The phenomenon of “true cosolvency”, which has only recently been observed in the system acetone/diethyl ether/polystyrene (AC/DEE/PS), is investigated with regard to its pressure dependence and compared with the thermodynamic behaviour of the corresponding binary sub-systems. For the determination of the limits of complete solubility, a pressure apparatus was used which had been constructed, in order to measure the turbidity of fluids in the temperature range of −70 to +500°Cand in the pressure range of 1 to 4000 bar (105 to 4·108 Nm−2). The critical line observed for the system DEE/PS (MPS=20400) looks similar to that reported for AC/PS in the literature, i.e. the upper critical solution …

Pressure influences on the viscosity of polymer solutions

Of all physico-chemical quantities characterizing the behavior of liquids, the viscosity coefficient η is normally most sensitive to pressure. Early measurements of η(p) date back almost 100 years [1] but they were carried out with very different objectives [2]. Currently, one is particularly interested in polymer solutions, for instance because of the additives to motor oils and of oil recovery. The present paper reports on measurements with polystyrenes of high molecular uniformity in eight different solvents. It confines itself to zero-shear viscosities and discusses the possibilities of discovering the influence of pressure via the molecular structure of the solvent and via its thermody…

Liquid/Gas and Liquid/Liquid Phase Behavior of n-Butane/1,4-Polybutadiene versus n-Butane/1,2-Polybutadiene

Solutions of 1,4-polybutadiene (1,4-PB, 98% cis) and of 1,2-polybutadiene (1,2-PB) in n-butane (n-C 4 ) were studied with respect to their vapor pressure and to their demixing into two liquid phases under isochoric conditions within the temperature range from 25 to 75 °C. 1,2-PB mixes homogeneously with n-C 4 at any ratio, in contrast to 1,4-PB, which exhibits a miscibility gap extending from practically pure solvent to approximately 40 wt % polymer. Corresponding to these solubility differences, the vapor pressures for the system n-C 4 /1,4-PB are considerably higher than for n-C 4 /1,2-PB at the same concentration and temperature. The experimental results are modeled accurately and consis…

Phase behaviour and interfacial tension of polysiloxane blends

Abstract The cloud point curve for blends of poly(dimethyisiloxane) (PDMS, M w = 2.5kg mol −1 ) and poly(hexylmethylsiloxane) (PHMS, M w = 113kg mol − ] was determined turbidimetrically. The system demixes upon cooling and the UCST amounts to 36°C. The interfacial tension γ was determined at the critical composition for three temperatures by means of a spinning drop tensiometer. The dependence of γ on the reduced critical temperature can be described within experimental error by both the mean field theory and the Ising-3D theory.

Liquid/Liquid Demixing in the System n-Hexane/Narrowly Distributed Linear Polyethylene

Demixing conditions were measured visually for solutions of three narrowly distributed polyethylene samples (M ranging from 6.5 to 380 kg/mol) in n-hexane up to 500 K and 150 bar. This information yields the critical line for infinite molar mass; i.e., it specifies the pT area within which one is safe from phase separation irrespective of the molar mass of the polymer and of the composition of the mixture. The experimental findings are in good qualitative agreement with the predictions of the Sanchez−Lacombe theory applied without any adjustable parameters. The influences of molar masses are, however, underestimated, and the resulting critical compositions are too small. For a more quantita…

Phase separation of blends of polydisperse polymers: Comparison between experiment and theory for the system poly(dimethylsiloxane)/poly(ethylmethylsiloxane)

Cloud point curves were measured turbidimetrically for blends (upper critical solution temperatures ; UCSTs) of poly(ethylmethylsiloxane) (PEMS) and four different samples of poly(dimethylsiloxane) (PDMS) ; the weight average molar masses in kg/mol are 31.2 for PEMS and 10.4, 15.5, 18.1 and 24.0 for PDMS ; all components have polydispersity indices D (= M w /M n ) within the range from 1.82 to 2.67. Corresponding calculations on the basis of the Flory-Huggins theory (three adjustable parameters) account for the polydispersity; molecular weight distributions are represented by the generalized Schulz-Flory equation. Calculated cloud point curves agree very well with those measured, if individ…

Demixing of unsheared and sheared solutions of polystyrene in tert-butylacetate and the pressure influence on their flow behaviour

For the system tert-butyl acetate/polystyrene (M= 670000) the phase separation behaviour (upper critical solution temperatures, upper critical solution pressures) is investigated by means of visual and turbidimetric cloud-point measurements and by viscometry. For near-critical concentrations the visually determined cloud-points are found at higher, for low concentrations at lower temperatures as compared with the turbidimetrically determined binodal temperature,Tbin Plots of the invers of the turbidity measured atTbin as a function of the polymer concentration,w2, yield a minimum from which the critical composition can be determined. The viscometrically obtained demixing points (break-down …

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…

Morphology of PEO/PDMS blends during shear: Coexistence of two droplet/matrix structures and additive effects

Abstract The morphologies of blends of polyethyleneoxide (PEO 37) and poly(dimethylsiloxane)s (PDSM), with viscosity ratios, λ , of approximately one (PDMS 230) or 2.8 (PDMS 314, being the component of higher viscosity) and interfacial tensions on the order of 10 mN/m, were investigated at 70 °C as a function of shear rate (up to 10 s −1 ) and of time. For the system PEO 37/PDMS 230 we have also studied the influence of the compatibilizer dimethyl–ethyleneoxide–copolymer (PDMS- co -PEO), which is only reasonably soluble in PEO. To investigate the morphologies we have used an optical shear cell in combination with a light microscope. The most important observation consists in the formation o…

Interfacial tension of demixed polymer solutions: augmentation by polymer additives

The interfacial tension between phase separated polymer solutions increases pronouncedly upon the addition of asmall amounts of incompatible polymers. This feature is demonstrated by means of measurements with solutions of polystyrene in cyclohexane and the folloowing additives: poly(styrene-block-dimethylsiloxane), polyisobutylene and polydimethylsiloxane. Theoretical considerations based on a correlation between the lenth of the tie lines and the corresponding interfacial tension corroborates this finding

Rheological studies of moderately concentrated polystyrene solutions. I. A new method for the extrapolation of the zero-shear viscosity

Measurements of the viscosity coefficient η of solutions of polystyrene (Mw = 6.0 × 105 and 1.77 × 106) in trans-decalin (TD, θ solvent) and toluene (TL, good solvent) as function of shear rate (11−104 s−1), concentration (4.24−11.21 wt %), and temperature (10–50°C) are reported. As a new theoretically grounded method for the determination of the zero-shear viscosity η0 it is proposed to plot η as a function of . The intercepts of the straight lines obtained by this procedure give η0 in good agreement with directly measured values.

Complex miscibility behaviour for polymer blends in flow

Abstract Experimental observations of the effect of shear flow on the miscibility of binary polymer blends are compared to calculations based on a generalized Gibbs energy of mixing Gγ˙. This mixing free energy characterizes the steady state established at shear rateγ˙, as the sum of G z , the equilibrium Gibbs energy and E s , the energy the system stores while flowing.

Interfacial tension between polymer-containing liquids - Predictability and influences of additives

The first part of the contribution deals with the interfacial tension, σ, of phase-separated polymer solutions in single or mixed solvents and of binary polymer blends as a function of the relative distance to the critical temperature of the system, special attention being paid to the possibilities of theoretical prediction. Two methods are discussed in more detail. One is based on a realistic description of the Gibbs energy of mixing as a function of composition, the second correlates σ with the length of the measured tie line. The second part is devoted to another aspect, namely the effects of additives on the interfacial tension between the coexisting phases of demixed polymer solutions …

Phase diagrams of the system tetrahydrofuran/γ-butyrolactone/poly(ether imide) and determination of interaction parameters

Abstract The thermodynamic interactions in the ternary mixture tetrahydrofuran/γ-butyrolactone/poly(ether imide) (THF/γ-BL/PEI) are investigated from 30 to 50°C. This is a membrane-forming system with a high He-selectivity. Cloud point measurements show that the two binary polymer solutions THF/PEI and γ-BL/PEI exhibit miscibility gaps which close towards the centre of the ternary phase diagram where the mixtures become homogeneous (cosolvency). Vapour pressures were determined for the subsystem THF/γ-BL. For the theoretical calculations the Gibbs energy of mixing is formulated according to the Flory-Huggins theory and the interaction parameter χ THF γ-BL calculated from the vapour pressure…

Fractionation of unsubstituted cellulose from solutions in either Ni-tren or (N,N-dimethylacetamide + LiCl)

Starting from solutions of unsubstituted cellulose (Avicel PH101, M w = 30.1 kg/mol and M w /M n = 3 or Solucell 500, M w = 230 kg/mol, M w /M n = 2.8) in either Nitren (0.8 M aqueous solution of the dihydroxotris(2-aminoethly)amine nickel(II) complex) or in a mixed solvent DMAc+LiCl (consisting of N,N-dimethylacetamide plus lithium chloride) it was investigated whether the segregation of a second phase caused by the addition of suitable precipitants leads to polymer fractionation. With Ni-tren the long chains accumulate in the precipitate formed upon the addition of sulfuric acid; as the pH falls below 9, the solution is free of cellulose. Nevertheless this route option for fractionation m…

Enthalpy and Entropy Contributions to Solvent Quality and Inversions of Heat Effects with Polymer Concentration

Vapor pressures above the solutions of polystyrene in either cyclohexane (32-60 °C) or toluene (10-70 °C) have been measured by a combination of head space sampling and gas chromatography as a function of the volume fraction φ of the polymer. The thus obtained Flory-Huggins interaction parameters Χ (φ; T) were complemented by data for three other systems (tert-butyl acetate/polystyrene, cyclohexane/poly(vinyl methyl ether), 2-propanol/poly(butyl methacrylate)) reported in the literature and analyzed in terms of their enthalpy and entropy parts Χ H and Χ s . Furthermore these experimental findings were modeled by means of an approach splitting the mixing process conceptually into two parts a…

Quick and reliable routes to phase diagrams for polyethersulfone and polysulfone membrane formation

Phase diagrams were measured and calculated for the ternary membrane forming systems DMF/water/polysulfone and DMF/water/polyethersulfone at different temperatures. Customary experiments yielded cloud point curves, tie lines, and critical compositions. The theoretical computation starts from the Flory-Huggins theory and employs binary interaction parameters g ij that vary with the composition. This information was mainly obtained by means of Headspace-Gas Chromatography (HSGC, yielding the partial pressures of the volatile components); these data were complemented by light scattering and swelling experiments. The calculation of binodals, spinodals, tie lines, and critical points avoids the …

Phase diagrams calculated for flowing polymer solutions: spinodal and three phase conditions

Spinodal lines and critical points (CPs) are calculated for flowing solutions of polystyrene in trans-decalin. Three types of CPs can be distinguished: The first consists of stable CPs (ordinary critical line) and originates from the CP of the quiescent system. The other two CPs are bound to shear. Additional stable CPs (extraordinary critical line) result for higher polymer concentrations and unstable CPs for intermediate concentrations. Ordinary and unstable critical line merge in a heterogeneous double CP. The coexistence of three phases in the flowing system (eulytic points) comes to an end as two of them merge upon an increase in shear rate at a critical end point.

