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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1183-1202 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crosslinked samples of polyethylene were prepared by electron irradiation of both high- and low-density polymers in the crystalline state. A further crosslinked sample was obtained by curing a high-density polyethylene by reaction with dicumyl peroxide at 180°C. The stress-strain-birefringenece relations were obtained on specimens cut from these samples at temperatures between 130 and 250°C. All samples showed a substantial decrease in stress-optical coefficient with increasing degree of crosslinking and with increasing temperature. The stress-optical properties at each temperature were extrapolated to zero degree of crosslinking to give quantities characteristic of the Gaussian network. Comparison of these properties with the theory of networks of rotational isomeric chains with both independent and interdependent rotation allows estimates to be obtained for (1) the trans-gauche energy differences in rotation around skeletal bonds and (2) the difference in principal optical polarizabilities for the CH2 group in the elastomeric state. This latter quantity is shown to be more nearly given by Denbigh's than by Bunn and Daubeny's bond polarizability values.
    Additional Material: 7 Ill.
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  • 2
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(ethylene terephthalate) was exposed in vacuo γ-radiation from a Co60 source at a dose rate of 0.02 Mrad/min., and an ambient temperature of 47°C. Gaseous products were analyzed in a mass spectrometer and carboxyl groups estimated by titration with NaOH and by infrared analysis. Initial G values were —COOH = 0.77, CO2 = 0.17, CO = 0.11, H2 = 0.015, and CH4 = 0.003. All these values decreased markedly with increasing dose except G(CO)2, which, roughly, was maintained up to 5000 Mrad. It was considered whether the dependence on dose of the yields of the major reaction products could be accounted for by the following set of first-order reactions: It was found that the rate of formation of —COOH groups at low doses was much too high to fit this simple reaction scheme. However, a better fit was obtained over a range of higher doses (ca. 100-5000 Mrad). A final conclusion could not be reached concerning the validity of the above reaction scheme.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 809-819 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel gas-flow method of measuring the diffusion, solubility, and permeability of gases and vapors in polymer films is described. The specific advantages of this system over the time-lag technique are discussed. Transport data, including activation energies and enthalpies of solutions, for hydrogen and deuterium in poly(vinyl fluoride) are presented, and the effects of the glass transition and of orientation on the observed transport rates are discussed.
    Additional Material: 7 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 5 (1967), S. 481-501 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of poly(ethylene terephthalate) films was studied in vacuo with light of wavelengths 2537 and 3130 A. A very stable filter system which cuts out the 3025 A. line was developed to isolate 3130 A. from a mercury spectrum. Despite the fact that the penetration of 2537 A. light was limited to a depth of a ca. 103 A. whereas 3130 A. light was more uniformly absorbed it was possible to demonstrate that the quantum yields for CO and CO2 formation were in agreement for the two wavelengths. Quantum yields for fractures and crosslinks were estimated by sol-gel analysis. An absorption maximum which develops near 13 μ after exposure of poly(ethylene terephthalate) to light or γ-rays was attributed to the formation of groups formed by elimination of CO and CO2. ESR spectra for trapped radicals were tentatively assigned to the components p-C6H3· and ·O—CH2—CH2—. It is suggested that the former radicals combine to form crosslinks. Quantum yields (× 104) with 3130 A. light are: CO, 6; CO2, 2; crosslinks, 5.5; trapped radicals, 1.5; With 2537 A. light, quantum yields are: CO, 6-9; CO2, 2-3; the network formed was not characterized as to crosslinks and fractures; trapped radicals were observed to exist but not determined.
    Additional Material: 11 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 252-254 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 2001-2012 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Emulsion polymerization of methacrolein produces a polyacetal which can be converted through the action of sodium hydroxide to an alternating copolymer of methallyl alcohol and sodium methacrylate. Support for the alternating structure was gained primarily through a study of the polylactone formed through subsequent acidification of the sodium salt. Thus, the poly(methallyl alcohol-sodium methacrylate) copolymer was acidified under selected conditions to give a soluble polylactone containing 14.2 mole-% of residual acid and hydroxyl groups. This number agrees quite closely with the value of 13.5 mole-% which one would predict from the random cyclization of a true alternating copolymer. Cyclization of a random copolymer of poly(methallyl alcohol-sodium methacrylate) in a random fashion would have resulted in a value of about 36.8 mole-%. The results also support both the 1,2 vinyl polymerization of methacrolein and a nonrandom attack of the polymethacrolein by base. In a completely separate set of experiments, the value of r1 and r2 for the copolymerization of styrene (M1) and methacrolein (M2) were determined to be 0.22 ± 0.02 and 0.88 ± 0.02, respectively.
    Additional Material: 6 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 5 (1967), S. 2199-2201 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No. Abstract.
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 2253-2265 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Aryl- and 2-alkyl-2-oxazolines have been polymerized to poly-(N-aroyl)aziridines and poly(N-acyl)aziridines, respectively, in the presence of boron trifluoride. The polymers obtained were glassy, light yellow resins with molecular weights ranging from 3500 to 7500 (35-50 oxazoline units per chain). The polymerization rates have been determined for several of these monomers. A polymerization mechanism is proposed.
    Additional Material: 4 Ill.
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  • 9
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free radicals formed by γ-irradiation of oriented samples of poly(ethylene terephthalate) (PET) were studied at 25°C. by ESR spectroscopy. The G value for trapped free radicals is 0.02. The predominant radical is identified as $\text{O} - \text{\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\cdot}$}}{C} H} - \text{CH}_\text{2} - \text{O} -$, and a minor component of the spectrum is tentatively assigned to the radical —CO—Ċ6H3—CO—. The absence of cyclohexadienyl type radicals is discussed. Previously reported dose rate effects in PET are explained by reference to a chain reaction involving β-bond scission of the radical $\text{O} - \text{\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\cdot}$}}{C} H} - \text{CH}_\text{2} - \text{O} -$.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 463-477 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conductivity of dry poly(hexamethylene adipamide) (nylon 66) was measured as a function of time and temperature. Three temperature ranges were observed in which the time dependence of conductivity differed: (a) below 80°C. the conductivity decreased continuously with time; (b) between 80°C. and 110°C. the conductivity remained constant over long periods; (c) above 120°C. a continuous decrease in conductivity was again observed. In other experiments the volume of gas evolved from the nylon film was measured under continuous potential and compared with the total current passed through the sample. It was observed that above 120°C. the gas evolved corresponded to about one-half the volume calculated if the conduction process involved only protons. Below 120°C. the gas evolved corresponded to an increasingly small fraction of the total current until below 90°C. no evolution of gas was observed. This suggests that at temperatures above 120°C. conduction involves the transport of both protons and electrons, whereas at lower temperatures it is electronic. Mechanisms of conduction are discussed.
    Additional Material: 7 Ill.
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