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  • 1
    Electronic Resource
    Electronic Resource
    ESCA investigation of the electronic structure of polyhexafluorobut-2-yneThis is considered as Part X of Reactions Involving Fluoride Ion and Part VI of Applications of ESCA to Structure and Bonding in Polymers. A preliminary account of this work has been presented at the Faraday Discussion Meeting No. 54 on the photoelectron spectroscopy of molecules, Sussex University, 1972. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1647-1652 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyperfluorobut-2-yne is prepared by a fluoride ion-induced polymerization of hexafluorobut-2-yne. The mass spectrum indicates a regular fragmentation pattern but the ESCA spectrum establishes the structure as a polyene, rather than a crosslinked system, and the occurrence of a shake-up peak assists in this assignment.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120805
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  • 2
    Electronic Resource
    Electronic Resource
    Copolymerization of styrene and diethyl fumarate with ZnBr2. IV. Comparison between photoinitiation and electroinitiation (1972)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 3253-3265 
    Details
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A comparative analysis of photoinitiation and electroinitiation can help elucidate initiation processes in donor-acceptor charge-transfer copolymerization. The technique has been applied to the zinc bromide-catalyzed copolymerization of styrene and diethyl fumarate in methanol. The photocopolymer product was analyzed by GPC, NMR, and elemental analysis. The results showed that 1:1 copolymers were formed initially, but changes occurred in both the kinetics and products after the early stages of the reaction. Significant correlations found between the two initiation methods included the initial kinetic order with respect to the initiating process and the effect on product yield of equivalent increases in total initiation energy. The limiting value of zinc bromide for both initiation methods was found to be the same. The data obtained support the contention that the copolymerization proceeds through a donor-acceptor process and that photoactivation of the preformed complex, inducing electron transfer, is a likely initiation process.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1972.170101112
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  • 3
    Electronic Resource
    Electronic Resource
    Copolymerization of styrene and diethyl fumarate with zinc bromide. III. Electroinitiation at low current densities (1972)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 3267-3277 
    Details
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electroinitiated preparation of equimolar copolymers of styrene and diethyl fumarate is described. The reaction medium consisted of these monomers dissolved in a methanol-zinc bromide solution. Rates of polymerization increased with increasing applied current and the copolymer yield increased linearly with the total number of Faradays transferred. The copolymer composition is 1:1 and is essentially invariant with the degree of conversion (〈15%), electroinitiation rate, and monomer feed ratios. A reaction mechanism involving donor-acceptor complexes and electroinitiated excitation of these complexes at the electrode is postulated.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1972.170101113
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  • 4
    Electronic Resource
    Electronic Resource
    Applications of ESCA to polymer chemistry. III. Structures and bonding in homopolymers of ethylene and the fluoroethylenes and determination of the compositions of fluoro copolymers (1973)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 389-411 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular core binding energies have been measured by ESCA for the homopolymers of ethylene and the fluoroethylenes. The data are interpreted in terms of semiempirical all-valence electron SCF MO calculations in the CNDO/2 formalism, in conjunction with the charge potential model. The results are used as a basis for interpreting the measured core binding energies of some Viton and Kel F type polymers. The routine application of ESCA to the determination of copolymer compositions is described.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1973.170110207
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  • 5
    Electronic Resource
    Electronic Resource
    Copolymerization of styrene and diethyl fumarate with zinc bromide. V. Electroinitiated copolymerization at high current strengths (1973)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 1867-1879 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electroinitiated copolymerization of styrene and diethyl fumarate in methanol solvent with zinc bromide as electrolyte has been investigated at high current strengths (200-500 mA). Unlike the copolymerization behavior observed at lower current strengths (〈 200 mA), it is found that the cathodically produced copolymers deviate from a 1:1 composition and show a significant deficiency in styrene. The copolymer products can be separated into two well-defined fractions: a toluene-soluble fraction (normal copolymer) and a toluene-insoluble one (styrene-deficient copolymer). These deviations in copolymer composition from a 1:1 monomer ratio are attributed to the occurrence of cathodically induced electroreductive hydrolysis side reactions with diethyl fumarate leading to the formation of carboxylate or acid salt species. Reaction of these hydrolyzed species with diethyl fumarate results in the formation of fumarate-rich copolymers.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1973.170110809
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  • 6
    Electronic Resource
    Electronic Resource
    Photostabilization of polypropylene. II. Stabilizers and hydroperoxidesFor the previous paper in this series, see Carlsson et al.1Issued as NRCC 14164. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2217-2233 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of various polyolefin photostabilizers on the thermal and photodecomposition of model and polymeric hydroperoxides have been investigated, both in the liquid and solid phases. Several extremely effective ultraviolet stabilizers belonging to the metal chelate class can cause the rapid thermal decomposition of model and polymeric hydroperoxides. Although stabilizers did not reduce the quantum yield for polypropylene hydroperoxide photolysis, several additives can scavenge hydroxyl and macroalkoxy radical products which result from hydroperoxide photolytic cleavage. Ultraviolet stabilizers which were found to trap radicals were able to prevent the photodegradation of polypropylene which already contained a significant concentration of hydroperoxide groups. Highly effective polypropylene ultraviolet stabilizers probably operate by a range of mechanisms including hydroperoxide decomposition, radical scavenging and singlet oxygen quenching.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121006
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  • 7
    Electronic Resource
    Electronic Resource
    Heat capacity of polyoxymethylene (1973)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 391-392 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1973.180110218
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  • 8
    Electronic Resource
    Electronic Resource
    Surface stresses and crystal twisting in hippuric acid and in polymers (1973)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 457-465 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An approximate model is developed which relates the twisting seen in the spherulitic crystallization of many materials to surface stresses. Expressions are presented for the twist period as a function of the surface stress. These are compared with previous experimental data on polyethylene and data on hippuric acid obtained in the present investigation. In both cases the experimental data are in accord with the predictions of the model.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1973.180110305
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  • 9
    Electronic Resource
    Electronic Resource
    Gas sorption in polymer membranes containing adsorptive fillers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 485-500 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The equilibrium and kinetics of gas sorption by a silicone rubber filled with highly adsorptive molecular sieves was studied. Sorption in this system is by two mechanisms: gas is simply dissolved in the polymer matrix according to Henry's law, while it is adsorbed by the dispersed sieve phase in accordance with a Langmuir's isotherm. The latter effectively immobilizes the gas molecules preventing their further diffusion. All equilibrium parameters were determined experimentally. Immobilization greatly affects sorption kinetics and renders conventional analyses invalid. A theory to account for this process was adapted from a previous analysis by Vieth and Sladek which assumes that the kinetics of adsorption is very fast compared to diffusion. For this situation the kinetics always assume a Fickean form. The experimental data agreed very well with the predictions of this theory in a comparison where all parameters were defined by independent experiments. It was found that a single effective diffusion coefficient describes sorption kinetics, steady-state permeation, and time-lag results once the effects of immobilization are properly accounted for.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180120304
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  • 10
    Electronic Resource
    Electronic Resource
    Nuclear magnetic resonance study of rubber-carbon black interactions (1971)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 829-839 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mobilities of polymer chain segments in mixtures of rubber and carbon black were investigated by nuclear magnetic resonance. Spin-spin relaxation time (T2) measurements on cis-polybutadiene and ethylene-propylene-diene rubber (EPDM) bound rubbers detected at least two relaxing regions: an immobile region and a relatively free region. The molecular motions in the relatively free region are still constrained compared to those of the pure gum.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1971.160090505
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