Blends of PDMS and random copolymers of dimethylsiloxane and methylphenylsiloxane: Phase separation in the quiescent state and under shear

The miscibility of random copolymers (COP), consisting of dimethylsiloxane and methylphenylsiloxane units, with poly(dimethylsiloxane)s (PDMS) was studied in the absence and in the presence of shear experimentally as well as theoretically. Blends of COP 0.86 28 with PDMS 33 (subscripts: volume fraction of DMS in the copolymer, numbers after the abbreviations: weight average molar masses in kg/mol) were investigated far from critical conditions on the PDMS side of the phase diagram. According to these experiments the two phase regime increases by shear without exception and the maximum effects grow from 3 to 12 K as the PDMS concentration increases. Theoretical calculations were performed un…

Continuous polymer fractionation of polysaccharides using highly substituted trimethylsilylcellulose

Trimethylsilylcellulose (TMSC) was prepared from commercial cellulose with a mixture of hexamethyldisilazane and chlorotrimethylsilane in the solvent system N,N-dimethylacetamide/lithium chloride. The soluble, highly silylated polymer (degree of substitution, DS 2.9) had a molar mass M, of 500 kg/mol and a molecular non-uniformity U = (M w /M n )- 1 of 2.9. In order to investigate the principal suitability of a continuous polymer fractionation for polysaccharides like cellulose derivatives and to obtain TMSC with different molecular weights and lower non-uniformity TMSC was fractionated by means of CPF (Continuous Polymer Fractionation), well-established in the field of synthetic polymers. …

Joint Aqueous Solutions of Dextran and Bovine Serum Albumin: Coexistence of Three Liquid Phases

The phase diagram of the system water/dextran (DEX)/BSA was measured as well as modeled. On the experimental side, cloud points were determined and the coexisting phases were analyzed. The theoretical calculations use an approach capable of describing solutions of chain polymers and of globular proteins with the same formalism. The required thermodynamic input comes from experiments concerning the binary subsystems, except for the polymer blend for which one interaction parameter had to be adjusted. Both sources of information yield the same essential features: the existence of a large composition area of immiscibility, starting from the subsystem DEX/BSA and extending well into the region …

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…

Influence of Molar Mass Distribution on the Compatibility of Polymers

Abstract Phase equilibria were calculated by means of a new method (direct minimization of the Gibbs energy of mixing) for polymer blends consisting of monodisperse polymer A and polydisperse polymer B. The results obtained for a Schulz-Flory distribution of B (molecular nonuniformity U = (M w/M n) −1 = 1 and 100 components of model B) agree quantitatively with that of computations on the basis of continuous thermodynamics. The influence of U B on the miscibility of A and B in 1:1 mixtures was studied for constant M w of B, quantifying the incompatibility of the polymers by the length of the tie lines. The outcome of these calculations demonstrates that the typical effect of an augmentation…

Shear Effects on the Phase Diagrams of Solutions of Highly Incompatible Polymers in a Common Solvent. 2. Experiment and Theory

Cloud point temperatures (Tcp) were measured at different constant shear rates for three representatives of the ternary system cyclohexanone/polystyrene/poly(n-butyl methacrylate) (CHO/PS/PBMA) by means of a newly constructed rheo-optical apparatus that can be operated in the temperature range from 0 to 100 °C up to maximum shear rates of 1440 s-1 and maximum stresses of 384 Pa. In all cases one observes an extension of the homogeneous region as the shear rate γ is raised. With the system CHO/PS 196w/PBMA 2050 (the figures denote the molar masses of the polymers in kilograms/mole) the effects become maximum for high concentrations of PBMA, where the demixing temperatures increase by more th…

Shear influences on the solubility of LDPE in ethene

Abstract The influence of shear on the demixing pressures of the binary system ethene/polyethene was determined viscometrically in the temperature range 147–195°C up to pressures of 1400 bar at polymer concentrations of 18.4, 22.5 and 27.4 wt%, respectively. Autoclaves were used to prepare the solutions and to measure cloud points for the stagnant system. A high-pressure viscometer was used to perform experiments at shear rates γ up to 1500 s −1 . Under all conditions investigated here the two-phase area grows as γ becomes larger and the demixing pressures increase up to 23 bar. This observation is in contrast to theoretical expectation according to which it should be the one-phase region w…

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.

Continuous fractionation of poly[(dimethylimino)decamethylene bromide] and molecular weight dependence of the glass transition

30 g of the ionene poly[(dimethylimino)decamethylene bromide] were fractionated by a continuous counter-current extraction method (CPF) using ethylene glycol monoethyl ether as the solvent and diisopropyl ether as the non-solvent component. The efficiency of the separation was checked by viscometry and gel-permeation chromatography (GPC) measurements. Eight fractions of different molar mass were prepared for differential scanning calorimetry (DSC) experiments. With bromide as counter-ion, the glass transition temperature of the ionene increases from ca. 60 to 85°C as the intrinsic viscosity of this material (in 0,4 M aqueous solutions of KBr at 25°C) rises from ca. 14 to 22 mL/g. When bromi…

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.

Viscosities were measured as a function of pressure and temperature with solutions of PVC 75 000 in cyclohexanone (CHO) and polymer contents ranging from 0,6 to 12 wt.-%, by means of a Searle-type (≥3 wt.-%) and a rolling-ball viscometer (<3 wt.-%). Furthermore, the influence of molecular weight was determined with solutions of 8 wt.-% of PVC 20 000, PVC 37 000 and PVC 100 000. (The numbers in the codes of the PVC specimens are their approximate molecular weights.) For all concentrations and molecular weights, the viscosity increases in a more or less exponential manner with increasing pressure. The ratio f1000 of the viscosity of the solution at 1 000 and 1 bar can be varied by the change …

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…

Polymer solutions: Equilibrium clusters versus shear clusters

Abstract Polymer solutions are inhomogeneous on mesoscopic scales as a result of chemical bonds linking their monomeric units. This situation leads to polymer clusters within which the polymer concentration c cluster is only a small fraction of the overall concentration c. The ratio c/ c cluster (overlap parameters Ω ) quantifies the number of clusters that need to overlap to yield c. Equilibrium clusters (minimization of Gibbs energy) and shear clusters (minimization of entropy production) differ fundamentally where Ω equil ≥ Ω shear . Only in the vicinity of the glass transition temperature and at high concentration the opposite is the case. Experimental information on Ω equil as a functi…

Temperature and pressure dependence of the viscosities of perfluoropolyether fluids

The viscosities of two structurally different perfluoropolyether fluids were determined at a series of temperatures and pressures, from 25 to 100°C and from 1 to 1000 bars. Flow activation energies and volumes as well as their temperature and pressure coefficients were derived. An attempt was made to relate measured and derived quantities to the compound structures.

Proposition d'une methode qui utilise l'information contenue dans la relation entre la vitesse de cisaillement et la viscosite. Solutions de polystyrene dans la trans-decaline

Solidification behavior of the theta system 2-propanol/poly(n-butyl methacrylate)

Thermoreversible gelation of the system 2-propanol/poly (n-butyl methacrylate) — as detected by D'SC or dielectric experiments — does not manifest itself in a straightforward manner in the dynamic-mechanical properties. Its occurrence can, however, be seen in many ways: i) For constant composition of the system and a reference temperature lower than Tgel, the storage modulus G′ is larger than the loss modulus G″ in the glass transition zone of the master curve and both vary in an almost parallel manner with the angular frequency ω over almost two decades (whereas this feature is normally found for other gelling systems within the rubber plateau or the flow region). ii) The entanglement mole…

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.

Influence of chain length on the molecular dynamics of an aliphatic ionene

An aliphatic random copolymer ionene (a cationic polyelectrolyte with N + in the repeat unit), was fractionated with the continuous polymer fractionation and investigated for its molecular weight dependent properties. The fractions were analyzed with GPC and capillary viscometry for their molecular weight. Glass transition temperatures were determined with DSC and a strong molecular weight dependence was observed, but no influence in the ionic conductivity was observed. The temperature dependency of ionic conductivity in ionenes is described.

CPF : Continuous polymer fractionation

A method is presented by means of which it is possible to fractionate polymers according to their solubility on a technical scale. The CPF consists of a continuous counter-current extraction process in which a homogeneous mixture of a molecularly or/and chemically non-uniform high molecular weight product is divided into two portions of considerably lower non-uniformity. The principle of the CPF is described in general terms and examples are given for the fractionation of homopolymers.

Concentration-dependent switch between chain association and dissociation of oppositely charged weak polyelectrolytes in solution

Abstract Joint solutions of oppositely charged weak polyelectrolytes are considerably less studied than their strong counterparts; as a result, their thermodynamic understanding is still unsatisfactory. This shortcoming hampers the development of a general picture about the physical properties of these mixtures, which further hampers their use to design new materials. To close this gap, we investigate the ternary system ethanol/polyacid/polybase (polyacid: methacrylic acid containing copolymer; polybase: N,N-dimethylaminoethyl methacrylate containing terpolymer) with respect to its demixing and viscometric behavior. Complete homogeneity can only be reached if the total polymer concentration…

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…

Interrelation between the thermodynamic and viscometric behaviour of aqueous solutions of hydrophobically modified ethyl hydroxyethyl cellulose

Abstract Aqueous solutions of a commercial sample of hydrophobically modified ethyl hydroxyethyl cellulose (HC, Mw=100 kg/mol, nonylphenol substitution ca. 1.7 mol%) were studied with respect to their demixing behaviour and flow characteristics. Phase separation temperatures were measured turbidimetrically and by determining the first discernible macroscopic phase separation. In some cases demixing was also monitored viscometrically. Phase volume ratios yielded a critical polymer concentration of 1.87 wt.% HC (displaced considerably out of the minimum of the demixing curve towards higher polymer concentrations) and a lower critical solution temperature of 47°C. Model calculations of the spi…

Viscosity measurements were carried out as a function of pressure and temperature with solutions of 8 wt.-% PVC (Mw ≈ 75 000) in ten thermodynamically good solvents by means of a Searle-type viscometer. A rollingxyhball viscometer was used for the investigation of the pure solvents. In all cases the viscosity increases in a more or less exponential manner when the pressure is raised. The viscosity ratio f1000 = η1000 bar/η1bar can be varied by the choice of the solvent from ca. 2 (tetrahydrofuran) to 3,0 (cyclohexanone) at 40°C. For a constant temperature of 40°C, the volumes of activation for the viscous flow of the solutions, V≠, or f1000 exceed that of the pure solvent, by typically 25%.…

Measured and calculated solubility of polymers in mixed solvents: Monotony and cosolvency

Inducing mixing of water-in water BSA/dextran emulsion by a strong polyelectrolyte

Abstract We examine whether a small amount of strong polyelectrolyte (dextran sulfate sodium salt/DSS/) can induce mixing in water-in-water bovine serum albumin/dextran (BSA/DEX) emulsion and how intermacromolecular interactions affect its the rheological properties. Addition of DSS to water-in-water emulsion at pH 5.4 leads to its mixing at the DSS/BSA weight ratio, ( q ( DSS / BSA ) ) ≥ 0.07 , a noticeable increase in viscosity and storage modulus (G′). Mixing is reversible: increasing the ionic strength leads to phase separation in the water/BSA/DEX/DSS system. The increase in viscoelasticity results from the interaction of DSS with both macromolecular compounds of the emulsion. We assum…

Theory-based improvements of continuous polymer fractionation demonstrated for poly(carbonate)

For the first time, a quantitative theoretical analysis (liquid/liquid phase equilibria treated by means of the continuous thermodynamics) of the operating characteristics of continuous polymer fractionation (CPF) was performed. The results of these calculations were compared with data published for CPF of polyethylene. It turned out that the efficiency of the conventional CPF corresponds to approximately two theoretical plates only. For this reason, several improvements, suggested by theoretical considerations, were realized experimentally, for which purpose the system dichloromethane/diethylene glycol/bisphenol-A polycarbonate was chosen. The pulsating sieve-bottom column was replaced by …

Phase separation of flowing polymer solutions

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…

About 340 g of a cycloaliphatic ionene (see formula given in the introduction) were fractionated by a continuous countercurrent extraction method (CPF). The efficiency of the separation was checked by viscometry and gel permeation chromatography (GPC). Ten different fractions with number average molecular masses between 16 000 and 29 000 D were obtained and their glass transition temperatures T g determined by differential scanning calorimetry (DSC) for their bromide and tetrafluoroborate salts. No molecular weight dependence of T g was found, in contrast to recently reported results with aliphatic ionenes, where - in case of the bromide - T g increases with rising molecular weight.

Phase equilibria and interfacial tension between coexisting phases for the system water/2-propanol/poly(acrylic acid)

The cloud point curve, tie-lines and interfacial tensions were measured for solutions of 50 mol-% neutralized (counter-ion Na ○+ ) poly(acrylic acid) (molar mass M w = 9 700 g/mol; polydispersity index M w /M n = 2,0) in the mixed solvent water/2-propanol at 30°C. Due to the non-uniformity of the polymer, the end-points of the tie-lines are not situated on the cloud-point curve. The interfacial tension σ, determined by means of the spinning drop method, increases in sigmoidal manner with R tl , the length of the tie-line, expressed in terms of weight fractions. An evaluation of these data in a double-logarithmic plot of σ.M -0,5 versus R tl yields a critical exponent of 4,23 as compared wit…

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…

(Vapour + liquid) equilibria of (water + dimethylformamide): application of the headspace-gas chromatography for the determination of thermodynamic interactions

Abstract Isothermal measurements of the partial vapour pressures have been carried out on {water + dimethylformamide (DMF)} at temperatures betweenT=305.15 K andT=323.15 K using an apparatus composed of a headspace sampler and a normal gas chromatograph. These data were simultaneously evaluated in one step with respect to the (composition dependent, integral) Flory-Huggins interaction parametergby means of a new method which minimizes the Gibbs energy of mixing and does not require chemical potentials. The expression forggiven by Koningsveld and Kleintjens, originally designed for polymer solutions, describes the present results best.

A new Continuous Polymer Fractionation method, called CPF, is described. The polymer to be fractionated is dissolved in a solvent/non-solvent mixture, and this solution (feed) is extracted continuously by a second liquid (extracting agent), which contains the same solvent components as the feed. In the case of PVC, the fractionation was carried out with a pulsed counter current extraction apparatus and THF/water was used as solvent/non-solvent mixture. Fractionation is achieved by the fact that the molecules are distributed over the counter current phases according to their chain length; the feed leaves the column as gel and the extracting agent as sol. First some explorative experiments we…

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…

Combined Effects of Pressure and Shear on the Phase Separation of Polymer Solutions

Experimental information available in the literature on the phase separation behavior of the system trans-decalin/polystyrene as a function of pressure and shear rate for different molar masses M o...

