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…
Vapor Pressures of Polymer Solutions and the Modeling of Their Composition Dependence
Equilibrium vapor pressures, p, are reported for the systems tetrahydrofuran + poly(vinyl methyl ether) and tetrahydrofuran + polystyrene at 20, 40, and 60 °C. These data plus information from the literature serve to demonstrate that the composition dependence of p can be modeled quantitatively for polymer solutions in thermodynamically very different solvents by means of three, physically meaningful parameters.
Islands of Immiscibility for Solutions of Compatible Polymers in a Common Solvent: Experiment and Theory
Experimentally obtained islands of immiscibility are reported for the systems PS/PVME/THF at 20 °C and for PS/PVME/CH at 55 °C (PS: polystyrene, PVME: poly(vinyl methyl ether), THF: tetrahydrofuran, CH: cyclohexane). THF is a good solvent and CH is a marginal solvent for both polymers. In the case of THF, information on the Flory−Huggins interaction parameters of the three binary subsystems suffices for a qualitative prediction of the phase behavior of the ternary system. Quantitative agreement can be achieved by means of composition-independent ternary interaction parameters. For the marginal solvent CH, the exclusive use of binary interaction parameters wrongly predicts complete miscibili…
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…
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…
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…
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…
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…
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…
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…
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 …
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 …
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…
Dextran-Based Polycations: Thermodynamic Interaction with Water as Compared With Unsubstituted Dextran, 2 - Flory/Huggins Interaction Parameter
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…
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…
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…
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…