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  • 11
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2919-2933 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A sample of polystyrene with narrow molecular weight distribution (M̄w/M̄n = 1.03) has been formed into a 3-mm sheet and subjected to γ-irradiation at 25°C in air. Simultaneous crosslinking and scission of polymer chains resulted. Analyses by velocity and equilibrium sedimentation, gelpermeation chromatography, and osmometry of the polystyrene subjected to doses in the range 0-90 Mrad, all within the pre-gel region, have yielded average values of G(S) = G(X) = 0.022 ± 0.002 for the complete sample. Combination of these various experimental techniques has been successful in yielding consistent values of G(S) and G(X) and should be applicable with advantage to other polymers, particularly when neither G(S) nor G(X) is zero. The wide variation in literature values of G(S) and G(X) for irradiation of polystyrene under vacuum precludes any unequivocal conclusion on the effect of air on the radiation yields.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 131-139 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of γ-irradiation on poly(tert-butyl crotonate) has been investigated by velocity sedimentation and solubility studies. Evidence of significant crosslinking as well as of chain scission has been obtained, the estimates of G(X) and G(S) being 0.66 and 0.59, respectively.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 4081-4088 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of molecular weight averages and distributions have been made on three samples of narrow molecular size distribution polystyrene with molecular weights from 100, 000 to 400, 000 subjected to 60Co γ irradiation in vacuo for various doses within the pregel region+ G(X), the radiation chemical yield of crosslinking, has been determined as 0.043 ± 0.002 and G(S)/G(X), the ratio of scission to crosslinking, as 0.02; no effect of molecular weight was observed. By comparison with previous experimental results for polystyrene irradiated in air it has been established unequivocally that an oxygen environment leads to enhanced scission at the expense of crosslinking. Literature values of G(X) and G(S)/G(X) are reviewed in the light of these results and explanations are offered to account for major discrepancies.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 241-244 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simplified approximation method for the treatment of dead-end and high conversion polymerization kinetics is presented. The method is based on the treatment of dead-end polymerization first described by Tobolsky. In appropriate circumstances, by contrast with Tobolsky's method, this method provides measurements of kd and kp/kt1/2 without recourse to the measurement of the monomer conversion at infinite time.Kinetic studies of free radical polymerizations are normally confined to measurements of initial rates. At low conversions the predictions of the general mechanism for chain-growth polymerization involving initiation, propagation, and termination steps are generally obeyed. Thus the polymerization rate should be first order in the vinyl monomer and half-order in the initiator concentrations.At high conversions, however, large deviations which can be ascribed to various effects can occur; for example, (1) the effect of the increasing viscosity of the polymerization medium on the termination rate constant kt, and possibly also on the propagation rate constant kp, which have been considered by North1 and Cardenas and O'Driscoll,2 or (2) depletion of the initiator as the polymerization progresses. This depletion will occur in all polymerizations but its significance will depend on the magnitude of the rate constant for initiator decomposition (kd) and the period of polymerization. Appropriate conditions will lead to limiting monomer conversion even after infinite polymerization time; this phenomenon has been called dead-end polymerization by Tobolsky.3Free radical polymerizations to high conversion are particularly important in the industrial context when initial kinetics are obviously inadequate. Suitable treatment of the conversion/time relationship is highly desirable.Senogles and Woolf4 have examined the polymerization of n-lauryl methacrylate at 60°C with 2-azobisisobutyronitrile as initiator under dead-end conditions.Here we propose a modification of Tobolsky's treatment of such polymerizations by using an approximation for the exponential decay in the initiator concentration. This method permits easy manipulation of the experimental data and the estimation of values for the kinetic parameters in favorable circumstances without recourse to the measurement of the conversion at infinite time or the evaluation of complicated functions of the monomer conversion. The method thus allows the duration of the laboratory experimentation to be significantly shortened and the complexity of the subsequent data analysis to be considerably reduced.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 15