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

Cover Picture: Macromol. Biosci. 10/2005

Intrinsic viscosities of polyelectrolytes: specific salt effects and viscometric master curves.

Dilute solutions of the sodium salt of polystyrene sulfonic acid (PSS-Na) were measured viscometrically as a function of composition in aqueous solvents of different salinity, where the extra salt was either NaCl or CaCl2. Such experiments yield {η}, the generalized intrinsic viscosities (hydrodynamic specific volume) of the polyelectrolyte for arbitrary polymer concentrations, c. In the limit of infinite dilution {η} becomes identical to the intrinsic viscosity [η]. For NaCl {η} decreases monotonously with rising c, whereas maxima are passed in the case of CaCl2. Condensing c and the concentration of extra salt in the mixed solvent into a single variable enables the establishment of predic…

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–…

Isobornyl Methacrylate as a Reactive Solvent of Polyethylene

Solutions containing 15 wt, -% of a low-molar-mass polyethylene (PE) in isobornyl methacrylate (IBoMA), containing 0, 5 or 10 wt.-% of 1,4 butanediol dimethacrylate (BDDMA) as crosslinker, were polymerized using either benzoyl peroxide (BPO), at 80°C, or dicumyl peroxide (DCPO), with a thermal cycle attaining 150°C, as initiators. Phase separation of an amorphous PE-rich phase took place when carrying out the reaction at temperatures higher than the PE melting temperature. Partial crystallization of PE was observed when cooling to room temperature. Depending on the initial amount of BDDMA, the fraction of PE that was phase separated varied between 57 and 66% of the initial amount, with crys…

Liquid–liquid phase behavior of toluene/polyethylene oxide/poly(ethylene oxide-b-dimethylsiloxane) polymer-containing ternary mixtures

The experimental data of phase diagrams for both polyethylene oxide/poly(ethylene oxide-b-dimethylsiloxane) binary and toluene/polyethylene oxide/poly(ethylene oxide-b-dimethylsiloxane) ternary polymer-containing systems was obtained at atmosphere pressure by light scattering method. The critical points for some pre-selected compositions and the pressure effect on the phase transition behavior of ternary system were investigated by turbidity measurements. The chosen system is a mixture of ternary which is one of the very few abnormal polymer-containing systems exhibiting pressure-induced both miscibility and immiscibility. This unusual behavior is related to the toluene concentration in the…

Effect of block copolymer architecture on the interfacial tension between immiscible polymers

The effect of block copolymer additives on the interfacial tension (σ) is studied for the systems polydimethylsiloxane/polyethyleneoxide (A/B) and polyethylmethylsiloxane/polypropyleneoxide by means of a sessile-drop and a pendant-drop-apparatus. Diblockcopolymers (A-block-B), triblockcopolymers (A-block-B-block-A) and “tooth-brush” like copolymers (A backbone, B brushes) served as additives.

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…

Liquid-liquid phase equilibria in polymer solutions and polymer mixtures

The pressure dependence of liquid-liquid equilibria in weakly interacting binary macromolecular systems (homopolymer solutions and blends) will be discussed. The common origin of the separate high-temperature/low-temperature and high-pressure/low-pressure branches of demixing curves will be demonstrated by extending the study into the region of metastable liquid states including the undercooled, overheated and stretched states (i.e. states at negative pressures). The seemingly different response of the UCST-branch of solutions and blends when pressurized (pressure induced mixing for most polymer solutions, pressure induced demixing for most blends) will be explained in terms of the location…

Phase behavior of aqueous solutions of bovine serum albumin in the presence of dextran, at rest, and under shear.

The demixing conditions for aqueous solutions of bovine serum albumin (BSA, fraction V) and for joint solutions of BSA plus dextran (DEX, M(w) = 2000 kg/mol) were determined by turbidimetric measurements as a function of composition, temperature, and shear rate. Aqueous solutions of BSA phase separate upon heating. Within the region of BSA concentrations between 0.05 and 32 wt %, the demixing temperature, T1, falls from ca. 65 degrees C to an almost constant value of 45 degrees C. Adding DEX to the BSA solutions reduces the homogeneous region of the mixture drastically where the amount of DEX required to lower T1 to 25 degrees C decreases rapidly as the concentration of BSA is raised. Exper…

Chain Connectivity and Conformational Variability of Polymers: Clues to an Adequate Thermodynamic Description of Their Solutions, 1

This is the first of two parts investigating the Flory-Huggins interaction parameter, χ, as a function of composition and chain length. Part 1 encompasses experimental and theorical work. The former comprise the synthesis of poly(dimethylsiloxane)s with different molar mass and the measurements of their second second osmotic virial coefficients, A 2 , in solvents of diverse quality as a function of M via light scattering and osmotic pressures. The theorical analysis is performed by subdividing the dilution process into two clearly separable steps. It yields the following expression for χ ο , the χ value in range of pair interaction : χ ο = α - ζ λ. The parameter α measures the effect of con…

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…

In a new theoretical approach the separation of a pair of chain molecules (measured thermodynamically by the second osmotic virial coefficient A2) is treated as a two-step process: In the first step the molecules are detached from each other by the addition of solvent—keeping their dimensions constant—and in the second step the now isolated coils are allowed to relax into their equilibrium dimensions. For the description of the second step, in which only segments belonging to one molecule take part, an intra-molecular interaction parameter is introduced on the basis of the intrinsic viscosity. The present two-parameter approach yields A2 = A + σ M−(1−a) for the dependence of A2 on the molec…

Poly(methylmethacrylate) (PMMA), poly(butylmethacrylate) (PBMA), and poly(decylmethacrylate) (PDMA) are completely miscible with toluene at normal pressure from room temperature up to the boiling point of the solvent. In alkanes (C6 to C10) and 1-pentanol the solubility increases with the length of the side chain of the polymer: PMMA always exhibits a solubility gap within the above temperature range, PBMA shows upper critical solution temperatures (except n-hexane, which is a non-solvent), and PDMA mixes completely with all alkanes under consideration. Alcohols (up to C4) are non-solvents for PMMA but theta solvents for PBMA and PDMA (except ethanol which is a non-solvent for the latter). …

Abbau von polystyrol in cyclohexanlösung bei kleiner schergeschwindigkeit

Pressure dependence of the demixing of polymer solutions determined by viscometry

From the break-down in the viscosity of a polymer solution, associated with the entrance into the two phase region, the pressure dependence of the demixing temperatures of solutions of polystyrene (M = 600.000) in cyclohexane, cyclopentane, diethylmalonate and 1-phenyldecane was measured up to 1000 bar. The application of pressure increases the solubility of polystyrene in cyclopentane and diethylmalonate, but decreases that in 1-phenyldecane; in the case of cyclohexane, a pressure of optimum miscibility is observed at ca. 120 bar.

From the break-down in the viscosity and from the increase of the intensity of the scattered light, associated with the entrance into the two-phase region, the pressure dependence of the demixing temperature of solutions of PVC 37 000, PVC 75 000 and PVC 100 000 in phenetole and PVC 75 000 in o-xylene was measured up to 1 000 bar. (The numbers in the codes of the PVC specimens are their approximate molecular weights.) The application of pressure increases the demixing temperatures of PVC in both solvents by about 1 K/100 bar. For a qualitative forecast of the pressure effects, the solubility parameter theory in combination with the corresponding states principle, and an empirical correlatio…

Fractionation of cellulose acetate for the investigation of molecular weight influences on the morphology of membranes

Abstract Cellulose acetate (CA) with an apparent weight average molar mass, M w ∗ , of 150 kg/mol was fractionated with respect to M by means of the mixed solvent methyl acetate (MeAc)/2-propanol (2-POH) applying a new method that uses spinning nozzles to promote the rapid attainment of phase equilibria. Two of the fractions obtained in this manner were employed to prepare membranes from solutions in methyl acetate with 2-propanol as coagulating agent. Electron micrographs demonstrate that the molar mass of CA influences the morphology of the membranes markedly under otherwise identical conditions. For M w ∗ =128  kg/mol, one obtains considerably denser structures than for M w ∗ =263  kg/mo…

A new rotational viscometer is presented which can be operated up to 2 000 bar and a maximum shear stress of 420 Pa. It allows, for the first time, to investigate the non-Newtonian flow behaviour of moderately concentrated polymer solutions. Results of measurements with two representatives of the system 2-propanol/poly(butyl methacrylate) with weight-average molecular weights Mw = 520 000 and Mw = 2 050 000, and ratios of weight- to number-average molecular weights Mw/Mn = 1,08 and Mw/Mw = 1,23, resp. in the region of moderate polymer concentrations are reported. For a ca. 7 wt.-% solution of the higher-molecular-weight polymer one obtains viscometric relaxation times τ0 varying from 1 to 1…

The phenomenon of co-nonsolvency, i.e. the formation of nonsolvents by mixing two solvents, was studied for the system N,N-dimethylformamide/cyclohexane/polystyrene (DMF/CH/PS) which is characterized by the fact that the components of the mixed solvent are only incompletely miscible below 48,6°C. A number of quasibinary sections (stepwise addition of the second solvent to given solutions of the polymer in the first solvent) for a sample (M = 110000) of high molecular uniformity yielded a cloud point surface which gives “island curves” (closed solubility gaps) for constant temperatures between the critical temperature of DMF/CH and the top of the cloud point surface (51,3°C). The attainment …

Equilibrium phase behavior of polyethylene oxide and of its mixtures with tetrahydronaphthalene or/and poly(ethylene oxide-block-dimethylsiloxane)

Liquid/solid and liquid/liquid (LL) transition temperatures were measured by means of an automated device that monitors the light passing through the systems as a function of T at different constant cooling or heating rates q. For pure polyethylene oxide (PEO) crystallization and melting temperatures depend on |q|0.3 and become identical at the equilibrium transition temperature Tm=61.0 °C in the limit of infinitely slow cooling/heating. The reduction of Tm for PEO dissolved in tetrahydronaphthalene (THN) yields information on the Flory–Huggins interaction parameter ξ between these two compounds; ξ results negative and decreases markedly with rising polymer concentration. A tentative explan…

Continuous fractionation and solution properties of PIB. I. Search for the best mixed solvent and first results of the continuous polymer fractionation

To adopt a recently developed method for large scale fractionation (CPF = continuous polymer fractionation, a special kind of counter current extraction) to polyisobutylene (PIB), a systematic search for the best mixed solvent was performed. For this purpose, the essential parts of the phase diagrams solvent/nonsolvent/PIB were determined for 21 mixed solvents by cloud-point measurements; with eight systems of special interest, the molecular weight distributions of the polymers contained in the coexisting phases were also studied. On the basis of these experiments and of considerations concerning additional criteria for the performance of the continuous counter current extraction, the mixed…

The viscosity of solutions of poly(decyl methacrylate)s, PDMA, in 1-pentanol (thermodynamically poor solvent) and in toluence or isooctane (good solvents) was measured up to shear rates of 3 · 104s−1 by means of rotational viscosimeters. The observed pronounced shear thinning is for all solutions well described by the theory of Graessley, with the extension, introduced by Ito. Two parameters, resulting from the evaluation of the flow curves on the basis of the above theory, are discussed: τ0, a characteristic relaxation time of the polymer chain, is found to be in the range of ms. ηfric, a frictional parameter, independent of shear rate, amounts upto 50% of the zero-shear viscosity for the …

Inverse Spin Fractionation:  a Tool to Fractionate Sodium Hyaluronate

Consequences of linking charged and uncharged monomers to binary copolymers studied in dilute solution. Part I: Viscometric behavior of the homopolymers, the effects of charging, and uncommon salt effects

Abstract Intrinsic viscosities, generalized intrinsic viscosities and viscometric interaction parameters were measured for aqueous solutions of poly(ethylene oxide) [PEO], poly(N,N-dimethyl aminoethyl methacrylate) [PR] (uncharged) and for poly{[2-(methacryloyloxy)ethyl] trimethylammonium iodide} [PR+] (charged) within a wide range of molar masses. In this manner it was possible to establish the information required for the study of non-additivity effects upon the formation of binary copolymers from the monomers specified above. The following additional items were of particular interest: The effects of charging PR to PR+ and the composition dependence of the coil overlap in the case of sali…

Solvent quality as reflected in concentration- and temperature-dependent Flory-Huggins interaction parameters

Flory-Huggins interaction parameters (χ) between poly(dimethylsiloxane) (weight-average molecular weight = 152 kg/mol) and various solvents (methyl ethyl ketone, toluene and n-octane) were determined as a function of composition and temperature with vapor-pressure measurements. These data, complemented by independent information for dilute and very concentrated solutions, serve as the basis for a discussion of solvent quality via different theoretical relations. Regardless of polymer concentration, the χ values fall from methyl ethyl ketone via toluene to n-octane, the ketone being the worst solvent and the hydrocarbon being the best solvent. The variation of χ with composition and temperat…

Thermodynamics of copolymer solutions: how the pair interactions contribute to the overall effect.

