Thermodynamic Interaction Parameters for the System Water/NMMO Hydrate

Vapor pressures of water were measured for aqueous solutions of N-methyl-morpholine N-oxide (NMMO) at 80, 90 and 100 degrees C. The Flory-Huggins interaction parameters, chi, calculated from these data as a function of phi, the volume fraction of NMMO, are negative at all concentrations; at low phi, they decrease by more than a factor of 2 as T is raised, whereas they remain almost unchanged as phi approaches unity. Accordingly, the heat of mixing is pronouncedly endothermal at low NMMO concentrations but close to athermal at low water content. The composition dependence of chi can be equally well described by the Redlich-Kister equation and by an approach subdividing the mixing process int…

Solubility of Polymers

Detailed knowledge concerning the phase state (homogeneous or coexistence of two or more condensed phases) of polymer containing mixtures is indispensible in virtually any area related to the production or application of macromolecules. In addition to this qualitative information it is for many purposes highly desirable to dispose of quantitative data regarding solvent quality or, more generally, with respect to the thermodynamic interaction between the components of the mixtures. This contribution starts with a brief presentation of the thermodynamic criteria deciding on the phase state and presents the experimental methods used in this area. The next section gives an overview on typical b…

Investigation of the Interpolymer Complex between Hydroxypropyl Cellulose and Maleic Acid-Styrene Copolymer, 1

The hydrogen bonding-interpolymer association of hydroxypropyl cellulose (HPC) with maleic acid-styrene (MAc-S) copolymer has been investigated in dilute aqueous solution by viscometry, turbidimetry and potentiometry. At a mixing ration between MAc-S and HPC of 10:90, the solution exhibits a phase separation upon heating, while for other mixing ration no phase separation could be detected. The stability of the interpolymer complex (IPC) increases as the temperatures rises. The stoichiometry of the IPC, in mole units, was estimated as being MAc-S:HPC=5:2. The thermodynamic functions (enthalpy and entropy) of the complexation process have been determined.

Large scale fractionation of pullulan and dextran

Abstract A recently developed large scale fractionation technique named continuous spin fractionation (CSF) was applied to fractionate pullulan and dextran. 450 g of pullulan with a broad molecular weight distribution were fractionated using water as solvent and acetone as precipitant. In this study, we have in five CSF runs prepared three fractions with apparent M ¯ w * values ranging from 17.6 to 413 kg mol−1. Seventy grams of dextran were fractionated with a mixed solvent of water plus methanol. Five fractionation steps resulted in four samples with M ¯ w values between 4.36 and 18.2 kg mol−1.

Branched versus linear polyisoprene: Fractionation and phase behavior

Abstract Branched polyisoprene (PI) was prepared from PI-macromonomers. Linear byproducts of the synthesized polymer were removed by means of inverse spin fractionation, using the solvent cyclohexane (CH) and the precipitant acetone (AC). A well-defined fraction (Mw = 17.5 kg/mol, Mw/Mn = 1.8) of the branched polyisoprene obtained in this manner was used to determine different phase diagrams with branched and/or linear PI in the mixed solvent CH/AC at 25 °C. For comparable molar masses of the polymers the two-phase area is smallest for the branched PI and slightly larger for the linear PI; in the case of the unfractionated original sample of the branched polymer one observes a pronounced pe…

Vapor Pressures of Polymer Solutions and the Modeling of Their Composition Dependence

Equilibrium vapor pressures, p, are reported for the systems tetrahydrofuran + poly(vinyl methyl ether) and tetrahydrofuran + polystyrene at 20, 40, and 60 °C. These data plus information from the literature serve to demonstrate that the composition dependence of p can be modeled quantitatively for polymer solutions in thermodynamically very different solvents by means of three, physically meaningful parameters.

