and low molecular weight molecules was studied using a combination of modified Flory–Huggins theory and molecular simulation techniques. Three different atomistic approaches were used to investigate the phase behavior and χ parameters of binary mixtures consisting of polymethyl methacrylate (PMMA) and 4-n-pentyl-4′-cyanobiphenyl (5CB). Binary mixtures of methyl methacrylate monomer/5CB and methyl methacrylate oligomer/5CB were also studied. As a first approach, a fast method that calculates the local interaction between a fragment of the polymer and the organic molecule and then extends it to determine the energy of mixing using an estimated coordination number was used. By using modified coordination numbers, we were able to extend this method to include cases where the polymer segment and the small molecules are slightly dissimilar in size. More detailed studies which take into account bulk effects were also carried out where the cohesive energies of the pure compounds were derived from molecular dynamics simulations and the interaction parameters were determined from the differences in the cohesive energies. The concentration and temperature dependence of the χ parameters was evaluated by calculating the energy of mixing from the differences in the cohesive energy densities of the mixed and demixed systems. The present study provides a detailed understanding of the miscibility of PMMA and 5CB as PMMA polymerizes from its monomer, and the results indicate that although methyl methacrylate and 5CB are completely miscible, 5CB is not miscible in PMMA even in small quantities.

Measurements and theoretical analysis of excess enthalpies and excess volumes of methyl methacrylate+ n-alkanes ( n-pentane, n-hexane, n-heptane, n-decane and n-dodecane)

Excess molar enthalpies ( H m E) and excess molar volumes ( V m E) have been measured for liquid binary mixtures of methyl methacrylate (MMA)+ n-alkanes ( n-pentane, n-hexane, n-heptane, n-decane and n-dodecane). The H m E and V m E values are positive over the whole composition range and vary quasi-regularly with the increase in carbon chain length of n-alkanes. The Flory (F) and Prigogine–Flory–Patterson (PFP) theories of solution thermodynamics have been used to analyze the H m E and V m E data. The key parameter needed for the analysis is the interaction parameter χ 12 and has been treated as an adjustable parameter to be fitted to the H m E and V m E values of the binary mixtures. We have applied Flory as well as Patterson models to evaluate the single value for χ 12 over 50 data points. The H m E and V m E values are split into interactional, free volume and P * contributions by using PFP theory. The free volume contributions to H m E and V m E data are found to be smaller and mostly negative. The interactional contribution calculated from PFP theory is not only in sign agreement but also close to measured H m E values. The interactional contribution to V m E values are always large and positive. The free volume and P * effects are found to be dominant and balance the over estimation of interactional term in MMA+ n-pentane, + n-hexane and + n-heptane. The P * contribution, however, becomes positive in MMA+higher n-alkanes (> n-heptane).

Densities, Viscosities, Sound Speeds, and Excess Properties of Binary Mixtures of Methyl Methacrylate with Alkoxyethanols and 1-Alcohols at 298.15 and 308.15 K

The densities, viscosities, and sound speeds were measured for six binary mixtures of methyl methacrylate (MMA)+2-methoxyethanol (ME), +2-ethoxyethanol (EE), +2-butoxyethanol (BE), +1-butanol (1-BuOH), +1-pentanol (1-PeOH), and +1-heptanol (1-HtOH) at 298.15 and 308.15 K. The mixture viscosities were correlated by Grunberg–Nissan, McAllister, and Auslander equations. The sound speeds were predicted by using free length and collision factor theoretical formulations, and Junjie and Nomoto equations. The excess viscosities and excess isentropic compressibilities were also calculated. A qualitative analysis of both of these functions revealed that structure disruptions are more predominant in MMA+1-alcohol than in MMA+alkoxyethanols mixtures. The estimated relative associations are found to become less in MMA+alcohol mixtures than in pure alcohols. The solvation numbers derived from the isentropic compressibility of the mixtures, considering MMA as a solvent, showed that structure making interactions are also present in MMA + alkoxyethanols in addition to the structure disruptions.

Ultrasonic behaviour of methyl methacrylate+hydrocarbon mixtures at 298.15 and 308.15 K

The excess isentropic compressibilities, K s E for seven binary mixtures of methyl methacrylate+benzene, + o-xylene, + m-xylene, + p-xylene, +toluene, +ethylbenzene and +cyclohexane were estimated from the measured densities and speeds of sound at 298.15 and 308.15 K. The K s E values were large and positive for MMA+cyclohexane and + m-xylene, while they were negative for other mixtures. A qualitative analysis of K s E values was made in terms of molecular interactions. The speeds of sound of all the mixtures were also predicted from the free length theory (FLT) and collision factor theory (CFT).

Thermodynamics of acrylic ester—organic solvent mixtures II. Viscosities of mixtures of methyl methacrylate, ethyl methacrylate or butyl methacrylate with n-hexane, n-heptane, carbon tetrachloride, chlorobenzene or o-dichlorobenzene at 303.15 K

Abstract The viscosities of fourteen binary mixtures of methyl methacrylate (MMA), ethyl methacrylate (EMA) or butyl methacrylate (BMA) with n -hexane, n -heptane, carbon tetrachloride, chlorobenzene or o -dichlorobenzene were measured at 303.15 K. The mixture viscosities were found to correlate reasonably well with the Grunberg-Nissan, Heric, McAllister and Auslaender equations. The dependence of the derived viscosity deviations both on the size of the alkyl chain in the ester molecules and on the nature of the second component revealed the complex nature of the interactions in these mixtures. The equimolar mixture viscosities of MMA-containing mixtures were analysed by the Bloomfield—Dewan approach on the basis of Flory free-volume theory and the thermodynamic contributions, viz. enthalpy, entropy and free volume terms, were evaluated. The results of the analysis show that dispersing interactions are predominant in the aliphatic hydrocarbon- and carbon tetrachloride-containing mixtures, while both specific and dispersing interactions were found to contribute equally in binary mixtures of MMA and chlorobenzenes.

Viscosity of nonelectrolyte liquid mixtures. III Binary mixtures of methyl methacrylate with hydrocarbons, haloalkanes, and alkylamines

Measurements of the viscosityη and the densityϱ are reported for 14 binary mixtures of methyl methacrylate (MMA) with hydrocarbons, haloalkanes, and alkylamines at 303.15 K. The viscosity data have been correlated with equations of Grunberg and Nissan, of McAllister, and of Auslaender. Furthermore, excess viscosityΔ Inη and excess Gibbs energy of activationΔG* E of viscous flow have been calculated and have been used to predict molecular interactions occurring in present binary mixtures. The results show the existence of specific interactions in MMA + aromatic hydrocarbons, MMA + haloalkanes, and MMA + primary amines.

Excess volumes and excess enthalpies for binary mixtures of methyl methacrylate with cyclopentane and with cyclohexane

Excess volumes and excess enthalpies for binary mixtures of methyl methacrylate with cyclopentane and with cyclohexane