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  • 1
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the oxygen-initiated polymerization of ethylene show some features previously unrecorded in vinyl polymerizations. Preceding formation of polyethylene, there is an induction period which depends strongly on temperature and pressure but only slightly on oxygen concentration. During the induction period the rate of oxygen consumption increases exponentially with time and approximately one-half of the oxygen is consumed prior to polymerization which can take place only if certain critical conditions depending primarily on pressure and oxygen concentration are exceeded (critical boundary). A formal reaction mechanism with degenerate kinetic chain branching is postulated from which the most important experimentally observed relations can be deduced. The induction period for polymerization then becomes the reciprocal branching factor for the oxidation of ethylene and the critical boundary a kinetic limit familiar in hydrocarbon oxidations with degenerate branching. The shape of the critical boundary can be derived by postulating, in addition, a sequence of reaction steps similar to those frequently used to represent the low temperature oxidation of hydrocarbons. Under the conditions investigated, the initiation mechanism dominates the polymerization, and an interpretation of the propagation and termination steps cannot be made.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 1053-1063 
    ISSN: 0887-6266
    Keywords: polyethylene ; polypropylene ; supercritical propane ; morphology ; microporosity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphologies of solvent-free, microporous, mechanically self-supporting cylinders of linear polyethylene and isotactic polypropylene, crystallized from solution in supercritical propane, were examined by an SEM technique. The morphology of gels (or foams), obtained with little or no shrinkage from 2% to 35% solutions by weight of polyethylene (99% to 85% porosities), is shown in some detail. Lamellae with very little or considerable mutual organization occur, often in the form of stacks with straight or coiled axes (axialites). Further growth of these can lead to particles with a roughly spherical overall shape and a predominantly radial orientation of the lamellae at the particle surface. Subcooled isotactic polypropylene, on the other hand, crystallizes in the form of perfectly shaped birefringent microspheres of very uniform size. ©1995 John Wiley & Sons, Inc.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 117-131 
    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: The viscosities of moderately concentrated solutions of low-density polyethylenes in ethane, propane, and ethylene have been measured at low shear rate in the temperature range of 150-250°C and in the pressure range of about 15000-30000 psi. Within the precision of the measurements, the relative viscosity is independent of pressure over the range investigated but increases as the solvent is changed from propane through ethane to ethylene. The activation energy for the relative viscosity in ethane varies from about 0.5 to 2.5 kcal/mole as the concentration changes from 5 to 15 g/dl. Effects of polymer concentration and molecular weight on solution viscosity in ethane at 150°C have been determined, and all of the data can be represented by a single straight-line plot of the logarithm of relative viscosity versus the intrinsic viscosity (in p-xylene at 105°C) times concentration. This simple relation is valid over wide ranges of polymer concentration and molecular weight and over more than two orders of magnitude of relative viscosity. The solution viscosities of the polyethylenes in the three supercritical fluid solvents used appear surprisingly low at first sight. This behavior is partly a result of the low solvent viscosities but also might mean that the polymer has an abnormally low segmental friction factor compared to that in solutions under more familiar conditions.
    Additional Material: 6 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 3 (1965), S. 131-136 
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The system polyethylene-ethylene exhibits the same type of phase behavior as that described earlier for polyethylene-n-alkane systems well above the boiling points, or above the critical points of the solvents. In this case, the solvent is always above its critical temperature in the region investigated, and one has here another case of infinite polymer-gas miscibility. The critical locus was determined, from its intersection with the crystallization surface at about 115 to 200°C., and the three-dimensional phase model in (P, T, composition) space is visualized.
    Additional Material: 3 Ill.
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  • 5
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Above the crystallization temperature slightly branched polyethylene and propane are miscible in all proportions above a critical pressure, defined as upper critical solution pressure (UCSP). This pressure decreases only very slightly from 110 to 150°C. At 110°C. the UCSP varies from 450 atm. for a polymer fraction of molecular weight 17,000, to 580 atm. for one of molecular weight 250,000. The critical polymer concentrations are low as in conventional polymer-solvent systems and shift with molecular weight in a similar manner. The pressures required to achieve solubility of the polymer in the gas at polymer concentrations less than critical (dew-point pressures) are nearly as high as the UCSP down to very low polymer concentrations. The data determine part of the critical locus in (P, T, composition) space. Experiments with other polyethylene-n-alkane systems (ethane, butane, and pentane) show that the critical locus changes gradually from a liquid-liquid to a gas-liquid boundary and might be termed a fluid-liquid locus. If crystallization of polymer does not intervene, this locus intersects the saturated vapor pressure curve at a lower critical end point (LCEP) which is the lower critical solution temperature (LCST) found only recently by Freeman and Rowlinson in many hydrocarbon polymers with hydrocarbon solvents. Incomplete miscibility extends over greater regions of temperature and pressure as the solvent molecule becomes smaller, but the critical locus would probably be closed along the pressure axis for a hypothetical amorphous polymethylene with ethane.
    Additional Material: 6 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 5 (1967), S. 2973-2973 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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