Islands of Immiscibility for Solutions of Compatible Polymers in a Common Solvent: Experiment and Theory

Experimentally obtained islands of immiscibility are reported for the systems PS/PVME/THF at 20 °C and for PS/PVME/CH at 55 °C (PS: polystyrene, PVME: poly(vinyl methyl ether), THF: tetrahydrofuran, CH: cyclohexane). THF is a good solvent and CH is a marginal solvent for both polymers. In the case of THF, information on the Flory−Huggins interaction parameters of the three binary subsystems suffices for a qualitative prediction of the phase behavior of the ternary system. Quantitative agreement can be achieved by means of composition-independent ternary interaction parameters. For the marginal solvent CH, the exclusive use of binary interaction parameters wrongly predicts complete miscibili…

Polyelectrolytes:  Intrinsic Viscosities in the Absence and in the Presence of Salt

Intrinsic viscosities were determined at 25 °C for 10 samples of narrowly distributed sodium polystyrene sulfonate (the molecular weights M ranging from 0.9 to 1000 kg/mol) in pure water and in aqueous solutions containing 0.9 wt % NaCl from the slope of ln ηrel versus polymer concentration. In the middle range of M, the [η] values are in the former case almost 2 orders of magnitude larger than in the latter case. In the absence of salt, the plot of log [η] as a function of log M exhibits a sigmoidal shape, which can be approximated within the interval 3 < M (in kg mol-1) < 30 by log[η] = −0.17 + 2.1 log M. In the presence of salt, the following relation holds true in the entire regime:  lo…

Continuous spin fractionation and characterization by size-exclusion chromatography for styrene-butadiene block copolymers.

Abstract Linear and star-shaped styrene–butadiene block copolymers synthesized by anionic polymerization of butadiene and styrene were fractionated by applying a newly developed large-scale fractionation technique, named continuous spin fractionation (CSF). Their molecular weight and polydispersity index ( d  =  M w / M n ) were measured with size-exclusion chromatography and static light scattering. For the linear triblock copolymer a fractionation via temperature variation turned out to be better suited than the usual isothermal procedure. The star-shaped polymer with the d value of 1.33 was fractionated in two CSF steps to get the targeted sample, which has a considerably more uniform st…

Rheology of Sodium Hyaluronate Saline Solutions for Ophthalmic Use

The aim of this work was to investigate the rheological properties of different saline solutions of sodium hyaluronate (NaHA) with special interest for medical applications. The experimental results were compared with literature data for commercial ophthalmic viscosurgical devices (OVDs) used in cataract surgery. We offer some tools to tailor the rheological behavior of OVDs for different purposes. We have investigated to which extent surgical requirements can be fulfilled by adjusting either the molecular weight of NaHA or its concentration, parameters that are in some respects equivalent but not in others. Furthermore, we demonstrate that moduli and complex viscosities of NaHA saline solu…

Membranes Directly Prepared from Solutions of Unsubstituted Cellulose

Summary: Starting from 5 wt.-% solutions of a prehydrolysis kraft pulp ( = 135 kg · mol−1) in the mixed solvent (dimethylacetamide + 7 wt.-% LiCl) we have prepared cellulose membranes on different supports according to the phase inversion process using above all acetone (AC) and 2-propanol as precipitants. In this context we have studied the phase behavior of the quasiternary system (DMAc+LiCl)/AC/cellulose. The obtained membranes are mechanically stable and in their mechanical and separation properties on the whole comparable to membranes consisting of regenerated cellulose. With respect to gas separation the ideal selectivity of CO2 in combination with N2 and O2 turns out to be opposite f…

Cover Picture: Macromol. Mater. Eng. 5/2004

Cover Picture: Macromol. Biosci. 10/2005

Branched Versus Linear Polyisoprene: Flory-Huggins Interaction Parameters for their Solutions in Cyclohexane

Flory-Huggins interaction parameters were determined as a function of composition for solutions of linear and of branched polyisoprene in cyclohexane (CH) at 25, 45, and 65 °C by means of vapor pressure measurements (moderate to concentrated solutions) and by vapor pressure osmometry (dilute solutions). The results demonstrate that CH is a considerably worse solvent for branched polyisoprene than for the linear analog at all temperatures and at all compositions. This observation corroborates the expectation based on a recent phenomenological approach, which accounts explicitly for the incapability of the segments of an individual polymer molecule to spread out over the entire volume of the …