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Vinyl acetate emulsion polymerization at 70°C. using potassium peroxydisulfate as initiator and a partially hydrolyzed polyvinyl acetate as emulsifying agent has been studied. In agreement with the Smith and Ewart scheme for emulsion polymerizations, the polymerization rate was found to be independent of the total monomer amount present and approximately dependent on the 3/5 power of the emulsifier concentration. Instead of a 2/5 power dependence on initiator concentration for the rate of polymerization, a 0.7 power dependence was found. From surface tension measurements an “apparent critical micelle concentration” was determined for aqueous solutions of the emulsifier. However, light scattering studies gave no indication that aggregates of the emulsifier exist in aqueous solutions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 16
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das kristalline Dihydrat des Bariummethacrylates wurde durch Einwirkung von Gammastrahlen bei 15-35°C polymerisiert. Man erhielt S-förmig gekrümmte Zeit-Umsatzkurven. Die Induktionsperiode fiel merklich mit steigender Temperatur oder Strahlungsintensität ab. Die Polymerisationsgeschwindigkeit (annähernd konstant bei einem Umsatz von 25-75%) stieg mit der Bestrahlungsintensität entsprechend einem Exponenten von etwa 0,5 an, war jedoch nahezu unabängig von der Temperatur. ESR-Spektren zeigten, daß die Radikalkonzentration linear mit der Zeit von Beginn der Bestrahlung an steigt und bei 25°C ebenso wie auch bei 15°C G(Radikale) + 7,6 ± 0,5 ergibt. Während der Polymerisationsperiode fiel die Radikalkonzentration, stieg dann jedoch wieder an. Die Induktionsperiode wird auf einen physikalischen Abfangvorgang wachsender Radikale kurzer Kettenlänge zurückgeführt.
    Notes: Crystalline barium methacrylate dihydrate polymerized during gamma irradiation at 15-35°C. Sigmoidal shaped conversion curves were obtained. The induction period decreased markedly with increase in temperature or dose rate. The polymerization rate(approximately constant from 25-75% conversion) increased with dose rate, corresponding to an exponent of about 0.5, but was almost independent of temperature. ESR spectra showed that the radical concentration increased linearly with time from the commencement of irradiation giving G(radicals) = 7.6 ± 0.5 at 25°C and the same value at 15°C. The radical concentration decreased during the polymerization period, but then increased again. The induction period was attributed to physical trapping of short-chain propagating radicals.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 7 (1969), S. 129-134 
    ISSN: 0449-2986
    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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  • 18
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 15 (1977), S. 659-669 
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 19
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Homopolymers and vinyl chloride copolymers have been prepared from the vinyl esters of mixed hydrogenated cyclized linolenic acid, 9,10-dichlorostearic acid, 9,10,12,13-tetrachlorostearic acid, 13,14-dichlorobehenic acid, 9(10)-phenylstearic acid and technical behenic acid. Vinyl 13,14-dichlorobehenate (29%)-vinyl chloride (71%) gave a copolymer with a brittle temperature of -2°C. All of the other copolymers with vinyl chloride had brittle temperatures of 16°C. or higher and behaved more like rigid plastics.
    Additional Material: 5 Tab.
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  • 20
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 7 (1969), S. 1665-1674 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electron spin resonance spectrum of gamma-irradiated octadecyl methacrylate (m.p. ≈ 12°C.) was due to a mixture of three radicals formed by (1) loss of a hydrogen atom from the paraffin chain, (2) addition of a hydrogen atom to the double bond, and (3) addition of a monomer molecule to radicals formed by (1) or (2). On warming monomer added to radicals (1) and (2) between -170 and -50°C., and above -50°C. the spectrum was solely due to propagating methacrylate radicals. The total radical concentration decreased slightly at -150°C. and was then constant up to -30°C. A marked decrease in radical concentration occurred from -30 to +12°C., it took place rapidly and reached an equilibrium value after each successive increase in temperature. Differential thermal analysis indicated a solid - solid phase change at -30°C. When the sample was kept at 0°C. there was no further decrease in radical concentration even with 50% conversion to polymer. With 2% added chloranil the (chloranil)- was observed to be of about the same concentration as methacrylate radicals. The initial total radical concentration was lower and decreased to zero by 0°C. on warming. No polymer was obtained.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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