Diffusion constants of polymers in mixed solvents

Dynamics of polymers in mixed solvents are investigated on the basis of linear response theory and mean field arguments. Particular attention is given to the coupling between polymer and fluid fluctuations. This coupling is enhanced by polymer–solvent interaction asymmetry and mixed solvent incompatibility. Cooperative and fluid diffusion constants are analyzed in terms of the interactions in the medium and some predictions for light scattering experiments are made. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3976–3980, 2004     

Intrinsic viscosities of polymers in mixed solvents

The intrinsic viscosity of a polymer in a solvent mixture is related to the excess free energy of the solvents. Intrinsic viscosities at different temperatures are obtained for poly-2-vinylpyridine–chloroform–ethyl alcohol, poly(methyl methacrylate)–chloroform–ethyl alcohol, polystyrene–cyclohexane–benzene, polystyrene–dioxane–chloroform, and polystyrene–cyclohexane–ethanol. Qualitative, but not quantitative, agreement is found between theory and experiment.     

Mechanical relaxations in episulfide network polymers

A variety of condensation network polymers have been prepared by the reaction between amine, episulfide, and epoxide monomers. The mechanical relaxations occurring in these systems have been examined using a torsion pendulum and the role of hydrogen bonding in the mechanism of the β relaxation is shown to be insignificant. The chemical reaction between amine and episulfide groups has been investigated by IR spectroscopy and is shown to parallel the reaction between amine and epoxide groups. However, steric and electronic factors are suggested to decrease the extent of reaction when aromatic amines are involved. In the case of networks prepared from blends of episulfide and epoxide monomers, measurements of the gel time, together with the mechanical behavior around the glass transition, indicate that either interpenetrating or two-phase networks are formed. This is postulated to be a consequence of the high reactivity of the episulfide ring compared to the epoxide ring. The blending of small amounts of episulfide monomer with the epoxide monomer prior to curing may provide an effective method for lowering gel times without reducing the crosslink density and its dependent physical properties.     

Transitions and relaxations in aromatic polymers

Transition and relaxation phenomena in 26 structurally related polyquinoxalines and other aromatic polymers were studied over a temperature range from 70 to 770°K by means of calorimetric, dilatometric, dynamic mechanical, and dielectric techniques. Differential thermal analysis and x-ray data showed these polymers to be essentially amorphous. The lack of crystallinity is attributed to geometric isomerism, resulting in conformational as well as configurational disorder. Calorimetric measurements gave discontinuities in heat capacities ranging from 12 to 54 cal/°C per mole of repeat-unit structures and provided unambiguous assignments of glass transition temperatures of these polymers. Depending upon structure, T_g varied from 489 to 668°K. Thermal expansion curves of annealed bulk polymer samples between 70 and 770°K exhibited only one discontinuity over the entire temperature range, namely at T_g, thus indicating the absence of any motion leading to transitions in the solid state of these polymers. Viscoelastic properties were obtained by means of torsional braid analysis and a longitudinal vibrational apparatus. In a typical case, the dynamic mechanical relaxation spectrum contained three loss maxima. A peak of low amplitude occurring at 483°K was attributed to impurity effects, resulting from endgroups and species of low molecular weight. The second and only major relaxation process occurred at 579°K, in the glass transition interval. A third, weak loss peak of unknown origin was found in the liquid state at 683°K. On the other hand, the dielectric loss curves of various polymers exhibited only one broad and strong absorption maximum at temperatures 30 to 100°K higher (depending upon a particular polymer) than equivalent major mechanical loss peaks. These differences are interpreted from a mechanistic point of view. Major mechanical relaxations occurring in the glass transition interval of these polymers are proposed to result from translational motions.     

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

By a study of two ternary systems, 4-heptanon–1-chlorobutane–poly(methyl methacrylate) and 2-butanol–1-chlorobutane–poly(methyl methacrylate), differing only in one component of the mixed solvent, two types of demixing behavior are demonstrated: i.e., a monotone change with composition of the mixed solvent (monotony), of which the first system is a good example, and the synergistic behavior (cosolvency) exhibited by the second system. The situation can be seen most clearly from the binodal edges (precipitation thresholds as a function of solvent composition) which were constructed from various types of sections through the binodal surface of the systems. In order to compare experimental results with theoretical calculations, we first characterized the binary subsystems. The polymer solutions, representing conventional (endothermal) theta systems, were investigated by light scattering and cloud point measurements. For the cosolvent 2-butanol–1-chlorobutane the necessary thermodynamic information was accessible from vapor pressure measurements. Applying the Prigogine–Patterson theory to the polymer solutions and using the single-liquid approximation of Scott for the ternary systems yielded theoretical binodal edges in good agreement with experiment except for the branch belonging to mixed solvents rich in 2-butanol. This finding is explained by an abnormal amplification of preferential solvation effects due to the existence of an association equilibrium of the alcohol via hydrogen bonds.     