Vapor pressure measurements were performed for solutions of poly(methyl methacrylate-ran-tert-butyl methacrylate) with different weight fractions of tert-butyl methacrylate units, and their parental homopolymers in chloroform at 323 K, over a large domain of concentrations. The Flory–Huggins interaction parameters obtained from these experimental investigations show complex dependences of the Flory–Huggins interaction parameter on concentration and copolymer composition. This behavior can be modeled by taking into account an approach which considers the ability of the polymers to rearrange in a response to changes in their molecular surroundings [Adv. Polym. Sci. 2011, 238, 1–66]. According…

Evidence of ternary interaction parameters for polymer solutions in mixed solvents from headspace-gas chromatography

Partial vapor pressures of the volatiles have been measured for four solvent/precipitant/polymer systems at different temperatures. The high molecular weight compounds were polysulfone or polyethersulfone and the mixed solvent was either DMF/acetone or DMF/water. Systems containing the very powerful precipitant water exhibit a special phenomenon: Upon the addition of polymer to a mixed solvent of constant composition the partial vapor pressure of water increases by a factor of more than two before it falls to zero as the volume fraction of the polymer approaches unity. This particular situation cannot be modeled using binary interaction parameters only, in contrast to the results obtained w…

An apparatus for turbidimetric measurements of demixing temperatures under shear flow is presented, and the results of experiments with trans-decahydronaphthalene/polystyrene (TD/PS) solutions, investigating molecular weights ranging from 100 kg/mol to 1770 kg/mol, are compared with viscometric data. It is found that the sign and magnitude of shear effects depend on molecular weight (Mw), polymer concentration (c2), and shear rate (). For the first time, it was possible to study a solution which exhibits shear dissolution at low shear rates but shear demixing at high shear rates.

Shear Effects on the Phase Diagrams of Solutions of Highly Incompatible Polymers in a Common Solvent. 1. Equilibrium Behavior and Rheological Properties

Phase diagrams (cloud points, tie lines, critical compositions) and viscosities of homogeneous solutions were determined at temperatures ranging from 20 to 100 °C for three representatives of the ternary system cyclohexanone/polystyrene/poly(n-butyl methacrylate) [CHO/PS/PBMA] in preparation of a study on shear influences. An only moderate increase of the two-phase region observed upon heating (LCST behavior) witnesses little heat effects upon mixing. Tie lines which are nearly parallel to the PS/PBMA edge of the Gibbs phase triangle indicate comparable solvent quality of CHO for both polymers. The quantitative mathematical description of the equilibrium behavior-required for a theoretical …

Poly(n-decyl methacrylate), a statistical copolymer of ethylene and propylene, and a diblock copolymer of styrene and hydrogenated butadiene were studied as representatives of various kinds of viscosity-index (VI) improvers. Essomarcol 52 and AF 1 from Schindler served as base-oils, toluene and 1-phenyl dodecane were also studied. By means of viscosity measurements in the temperature interval from 37.8 to 98.9°C up to a concentration of typically 1 wt.-% polymer, the viscosity indices of the different systems and the corresponding intrinsic viscosities, Huggins coefficients, and activation energies of flow, E≠, were determined. The discussion of the obtained experimental material demonstrat…

On the factors governing the pressure dependence of the viscosity of moderately concentrated polymer solutions

Viscosity measurements were carried out as a function of pressure and temperature with solutions of polystyrene in eight (endothermal) θ-solvents at the respective critical composition by means of a Searle-type apparatus. A rolling-ball viscometer was used for the investigation of the pure solvents. In all cases the viscosity coefficient increases in a more or less exponential manner when the pressure is raised. For θ-conditions, the volumes of activation of the solutions exceed that of the pure solvent by typically 10–15%. The exact amount of this extra efffect stemming from the presence of the polymer and its variation with temperature can be qualitatively correlated with the heats of mix…

On what terms and why the thermodynamic properties of polymer solutions depend on chain length up to the melt

Theoretical considerations based on chain connectivity and conformational variability of polymers have lead to an uncomplicated relation for the dependence of the Flory-Huggins interaction parameter, chi, on the volume fraction of the polymer, phi, and on its number of segments, N. The validity of this expression is being tested extensively by means of vapor pressure measurements and inverse gas chromatography (complemented by osmotic and light scattering data from literature) for solutions of poly(dimethylsiloxane) in the thermodynamically vastly different solvents n-octane (n-C8), toluene (TL), and methylethylketone (MEK) over the entire range of composition for at least six different mol…

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…

Sedimentation of dissolved macromolecules in the vicinity of the consolute point 1. Strictly binary systems and kinetic considerations

This paper analyzes the effect of gravity on polymer solutions near the consolute point. Calculations are carried out for monodisperse polystyrene in cyclohexane using the Flory-Huggins expression with a concentration-dependent interaction parameter for the free energy of mixing. Depending on molecular weight and distance to the demixing temperature, the influence of gravity leads to non-negligible gradients of the volume fraction in the one-phase region as well as in the two-phase region. In particular, the effect of gravity on the measurement of the coexistence curve in a finite sample is calculated explicitly.

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…

Polyelectrolytes in dilute solution: viscometric access to coil dimensions and salt effects

Copolymers of acrylamide (AM) and diallyldimethylammonium chloride (DADMAC), differing in molar masses M (52.3 to 227 kDa) and degrees of charging y (0.2 to 0.6), were studied with respect to their viscometric behavior in dilute aqueous solutions containing variable amounts of NaCl. Complementary measurements were performed on a Brookhaven 90 plus particle size analyzer. M dominates the intrinsic viscosities [η]. For the viscometric interaction parameters B this is only true for large concentrations of extra salt. [η] and B as a function of solvent salinity follow Boltzmann laws. Coil dimensions, determined either via dynamic light scattering or viscometry, agree well. For low salt contents…

Pressure Effects on the Thermodynamics oftrans-Decahydronaphthalene/Polystyrene Polymer Solutions: Application of the Sanchez-Lacombe Lattice Fluid Theory

The cloud-point temperatures (T-cl's) of trans-decahydronaphthalene(TD)/polystyrene (PS, (M) over bar (w) = 270 000) solutions were determined by light scattering measurements over a range of temperatures (1-16degreesC), pressures (100-900 bar), and compositions (4.2-21.6 vol.-% polymer). The system phase separates upon cooling and T-cl was found to increase with rising pressure for constant composition. In the absence of special effects, this finding indicates positive excess volume for the mixing. Special attention was paid to the demixing temperatures as a function of pressure for different polymer solutions and the plots in the T-phi plane (where phi signifies volume fractions). The clo…

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…

Viscosity of Polymer Solutions over the Full Range of Composition: A Thermodynamically Inspired Two-Parameter Approach

The approach yields the following relation for the relative viscosity η rel as a function of polymer concentration c (mass/volume): ln ηrel = c/(1 + pc + qc2). Reduced concentrations c (defined as c = c[η], where [η] is the intrinsic viscosity) are used instead of c to incorporate thermodynamic information. The parameters p and q account for changes in the free volume of the solvent caused by the polymer. The analysis of literature data for seven very dissimilar systems discloses the following common feature: p > 0 and q < 0. This means that the curves in the plots of ln ηrel as a function of c are normally located below the tangent at low c and above it at high c. The values of p and q cor…

Intrinsic Viscosities of Polymer Blends: Sensitive Probes of Specific Interactions between the Counterions of Polyelectrolytes and Uncharged Macromolecules

In joint dilute aqueous solutions of pullulan (PUL) and poly(sodium 4-styrenesulfonate) (PSS-Na) the Na+ ions of the polyelectrolyte interact so favorably with the monomeric units of PUL that isolated coils containing both types of macromolecules are formed upon dilution. When water is replaced against a 1 M solution of NaCl, this effect dies out because of the large surplus of Na+ ions. On the other hand, if the water contains increasing amounts of the respective counterpolymer instead of NaCl, the formation of mixed isolated coils is fostered, where a further diminution of the intrinsic viscosities is caused by the lower the solvent quality. The molar mass of PSS-Na plays an important rol…

Calculation of shear influences on the phase separation of polymer blends exhibiting upper critical solution temperatures

Calculations were performed on the basis of a generalized Gibbs energy of mixing G γ, which is the sum of the Gibbs energy of mixing of the stagnant system and E s, the energy stored in the system during stationary flow. With increasing shear rate γ, the demixing temperatures shift to lower values (shear-induced mixing; diminution of the heterogeneous area), then to higher values (shear-induced demixing), and finally to lower values again before the effects fade out. The details of the rather complex phase diagrams resulting for a given shear rate are primarily determined by a band in the T/χ plane (χ = mole fraction) within which (∂2 E s/∂χ2) T UCST where they submerge. Bound to a suitable…

Solidification behavior of the theta system 2-propanol/poly(n-butyl methacrylate) I. Influences of thermoreversible gelation on stationary flow

Zero shear viscosities, η0, were determined by means of a magnetoviscometer for melts of poly(n-butyl methacrylate) (M = 8.7 to 450 kg/mol, T =53.5 to 200°C) and for concentrated solutions of the highest molecular weight sample in isopropanol (T = 34.8 to 131.5 °C). Master curves can be constructed in both cases if the reference temperature is set proportional to the gelation temperature of the particular fluid. Special intersegmental interactions (eventually leading to thermoreversible gelation) can above all be felt in η0 (T) and in M c , the critical molecular weight determined in plots of log η0 vs. log M. As the temperature is lowered, the behavior changes from WLF to Arrhenius, and M …

Detection of polymer compatibility by means of self-organization: poly(ethylene oxide) and poly(sodium 4-styrenesulfonate)

Information on the miscibility of different polymers A and B on a molecular level is important in many ways. However, along the traditional lines this knowledge is difficult and time consuming to achieve. The current study presents a simple alternative, based on the determination of the intrinsic viscosities (specific hydrodynamic volume of isolated coils) for blend solutions in a common solvent. In the case of incompatible polymers, isolated coils contain one macromolecule only, either A or B. In contrast, compatible polymers form mixed isolated coils, because of favorable interactions. The present investigation was carried out for the system water/poly(ethylene oxide)/poly(sodium 4-polyst…

Thermodynamically induced shear degradation

The shear degradation of polymers in semiconcentrated solutions is viewed as a function of solvent quality. It is shown that the deterioration of the thermodynamic quality of the solvent leads to a marked flow resistance due to an increasing number of contacts between the chains. This may be probed by viscosimetric measurements as well as by degradation experiments (“thermodynamically induced shear degradation”). For a detailed discussion of this phenomenon the experimental setup for the mechanochemical experiment is outlined first, followed by a survey of the kinetics of chain scission. Finally, experiments mostly obtained on polystyrene in the theta-solvent trans-decalin are discussed. Th…

On the Reasons for an Anomalous Demixing Behavior of Polymer Solutions

Some extraordinary solutions of polymers in single solvents exhibit two liquid/liquid critical points, one within the usual composition range and a second one in the range of moderate to high polymer concentration. This particularity was studied theoretically by means of a recently established approach, which accounts explicitly for chain connectivity and for the ability of polymer molecules to respond to changes in their environment by conformational rearrangements. On the basis of model calculations, it is shown that the anomalous demixing behavior, i.e., the emergence of a second critical point, is bound to the necessary but not sufficient condition that a thermodynamically very unfavora…

Effect of random copolymer additives on the interfacial tension between incompatible polymers

Interfacial tensions γ were measured for mixtures of poly(methylphenylsiloxane) (4 kg/mol) and poly(dimethylsiloxane) (24 kg/mol) in the absence and in the presence of small amounts of the random copolymer poly(dimethylsiloxane-ran-methylphenylsiloxane) (89 mol-% of dimethylsiloxane units, 28 kg/mol) from 25 to 110°C. Approximately 1 wt.-% of the copolymer additive suffices to reduce γ from ca. 2.2 to 1.6 mN/m. The time dependence of the apparent γ value in the course of the attainment of equilibria also indicates surface acivity. The hypothesis is formulated that the efficiency of the random copolymer for a reduction of γ is bound to the condition that it is only sparingly soluble in both …

Intrinsic Viscosities of Polyelectrolytes: Determination and Modeling of the Effects of Extra Salt

Based on early measurements of J. J. Hermans and co-workers (D. T. F. Pals, J. J. Hermans, Recl. Trav. Chim. Pays-Bas 1952, 71, 513-520; D. T. F. Pals, J. J. Hermans, J. Polym. Sci. 1950, 5, 733-734; D. T. F. Pals, J. J. Hermans, J. Polym. Sci. 1948, 3, 897-898), the present contribution demonstrates how primary data should be evaluated in order to obtain reliable intrinsic viscosities. This procedure yields detailed information on the changes of the intrinsic viscosities and of the corresponding viscometric interaction parameters caused by an increasing salinity of water. Both quantities decline from a maximum value in the pure solvent to a minimum value, which is approached in the limit o…

Using a self-constructed light scattering apparatus, the pressure dependence of the demixing temperature of solutions of PVC 20 000, PVC 37 000 and PVC 70 000 in THE/water was determined up to 1 000 bar for different compositions of the mixed solvent. (The numbers in the codes of the PVC specimens are their approximate molecular weights.) In contrast to the thetasolvents o-xylene and phenetole, the solubility decreases with increasing pressure for all molecular weights and compositions under investigation typically by about 1 K/100 bar. The evaluation of the experimental findings demonstrates that the volume fraction of the nonsolvent in the mixed solvent, φ, is the variable that governs ph…

Making Floryr–Huggins Practical: Thermodynamics of Polymer-Containing Mixtures

The theoretical part of this article demonstrates how the original Flory–Huggins theory can be extended to describe the thermodynamic behavior of polymer-containing mixtures quantitatively. This progress is achieved by accounting for two features of macromolecules that the original approach ignores: the effects of chain connectivity in the case of dilute solutions, and the ability of polymer coils to change their spatial extension in response to alterations in their molecular environment. In the general case, this approach leads to composition-dependent interaction parameters, which can for most binary systems be described by means of two physically meaningful parameters; systems involving …

Detection of the liquid ? liquid demixing by differential scanning calorimetry

From theoretical considerations it is concluded that the demixing temperatures of moderately concentrated polymer solutions should manifest themselves in a change of the slope of the corresponding DSC trace; the effects are expected to suffice for detection by means of the commercially available dual furnace instrument DSC-2C from Perkin-Elmer.