Formation of micro- and nano-spheric particles (filter dust) during the preparation of cellulose acetate membranes

Abstract Membranes were prepared from six samples of cellulose acetate (CA) differing in their average molecular weight (75–260 kg/mole) and molecular weight distribution using methyl acetate as solvent and 2-propanole as precipitant. The routes through the phase diagram and the evaporation times were varied in these experiments. Electron microscopy demonstrates that the amount of filter dust (CA particles deposited on the membrane surface) decreases as the fraction of low molecular weight material in the starting polymer becomes less. For low average molar mass of CA and moderate polymer concentrations in the casting solution the dust consists of individual spheres of relatively uniform si…

Viscosity-molecular weight relationship for cellulose solutions in either NMMO monohydrate or cuen

The intrinsic viscosities, [η], of nine cellulose samples, with molar masses from 50 × 103 to 1 390 × 103 were determined in the solvents NMMO*H2O (N-methyl morpholin N-oxide hydrate) at 80°C and in cuen (copper II-ethlenediamine) at 25°C. The evaluation of these results with respect to the Kuhn–Mark–Houwink relations shows that the data for NMMO*H2O fall on the usual straight line in the double logarithmic plots only for M ≤ 158 103; the corresponding [η]/M relation reads log ([η]/mL g−1) = –1.465 + 0.735 log M. Beyond that molar mass [η] remains almost constant up to M ≈ 106 and increases again thereafter. In contrast to NMMO*H2O the cellulose solutions in cuen behave normal and the Kuhn–…

Interpolymer complex between hydroxypropyl cellulose and maleic acid-styrene copolymer: phase behavior of semi-dilute solutions.

Summary: The phase behavior of a water/hydroxypropyl cellulose/maleic acid–styrene copolymer (H2O/HPC/MAc-S) system was investigated in the semi-dilute range by turbidimetry, rheology, and optical microscopy. The two polymers under investigation form interpolymer complexes via hydrogen bonding. In the case of a total polymer concentration of cpol = 5 mg · mL−1 a second phase segregates upon heating the homogeneous ternary system. By applying a constant shear rate ( = 50 s−1) the phase separation temperature of the system is 10–15 °C lower than for an unsheared one. For cpol = 10 mg · mL−1 phase separation has already occurred at room temperature when the two binary polymer solutions are mix…

Thermodynamics of pseudo-ternary systems as a tool to predict the morphologies of cellulose acetate/polystyrene blends cast from tetrahydrofuran solutions

Abstract The demixing behavior of the ternary system THF/CA/PS (tetrahydrofuran/cellulose acetate/polystyrene) was investigated at 25 °C. Cloud point measurements show that the system exhibits a large miscibility gap caused by the incompatibility of CA and PS. Both ends of the experimentally determined tie lines are located inside the two-phase area of the phase diagram. By means of the measured critical composition of the ternary system and the Flory–Huggins interaction parameters published for two of the binary subsystems ( χ CA/THF =0.442 and χ PS/THF =0.475) the polymer/polymer interaction parameter was adjusted (directly minimizing the Gibbs energy) to χ CA/PS =0.057. These thermodynam…

Inverse Spin Fractionation:  a Tool to Fractionate Sodium Hyaluronate

Forces Between Solid Surfaces Across Polymer Melts as Revealed by Atomic Force Microscopy

Forces between solid surfaces across polymer melts are poorly understood despite their fundamental importance and their relevance for making composite materials. Such force measurements reveal information on the structure of polymers at surfaces and of confined polymers. Experiments with the atomic force microscope and polyisoprene (PI) confirmed theoretical predictions that no long‐range force should be present in thermodynamic equilibrium. In poly(dimethyl siloxane) (PDMS) repulsive forces are observed at high molar mass. We attribute this to the formation of an immobilized layer caused by a slow release of adsorbed segments enhanced by entanglement. In low molar mass PDMS attractive forc…

