Polymers in Mixed Solvents

Pouchlý, Julius; Patterson, Donald

doi:10.1021/ma60052a008

Cited by 34 publications

(21 citation statements)

References 7 publications

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“…h -solvent, or good ? non-solvent, was reported to be convex (Pouchly and Patterson 1976;Pingping et al 2006;Budtov et al 2010). A deviation from the classical Flory lattice theory based on statistical thermodynamics (Shultz and Flory 1955) was reported for predicting chain unperturbed dimensions when good ?…”

Section: Influence Of Water On Cellulose-emimac Solution Viscosity Anmentioning

confidence: 99%

“…It was interpreted by the preferential solvation (or preferential adsorption) introduced as ''local'' solvent composition being different from the ''bulk'' composition (Dondos and Benoit 1973;Hong and Huang 2000). These ideas and Flory-Huggins theory were extended by Prigogine-Flory approach which takes into account the interactions between the molecular surfaces and considers molecular surface/volume ratios of the polymer and solvent molecules (Pouchly and Patterson 1976;Horta 1979).…”

Section: Influence Of Water On Cellulose-emimac Solution Viscosity Anmentioning

confidence: 99%

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Influence of water on cellulose-EMIMAc solution properties: a viscometric study

Sescousse

Budtova

2011

Cellulose

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International audienceThe influence of water on cellulose dissolved in 1-ethyl-3-methylimidazolium acetate (EMIMAc) is analysed by measuring steady state viscosity of dilute solutions. The goal is to determine: (a) the maximal water content allowing keeping cellulose dissolved (in dilute regime) and (b) the influence of water on solution flow and cellulose hydrodynamic properties. Mixing EMIMAc and water is exothermal and EMIMAc-water viscosity does not obey a logarithmic mixing rule suggesting strong interactions between the components. Newtonian flow of cellulose-EMIMAc-water solutions was recorded at water concentrations below 15 wt% and a shear thinning was observed for higher water content. It was suggested that above 15 wt% water cellulose is not completely dissolved: swollen aggregates form a sort of a "suspension" which is structuring under shear. Cellulose intrinsic viscosity showed a peak at 10 wt% water-90 wt% EMIMAc. It was hypothesised that the addition of water leads to the formation of large cellulose aggregates due to the preferential cellulose-cellulose interaction

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Section: Influence Of Water On Cellulose-emimac Solution Viscosity Anmentioning

confidence: 99%

Section: Influence Of Water On Cellulose-emimac Solution Viscosity Anmentioning

confidence: 99%

Influence of water on cellulose-EMIMAc solution properties: a viscometric study

Sescousse

Budtova

2011

Cellulose

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“…Comparison of the theoretical (lines) association constants of Table 2 and the experimental (points) l values for the PROH system. In a) g 23 ¼ w 23 , and in b) g 23 ¼ g 23 . Numbers in curves and points are as in Figure 6.…”

Section: Resultsmentioning

confidence: 99%

“…Although the found relationships between ternary and the corresponding binary parameters has been ascertained both phenomenologically and semiempirically for polymer-mixed-solvent [16][17][18][19] and polymer blends in solution, [20][21][22] the physical origin of the above deviations could be explained by more advanced theories such as the FPP one. [23][24][25] In this case, FH, FHP, and FPP formalisms are based upon the assumption of random mixtures without preferential contacts, or on uniform distributions of energy density on homogeneous molecular surfaces. Both approaches are valid for systems with non-polar components, but inappropriate for systems with molecules having strong and specifically interacting groups.…”

Section: Introductionmentioning

confidence: 99%

Association Equilibria Theory for Polymers in Mixed Solvents with Specific Interactions

Soria

Figueruelo

Abad

et al. 2004

Macro Theory & Simulations

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Summary: Hydrogen bonding plays an important role in determining the physical and thermodynamic properties of polar fluids. Theoretical and experimental aspects of polymers, in mixed solvents with hydrogen‐bonding‐specific interactions, are investigated using a simple association model based on the theory of association equilibria developed by Pouchlý et al. The thermodynamic non‐idealities are accounted for using a modified Flory‐Huggins theory with effective gij parameters. The entropic term of the above formalism has been formulated taking into account the polymer segment‐solvent as well as the solvent‐solvent hydrogen‐bond formation. Four equilibrium constants are introduced to make a realistic picture between the associated and non‐associated species. By application of “multiple association equilibria theory”, sorption coefficients λ and Y have been deduced for the ternary systems with specific interactions i.e., alcohol(C1–C3)/heptan‐3‐one/poly(N‐vinyl pyrrolidone). Numerical values for the self‐association constants of the alcohols, association constants for the alcohols and ketone and for the alcohols and polymer, have been evaluated. These were determined as parameters adjusting best the predicted values of both preferential solvation, λ, and the second virial coefficient, A2, to experimental ones.Comparison of the theoretical (lines) and experimental (points) λ values as a function of propanol/heptan‐3‐one mixture composition for diverse poly(N‐vinyl pyrrolidone) samples. PVP‐K90 (, ×); PVP‐700K (, ⋄); PVP‐K40 (, ♦); PVP‐K24 (, ▴); and PVP‐K15 (, ▪).imageComparison of the theoretical (lines) and experimental (points) λ values as a function of propanol/heptan‐3‐one mixture composition for diverse poly(N‐vinyl pyrrolidone) samples. PVP‐K90 (, ×); PVP‐700K (, ⋄); PVP‐K40 (, ♦); PVP‐K24 (, ▴); and PVP‐K15 (, ▪).

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“…Therefore, the segment-surface ratios for the Flory model represent additional parameters that must be estimated. These ratios can be estimated from crystallographic or other geometric considerations (Eichinger and Flory, 1968;Pouchly and Patterson, 1976), or via the group contribution format of Bondi (1968). A third possible method considered here is from gas chromatographic data as an additional adjustable-fit parameter.…”

Section: Segment-surface Ratiosmentioning

confidence: 99%

Vapor‐liquid equilibria from perturbation gas chromatography. Part II: Application to the polybutadiene/benzene/cyclohexane ternary system

et al. 1986

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This work brings together recent gas chromatography experiments and theory involving multiple sorbing species at finite concentration, and theories for multicomponent polymer solutions by means of the parameter estimation procedure of Part 1. Results quantitatively describe the wide variation in peak retention times that are caused by phase equilibrium and chromatographic interference, the best solution models doing so to within or near experimental error. The chromatographic method is capable of detecting differences and peculiarities in the various polymer solution models in both the accuracy of the calculated retention times and the sensitivities of the calculations to the model parameters. Perturbation chromatography offers some unique capabilities for multicomponent vapor-liquid equilibrium determinations.

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Polymers in Mixed Solvents

Cited by 34 publications

References 7 publications

Influence of water on cellulose-EMIMAc solution properties: a viscometric study

Influence of water on cellulose-EMIMAc solution properties: a viscometric study

Association Equilibria Theory for Polymers in Mixed Solvents with Specific Interactions

Vapor‐liquid equilibria from perturbation gas chromatography. Part II: Application to the polybutadiene/benzene/cyclohexane ternary system

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