Rheology of a Lower Critical Solution Temperature Binary Polymer Blend in the Homogeneous, Phase-Separated, and Transitional Regimes

Small amplitude oscillatory shear rheology is employed in order to investigate the linear viscoelastic behavior of the lower critical solution temperature blend polystyrene/poly(vinyl methyl ether), PS/PVME, as a function of temperature and composition. At low temperatures, where the mixture is homogeneous, the dependence of the zero shear viscosity (η0) on concentration is measured and is well-described by means of a new mixing rule, based on surface fractions instead of volume fractions. Shift factors from time-temperature superposition (TTS) exhibit a Williams−Landel−Ferry (WLF) behavior. As the macrophase separation temperature is approached (the phase diagram being established by turbi…

Polyelectrolytes Revisited: Reliable Determination of Intrinsic Viscosities

The linear extrapolation of (hh0)/(h0c) towards c !0 constitutes the basis of traditional methods to determine intrinsic viscosities (h), where h is the viscosity of polymer solutions of concentration c and h0 is the viscosity of the pure solvent. With uncharged macromolecules this procedure works well; for polyelectrolytes it fails because of the pronounced non-linearity of the above dependence at high dilution resulting from the increasing electrostatic inter- actions. This contribution presents a new method for the determination of (h). It rests upon the application of the laws of phenomenological thermodynamics to the viscosity of polymer solutions and introduces a generalized intrinsic…

Preparative fractionation and characterization of polycarbonate/eugenol-siloxane copolymers

Bisphenol-A polycarbonate/eugenol-siloxane copolymers were fractionated at the preparative scale by the continuous polymer fractionation (CPF) technique. It is the first example of copolymer fractionation by CPF. The distribution of siloxane species across the fractions was assessed for copolymers differing in initial siloxane concentration and block length. On- and off-line combinations of size exclusion chromatography and infrared spectroscopy were used to analyze chemical composition (CC) of the unfractionated samples across the molecular weight distribution enabling comparison with the fractions. A polycarbonate-siloxane copolymer containing 10 wt% of very short siloxane blocks (dp = 2)…

Thermodynamic Properties of Liquid Oligomer-1/Oligomer-2 Systems: Transition from Mixtures of Low Molecular Weight Compounds to Polymer Solutions and Polymer Mixtures

Fractional dissolution of “solid” unsubstituted cellulose

Activated cellulose (Solucell, DP w = 1400) was extracted stepwise at room temperatures by means of mixed solvents consisting of N,N-dimethylacetamide (DMAc) and LiCl, starting with a salt concentration of 1 wt.-% and increasing it in increments of 1 wt.-% up to 7 wt.-%. Upon the regeneration of the thus obtained cellulose fractions by pouring the solutions dropwise into a large surplus of water, part of the mixed solvent is occluded in the polymer. For that reason the cellulose samples were purified by redissolving them in Ni-tren and by a second precipitation. This process, however, leads to pronounced polymer degradation. For that reason we have used a spinning nozzle to press the extrac…

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…

Phase diagrams were calculated for flowing solutions of polystyrene in trans-decahydronaphthalene assuming that the energy (Es) stored in the sheared state has to be added to the Gibbs energy of mixing; Es is computed from viscometric data (flow curves). The resulting phase diagrams exhibit two maxima in most of the cases instead of only one for the stagnant solutions. A comparison with experimental data (Part 1) shows that the calculated demixing behaviour agrees well for moderate shear rates and concentrations of the polymer. Deviations in the semidilute region, particularly for higher values, are a consequence of the fact that so far no reliable theoretical relation has been given for th…

Thermal diffusion of dextran in aqueous solutions in the absence and the presence of urea.

The Ludwig-Soret effect was studied for aqueous solutions of dextran in the temperature range 15T55 degrees C taking into account the effect of the addition of urea. In the absence of urea, the Soret coefficient S(T) changes sign; it is positive for T45.0 degrees C but negative for T45.0 degrees C. The positive sign of S(T) means that the dextran molecules migrate toward the cold side of the fluid; this behavior is typical for polymer solutions, whereas a negative sign indicates the macromolecules move toward the hot side. The addition of urea to the aqueous solution of dextran rises S(T) and reduces the inversion temperature. For 2 M urea the change in the sign of S(T) is observed at T = 2…

Die viskosität von polymerlösungen in der nähe von oberen und unteren entmischungstemperaturen

Die Viskositat flussiger Mischungen zeigt in der Nahe des kritischen Entmischungspunktes eine charakteristische Temperaturabhangigkeit. fur Polymerlosungen ist diese Erscheinung bei der oberen kritischen Entmischungstemperatur gut untersucht, wahrend in der Umgebung der unteren kritischen Entmischungstemperatur keine derartigen Messungen vorliegen. ES wurden Viskositatsmessungen im System Cyclohexan/Polystyrol (obere kritische Entmischungstemperatur) und im System Orthotrimethylformiat/Diathylather/Polystyrol (untere kritische Entmischungstemperatur) durchgefuhrt. Beim ersten System ergab sich qualitative Ubereinstimmung mit den Ergebnissen von Debye und Mitarbeitern. Die Untersuchungen in …

Reduction of the interfacial tension between ‘immiscible’ polymers: to which phase one should add a compatibilizer

Abstract The reduction of interfacial tension σ between polyethylene oxide (PEO) and polypropylene oxide (PPO) by either a triblock copolymer EO–PO–EO or a diblock copolymer styrene–EO was studied by means of the pendant drop method from 70 to 120°C. Time independent data correspond to stationary states and do not represent equilibrium information. The addition of the compatibilizer to the PPO phase is approximately twice as efficient as the addition to the PEO phase for both block copolymers. Knowing the concentration dependence of σ for one of the coexisting phases it is possible to forecast the effects resulting from the addition of the other phase by means of model considerations based …

Vitrification of polymer solutions as a function of solvent quality, analyzed via vapor pressures.

Vapor pressures (headspace sampling in combination with gas chromatography) and glass transition temperatures [differential scanning calorimetry (DSC)] have been measured for solutions of polystyrene (PS) in either toluene (TL) (10-70 degrees C) or cyclohexane (CH) (32-60 degrees C) from moderately concentrated solutions up to the pure polymer. As long as the mixtures are liquid, the vapor pressure of TL (good solvent) is considerably lower than that of CH (theta solvent) under other identical conditions. These differences vanish upon the vitrification of the solutions. For TL the isothermal liquid-solid transition induced by an increase of polymer concentration takes place within a finite …

A versatile viscometric method for the study of dissolved proteins, exemplified for casein micelles in ammoniacal solutions

Abstract Viscosities of casein solutions were measured within the dilute range in ammoniacal water and in saline solvents containing different amounts and different kinds of salt. All these data are modeled quantitatively by means of an approach accounting for the polyelectrolyte character of casein micelles. Two parameters are required: The intrinsic viscosity [ η ] and a viscometric interaction parameter β . The behavior of casein is compared with that of chain-like polyelectrolytes. For both polymers one observes a pronounced reduction of [ η ] with increasing salt concentration. However, for casein the decline of [ η ] is less pronounced by more than an order of magnitude and depends on…

Shear Induced Demixing and Rheological Behavior of Aqueous Solutions of Poly(N-isopropylacrylamide)

The interrelation between the phase separation behavior and the rheological performance of aqueous solutions of high molecular weight (M w = 1 600 kg/mol) poly(N-isopropylacrylamide) was investigated. The system demixes upon heating and the cloud point temperature, T cp decreases steadily with rising polymer concentration up to 10 wt.-%. The application of shear supports phase separation and reduces T cp markedly. This observation is interpreted in terms of destruction of intersegmental clusters formed in the quiescent state owing to favorable interactions. Intrinsic viscosities and Huggins coefficients as well as the viscosities, η at higher polymer concentrations are closely connected wit…

Temperature and pressure dependence of phase separation of trans-decahydronaphthalene/polystyrene solution

Abstract The cloud-point temperatures (Tcl’s) of trans-decahydronaphthalene (TD)/polystyrene (PS, Mw=270 kg/mol) solutions were determined by light scattering measurements over a range of temperatures (1–16 °C), pressures (100–900 bar), and compositions (4.2–21.6 vol% polymer). The system phase separates upon cooling and the Tcl was found to increase with the rising pressure for the constant composition. In the absence of special effects this finding indicates positive excess volumes. The special attention was paid to the demixing temperatures as a function of the pressure for the different polymer solutions and the plots in the T-volume fraction plane and P-volume fraction plane. The cloud…

Abnormal pressure dependence of the phase boundaries in TL/PEO/P(EO-b-DMS) ternary mixtures

The cloud-point temperatures (T-cl's) of both binary poly(ethylene oxide) (PEO)-poly(ethylene oxide-b-dimethylsiloxane) [P(EO-b-DMS)] and ternary[toluene/PEO/P(EO-b-DMS)] systems were determined by light scattering measurements at atmospheric pressure. The phase separation behavior upon cooling in the ternary system has been investigated at atmospheric pressure and under high pressure and compared to the phase behavior in the binary system. The phase transition temperatures have been obtained for all of the samples. As a result, the pressure induces compatibility in the binary mixtures, but for the ternary system, pressure not only can induce mixing but also can induce phase separation.

Shear-Induced Crystallization and Shear-Induced Dissolution of Poly(ethylene oxide) in Mixtures with Tetrahydronaphthalene and Oligo(dimethyl siloxane-b-ethylene oxide)

Cloud point temperatures (T cp ) and crystallization temperatures (T 1/s ) were measured at different constant shear rates for the ternary system tetrahydronaphthalene/poly(ethylene oxide)/oligo(dimethyl siloxane-b-ethylene oxide) using a rheo-optical device and in the case of T 1/s additionnaly a viscometer. This system enables for the first time a joint investigation of both transitions with a given mixture. Shear favors the homogeneous liquid state and the formation of crystals. T cp (liquid/liquid demixing, UCST) shifts to lower and T 1/s (liquid/solid, segregation of PEO) to higher temperatures by several degrees as the shear rate, γ, is increased up to 500 s -1 . The normalized shift …

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…

On the significance of molecular surfaces and thermodynamic interactions for the excess viscosities of liquid mixtures

The viscosities η of homogeneous binary mixtures of liquids are usually approximated as In η = ϕ1 In η1 + ϕ2 In η2 where ϕi and ηi are the volume fractions and the viscosities, resp., of the i-th pure substance; the behavior of real systems is then discussed in terms of Δ In η, the deviations from the above reference behavior. Here a semi-empirical approach is presented according to which volume fractions are replaced by the surface fractions Ωi to create a more realistic reference state, and the thermodynamic interaction parameter g is taken into account. The new equation reads (expressing it for practical purposes still in the terms of ϕi) γ is a geometric factor, measuring the difference…

Asymmetric polysulfone and polyethersulfone membranes: effects of thermodynamic conditions during formation on their performance

Abstract Membranes of polysulfone (PSU) and polyethersulfone (PES) were prepared from ternary and quaternary mixtures containing N , N -dimethylformamide (DMF) as solvent, water as non-solvent, and acetone (AC) as additive. The conditions for phase inversion and the desired phase separation mechanisms were selected on the basis of the phase behavior determined for the solvent/non-solvent/polymer systems. The influences of the composition of the casting solution, of the support, and of film thickness on structure and permeation properties of the membranes were analyzed by scanning electron microscopy (SEM) plus flux and separation experiments. The mechanisms of phase inversion that should pr…

Crystallization kinetics of poly(ethylene oxide) from its melt and from mixtures with tetrahydronaphthalene and oligo(ethylene oxide-block-dimethylsiloxane)

The crystallization of poly(ethylene oxide) (PEO) from the pure state and from its mixtures with oligo(dimethyl siloxane-b-ethylene oxide) (COP) and tetrahy- dronaphthalene (THN) was investigated. The crystallization kinetics was studied iso- thermally and nonisothermally with an automated device that monitored the light passing through the corresponding liquids as functions of time and/or temperature. The rate was strongly influenced by the concentration of COP in the mixture. A substantial decrease in the induction time (the time required for the onset of crystallization) and a considerable shift in the crystallization temperature (the transition from a liquid state to a solid state) to h…

Polymer Incompatibility Caused by Different Molecular Architectures: Modeling via Chain Connectivity and Conformational Relaxation

The calculation of phase diagrams for blends of linear and branched polymers made up of identical monomeric units is modeled using an approach that subdivides the mixing process into two steps: i) contact formation between the different components, keeping their chain conformations and the volume of the system constant; and, ii) relaxation of the macromolecules into their equilibrium state by molecular rearrangements. It is assumed that step (ii) causes shape-induced polymer incompatibility and that the degree of branching can be quantified in terms of the volumes the isolated coils of the branched polymer occupy in relation to the volume the linear product with the same molecular weight oc…

Intrinsic viscosities of polyelectrolytes in the absence and in the presence of extra salt: Consequences of the stepwise conversion of dextran into a polycation.