Cooperative relaxations/transitions in ferroelectric polymers

Dielectric relaxation and thermal transitions in β-PVDF have been investigated by Thermo-Stimulated Current spectroscopy and Differential Scanning Calorimetry respectively. A comparative study of spectra and thermograms has been performed. The relaxation mode associated with the glass transition of the true amorphous phase is characterized by relaxation times obeying a compensation law due to cooperative molecular movements. A conformationally disordered structure is proposed for β-PVDF to explain thermal events occurring around 60°C. Ageing of ferroelectric properties of β-PVDF has been associated with cooperative molecular movements liberated largely below the melting point.     

Light scattering behaviour of low-molecular-weight polymers in mixed solvents with very high selective sorption

Some low-molecular-weight polymers (poly(butyl methacrylate), nylon 6, nylon 12) in the solvent system m-cresol/n-heptane, with effective refractive index increments (?n/?c)_μ in the range 0.34?0.81 ml/g, have been studied by light scattering. These extremely large values, measured by differential refractometry of solutions in the state of dialysis equilibrium, are mainly due to very great selective sorption of one solvent component (m-cresol) on the polymers studied. The effect inherent to these systems, viz. that of the free solvent composition change, has been discussed and exemplified by the light scattering behaviour of solutions of oligomers of butyl methacrylate. The light scattering anomalies observed with solutions of some nylons in m-cresol/n-heptane have been interpreted as due to interaction of polymer end-groups. It has been demonstrated that the determination of $\text{M}{}_{\mathrm{w}}$ of the order of 10³ by light scattering in systems with large (?n/?c)_μ values, i.e. with large scattering power, is possible with good accuracy.     

Oleophilic ion-exchange resins. IV. Swelling of quaternary ammonium polymers in mixed solvents

The swelling characteristics of an oleophilic anion-exchange resin in methanol–benzene and ethanol–chloroform mixed solvent systems were compared with those of a conventional anion-exchange resin. The oleophilic resin was prepared by amination of chloromethylated polystyrene 1% DVB with N,N-dimethyldodecylamine. It showed a large shift of the swelling peak from polar to less polar solution compositions in both methanol–benzene and ethanol–chloroform systems as compared with the swelling of conventional resins. Total solvent uptake and solvent distribution between resin and solvent phases were also determined. The less polar solvent (benzene or chloroform) was sorbed preferentially by the oleophilic resin over a wide range of composition, while preference for the more polar solvent (methanol or ethanol) by the conventional resin was shown over the entire composition of the mixed solvent systems. The Newman-Krigbaum treatment of mixed solvents was applied to swelling data on the ethanol–chloroform–oleophilic resin system, where the volume of the gel network plus the solvent imbibed was relatively constant over the entire range of composition. The result suggests a strong similarity of the liquid–liquid interaction terms in this gel phase compared with those in the pure binary liquid phase.     

Low-temperature mechanical relaxations in polymers containing aromatic groups

Studies have been made of the secondary relaxation processes in the solid state of a number of polymers containing aromatic groups in the polymer chain. The polymers investigated include one, polystyrene, with the aromatic group in side-chain positions, and six high polymers in which phenylene rings lie in the main backbone chain. In polystyrene, wagging and torsional motions of the side chain phenyl rings give rise to a low-temperature δ-relaxation which is centered at 33°K (1.7 Hz) and which has an activation energy of about 2.3 kcal/mol. Most of the polymers with phenylene rings in the main chain exhibit a low-temperature relaxation in the temperature region from 100°–200°K. This relaxation process is centered at 159°K (0.54 Hz) in poly-p-xylylene, at 162°K (0.67 Hz) in polysulfone, and at 165°K (1.24 Hz) in poly(diancarbonate). In poly(2,6-dimethyl-p-phenylene oxide), two overlapping low-temperature relaxations are found, one in the range 125–140°K and the other near 277°K (ca. 1 Hz). The low-temperature secondary relaxation process in all of these polymers is believed to be associated with local reorientational motion of the phenylene, or substituted phenylene, rings or with combined motion of the phenylene rings and nearby chain units. For these low temperature relaxation processes, the activation energy is about 10 kcal/-mole. The temperature location of the relaxation appears to depend on the specific units to which the phenylene rings are attached and on steric and polar effects caused by substituents on the ring. In the poly-p-xylylenes the relaxation is shifted to much higher temperatures by a single Cl substitution on the ring but remains at essentially the same temperature position when dichlorosubstitution is made. The effects of water on the magnitude and temperature location of the observed low temperature relaxations, as well as the implications of the study for other polymers containing aromatic groups in their backbone chains, are discussed.     

