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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2363-2374 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ESR spectra of purified and ferric ion-sensitized celluloses irradiated with ultraviolet light in vacuo at 45, 20, -80, and -196°C were recoreded and compared. Generally, several kinds of spectra, viz., singlet, three-line, five-line, and seven-line spectra, were observed. At higher temperatures, only singlet and three-line spectra of stable free-radical species were detected, whereas at lower temperatures such as at -196°C, two doubled spectra of formyl radicals and hydrogen atoms were also detected in addition to cellulose radicals. It is believed that the intricate spectra observed at low temperatures are superimposed upon spectra generated by free radicals which may or may not be stable at high temperatures. During reirradiation at -196°C with an alternative light sources, i.e., λ 〉 2537 Å and λ 〉 3400 Å, of samples which were irradiated at 20°C or at -196°C, phenomena indicative of radical transformation and formation of new radicals or of decay of radicals in terms of ultraviolet bleaching were observed on studying the changes of line-shapes and relative signal intensities of the spectra.
    Additional Material: 7 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2513-2525 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free-radical formation in various modifications of celluloses, namely, wood cellulose I, II, III, and IV, rayon cellulose, amorphous cellulose, cotton linters, and absorbent cotton, irradiated with ultraviolet light, has been studied by means of ESR spectroscopy at 77°K. Various types of free radicals were generated from these samples. The line shapes and the signal intensities of the ESR spectra depended greatly upon the degree of crystallinity, the lattice type, and the arrangement of molecules in cellulose. The effect of degree of crystallinity and the amount of sensitizer (Fe3+) absorbed revealed that photochemical reactions in cellulose occurred exclusively in the amorphous regions of the polymer. Free radicals formed in these samples behaved distinctively upon a warm-up process. Phenomena of radical migration and formation of new radicals were observed from the sensitized samples of rayon cellulose and amorphous cellulose.
    Additional Material: 9 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 14 (1976), S. 225-229 
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 955-959 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of moisture content upon free radical formation in celluloses irradiated with ultraviolet light has been studied by means of ESR spectroscopy at 77°K. As studied from the variation of the line-shape and the relative signal intensity of the spectra observed, it is clear that moisture content in the sample greatly influences the formation of free radicals when irradiated with ultraviolet light. The moisture content in the range of 5-7% leads to a significant decrease of radical formation; and alternatively, when moisture content is lower or higher than this range, the formation of free radicals is increased.
    Additional Material: 2 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1933-1941 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of several photosensitizers on the formation of free radicals in cellulose has been investigated. Radicals were generated with ultraviolet light, and examined by means of ESR techniques; irradiations were carried out at 77°K. On irradiation of the sensitized celluloses with light of λ 〉 3400 Å, samples treated with benzoyl peroxide, hydrogen peroxide, benzophenone, riboflavin, azobisisobutylonitrile, and metallic ions Cr2+ and Ni2+ exhibited single-line spectra with line widths of 16 to 26 gauss. Samples treated with Pb2+ and Fe3+ exhibited three-line and five-line spectra, respectively. On irradiation with light of λ 〉 2537 Å, most of the sensitized samples exhibited five-line spectra with different relative signal intensities. Among these, samples treated with Fe3+ manifested the most prominent spectra with the strongest relative signal intensities.
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2641-2652 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of lignin on free-radical formation in photoirradiated pulp was studied by means of electron spin resonance spectroscopy. Samples were irradiated with light of wavelength longer than 3400 Å as well as longer than 2537 Å. Radical formation in aspen lignin was observed before and after irradiation with light of wavelength longer than 3400 Å. Upon irradiation, free radicals were formed in a pulp sample with 0% lignin content only when oxygen was present. On irradiation with light longer than 2537 Å, in the presence of nitrogen, oxygen, and under vacuum, free-radical formation was found in all cases. The largest concentration of radicals was obtained under vacuum, the smallest in oxygen. It is evident that cellulose was protected from radiation by the presence of lignin. Increased aspen lignin content in pulp led to a decrease in the relative signal intensity of ESR spectrum, that is, a decrease of the yield of free radicals in the cellulose fraction in pulp. Irradiation with light in the presence of oxygen caused significant yellowing of the pulp sample, and these photooxidation and discoloration reactions occurred primarily on the surface of the sample irradiated.