Abstract Viscosities of dilute polymer solutions were measured in capillary viscometers for samples varying in their fraction f of charged units from 0.00 to 0.90. The dependence of the logarithm of the relative viscosity on polymer concentration c is in all cases reproduced quantitatively by three characteristic parameters: [ η ], the intrinsic viscosity; B , a viscometric interaction parameter (related to the Huggins constant); [ η ] , a parameter required only for polyelectrolytes at low concentrations of extra salt. In pure water [ η ] increases more than 80 times as the fraction f rises from zero to 0.90 and [ η ] starts from zero and goes up to ≈71 mL/g. Upon the addition of NaCl [ η …

Viscometry of polyelectrolyte solutions: Star-like versus linear poly[[2-(methacryloyloxy)ethyl] trimethylammonium iodide] and specific salt effects

Abstract The intrinsic viscosities, [η], of the 3-arm star polyelectrolyte in pure water are for a given molar mass considerably lower than for the linear product because of the higher monomer concentration and charge density in isolated coils. These effects are much more pronounced than in the case of uncharged macromolecules. Extra salt (NaCl, NaI, CaCl2) reduces the solution viscosities of the 3-arm star polymer less than of the linear product. The transition of [η] from the value in pure water to the minimum saturation value at high salt concentrations follows a Boltzmann sigmoid. In saline solvents the changes of the viscosities with rising polymer concentration depend strongly on the …

Calorimetric and structural investigation of the interaction between bovine serum albumin and high molecular weight dextran in water.

This work studies specific interactions between a small globular protein and a highly flexible, branched polysaccharide using differential scanning calorimetry (DSC), circular dichroism (CD), fluorescence, and turbidimetry measurements. It uses the system water/bovine serum albumin (BSA)/dextran (D 2000) as a model. Dextran molecules are able to form interpolymeric complexes with BSA in water at both low and high temperatures if the polysaccharide is in excess and if the protein exists in its associated state. It leads to a partial destabilization of the secondary and tertiary structures of the protein and an additional exposure of the hydrophobic tryptophan residues to the surface of globu…

An apparatus is presented for the precise measurement of vapour pressures. It is tested with diethyl ether and applied to the system tert-butyle acetate/polystyrene (weight-average molecular weight Mw = 110000) up to polymer concentrations of ca. 60 wt.-% in the temperature range from 10 to 90°C; by means of the Redlich-Kister equation the results can well be described analytically. The data are evaluated to yield the Flory-Huggins parameter in the subsequent article in conjunction with other experimental information.

Solutions of poly (decyl methacrylate) in isooctane (2,2, 4-trimethylpentane) show lower critical solution temperatures (LCST) that lie well below the thermal degradation of the polymer. The corresponding exothermal theta-temperature (from the Shultz-Flory plot) amounts to 210°C. The increase in solvent quality by pressure turns out to be very pronounced (d Tc/dp ≈ +1 K/bar). With solutions of the polymer in motor oils, high temperature demixing is unlikely to occur below their boiling point. The theoretical evaluation of published experimental data for 11 different systems exhibiting LCSTs demonstrates the following: Under the equilibrium vapour pressure of the solution high temperature de…

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…

Investigations with ca. 100 organic liquids in a temperature range from −20°C to 90°C result in a survey of the solubility behaviour of PVC. The experimental results were compared with the predictions of the solubility parameter theory: Accepting δ = 9,75 (cal/cm3)1/2 as the solubility parameter for PVC, all solvents (except ketones in which PVC is soluble independent of their solubility parameters) are located within the range of δPVC ± 0,75. Only three of the 100 liquids examined turned out to be (endothermal) theta-solvents, namely the aromatic solvents o-xylene, phenetole and dimethyl phthalate. The theta-temperatures in o-xylene and phenetole were determined viscometrically by means of…

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, …

Continuous polymer fractionation of poly(methyl vinyl ether) and a new Kuhn-Mark-Houwink relation

Continuous polymer fractionation (CPF) — a new large-scale method — was applied to the technical poly(methyl vinyl ether) (PVME) using toluence as solvent and petroleum ether as non-solvent. Two different devices served as fractionation apparatus, namely a column packed with glass beads and a set of mixer-settler extractors. Advantages and draw-backs of these devices are discussed. The experiments yielded numerous PVME fractions, varying in molar mass from 22 to 87 kg/mol and in molecular non-uniformity U = (M¯w/Mn) – 1 from 0,25 to 0,41 according to gel-permeation chromatography as compared with ca. U = 1,30 for the starting material. The following Kuhn-Mark-Houwink relation was establishe…

The variation of the Huggins coefficient KH with the relative molecular mass M of the polymers was measured for solutions of polystyrene and of polyisobutylene and found to be most pronounced in the case of thermodynamically good solvents but vanishing at the theta-temperature, where the individual curves kH (T; M) intersect with each other. The experimental results are interpreted as a consequence of the rheological inequality of inter- and intra-molecular contacts between polymer segments. A model is presented according to which kH should be a linear function of M−(a−0,5), where a is the exponent of the intrinsic viscosity-relative molecular mass relationship (Kuhn-Mark-Houwink). The eval…

Intrinsic Viscosities of Polymer Blends and Polymer Compatibility: Self-Organization and Flory-Huggins Interaction Parameters

Characterization of melt-polymerized polycarbonate: preparative fractionation, branching distribution and simulation

Melt-polymerized bisphenol-A polycarbonate materials characterized by a low degree of branching were fractionated according to molecular weight by the continuous polymer fractionation (CPF) method. The distribution of two types of end-groups and in-chain salicylate moieties arising from thermal rearrangement reactions were assessed across the molecular weight distribution by analysis of the fractions. Experimentally determined branching densities of the fractions agreed well with a molecular simulation based on a random sampling polycondensation model. Both simulation and experiments showed that the branching density increases with molecular weight in the experimentally accessible range. (C…

In order to investigate the influences of different end-groups on oligomer miscibility with other substances, oligo(propylene glycol)s bearing OH groups (OPG-OH) studied in the previous paper2, were acetylated at both ends (OPG-AC). The limits of miscibility of OPG-AC with oligo(dimethylsiloxane) (ODMS) were measured turbidimetrically. A simple and reliable method for the determination of the critical points from turbidity data is presented. The observed upper critical temperatures (Tc) increase with degree of oligomerization of ODMS (ranging from 1 to 5), whereas Tc shows a minimum when the degree of oligomerization of the OPG-AC is raised (from 1 to 57,5). For lower mol. wt. oligoglycols,…

Dependence of solvent quality on the composition of copolymers: experiment and theory for solutions of P(MMA-ran-t-BMA) in toluene and in chloroform.

The interaction of toluene with P(MMA-ran-t-BMA) and with the corresponding homopolymers was determined via vapor pressure measurements at 30, 50 and 70 °C. A unified thermodynamic approach served for the modeling of the results. It is capable of describing the behavior of the different solutions by means of two adjustable parameters, one representing the effective number of solvent segments and the other accounting for the interactions between the components. The solvent quality of toluene passes a maximum, a minimum and another maximum upon an increase of the t-BMA content of the copolymer at all temperatures. A similar behavior is discernable from vapor pressure data of chloroform publis…

Associative behaviour of κ-carrageenan in aqueous solutions and its modification by different monovalent salts as reflected by viscometric parameters

Abstract The viscometric behaviour of κ-carrageenan in aqueous solutions and in the presence of monovalent salts was investigated at 25 °C. Coil, helix or double helix conformations were induced by cooling hot κ-carrageenan solutions under appropriate ionic conditions. A new viscometric approach was used for modeling the behaviour of κ-carrageenan solutions. The intrinsic viscosity, [η], is markedly changed by the presence of different monovalent salts (NaCl, NaI and CsI). In pure water, the intrinsic viscosity amounts to 48 dL·g−1. In 0.1 M NaCl solutions (single helix state) [η] is 6.2 dL·g−1, whereas in 0.1 M NaI (double helix conformation) it is approximately twice as large. In 0.1 M Cs…

On the Role of Drop Break Up for Coalescence Processes and Morphology Development in Polymer Blends under Shear

Drop sizes and drop-size distributions were determined as a function of time at constant shear rates, γ, by means of an optical shear cell in combination with an optical light microscope after preshearing the samples at high γ. The systems under investigation were PIB 3/PDMS 152 (PIB:  polyisobutylene, PDMS:  poly(dimethylsiloxane), numbers:  average molar masses in kg/mol) and COP 26*/PDMS 48 (COP:  poly(dimethyl-co-methylphenylsiloxane), asterisk:  apparent molar mass); all measurements refer to 25 °C. Systems and conditions were chosen such that shear rates in the vicinity of the intersection of the coalescence and the break up curves become experimentally accessible. Under these conditi…

CPF: A New Method for Large Scale Fractionation

The paper demonstrates how the Continous Polymer Fractionation (CPF) functions and how it has been applied to polyvinylchlorid.

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

Molar Mass Distribution and Size of Hydroxyethyl Starch Fractions Obtained by Continuous Polymer Fractionation

By the use of continuous polymer fractionation (CPF) the initial polymer can be separated into fractions of different molar masses, which makes it possible to obtain hydroxyethyl starch (HES) fractions tailor-made for specific application. Two samples of HES (HES A and HES B) were fractionated by means of CPF. By size-exclusion chromatography-multi-angle laser light-scattering-differential refractive index (SEC/ MALLS/DRI) measurements it was shown that CPF is able to remove the low-molar-mass components and to adjust the samples to various desired molar masses with lower polydispersities than the original samples. In terms of the weight-average mean molar mass M w , the sol fractions have …

Reduction of the Interfacial Tension between Poly(dimethylsiloxane) and Poly(ethylene oxide) by Block Copolymers:  Effects of Molecular Architecture and Chemical Composition

Interfacial tensions σ were measured by means of the sessile drop method for mixtures of poly(ethylene oxide) [PEO, Mw = 41 kg/mol] with five samples of poly(dimethylsiloxane)s [PDMS, Mw ranging fr...

