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  • 1
    Call number: O 4281
    In: Sitzungsberichte der Akademie der Wissenschaften der DDR : N, Mathematik, Naturwissenschaften, Technik
    Pages: 16 S.
    ISBN: 3055008480
    Series Statement: Sitzungsberichte der Akademie der Wissenschaften der DDR : Mathematik-Naturwissenschaften-Technik 4 N
    Language: German
    Branch Library: GFZ Library
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 91-110 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden Untersuchungen zum Flüssig-Dampf- und Flüssig-Fliissig-Gleichgewicht in Mischungen aus den Monomeren Ethen, 1-Buten, 4-Methyl-1 -penten und einem Polyethylenwachs bei mittleren Drücken durchgeführt. Auf der Basis der Chain-of-Rotators (COR) Zustandsgleichung, die mit einem Gruppenbeitragsmodell modifiziert wurde, wurden die Phasendiagramme der binaren und ternären Subsysteme sowie für das quaternare Gesamtsystem berechnet. Die Berechnungen ergeben eine zufriedenstellende Beschreibung des Flussig-Dampf-Gleichgewichtes und dessen Überlappung mit einem Flüssig-Flussig-Gleichgewicht bei höheren Drücken und Temperaturen. Die Mischungslücken in den beiden Systemen aus dem Polyethylenwachs mit 1 -Buten bzw. 4-Methyl-1 -penten werden auch nach Zugabe von Ethen zu den binären Mischungen beobachtet. Die Berechnungen zeigen ein kleines Dreiphasengebiet in allen entsprechenden ternären Mischungen. Eine Flüssig-Flüssig-Mischungslücke, die das Flüssig-Dampf-Gebiet schneidet, wird auch im quäternaren Gesamtsystem durch die Berechnungen mit dem modifizierten COR-Model1 gefunden. Diese doch überraschend komplizierten Phasenverhältnisse rnüssen bei der Abscheidung der Monomeren nach dem Syntheseschritt ausreichend beachtet werden.
    Notes: Some measurements of the vapour-liquid and/or the demixing equilibrium at moderate pressures were carried out in systems containing the monomers ethene, 1-butene, 4-methyl-1-pentene and a polyethylene wax. A group-contribution-modified chain-of-rotators (COR) equation of state was used to calculate the phase diagrams in all binary and ternary subsystems and in the whole quarternary mixture. The calculations lead to a satisfying description of the vapour-liquid equilibrium and its intersection by a liquid-liquid region at higher pressures and temperatures. The miscibility gaps in both mixtures of the polyethylene wax with 1-butene and 4-methyl-1-pentene, respectively, were observed again after adding ethene to these binary mixtures. The calculations indicate a small three phase triangle in all corresponding ternary mixtures. A liquid-liquid demixing region intersecting the vapour-liquid surface could also be found in the whole quaternary system by calculation with the modified COR model. This surprisingly complicated phase behaviour has properly to be taken into account during the separation of the monomers after the co- or terpolymerization process.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvent activity data were obtained from vapour pressure measurements at 50°C, 70°C, 100°C and reduced to χ-functions in systems consisting of benzene or toluene on the one hand and blends or block copolymers of poly(ethylene oxide) and poly(methyl methacrylate) on the other. The χBC-values are negative for all polymer subsystems, but miscibility on a segmental scale is somewhat different for block copolymers and blends. χBC depends on the concentration of solvent and is mainly influenced by the Δχ-effect in solution and correlated with the syndiotacticity of the PMMA chains. There is only a small influence of temperature and blend composition or block ratio.
    Additional Material: 5 Ill.
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  • 4
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viscometric measurements were carried out to characterize poly(oxyethylene)-block-poly-(oxypropy1ene)-block-poly(oxyethy1ene) (POE-POP-POE) in aqueous solution. The results were discussed in terms of a core-shell model of intramolecular phase separation which is based on (i) the selectivity of the solvent water, and (ii) the incompatibility of the POE and POP blocks. The interaction between the two blocks was analysed by vapour pressure osmometry and vapour sorption investigations.The results are: 1The two homopolymer blocks (POE and POP) forming the triblock copolymer are incompatible with each other as vapour pressure osmometry and vapour sorption measurements using ethylbenzene as solvent have shown. This incompatibility of the blocks as well as the selectivity of the solvent water with respect to the different blocks causes the intramolecular (and intermolecular) phase separation of the copolymers in aqueous solution.2The viscometric data of the aqueous block copolymer solutions can be discussed in terms of the generally accepted core-shell model. This model for the structure of the self-organized molecules includes POP gel core (“melt”) surrounded by solvated POE shell. A quantitative analysis according to this simplified view shows that the hydrodynamic volume of the copolymer molecules is determined by the POE blocks. In the temperature range ϑ 〉 30°C, the influence of the POP block on the molecular dimensions is negligible, whereas at ϑ 〈 30°C the contributions of the POP and POE to the molecular volume are comparable.3Kuhn's statistical segment length of POE in the triblock molecules comprises about 4-5 monomeric units. The theta temperature of the triblock copolymer molecules is nearly identical to that of pure POE ((369 ± 3)K).