Liquid/Gas and Liquid/Liquid Phase Equilibria of the System Water/Bovine Serum Albumin

The thermodynamic behavior of the system H2O/BSA was studied at 25 °C within the entire composition range: vapor pressure measurements via head space sampling gas chromatography demonstrate that the attainment of equilibria takes more than one week. A miscibility gap was detected via turbidity and the coexisting phases were analyzed. At 6 °C the two phase region extends from ca. 34 to 40 wt % BSA; it shrinks upon heating. The polymer rich phase is locally ordered, as can be seen under the optical microscope using crossed polarizers. The Flory-Huggins theory turns out to be inappropriate for the modeling of experimental results. A phenomenological expression is employed which uses three adju…

Polydispersity effects on the phase diagram of the system chloroform/poly-l-(lactic acid)/poly(methyl methacrylate) and morphology of PLA/PMMA films

Abstract Cloud point curve, critical composition and several critical coexistence curves were measured at 25°C for the ternary system poly- l -(lactic acid) (PLA), poly(methyl methacrylate) (PMMA) — where both polymers exhibit broad molecular weight distributions — and the common solvent chloroform. In contrast to the situation encountered in the absence of the second polymer both branches of the critical coexistence curves are located without any doubt inside the miscibility gap as defined by the cloud point curve. This unexpected experimental finding is corroborated by model calculations on the basis of continuous thermodynamics. The removal of solvent from the ternary mixtures yields fil…

Polyelectrolyte Complexes: Phase Diagram and Intrinsic Viscosities of the System Water/Poly(2-vinylpyridinium-Br)/Poly(styrene sulfonate-Na)

In contrast to all earlier work on that subject, measurements are performed at high dilution up to total polymer concentrations wpol of 0.5 wt%. Aqueous solutions of poly(2-vinylpyridinium-Br) and of poly(styrene sulfonate-Na) are only fully miscible if wpol < 0.02 wt%. Decomposition into two liquid phases is observed upon an increase in wpol, where the extension of the miscibility gap is considerably larger at 60 than at 25 °C. Viscosity measurements demonstrate that the formation of the polyelectrolyte complexes may take hours. The intrinsic viscosity of the polyanion turns out to be 20 times larger than that of the polycation and to be much more sensitive toward the addition of extra sal…

Large Scale Fractionation of Macromolecules

Access to sufficiently large amounts of material with adequate molecular and chemical uniformity from polydisperse natural products or synthetic materials has been a long-standing challenge to polymer scientists. We have developed a broadly applicable preparative fractionation method consisting of a special kind of continuous extraction removing the easier soluble components from the initial product. It is rendered possible by the use of spinning nozzles throught which a concentrated polymer solution is pressed into a liquid of tailored thermodynamic quality. The initially produced jets of the source phase disintegrate rapidly into minute droplets of typically 50 μm diameter. This efficient…

Cellulose/Water:  Liquid/Gas and Liquid/Liquid Phase Equilibria and Their Consistent Modeling

Liquid/liquid and liquid/gas equilibria were measured for the water/cellulose system at 80 °C using three different polymer samples. For these experiments we prepared cellulose films of approximately 20−25 μm in thickness and determined their equilibrium swelling in water. Thereafter the polymer concentration in the mixed phase was increased by means of a stepwise removal of the volatile component, and the equilibrium vapor pressures were measured using an automated combination of head space sampling and gas chromatography. Contrary to the usual behavior of polymers, the swelling of cellulose increases as its molar mass becomes larger. The Flory−Huggins interaction parameters calculated fro…

Linear versus Three-Arm Star Polybutadiene: Effects of Polymer Architecture on the Thermodynamic Solution Behavior

The interaction of linear and of three-arm star polybutadiene (PB) with THF was studied in the temperature range between 25 and 55 °C. Information for dilute solution rests on light scattering experiments; Flory–Huggins interaction parameter χ stem from vapor pressure measurements as a function of φ, the volume fraction of polymer. Despite the minute divergence in the architecture, the second osmotic virial coefficients of the two PBs differ noticeably. The present work demonstrates that these disparities become much more pronounced as φ increases and that they depend strongly on temperature. These findings are interpreted on the basis of an approach accounting for the effects of chain conn…

Interpolymer complexes and polymer compatibility.

