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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 3271-3281 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to study the termination reaction of polymer radicals in the viscous media of wool fibers, reduced, methylated, and S-carboxymethylated wool fibers were used for graft copolymerization of methyl methacrylate and styrene. With termination of poly(methyl methacrylate) radicals, two different termination reactions, recombination and disproportionation, were together involved in the grafting systems studied. The occurrences of two termination reactions in the system could be correlated with the mobility of the wool chain controlling the radical end mobility. With decreasing disulfide content in the fibers, disproportionation predominantly takes place among the mobilized chains. At a constant disulfide, the thiol content or the concentration of thiol anions becomes the determining factor for the termination reaction. A possible explanation for these phenomena in terms of the thiol and disulfide interchange reaction is presented. On the grafting of styrene, additional evidence was obtained that prevention and retardation of the interchange reactions followed mechanochemical bond scission of the disulfide and other covalent bonds and produced new free radicals which could initiate chain reactions.
    Additional Material: 4 Tab.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 3283-3292 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The graft copolymerization of methyl methacrylate in S-carboxymethylated wool fibers was investigated in the aqueous LiBr-K2S2O8 system. The rate of grafting, the degree of polymerization of graft polymer, and the number of grafting sites were determined on varying the thiol content at a constant concentration of monomer. Kinetic considerations lead to the following expression in agreement with the experimental results: Z/DP = {(ktd + ktc)/kp2[M]2} Rp, where Z is the number of DNP endgroups of polymer; DP is the average degree of polymerization; kp, ktd, and ktc are the rate constants of propagation, termination by disproportionation, and termination by recombination, respectively; [M] is the concentration of monomer in fibers, and Rp is the overall rate of grafting. For wool fibers in media sufficiently high viscosity, the rate constants ktd and ktc of diffusion-controlled termination are approximately equal and not affected by the change in cross-link density, provided that the thiol and disulfide interchange occurs. The possibility of occurrence of mechanical bond scission through a radical mechanism is involved in systems with extremely small amounts of thiol groups.
    Additional Material: 6 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 27 (1982), S. 1259-1268 
    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 effect of the specific surface area of silica gels on the radiation-induced polymerization of styrene adsorbed on silica gel was studied by ESR. The same radicals were generated on the silica gels regardless of the specific surface area, but the stability of the radicals at room temperature depended on the specific surface area. This means that the decay of the radicals proceeded mainly on the surface of the silica gel. Almost all the radicals generated by irradiation were initially in the bulk of the silica gel and migrated from the interior to the surface of the gel. When styrene monomer was adsorbed on the surface of the silica gel, the silica gel radicals interacted with the monomer and initiated polymerization and then generated polymer. The rate of migration of the silica gel radical was rather fast in the case of silica gel with a large specific surface area. Thus, the polymerization behavior of styrene adsorbed on silica gel greatly depended on the specific surface area of the gel.
    Additional Material: 9 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 20 (1976), S. 1679-1688 
    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: Radiation degradation of cellulose fibers was investigated by gel permeation chromatography (GPC). Scoured cotton of Mexican variety (cellulose I), Polynosic rayon (cellulose II), and their microcrystalline celluloses obtained by hydrolysis of the original fibers were irradiated by Co-60 γ-rays under vacuum or humid conditions. The irradiated samples were then nitrated under nondegradative conditions. The molecular weights and molecular weight distributions were measured by GPC using tetrahydrofran as solvent. The relationship between molecular weight and elution count was obtained with cellulose trinitrate standards fractionated by preparative GPC. The degree of polymerization of the fibers decreased with increasing irradiation dose, but their microcystalline celluloses were only slightly degraded by irradiation, especially in microcrystalline cellulose from cellulose I. Degradation of the fibers irradiated under humid conditions was less than that irradiated under vacuum. It was found that the G-values for main-chain scission for the irradiated cellulose I, cellulose II, microcrystalline cellulose I, and microcrystalline cellulose II were 2.8, 2.9, less than 1, and 2.9, respectively, but the G-value for main-chain scission for the irradiated cellulose II was increased to 11.2 at irradiation doses above 3 Mrad. Consequently, it is inferred that cellulose molecules in the amorphous regions are degraded more readily, and the well-aligned molecules in crystalline regions are not as easily degraded by irradiation.