For the three different cases (R=polybutadiene, polypropylene oxide and EPDM) the isothermal cloud point curves of the system styrene/polystyrene/rubber (S/PS/R) show that at 25°C a decomposition into two phases occurs already in the presence of a few percents of polystyrene and rubber. By separating the phases (centrifuge) and analysis of coexisting phases, tie lines and thus critical points could be fixed. Evaluation of the results was made on the basis of the Flory and Huggins theory by means of approximations given for such systems by Scott. The interaction parameters resulting for 25°C are well in agreement with literature data—as far as available. By means of the approximations mentio…

On the effect of pressure on the phase transition of polymer blends and polymer solutions: Oligostyrene–n-alkane systems

Critical temperatures of some binary solutions of weakly interacting low molecular weight polystyrenes dissolved in linear alkanes (oligoethylenes) were measured over the range 0.1 to 100 MPa. While (dT/dP)crit along the upper critical solution (UCS) locus for a “typical blend” is positive, and for the “ typical solution” can be either positive or negative (but is usually negative), there is no essential difference between blend and solution. Rather, the difference in sign is a consequence of the location of the hypercritical point (that point in (T,P)crit space where (dT/dP)crit changes sign, [(dT/dP)crit = 0 and (d2T/dP2)crit>0], also called the double critical point, DCP), which is norma…

The countercurrent extraction method recently developed for the continuous polymer fractionation (CPF) was applied to linear polyethylene (Mw = 55 kg/mol; Mn = 16,7 kg/mol). At temperatures higher than 130°C, moderately concentrated solution of polyethylene were extracted to remove the low-molecular-weight components. Discontinuous fractionation experiments served to detect the best suited solvents. Diphenyl ether was chosen to demonstrate that the present extraction can be performed even with the same single solvent used to prepare the feed. For very high-molecular-weight polymers, mixed solvents are, however, normally better than single ones, since they allow an easier tailoring of thermo…

Phase diagrams calculated for sheared ternary polymer blends

Abstract On the basis of the generalized Gibbs energy of mixing G γ (which is the sum of the Gibbs energy for zero shear and the energy the system stores in steady flow) phase diagrams were calculated as a function of shear rate γ for ternary model blends. This modelling uses simple equations for the description of the stagnant systems (Flory-Huggins) and for the contributions resulting from flow. Surface and alignment effects are neglected. A new procedure, which does not require the derivatives of G γ with respect to composition, was used to that end. Choosing typical values for the binary interaction parameters and molar masses, four classes of ternary systems were studied in greater det…

Unified Thermodynamic Modeling of Polymer Solutions: Polyelectrolytes, Proteins, and Chain Molecules

The thermodynamic description of the systems specified in the title requires in general dissimilar theories. This contribution presents an approach that is capable of modeling all of them with a maximum of three adjustable parameters. The Ansatz starts from the Flory–Huggins theory and extends it in a 2-fold manner: The number of segments assigned to the solvent is no longer one but treated as an adjustable parameter to account for the differences in the molecular geometries and in the free volumes of the components. Furthermore, the modeling allows for effects resulting from ternary contacts of the solvent/polymer/polymer type. Examination of the acquired thermodynamic expressions by means…

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

Calculation of miscibility behavior of multinary polymer blends

A method for the calculation of phase diagrams (tie lines and binodal, spinodal, critical points and their stability) based exclusively on the Gibbs energy of mixing, δG, is presented which does not require the calculation of the derivatives with respect to the composition. The method is demonstrated for ternary mixtures of two homopolymers and the corresponding copolymer, and for quaternary and quinternary blends of five polymers exhibiting a closed miscibility gap. The advantages of the presented method become most obvious in the mathematical description of measured phase diagrams, where complex composition dependencies of the interaction parameter are observed.

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…

Polymer‐Solvent Interaction Parameters

Zur Thermodynamik der enthalpisch und der entropisch bedingten Entmischung von Polymerlösungen

Composition-dependent Flory-Huggins parameters: molecular weight influences at high concentrations

Flory-Huggins interaction parameters X were determined by means of equilibrium vapor pressures (measured via a combination of a head-space sampler with a gas chromatograph) and light scattering as a function of composition and temperature for the systems cyclohexanone/polystyrene [CHO/PS] and cyclohexanone/poly(butyl methacrylate) [CHO/PBMA]. The investigation of molecular weight influences on X with the system CHO/PBMA demonstrates that they persist almost up to the pure polymer. In order to rationalize this result, it is postulated (in accord with experimental findings and theoretical predictions) that the dimensions of polymer chains may vary upon the addition of solvent even in highly c…

Binary Interaction Parameters, Ternary Systems: Realistic Modeling of Liquid/Liquid Phase Separation

Random Copolymers:  Their Solution Thermodynamics as Compared with That of the Corresponding Homopolymers

Vapor pressure data (at 50 °C) of solutions of poly(methyl methacrylate) [PMMA], polystyrene [PS], and poly(styrene-ran-methyl methacrylate) [P(S-ran-MMA)], with different weight fractions f of styrene units, in either CHCl3, acetone [AC], methyl acetate [MeAc], or toluene [TL] were evaluated with respect to the dependence of the Flory−Huggins interaction parameter χ on polymer concentration and on f. For all solutions under investigation, χ varies considerably with the composition of the mixture, and only for four of them [CHCl3/PS, AC/PMMA, MeAc/PS, and TL/P(S-ran-MMA) f = 0.5] is this dependence linear; another four systems exhibit a minimum [CHCl3/PMMA, CHCl3/P(S-ran-MMA) f = 0.5, TL/PM…

Shear induced mixing/demixing: blends of homopolymers, of homopolymers plus copolymers, and blends in solution

Shear may shift the phase boundary towards the homogeneous state (shear induced mixing, SIM), or in the opposite direction (shear induced demixing, SID). SIM is the typical behavior of mixtures of components of low molar mass and polymer solutions, SID can be observed with solutions of high molar mass polymers and polymer blends at higher shear rates. The typical sequence with increasing shear rate is SIM, then occurrence of an isolated additional immiscible area (SLD), melting of this island into the main miscibility gap, and finally SIM again. A three phase line originates and ends in two critical end points. Raising pressure increases the shear effects. For copolymer containing systems S…

Basis for the Preparative Fractionation of a Statistical Copolymer (SAN) with Respect to Either Chain Length or Chemical Composition

The possibilities to fractionate copolymers with respect to their chemical composition on a preparative scale by means of the establishment of liquid/liquid phase equilibria were studied for random copolymers of styrene and acrylonitrile (SAN). Experiments with solutions of SAN in toluene have shown that fractionation does in this quasi-binary system, where demixing results from marginal solvent quality, take place with respect to the chain length of the polymer only. On the other hand, if phase separation is induced by a second, chemically different polymer, one can find conditions under which fractionation with respect to composition becomes dominant. This opportunity is documented for th…

By means of data from critical demixing and vapour pressure measurements and by inverse gas chromatography, including the results of published light scattering measurments, a consistent picture is obtained for the entire dependence of the Flory-Huggins parameter χ on the weight fraction w2 of the polymer and on the temperature T for the system tert-butyl acetate/polystyrene. Within the entire T-range (ca. 0°C – 140°C), χ increases stronger than exponentially with w2, the rise being the larger the larger χH (the enthalpy contribution to χ) becomes in the limit of infinite dilution. At sufficiently high temperatures (≳ 50°C), χH changes its sign from negative to positive as w2 is raised. This…

Potassium Triggers a Reversible Specific Stiffness Transition of Polyethylene Glycol

We use plasmon rulers made from two connected gold nanoparticles to monitor the conformation and stiffness of single PEG molecules and their response to cations. By observing equilibrium fluctuations of the interparticle distance, we obtain the spring constants or stiffness of the connecting single-molecule tether with pico-Newton sensitivity. We observe a transition of the PEG molecules’ extension and stiffness above about 1.2 mM K+ ion concentration which is specific to potassium ions. Molecular dynamics simulations reveal the formation of crown-like structures as the most likely molecular mechanism responsible for this specific effect.

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…

Ionic polymers based on dextran: hydrodynamic properties in aqueous solution and solvent mixtures.

Hydrodynamic properties of a series of ionic polysaccharides with different charge density but the same molecular weight have been evaluated in salt-free aqueous solution and aqueous/organic solvent mixtures by means of capillary viscometry. The polyelectrolytes investigated contain quaternary ammonium salt groups, N-ethyl-N,N-dimethyl-2-hydroxypropylammonium chloride, attached to a dextran backbone. The experimental viscometric data have been plotted in terms of the Wolf method. The results show that the experimental data fit well with this model and allow the calculation of intrinsic viscosities and other hydrodynamic parameters, which provide new information about the dependence of the p…

Consequences of linking charged and uncharged monomers to binary copolymers studied in dilute solution. Part II: Non-additivity effects in the viscometric behavior

Abstract Copolymers of ethylene oxide (EO) and N,N-dimethyl aminoethyl methacrylate (R) or [2-(methacryloyloxy)ethyl] trimethylammonium iodide (R+) were studied in dilute solution: P ( EO p – b – R n ) ( I ) , P(Rn(1−f) – ran – R+n f) ( II ) , and P ( EO p – b – R n + ) ( III ) ; n and p give the numbers of monomers and f is the degree of charging. For II (variable f) and III (variable n) the effects of charging on the intrinsic viscosities [η] are well described by Boltzmann sigmoids. The deviation of [ η ] from [ η ] add (calculated from the corresponding homopolymer data, assuming additivity of the individual contributions) are quantified by σ = [ η ] / [ η ] add - 1 measuring the segreg…

Extension of the Concept of Intrinsic Viscosities to Arbitrary Polymer Concentration: From [η] via {η} to Intrinsic Bulkiness

The capabilities of an alternative definition of intrinsic viscosities [η] published some years ago is being studied by means of comprehensive viscometric data reported in the early days of polymer science. It introduces the generalized intrinsic viscosity {η} as the specific hydrodynamic volume at arbitrary polymer concentration c. {η} quantifies the size of the flow unit and decreases monotonously for T ≫ Tg (glass transition temperature) as a function of c but passes a pronounced minimum as T approaches Tg. In the limit of the pure polymer melt, {η} becomes ; this newly introduced property is termed intrinsic bulkiness, by analogy to the intrinsic viscosity, and provides noncalorimetric …

Shear influence on the phase separation of oligomer blends

Shear influences on the phase separation behaviour of four different blends of ethylene glycol/propylene glycol oligomers, exhibiting upper critical solution temperatures, were investigated. Cloud point curves at rest (turbidity measurements) are reported for all systems, spinodal conditions (light scattering) and tie-lines (analysis of the coexisting phases) are given for some examples. Phase diagrams under shear were obtained from rheological data. They demonstrate that the demixing temperatures of systems where both glycols bear OH end-groups are lowered up to ca. 1°C by shear rates of 1000s−1; the critical composition, generalized to the non-equilibrium conditions of flow, is markedly s…

Über die möglichkeiten zur bestimmung von mischungsenthalpien und -volumina aus der molekulargewichtsabhängigkeit der kritischen entmischungstemperaturen und -drücke am beispiel des systems trans-decahydronaphthalin/polystyrol

Cloud-point curves and critical curves (Tc = f(p)) have been measured for the system trans-decahydronaphthalene/polystyrene and three different molecular weights of the polystyrene component (2,5 · 106; 3,9 · 105; 1,1 · 105). It turned out that by variation of the pressure the metastable region can be investigated up to the spinodal curve. A comparison of the theta-temperatures and the enthalpy contributions χH (to the Flory-Huggins interaction parameter χ) resulting from the measured critical temperatures according to Shultz-Flory, with the corresponding directly obtained literature data, demonstrates that, although the extrapolation of Tc to infinite molecular weight is feasible, χH obtai…

Excess viscosity and glass transition

Abstract Literature data on the viscosity of solutions of poly(butyl methacrylate) (PBMA) and poly(methyl methacrylate) (PMMA) in diethyl phthalate (DEP) for different temperatures, including the range around and below T g , the glass transition temperatures of the pure polymers, were evaluated by means of an approach that uses surface fractions as composition variables. The discussion of these results together with information on solutions of the isomeric polymers, poly(vinyl acetate) (PVAc) and poly(methyl acrylate) (PM(A)), in the same solvent testifies that the previously published relations remain valid for T T g . They enable the determination of viscosities of the pure polymers below…

Specific features of the interfacial tension in the case of phase separated solutions of random copolymers

Abstract Phase diagrams (cloud point curves, critical points, tie lines for constant critical composition) and interfacial tensions as a function of temperature were measured for solutions of two random copolymers: poly(dimethylsiloxane- ran -methylphenylsiloxane) [I] and poly(styrene- ran -acrylonitrile) [II]. Acetone and anisole served as solvents for I and toluene for II; all solutions exhibit UCSTs between 300 and 310 K. The phase separation behavior can be well modeled if one accounts for the molecular and chemical non-uniformities of the random copolymers used in this study. The interfacial tensions σ differ most markedly from that of comparable homopolymer solutions in their correlat…

45 g of poly(acrylic acid) (PAA 500) with a trimodal molar mass distribution (Mw = 500 kg/mol, (Mw/Mn) −1 = 2.33) were fractionated by means of CPF (continuous polymer fractionation) in two steps using 1,4-dioxane as solvent. The counter-current extraction was performed in a glass column (length: 190 cm, diameter: 1.5 cm) filled with a network of wires, introducing the feed 75 cm from its upper end. The distribution of the highest molar mass fraction (Mw = 760 kg/mol) is unimodal and comparatively narrow ((Mw/Mn) −1 = 0.66). Indications exits that fractionation is not only taking place with respect to molar mass but also with respect to tacticity. Mit Hilfe der kontinuierlichen Polymerfrakt…

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…

The Efficiency of Polymer Fractionation at Lower Critical Solution Temperatures

The efficiency of a single fractionation step (i.e. of the partition of a given polymer sample between the coexisting phases which form when its solution demixes) is governed by the variation of the mass ratio of the individual P-mers with chain length. These dependences have been measured for the system dimethoxymethane/diethylether/ polystyrene which exhibits lower critical solution temperatures by means of the Baker-Williams method and by means of g.p.c. Their comparison with the results of previous investigation on systems showing upper critical solution temperatures reveals no thermodynamic differences in the aptitude of upper and lower critical solution temperatures for fractionation …

Polymer-Polymer Interaction: Consistent Modeling in Terms of Chain Connectivity and Conformational Response