A reliable method to decide whether two polymers A and B are miscible or incompatible would be very helpful in many ways. In this contribution we demonstrate why traditional procedures cannot work. We propose to use the intrinsic viscosities [η] of the polymer blends instead of the composition dependence of the viscosities as a criterion for polymer miscibility. Two macromolecules A and B are miscible because of sufficiently favorable interactions between the two types of polymer segments. For solutions of these polymers in a joint solvent, this Gibbs energetic preference of dissimilar intersegmental contacts should prevail upon dilution and lead to the formation of interpolymer complexes, …

Dextran-Based Polycations: Thermodynamic Interaction with Water as Compared With Unsubstituted Dextran, 1 - Volumetric Properties and Light Scattering

Dextran-Based Polycations: Thermodynamic Interaction with Water as Compared With Unsubstituted Dextran, 2 - Flory/Huggins Interaction Parameter

Pullulan and dextran: uncommon composition dependent Flory-Huggins interaction parameters of their aqueous solutions.

Vapor pressure measurements were performed for aqueous solutions of pullulan ( M w 280 kg/mol) and dextran ( M w 60 and 2100 kg/mol, respectively) at 25, 37.5, and 50 degrees C. The Flory-Huggins interaction parameters obtained from these measurements, plus information on dilute solutions taken from the literature, show that water is a better solvent for pullulan than for dextran. Furthermore, they evince uncommon composition dependencies, including the concurrent appearance of two extrema, a minimum at moderate polymer concentration and a maximum at high polymer concentration. To model these findings, a previously established approach, subdividing the mixing process into two clearly separa…

Branched versus linear oligo(dimethylsiloxane): Differences in their thermodynamic interaction with solvents

The thermodynamic behavior of linear and of branched oligo(dimethylsiloxane) (O-DMS) solutions was studied by means of vapor pressure measurements and vapor pressure osmometry at different temperatures for the thermodynamically favorable solvent THF. The branched material required for that purpose was synthesized and afterwards fractionated by means of the single solvent acetone to eliminate components of low degrees of branching. The Flory-Huggins interaction parameters, χ, for the systems THF/O-DMS as a function of composition pass a minimum at all temperatures (25, 40, and 60 °C) in the case of the branched material. For the unbranched oligomer such a minimum is only observed at 60 °C. A…

On The Incompatibility of Dextran and Pullulan in Aqueous Solutions and Its Modeling

Joint aqueous solutions of branched dextran and linear pullulan are investigated with respect to their phase separation. The experiments demonstrate that the polymers are – depending on the molar mass of dextran – incompatible in aqueous solutions despite their chemical similarity. This finding can be modeled on the basis of an approach accounting for chain connectivity and conformational relaxation of the components. According to these calculations, the polymers exhibit a miscibility gap in joint solutions despite the favorable interactions between them. Using information on the subsystems H2O/dextran and H2O/pullulan, the assumption of complete miscibility of the polysaccharides is requir…

Intrinsic Viscosity of Aqueous Solutions of Carboxymethyl Guar in the Presence and in the Absence of Salt

Intrinsic viscosities were determined for solutions of CMG in pure water and 0.9 wt.-% aqueous NaCl. To avoid the 0/0-type extrapolation typical for Huggins plots, a new procedure was used. For CMG and pure water, this requires only two adjustable parameters: the specific hydrodynamic volume of the polymer in the limit of infinite dilution and a hydrodynamic interaction parameter. The intrinsic viscosity of CMG (no salt) at room temperature is 6 050 mL · g -1 ; approximately half as large as that of Na-PSS of comparable molar mass. The ratio of the intrinsic viscosities with and without salt is ≈7 for CMG, as compared to >100 for Na-PSS. The reasons for the different behaviors of the two ty…