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 193 (1992), S. 2433-2444 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvent activities were measured by an isopiestic sorption technique for solutions of poly(butyl methacrylate) and poly(tert-butyl methacrylate), respectively, in various solvents between 323 K and 373 K (or 403 K). The experimental data were reduced to segment-molar excess Gibbs free energies and to χ-functions. There is a clear difference in the thermodynamic behaviour of both polymers in their corresponding solutions due to the steric effect of the tert-butyl group. The chain-of-rotators equation-of-state model was used to calculate the thermodynamic quantities applying a group-contribution approach. In general, good agreement can be observed between experimental and calculated results.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 235 (1996), S. 175-191 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The polymer blend system PS/PVME shows a phase behaviour with lower critical separation temperature (LCST behaviour), which was simulated and discussed with the help of the model of Dee and Walsh as well as by means of the continuous thermodynamics. The results show that the Prigogine equation of state is able to fit advantageously the real PVT behaviour in the polymer melt. The spinodal curve used by the Dee/Walsh model gives a very good conformity with the results of the cloud point measurements. The model simulations show an increase of the compatibility of this polymer system with increasing pressure. By means of the continuous thermodynamics the influence of polydispersity on the phase behaviour of the blend system could be made clear. A marked shift of the critical point from minimum is seen because of the broad molecular mass distribution of PVME.
    Notes: Das Blendsystem PS/PVME weist ein Phasenverhalten mit einer unteren kritischen Entmischungstemperatur (LCST-Verhalten) auf, das mit dem Modell von Dee und Walsh sowie mit der kontinuierlichen Thermodynamik modelliert und diskutiert wurde. Die Berechnungsergebnisse zeigen, daß die Prigogine-Zustandsgleichung in der Lage ist, das reale PVT-Verhalten der Polymerschmelze recht gut anzupassen. Die mit dem Modell von Dee und Walsh erhaltene Spinodalkurve liefert eine sehr gute Übereinstimmung mit den Ergebnissen der Trübungsmessungen. Die Modellrechnungen zeigen eine Verbesserung der Verträglichkeit dieses Polymersystems bei hohem Druck. Mit der kontinuierlichen Thermodynamik konnte der Einfluß der Polydispersität auf das Phasenverhalten des Blendsystems deutlich gemacht werden. Eine merkliche Verschiebung des kritischen Punktes aus dem Minimum infolge der breiten Molmassenverteilung von PVME wird deutlich.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 48 (1993), S. 1923-1933 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: All the data for more than 100 polymer melts in a PVT data base were used to determine best-fit characteristic parameters for two different theoretical equations-of-state (eos): the chain-of-rotators (COR) and the Bruce Hartmann (BH) eos. Fitting was performed by applying an error in all-variables algorithm that was recently developed by Hartmann etal. Despite their very different theoretical basis, both equations-of-state led to close descriptions of the PVT surface with comparable average deviations. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 198 (1997), S. 2689-2714 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isopiestic vapor sorption measurements were carried out for concentrated solutions of poly(styrene-co-butadiene) (SBR) and poly(styrene-co-acrylonitrile) (SAN) in a number of aromatic solvents in the temperature range of 343 to 398 K. Henry constants were determined by means of inverse gas-liquid chromatography in the temperature range of 373 K (SBR) or 423 K (SAN) to 473 K, to obtain additional data at infinite dilution for the solvents, and for two of the monomers, styrene and 1,3-butadiene, in SBR.The chain-of-rotators (COR) equation of state model was used to calculate the thermodynamic quantities applying a group-contribution approach. In general, good agreement is observed between experimental and calculated results.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Basel : Wiley-Blackwell
    Die Makromolekulare Chemie, Theory and Simulations 2 (1993), S. 605-635 
    ISSN: 1018-5054
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Synthesis and application of copolymers are not seldom connected with different phase equilibria. Their precise knowledge is of importance for industrial processing as well as it is a profound basis for a better understanding of the nature and thermodynamics of such systems. As a common situation today, enough experimental information is seldom available in the necessary or desired amount, and a lot of model calculation is, therefore, more or less unavoidable to cover the desired ranges of application. Different equations-of-state as well as lattice models are discussed with respect to their applicability for calculating liquid-liquid and gas-liquid phase equilibria in copolymer solutions and blends. Examples for high-pressure phase equilibria in monomer/copolymer mixtures, liquid-liquid demixing in copolymer blends and for the isotropicnematic phase equilibrium in systems with rigid rod-like copolymers characterized by distributions of rigid and flexible chain parts are given. The effects of copolymer polydispersity are included by means of continuous thermodynamics. Literature references for original sources, earlier reviews and further applications round up this paper.
    Additional Material: 14 Ill.
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