    Additional Material: 3 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2653-2669 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ESR spectra of untreated and photosensitized celluloses irradiated with three different ultraviolet light sources, i.e., λ 〉 2537 Å, λ 〉 2800 Å, λ 〉 3400 Å, at 77°K under vacuum were studied. Based on the warm-up process, that is, warming the sample from 77°K to 273°K for a certain time and recorded at 77°K, the decay behavior of free radicals of celluloses was examined for changes of the pattern and the intensities of ESR spectra. For the untreated samples irradiated with light of λ 〉 2537 Å and λ 〉 2800 Å, beside the two doublet spectra originating from hydrogen atoms (508 gauss splitting) and formyl radicals (129 gauss splitting), the observed sevenline spectrum was resolved to be a superposition of a singlet (ΔHmsl = 16 gauss), a doublet (24 gauss splitting), a triplet (34 gauss splitting), and a quartet (overall width, 88 gauss) spectrum. For the photosensitized samples irradiated with light of λ 〉 3400 Å, the 1:1:1 three-line spectrum was resolved to be a superposition of a singlet (ΔHmsl = 27 gauss), a doublet (43 gauss splitting), and a triplet (34 gauss splitting) spectrum. The five-line spectra of the photosensitized samples irradiated with light of λ 〉 2537 Å and λ 〉 2800 Å were resolved to be a superposition of a singlet (ΔHmsl = 27 gauss), a doublet (43 gauss splitting), and a triplet (34 gauss splitting) spectrum. Based on these findings, the conclusion was drawn that at least six kinds of spectra, generated from six kinds of radical species, were formed in cellulose irradiated with ultraviolet light under appropriate experimental conditions.
    Additional Material: 16 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 725-744 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photodegradation of cellulose acetate fibers by ultraviolet light in vacuo at 77°K and at ambient temperature was studied. Three kinds of light sources with different wavelengths between 2353 and 6000 Å were employed. ESR studies at 77°K show that several kinds of free radicals are produced from cellulose diacetate (CDA) and cellulose triacetate (CTA) fibers when irradiated with light of wavelength shorter than 2800 Å. Among these methyl radicals formed decayed within 210 min at 77°K. When the temperature was raised above 77°K, radical transformation occurred at 87°K and most of the free radicals decayed at 193°K, whereas the cellulosic radicals were stable at this and even at higher temperatures. Ultraviolet spectroscopy studies revealed that the main chromophores are the carbonyl function of the acetyl group and acetal groups in the polymer. The photodegradation of the polymers at ambient temperature resulted in the formation of gaseous products (mainly CO, CO2, and CH4), together with the loss of bound acetic acid content and sample weight. Decreases in viscosity and reduction of tensile strength and elongation were also observed in the irradiated samples, revealing that the overt effects of ultraviolet light on cellulose acetate fibers are interpreted in terms of free-radical reactions ultimately leading to main-chain and side-group scissions, unsaturation, and the formation of small molecule fragments. Among these, main-chain scission took place predominantly in CDA fiber and side-group scission in CTA fiber. The mechanism of the fundamental photochemical degradation processes of cellulose acetate fibers is elucidated.
    Additional Material: 11 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1347-1361 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Formation of free radicals in photoirradiated cellulose has been studied by means of ESR spectroscopy at 77°K. Three kinds of light sources with different wavelengths between 2500 and 4000 ÅR were employed. No radicals detectable by ESR were recorded when cellulose was irradiated with light of wavelength longer than 3300-3400 ÅR. Hydrogen atoms that generated a doublet spectrum (ΔH = 508 G) were observed when cellulose was irradiated with light longer than 2800 ÅR. Hydrogen atoms and formly radicals that generated doublet spectra with splitting constants of 508 and 129 G, respectively, were observed when irradiated with light shorter than 2800 ÅR. The scission of the polymer chain in cellulose is evident from decrease of the degree of polymerization, and the results of mass spectrometric analysis indicated H2, CO, CO2, and H2O to be the main volatile products of cellulose upon photoirradiation.
    Additional Material: 8 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2497-2512 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photoinduced free radicals in cellulose were studies by means of ESR spectroscopy. Plausible mechanisms have been suggested for each type of intermediate radical to account for the ESR spectra observed and for the product balances. Based on the principles of photochemistry of cellulose, coupled with the findings of the ESR spectra, it becomes evident that localization of the energy absorbed in the cellulose molecule leads to formation of free radicals in terms of chain scission, dehydrogenation, dehydroxylation, and dehydroxymethylation. Emphasis has been placed on the correlation of the mechanisms of photodegradation and the mechanisms of photoinduced graft copolymerization.
    Additional Material: 1 Ill.
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