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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1411-1418 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electroinitiated polymerizations of styrene, 2-vinylnaphthalene, and 9-vinylanthracene were compared in sulfolane and acetone solvents in the presence of ZnCl2. The relative orders of polymerization rates and polymerization efficiencies, in both solvents, were 9-vinylanthracene 〉 2-vinylnaphthalene 〉 styrene, with faster rates and higher efficiencies occurring in sulfolane. Data obtained from viscosity and gel permeation chromatography (GPC) studies indicate that the molecular weights of the polymers produced in these systems are extremely low, 〈5000. Chemical composition and infrared (IR) spectral data suggest that abnormal transfer reactions (possibly from solvent) may be occurring in the electroinitiated 9-vinylanthracene polymerizations. The polymerization mechanism appears to be cationic in these monomer-solvent systems with ZnCl2.
    Additional Material: 7 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1153-1161 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To elucidate mechanisms in electroinitiated polymerization reactions a comparison was conducted between ultraviolet (UV) photoinitiation and electroinitiation of N-vinyl phthalimide with zinc chloride as a catalyst. Both methods give low yields of a complex polymer product. A detailed analysis, infrared (IR), gel permeation chromatography (GPC), elemental, and molecular weight, conducted on the polymeric products, indicated that phthalimide ring opening was occurring and that complex mixtures of poly(N-vinyl phthalimide) derivatives were formed. Both initiation methods gave comparable results, which further indicated mechanistic similarity between photo-and electroinitiation in these donor-acceptor charge transfer polymerizations.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1269-1274 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Earlier work showed that heating causes poly(diethylsiloxane) to undergo a first-order transition from a semicrystalline solid to a more mobile viscous - crystalline material. The latter is composed of two phases and analogies between polymer and liquid crystal morphology and behavior have been made. The viscous - crystalline phase in PDES appears to be unique since the literature is devoid of other documented examples. In this study, spin - lattice and spin - spin relaxation times were measured over a wide temperature range. They show a glass transition at 138°K, a crystal - crystal transition at 206°K, and a transition around 250°K which results from translational motion of the polymer chains with respect to each other. This motion is observed in the amorphous phase at a lower temperature than in the crystalline phase. Translational motion in the crystalline phase is observed on melting of the crystallites. The spin - spin data permitted monitoring of the molecular motions in each phase and the data suggest that these phases exert some influence on the molecular motions of each other. The viscous - crystalline phase in PDES may represent a unique model for studying and understanding “precrystalline” behavior and structure in amorphous solids.
    Additional Material: 2 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1201-1214 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experiments were designed to demonstrate that the chemical potential gradient required for liquid transport through swollen network polymer membranes manifests itself as a concentration gradient and that the rate of transport is independent of how this gradient is established. The fluxes of various liquids through a crosslinked rubber membrane were measured in hydraulic and pervaporation modes of permeation. The pressure applied downstream in the latter act simply to fix the activity of the liquid in the downstream membrane surface. The experiments show the flux is a unique function of this activity, and it does not matter how it is established. Sorption data were used to convert these results into a plot of flux versus concentration differential across the membrane which was analyzed by Fick's law using a model for the concentration dependence of the diffusion coefficient. Measured ceiling fluxes for pervaporation for a number of liquids were found to be the same as those estimated from hydraulic permeation data. A simple mathematical representation for an ideal system is used as a pedagogical device to demonstrate the conclusions.
    Additional Material: 6 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1945-1957 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been presumed in studies of the orientation of low-density polyethylene and its time dependence that the degree of crystallinity remained constant with elongation and did not vary with time following elongation. This paper represents a test of this hypothesis by several methods. The change in crystallinity accompanying stretching has been followed by a modification of an x-ray method for uniaxial orientation proposed by Ruland in which diffraction peaks are resolved into crystalline and amorphous components and their respective areas are determined by two-dimensional integration over both the Bragg angle and the azimuthal angle of diffraction. The weight-fraction crystallinity is then determined from the ratio of the weighted crystalline area to the total area. There appears to be no significant variation in crystallinity up to 50% sample elongation for both slowly and rapidly stretched samples at room temperature. The dynamic crystallinity change accompanying small amplitude vibration has also been determined by the dynamic x-ray diffraction technique and found to be negligible over a wide range of frequency. The degree of crystallinity has also been evaluated from the absolute infrared absorbance of crystallinity-sensitive bands and has also been found to be independent of elongation at room temperature up to 80% elongation. Changes have also been observed by this method during relaxation at constant length following rapid extension and have also been found to be negligible. These results also indicate negligible changes in rotational isomer population. Consequently, we conclude that changes observed during relaxation and vibration arise from orientational changes rather than changes in the degree of crystallinity.
    Additional Material: 11 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 977-983 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric behavior of poly(diethyl siloxane) supports the adiabatic calorimetric findings of Beatty and Karasz. In particular, a sub-Tg transition is observed near -180°C at 100 Hz, the glass transition near -135°C at 100 Hz, and a first-order transition near -70°C (crystal-crystal transformation). This glass-transition temperature is the lowest reported polymeric glass transition for polymers.
    Additional Material: 7 Ill.
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  • 7
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymers produced by glow discharge from three isomeric monomers are examined by ESCA. The polymer produced from 1,1-difluoroethylene is discussed in some detail and compared with those prepared from the two 1,2-difluoroethylene isomers. Charge distributions for the neutral molecules and their radical cations are calculated within the INDO SCF MO formalism and a possible reaction scheme that involves fluoroacetylene is outlined.
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1963-1967 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Tab.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2551-2570 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Temperature dependence of solute transport through aqueously swollen polymeric films and membranes can be altered to show even apparent negative activation energies by the use of polymers exhibiting a lower consolute behavior in solution. The principles by which we constructed a host of such polymers are discussed. A solubility rule is presented which predicts that solutes in water will show a lower critical solution temperature if the proper hydrophilic-hydrophobic balance is achieved.
    Additional Material: 19 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 987-999 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The variety of wide-angle x-ray scattering (WAXS) patterns exhibited by nylon-6 fibers with different fabrication histories is rationalized using a model comprising three limiting structures, viz., an α, a γ, and a pleated α structure. The γ and pleated α structures both have a single broad reflection in the range 2θ = 19° -25°, but differ in their annealing behavior. At 205° (in vacuo), the pleated α structure converts to the normal α structure by removal of the pleats, without breaking any hydrogen bonds. The γ structure, however, remains unchanged under this annealing condition since it is necessary to break all the hydrogen bonding in the structure to convert it to the α form. Different fabrication routes produce fibers which resemble the three ideal structures to varying extents. Fibers extruded at low speeds (and hence low spinline tension) resemble a mixed conventional α/pleated α structure with only a small γ component. Increasing the take-up speed (and hence the spinline tension) of the as-spun fiber, or in-line drawing of the low orientation fiber (without prior storage), increases the γ content. If drawing of the low orientation fiber takes place after several hours storage (off-line drawing), a largely α structure is produced. The intensity of the 020 reflection in the γ structure is shown to be very dependent on the degree of crystalline orientation in the sample.
    Additional Material: 6 Ill.
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