Search results for "solution"

A procedure for predicting sorption equilibrium in ternary polymer systems from Flory–Huggins binary interaction parameters and the inversion point o…

1989

A procedure has been developed, based on the Flory–Huggins theory as generalized by Pouchlý, which permits the calculation of preferential (λ) and total (Y) sorption coefficients from previous information on the binary interaction parameters, χ, χ, and g12(ϕ10) and on the mixture composition at which the sign of λ inverts. The expressions obtained were applied to 10 cosolvent polymer systems for which experimental values of λ and Y are known. Practically in all the studied systems, the theoretical predictions are in fair accordance with the experimental data.

A Flory–Huggins thermodynamic approach for predicting sorption equilibrium in ternary polymer systems

1989

The Flory–Huggins theory as modified by Pouchlý has been applied to calculate preferential (λ) and total (Y) sorption coefficients for a ternary polymer system. The ternary interaction function (ϕ1ϕ2ϕ3GT(u1, ϕ3)) is described as the product of three independent binary functions. This expression allows prediction of λ and Y from binary interaction parameters χ, χ, g, g, and g12(ϕ10). Three ternary polymer systems are used to check the validity of the expression. Moreover for polymer systems in which the parameters g and/or g are unknown, a procedure to evaluate them has been developed and verified on systems for which sufficient experimental information is available.

Cyclodextrins in polymer synthesis: Free radical polymerization of cyclodextrin complexes withN-methacryloyl-11-aminoundecanoic acid orN-methacryloyl…

1998

The hydrophobic monomers N-methacryloyl-11 -aminoundecanoic acid (1) or N-methacryloyl-1-aminononane (2) were incorporated as guests into the cavity of heptakis(2,6-di-O-methyl)-β-cyclodextrin (Me 2 -β-CD) as a host, yielding the water compatible monomers N-methacryloyl-l 11-aminoundecanoic acid/ Me 2 -β-CD-complex (1a) and N-methacryloyl-1 -aminononane/Me 2 -β-Cl complex (2a). These complexes were polymerized radically in aqueous medium. The resulting polymers 1b and 2b which were obtained from the complexes 1a and 2a, are insoluble in water because of the unthreading of the cyclodextrin during the polymerization. The polymerization rate of 1a and 2a is high in comparison to the rate of th…

Cyclodextrins in polymer synthesis: free radical polymerisation of cyclodextrin complexes of cyclohexyl and phenyl methacrylate in aqueous medium

1998

The polymerisation mechanism of 2,6-dimethyl-β-cyclodextrin (Me2-β-CD) complexes of phenyl methacrylate (1) and cyclohexyl methacrylate (2) is described. The polymerisation of the complexes 1 a and 2a was carried out in water with potassium peroxodisulfate/potassium hydrogensulfite as initiator. The unthreading of the Me2-β-CD during the polymerisation led to water-insoluble poly(phenyl methacrylate) (1b) and poly(cyclohexyl methacrylate) (2b). By comparison, analogously prepared polymers from uncomplexed monomers 1 and 2 in homogeneous organic solvent (THF) with AIBN as radical initiator showed significantly lower viscosities and were obtained in lower yields in both cases.

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

2009

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 …

Polymer and Dye Probe Diffusion in Poly(methyl methacrylate) below the Glass Transition Studied by Forced Rayleigh Scattering

1999

By dissolving tracer quantities of 9,10-phenanthrenequinone (PQ) in poly(methyl methacrylate) (PMMA) it was possible to study by forced Rayleigh scattering (FRS) the tracer diffusion of the unbleached PQ as well as the photoproduct which is covalently bound to the PMMA molecules. The PMMA samples with molecular weights, Mw, of 103−105 were intermittently annealed at 80 °C for diffusion times of up to one year. From the results we conclude that polymer chain diffusion may be possible at temperatures more than 20 K below the glass transition temperature Tg, but further experiments are necessary, in particular, since we cannot exclude that our results are due to yet unexplained long time aging…

1996

The major new developments in electron crystallography and high resolution imaging of organic molecules are discussed. The aim is to show that the recent rapid advances in computer technology have made it possible to analyze molecules at a level or resolution which was impossible less than a decade ago, thus bringing the concept of molecular design to produce specific physical properties much nearer to realization

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

2003

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…

Microstructure analysis of biocompatible phosphoester copolymers

2013

Copolymers with varying compositions of 2-ethoxy-2-oxo-1,3,2-dioxaphospholane (EEP) and 2-ethoxy-4-methyl-2-oxo-1,3,2-dioxaphospholane (EMEP) have been synthesized via 1,5,7-triazabicyclo[4.4.0]dec-5-ene-catalyzed anionic ring-opening polymerization. The molecular weights and comonomer ratios were well controlled and polymers with reasonable molecular weight distributions (<1.5) were obtained in all cases. The copolymers were investigated by 1H and 31P NMR spectroscopies to determine the underlying microstructure via detailed dyad analysis. The copolymers were found to be nontoxic to HeLa cells. Furthermore, the obtained copolymers of EEP and EMEP show thermoresponsive properties, i.e., exh…

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

1995

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…