Sub-Tg relaxations due to dipolar solutes in nonpolar glass-forming solvents

It is well known that rigid dipolar solutes (in smaller quantity) dispersed in a nonpolar glassy matrix exhibit a sub-T(g) (or beta(s)) relaxation due to the solute often designated as Johari-Goldstein (JG) relaxation, which is intermolecular in nature. In this article, we report the results of our study of such a sub-T(g) process in a wide variety of dipolar solutes in different glassy systems using dielectric spectroscopy over a frequency range of 20-10(6) Hz down to a temperature of 77 K. The T(g) of these solutions are determined using differential scanning calorimetry. The solvents used in this study are o-terphenyl (OTP), isopropylbenzene (IPB), and methylcyclohexane. In the case of rigid molecular solutes, like mono-halogen benzenes, the activation energy (DeltaE(beta)) of the beta(s) process is found to increase with decreasing T(g) of the solvent, with a corresponding decrease in the magnitude of the beta(s) process. In the case of more symmetrical molecular solute, for example, tert-butylchloride, the change in DeltaE(beta) is not very appreciable. These results emphasize the importance of the size of the cage of the host matrix in the relaxation of the solute molecules. We have also studied the sub-T(g) relaxation(s) due to some flexible molecular solutes, viz., 1butylbromide, 1hexylbromide, 1butylacetate, and benzylacetate. These solutes in IPB matrix exhibit only one relaxation, whereas in OTP matrix they exhibit an additional sub-T(g) process, which may be identified with a JG type of relaxation. These observations lead us to the conclusion that the beta process observed in the glassy states of these pure solutes is predominantly intramolecular in nature.     

Polymer solubility in mixed solvents

Modeling results indicate that polymer chains in mixtures of a good with a bad solvent exhibit preferential adsorption of the good solvent. That phenomenon is found to be strongly dependent on molecular weight and it increases with a decrease in chain length. These results have important consequences on polymer solubility. Thus, a low molecular weight chain in a solvent mixture behaves as if it were dissolved in the pure good solvent component, whereas the solubility of a longer chain is controlled by the average mixture composition. As a result, quenching a polydisperse system below the cloud point may induce molecular weight segregation between the two phases: the longer chains, which precipitate out first, tend to populate the polymer rich phase whereas the shorter chains, having greater solubility, remain in the solvent phase. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2782–2787, 1999     

Dehydration of glycine in mixed solvents

The analysis of changes in the partial volume of glycine $\Delta \bar V^0 $ in solutions of substances that have a different effect on water structure is presented. For glycine in mixtures of water with glycerol and ethylene glycol, we derive a single equation for the $\Delta \bar V^0 $ dependence on the volume fraction of alcohol. The addition of tert-butyl alcohol, ethylene glycol, glycerol, and urea to water leads to a decrease in the hydration number of the amino acid (glycine dehydrates). In 1m solutions the losses of hydration water are 3.2%, 4.5%, 5.7%, and 7.6% respectively. In a 4m solution of tert-butyl alcohol, glycine loses 44% of hydration water, the same as in a 15m urea solution and a 20m glycerol solution. A contribution of the structural dehydration of glycine is observed in dilute aqueous solutions of t-BuOH. In more concentrated solutions, intermolecular interactions in the binary mixed solvent counteract dehydration. These interactions compensate for 15-22% of water lost by glycine in a 20m solution of urea, glycerol, and ethylene glycol and a 4m solution of t-BuOH. The partial volumes are also discussed within preferential solvation concepts.     

