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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 1539-1548 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of investigation reported in previous papers was applied to preirradiation methods of reaction in vapor and in liquid. The absorption dose was varied from 2 to 0.1 Mrad. The monomer concentrations during reactions were determined gravimetrically. The patterns of increase of the degree of grafting did not change as the dose was varied in the liquid but changed considerably with dose in the vapor. The monomer concentration during the reaction did not vary with dose in the liquid but did so in the vapor. A model calculation was applied and improved to make the monomer concentration agree with that in the experiment. An attempt was made to describe the mechanism involved. There were some differences between the calculated values and the experimentally obtained ones, but the outline of the reaction mechanism was explained satisfactorily.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 3181-3192 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The graft polymerization of styrene onto high-density polyethylene films was carried out by γ-irradiation in the vapor phase. Two methods were used for grafting in these experiments: a preirradiation method and a simultaneous irradiation method. The effects of these grafting methods on the reaction mechanism of grafting and on the properties of the grafted samples were investigated. The amounts of styrene homopolymer in the grafted samples is under 2% in the case of the preirradiation method and above 10% in the case of the simultaneous irradiation method. The activation energies were calculated to be 18 kcal/mole for grafting in the preirradiation method and 15 kcal/mole for weight increase of polyethylene films in styrene vapor. The difference in the dimensional expansion between in the direction of stretching and the direction prependicular to it is smaller with preirradiation grafting than with grafting by the simultaneous irradiation method. Differential thermal analysis of the grafted films shows an endothermic peak due thermal decomposition which decreases gradually from 450°C to 415°C with increase in degree of grafting from 30 to 60%. The lowering of this peak temperature appears at a lower degree of grafting when the preirradiation method is used. On the basis of these results, it is concluded that the reaction rate of radiation-induced grafting in the vapor phase depends closely upon the processes of adsorption, dissolution, and diffusion of styrene monomer in polyethylene films; in the case of simultaneous irradiation method, the reaction proceeds comparatively uniformly in the amorphous region, while in the case of the preirradiation method, the reaction proceeds mainly at the boundary of the crystalline and amorphous regions.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2729-2739 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To investigate the mechanism of radiation-induced grafting in this system, the increase of monomer concentration in the polyethylene film in styrene vapor was evaluated by measuring the weight increase and formulated to be V([M∞] - [M]). The decay of radical concentration was also measured by ESR and the rate constant of the decay was determined. The alkyl type radical was affected only a little by styrene, while the allyl type radical was much affected by styrene. A new computer investigation method was proposed to clarify the reaction mechanism. The data obtained were substituted into differential equations and used to calculate the pattern of increase of the degree of grafting for the preirradiation method with reaction in the vapor phase. Results of these calculations suggest that only allyl type radicals induce grafting reactions and that the grafting reaction seldom occurs in the region of grafted polystyrene.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2887-2894 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The investigation method reported in the previous paper was applied to four reaction methods: preirradiation method with reaction in liquid monomer, preirradiation method with reaction in monomer vapor, simultaneous irradiation method in liquid, and simultaneous irradiation method in vapor. The increasing patterns and values of the degree of grafting experimentally obtained roughly agreed with those calculated by using the same rate constants. At high monomer concentration, the rate of grafting was small; at low monomer concentration, the rate of grafting was large. Strictly speaking, the data by simultaneous irradiation method were somewhat larger than those by calculation. Two additional factors, as homopolymerization and the grafting from the radicals formed on the grafted polystyrene, were considered and discussed. The rate constants obtained were also discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1689-1696 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The investigation method reported in earlier articles was applied to preirradiation methods of the reaction of low-density polyethylene (LDPE) in liquid and vapor and compared with high-density polyethylene (HDPE). Monomer concentrations during reactions and monomer feed rates were determined gravimetrically. Increasing patterns of the degree of grafting were obtained and compared. Monomer concentration during the reactions was lower in LDPE than HDPE and radical decay was more rapid in LDPE. A model calculation was applied to this experiment and a schematic explanation was attempted. The differences between the reaction mechanisms of HDPE and LDPE are explained.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 15-23 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: With high-density polyethylene (HDPE) and low-density polyethylene (LDPE) films the grafting reactions were performed by the preirradiation method. By holding the total absorption dose constant irradiation time was varied. The initial rate of grafting decreased with irradiation time. The relative concentration of alkyl radical in the polyethylene film also decreased with irradiation time, but the relative concentration of allyl increased. The differences in the ESR spectrum before and after the introduction of styrene indicate that the allyl-type radical reacted with styrene. To elucidate these results the allyl radical in the amorphous region was considered.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 13 (1975), S. 299-301 
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 1763-1773 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polypropylene films were irradiated with 60Co γ-rays in vacuum or in air and stored in air. Just after irradiation, the concentration of carbonyl group of the sample irradiated in air only increased with dose. The concentrations of both samples increased with storage time. The more the absorbed doses, the higher the increasing rates. The increasing rate of the concentration of carbonyl group during irradiation in air was higher than those during storage in air. Just after irradiation, the tensile strengths and the elongations of the both samples somewhat increased with dose at the doses less than 5 Mrad, but decreased at doses more than 13 Mrad. The tensile strength and the elongation of the sample irradiated in air decreased with storage time. Those of the sample irradiated in vacuum also decreased with storage time but the decreasing rates were much smaller than those in the sample irradiated in air. The gel fractions of the samples irradiated in vacuum and annealed in vacuum were somewhat higher than those irradiated in vacuum and not annealed. To elucidate high oxidation rate in the sample irradiated in air during and after irradiation, reaction mechanisms were discussed. To clarify the difference of mechanical properties between the samples irradiated in vacuum and in air, the effect of crosslink was considered, together with the oxidation.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 26 (1988), S. 2465-2473 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polypropylene films were irradiated with 60Co γ-rays in divinylsulfone (DVS) or butadiene (BD) gases. The variations of the intrinsic viscosities of the samples irradiated in vacuum or in DVS with dose showed usual patterns but the variation of the latter was somewhat more rapid. The intrinsic viscosity of the sample irradiated in BD could not be measured due to the early appearance of gel. The gel fraction of the sample irradiated in DVS appeared at lower dose than that irradiated in vacuum, but the former did not increase as much as the latter. The gel fraction of the sample irradiated in BD increased remarkably. The concentrations of the two kinds of double bonds increased in the sample irradiated in BD but levelled off gradually with dose. ESR study showed that the polypropylene radical reacted with DVS to form anisotropic radicals. The mechanisms of the effects of both reagents on irradiation of polypropylene were discussed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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