    Additional Material: 7 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 18 (1974), S. 3379-3386 
    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 types of free radicals formed in decrystallized cellulose prepared from cellulose I and II after γ-irradiation in nitrogen atmosphere at room temperature were studied by ESR spectroscopy. X-Ray diffraction revealed that decrystallized cellulose I and II have the same microstructure. The ESR spectra obtained with the γ-irradiated decrystallized samples are simple. By contacting the irradiated sample with moisture in nitrogen atmosphere, the ESR spectrum changed to a narrow singlet, which gradually decreased in intensity until the spectrum completely disappeared. It was found that the types of free radicals generated in the decrystallized cellulose by γ-irradiation consist of the overlap of singlet and doublet. The singlet spectrum is mainly attributed to alkoxyl radical formed by the rupture of glycosidic linkage at the C 1 or C 4 position, and the doublet spectrum is ascribed to radical formed by hydrogen abstraction from the C 1 position in cellulose molecule.
    Additional Material: 7 Ill.
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  • 6
    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 types of free radicals produced in the water-accessible regions of cellulose I and cellulose II fibers by γ-irradiation in nitrogen atmosphere at room temperature were studied by ESR spectroscopy. The ESR spectra of the irradiated cellulose I and II change by contacting the fibers with water, and after immersion in water the spectral shape depends on the orientation of the fiber axes to the magnetic field. These spectra are probably related to the free radicals generated in the highly ordered regions inaccessible to water in irradiated cellulosic fibers. The ESR spectrum of free radicals generated in decrystallized cellulose after irradiation consists of a singlet and a doublet. When the ESR spectra of free radicals formed in the highly ordered regions of cellulose I and II and the singlet and the doublet are combined in adequate ratio, the constructed spectra are similar to those of the radicals scavenged by water in the irradiated cellulose I and II fibers. From these facts, the spectra due to the free radicals in the water-accessible regions in irradiated cellulose I and II are considered to consist of the singlet and the doublet formed by free radicals in the typical amorphous regions and the spectra of other types of radicals generated in the semicrystalline regions.
    Additional Material: 8 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 24 (1979), S. 1017-1029 
    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 fine structure of cotton cellulosic fibers carbamoylethylated and carboxyethylated at 30 and 20°C in the presence of 3% and 20% sodium hydroxide was investigated by measuring moisture regain, water imbibition, x-ray photograph, degree of crystallinity, spacing, and crystallite size under dry and wet conditions. As carbamoylethyl and carboxyethyl substituents are introduced in amorphous regions of the samples reacted with acrylamide in 3% sodium hydroxide, the fine structure of the crystalline regions is not affected by the reaction. On the other hand, in the samples reacted in 20% sodium hydroxide, the substituents are introduced not only in amorphous regions but also in crystalline regions to make them disordered. Although spacing between (101) planes does not change, spacing between (101) planes increases by the reaction in 20% sodium hydroxide. Comparing crystallite sizes normal to (hkl) planes under dry conditions with those under wet conditions, it is supposed that cohesive forces between (101) planes are different from those between (101) planes, and the former is hydrogen bonds and the latter resemble Van Der Waals forces. As a result, carbamoylethyl and carboxyethyl groups are introduced selectively between (101) planes.
    Additional Material: 6 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 48 (1993), S. 1121-1126 
    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: Graft copolymerization of methyl methacrylate onto novoloid fiber was carried out by the electron beam mutual irradiation method. The characteristics of the grafted fiber were almost the same as those of the original novoloid fiber. The grafted fiber was carbonized and activated to yield an efficiently activated carbon fiber. The yield and the specific surface area of the activated carbon fiber, derived from the grafted novoloid fiber, were much greater than those derived from the original novoloid fiber. This is because grafted poly(methyl methacrylate) decomposes into monomer and gaseous products, forming pores on the surface and inside of the novoloid fiber on heating. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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