Effect of sub-Tg relaxations on chromophore reorientation in corona-poled polymers

Activation volumes for chromophore reorientation were measured for a series of guest–host polymeric materials, indicating a significant coupling between chromophore motion and the glassy α and β relaxation dynamics of the polymer host. The specific systems studied were formed by individually dissolving N,N-dimethyl-p-nitroaniline (DpNA), 4-(dimethylamino)-4′-nitrotolane (DMANT), 4-(diethylamino)-4′-nitrotolane (DEANT), and 1-((4-(dimethylamino)phenyl)ethynyl)-4-((4-nitrophenyl)ethynyl)benzene (DMAPEANT) in poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), and poly(isobutyl methacrylate) (PiBMA). In each of these systems, the isothermal, sub-T_g decay of the second-order optical susceptibility χ⁽²⁾ was monitored as a function of pressure using second harmonic generation. In each system, the observed decay of χ⁽²⁾ was represented by a stretched exponential equation from which the decay time τ₀ and decay distribution width β_KWW were determined. For each dopant molecule, the decrease in activation volume with the increasing size of the polymer host's alkyl side group and the pressure dependence of β_KWW were indicative of partial coupling between chromophore rotation and the glassy β relaxation dynamics of the polymer host. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1013–1024, 1998     

Mean‐field‐theory for polymers in mixed solvents. Thermodynamic and structural properties

Theoretical aspects of polymers in mixed solvents are considered using the Edwards Hamiltonian formalism. Thermodynamic and structural properties are investigated and some predictions are made when the mixed solvent approaches criticality. Both the single and the many chain problems are examined. When the mixed solvent is near criticality without solute, addition of a small amount of polymers shifts the criticality towards either enhanced compatibility or induced phase separation depending upon the value of the parameter describing the interaction asymmetry of the solvents with respect to the polymer. The polymer‐solvent effective interaction parameter increases strongly when the solvent mixture approaches criticality. Accordingly, the apparent excluded volume parameter decreases and may vanish or even become negative. Consequently, the polymer undergoes phase transition from a swollen state to an unperturbed state or even takes a collapsed configuration. The effective potential acting on a test chain in strong solutions is calculated and the concept of Edwards screening discussed. Structural properties of ternary mixtures of polymers in mixed solvents are investigated within the Edwards Hamiltonian model. It is shown that the effective potential on a test chain in strong solutions could be written as an infinite series expansion of terms describing interactions via one chain, two chains etc. This summation can be performed following a similar scheme as in the Ornstein‐Zernike series expansion.     

Intrinsic viscosity of polystyrene in mixed solvents

The intrinsic viscosity of a single sample of polystyrene was measured as a function of the composition of solvent in three mixed solvent pairs. The parameter Y introduced by Shultz and Flory was useful for prediction of trends, but severely overestimated the effect of solvent (1)–solvent (2) interaction on the expansion of polymer coils. The system polystyrene–cyclohexane–ethyl acetate was studied in detail for five samples of polystyrene. The analysis of the data provided strong experimental proof of a strict validity of the Mark–Houwink–Sakurada relation. The dependence of the Mark–Houwink–Sakurada exponent α on the composition of the solvent mixture was unexpectedly unsymmetrical. The unperturbed dimentions of the polystyrene chain are reduced by specific interaction of polystyrene with carbonyl groups in the solvent mixture.     

Solubility of porphyrin macrocycles in mixed solvents

A method based on the statements of molecular association theory and a simple lattice model (ASL = Associated Solution + Lattice) is used to calculate the solubility of a series of porphyrin macrocycles (blood porphyrins) in binary solvents (tetrachloromethane-ethyl acetate, tetrachloromethane-methanol). Separate contributions to solubility are identified and the relative role of different factors determining the solubility dependence on the mixed solvent composition is analyzed. The calculated solubility values are in good agreement with the experimental data obtained for the studied systems by the isothermal saturation method with a spectrophotometric control of concentrations.     

Conductance of potassium lodide in mixed solvents

The conductance of potassium iodide has been measured in the solvents ethylene carbonate, water, methyl ethyl ketone, and pairwise mixtures of these solvents at 40°C; and ethylene carbonate-water, tetramethylene sulfone-water, dimethyl sulfoxide-water, tetrahydrofuran-water, ethylene carbonate-tetramethylene sulfone-water, ethylene carbonate-tetramethylene sulfone, and tetrahydrofuran-dimethyl sulfoxide at 25°C. For dielectric constants greater than about 60, the pairing constants K_A are in the range 0.3–2.0; no correlation between K_A and solvent properties could be established. For lower dielectric constants, K_A increases exponentially with decreasing dielectric constant. Addition of a proton, acceptor to water initially decreases K_A regardless of whether the dielectric constant of the mixture is higher or lower than that of water, suggesting that ion pairs in water may be stabilized by cage structures. The Walden product A_o is also decreased by the addition of proton acceptors.