An approach developed for the modeling of polymer solutions is extended to polymer blends. It accounts explicitly for the fact that the segments of a given macromolecule cannot spread out over the entire volume of the system (chain connectivity) and that the space a polymer molecule occupies may change after contact formation between the components of a mixture (conformational response ζ). The validity of the equation obtained for the Flory-Huggins interaction parameter between polymers is tested by means of critical data published for the system PVME/PS. The measured phase diagrams can be modeled equally well by two limiting assumptions concerning the temperature dependence of the conforma…

Self-assembling of poly(aspartic acid) with bovine serum albumin in aqueous solutions

Abstract Macromolecular co-assemblies built up in aqueous solutions, by using a linear polypeptide, poly(aspartic acid) (PAS), and a globular protein, bovine serum albumin (BSA), have been studied. The main interest was to identify the optimum conditions for an interpenetrated complex formation in order to design materials suitable for biomedical applications, such as drug delivery systems. BSA surface possesses several amino- and carboxylic groups available for covalent modification, and/or bioactive substances attachment. In the present study, mixtures between PAS and BSA were investigated at 37 °C in dilute aqueous solution by viscometry, dynamic light scattering and zeta potential deter…

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…

The viscosities of moderately concentrated solutions of poly(butyl methacrylate)—Mw = 1820 kg/mol–in the thermodynamically good solvent toluene and in the theta solvent 2-propanol were measured up to pressures of 2000 bar as a function of shear rate in the temperature interval from 40 to 70°C. Both systems obey Graessley's equation so that it is possible to obtain the following rheological parameters in addition to the zero-shear viscosity η0 from the dependences . η can be split into an entanglement part ηent plus a frictional contribution ηfric, and the characteristic viscometric relaxation time τ0 becomes accessible. The present results demonstrate that the application of pressure raises…

Bimodal drop size distributions during the early stages of shear induced coalescence

Drop sizes and drop size distributions were determined by means of an optical shear cell in combination with an optical microscope for the systems polyisobutylene/poly(dimethylsiloxane) (I) and poly(dimethyl-co-methylphenylsiloxane)/poly(dimethylsiloxane) (II) at low concentrations of the suspended phases and at different constant shear rates ranging from 10 to 0.5 s-1 . After pre-shearing the two-phase mixtures (I: 50 s-1; II: 100 s-1) for the purpose of producing small drop radii, the shear rate was abruptly reduced to the preselected value and coalescence was studied as a function of time. In all cases one approaches dead end drop radii, i.e. breakup is absent. The drop size distribution…

Preferential evaporation of precipitants from polymer solutions in mixed solvents

Partial vapor pressures were measured for the volatiles of solutions of polysulfone or polyethersulfone in mixtures of N,N-dimethylformamide (DMF, solvent) and water or acetone (precipitants) by means of headspace gas chromatography. The results demonstrate that the enrichment of water in the gas phase increases exponentially with rising polymer concentration, in contrast to that of acetone which remains constant. The reinforced expulsion of water resulting from the presence of polymers is theoretically conceivable and should be useful in the field of separation techniques.

The present paper demonstrates theoretically as well as experimentally, that the gravitational field of the earth produces very pronounced changes in the equilibrium concentration of dissolved macromolecules with height, under near critical conditions. Thus it could be observed for the system polystyrene/cyclohexane that the equilibrium concentration at the bottom of a tube is approximately three times that at a height of 10 cm, under such conditions. In the case of polymolecular samples the sedimentation is associated with a corresponding fractionation. Die vorliegende Arbeit zeigt sowohl theoretisch als auch experimentell, das das Schwerefeld der Erde unter annahernd kritischen Bedingunge…

Continuous fractionation and solution properties of PIB. II. CPF optimization

The quality of polymer fractionation depends on the choice of the mixed solvent as well as on the particular conditions of operating the continuous countercurrent extraction. With a polyisobutylene (PIB) sample of medium molecular weight Mw = 98,400 g/mol and U = (Mw/Mn) − 1 = 1.4 plus the mixed solvents toluene/2-butanone (TOL/MEK) and n-heptane/2-butanone (HEP/MEK) (both giving comparably good fractionation in equilibrium experiments), possible ways to optimize the CPF were tested. The mixed solvent HEP/MEK turns out to be superior to TOL/MEK for kinetic reasons. Due to the larger gap between its density and that of the pure polymer, the coexisting phases can still move through the column…

Synergistic behavior of poly(aspartic acid) and Pluronic F127 in aqueous solution as studied by viscometry and dynamic light scattering.

Abstract Pluronic F127/poly(aspartic acid) mixtures were investigated in dilute solutions by viscometry and dynamic light scattering. The two polymers were chosen due to well known applications in biomedical field, taking into account the final purpose (the use of the complex structure as drug delivery systems). The central item was to identify the possibility of complexation between the poly(carboxylic acid) and a non-ionic polymer and to investigate the conditions of the interpolymer complex formation. The ability of Pluronic F127 to form micelle is well known. Poly(aspartic acid), as a polycarboxylic acid with resemblance with polyacrylic acid, can act as dispersant, antiscalant, superab…

The demixing behavior of 20 representatives of the system oligo(dimethylsiloxane)/oligo(propylene glycol) (ODMS/OPG)1 is investigated at pressures up to 1 500 bar. The degrees of oligomerization range from 2 to 5 for the first and from 1 to 57, 6 for the second component. The experimental results are compared with those for the previously studied system oligoisobutene/oligo(propylene glycol) (OIB/OPG). In both cases the observed upper critical temperatures Tc increase with the number of monomeric units of the less polar component, whereas they run through a minimum when the number of monomeric units of the glycol is raised. For the present system the Tc values are found to be considerably h…

Interfacial tension between coexisting polymer solutions in mixed solvents and its correlation with bulk thermodynamics: phase equilibria (liquid/gas and liquid/liquid) for the system toluene/ethanol/PDMS

Abstract Vapor pressures, phase equilibria and interfacial tensions σ were measured for solutions of poly(dimethylsiloxane) (PDMS, M w [equals]75 kg/mol and M n [equals]50 kg/mol) in mixed solvents of toluene (TL) and ethanol (EtOH) at 30, 40, 50 and 60 °C. The experimental ternary phase diagrams can be modeled quantitatively from the determined concentration and temperature dependent binary interaction parameters χ ij if the experimentally inaccessible composition dependence of χ EtOH/PDMS is adjusted. The relations between σ and the equation of state of the system differ from that applying to single solvents. The exponents as well as the amplitude prefactors of the corresponding scaling l…

Thermodynamics of Phase Behavior in PEO/P(EO-b-DMS) Homopolymer and Block Co-Oligomer Mixtures under Pressure

The cloud-point temperatures (T-cl's) of poly(ethylene oxide) (PEO) and poly(ethylene oxide)-block-polydimethylsiloxane (P(EO-b-DMS)) homopolymer and block-oligomer mixtures were determined by turbidity measurements over a range of temperatures (105 to 130degrees), pressures (1 to 800 bar), and compositions (10-40 wt.-% PEO). The system phase separates upon cooling and T-cl was found to decrease with an increase in pressure for a constant composition. In the absence of special effects, this finding indicates negative excess volumes. Special attention was paid to the demixing temperatures as a function of the pressure for the different polymer mixtures and the plots in the T-phi plane (where…

Interfacial tension and interaction parameters

In view of various contradictory theoretical equations relating the interfacial tension σ between phase-separated polymer solutions to the Flory-Huggins interaction parameter of the system, the idea that σ should depend on the extent of the ‘hump’ in the concentration dependence of the Gibbs energy of mixing was studied. This investigation is based on 12 series of σ( T ) measurements reported in the literature and on additional experiments for the system cyclohexane/polystyrene. To quantify the extent of the ‘hump’, a reduced ‘hump energy’ ɛ was introduced and its value calculated for different temperatures from the measured critical data of the systems. The analysis of the entire experimen…

PEO/CHCl3. Crystallinity of the Polymer and Vapor Pressure of the Solvent. Equilibrium and Nonequilibrium Phenomena

Vapor pressures were measured for the system CHCl3/PEO 1000 (PEO stands for poly(ethylene oxide) and 1000 for Mw in kg/mol) at 25 °C as a function of the weight fraction w of the polymer by means of a combination of headspace sampling and gas chromatography. The establishment of thermodynamic equilibria was assisted by employing thin polymer films. The degrees of crystallinity α of the pure PEO and of the solid polymer contained in the mixtures were determined via DSC. An analogous degree of polymer insolubility β was calculated from the vapor pressures measured in this composition range. The experiments demonstrate that both quantities and their concentration dependence are markedly affect…

Continuous polymer fractionation

Molecular surfaces: An advantageous starting point for the description of composition-dependent viscosities applied to polymer solutions

The viscosity of polymer/solvent systems is modeled as a function of composition under the premises that the dissipation of energy is taking place at the molecular interfaces and that the friction between solvent and solute varies with composition due to a change in the flow mechanism (drainage of coils). The simple expression obtained in this manner contains three system-specific parameters: a geometric factor γ, which accounts for the differences of the surface to volume ratios of the components; a hydrodynamic parameter α, which measures the friction between solute and solvent in the case of fully draining polymer coils; and β, which corrects for changes in the friction between unlike mo…

Shear Thinning: Determination of Zero‐Shear Viscosities from Measurements in the Non‐Newtonian Region

Interfacial Tensions from Drop Retraction versus Pendant Drop Data and Polydispersity Effects

Interfacial tensions sigma were measured by means of both methods for the following polymer pair: polyisobutylene (PIB 3) plus poly(dimethylsiloxane) (PDMS 152) and poly(dimethyl-co-methylphenylsiloxane) (CoP26*) plus PDMS 48. The numbers after the abbreviation state the molar masses in kilograms; the homopolymers exhibit polydispersities on the order of 2. The reliability of the method of drop retraction is backed up by systematic measurements, which demonstrate that it is possible to study the time evolution of sigma. Because of the free choice of the phases (drop or matrix) and the possibility to vary the overall composition of the system in a wide range, drop retraction yields more info…

On the viscosity of moderately concentrated solutions of poly(ether imide) in a mixed solvent of marginal quality

Abstract Viscosities η were measured for moderately concentrated (15.5 wt%) solutions of poly(ether imide) (PEI) as a function of the composition of the cosolvent tetrahydrofuran (THF) plus γ-butyrolactone (γ-BL). The solutions are almost by a factor of four less viscous when THF predominates than when γ-BL is the major component of the solvent mixture. Furthermore, the viscosity passes a minimum as the composition of the mixed solvent is varied. Both observations can be well understood in terms of the viscosities of the mixed solvents and the hydrodynamic interaction between the polymer molecules. The pronounced dissymmetry of η as a function of the composition of the mixed solvent η resul…

Rheological studies of moderately concentrated polystyrene solutions in the vicinity of the θ temperature. II. Shear-rate dependence for different thermodynamic conditions

The viscosity data of moderately concentrated polystyrene solutions in trans-decalin (TD) (θ solvent, θ temperature 21°C) and toluene (TL) (good solvent) reported in Part I are discussed in terms of Graessley's entanglement theory. Under good solvent conditions, Graessley's master curve provides an excellent fit up to high shear rates, whereas in the vicinity of the θ conditions the data have to be modified by a parameter ηfric introduced by Ito and Shishido. The characteristic time of mechanical response to flow of chains approximately given by the shift factor τ0 is found in good solvents to be on the order of the Rouse relaxation time. In poor solvents, close to demixing, τ0 tends to muc…

Phase separation of flowing polymer solutions studied by viscosity and by turbidity

Synthesis and large scale fractionation of non-linear polymers: brushes and hyperbranched polymers

Polymer brushes with poly(methyl methacrylate) (PMMA) backbone and polystyrene side chains were synthesized by radical polymerization of ω-methacryloyl-polystyrene macromonomers. Hyperbranched PMMA was obtained by means of self-condensing group transfer copolymerization of methyl methacrylate with an initiator-monomer containing a polymerizable methacryloyl moiety and an initiating silylketeneacetal function. Both non-linear products were fractionated using the method of continuous polymer fractionation, consisting in a particular type of continuous countercurrent extraction. The combination of methyl ethyl ketone (solvent) with acetone (AC) (precipitant) turned out to be suitable for the f…

Coil overlap in moderately concentrated polyelectrolyte solutions: effects of self-shielding as compared with salt-shielding as a function of chain length

The generalized intrinsic viscosity {η} (hydrodynamic volume of the solute at arbitrary polymer concentration c) – introduced by analogy to the intrinsic viscosity [η] – provides access to the degree of coil overlap Ω for polyelectrolyte solutions in pure water or in saline water. The experimental basis of this investigation consists in viscosity measurements as a function of c for a large number of sodium polystyrene sulfonate (Na-PSS) samples covering the molecular weight range from 0.91 to 1000 kg mol−1. The accurate modeling of these dependencies with a maximum of three parameters yields detailed information on Ω as a function of (c[η]) in the absence and in the presence of extra salt. …