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  • Wiley-Blackwell  (13)
  • 1975-1979  (13)
Document type
Publisher
  • Wiley-Blackwell  (13)
Years
Year
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2773-2783 
    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 preirradiated poly(isobutylene oxide) (PIBO) with methanol and benzene was studied. The order of grafting yield and of the number-average molecular weight of graft chains decrease in the order; undiluted styrene 〉 styrene-methanol (1:1) solution 〉 styrene-benzene (1:1) solution. A kinetic treatment to calculate rate constants from the rate of grafting and the molecular weight of the graft chain was proposed. The propagation rate constant kp was 0.2-0.3 l./mole-sec and the termination rate constant kt was 1.0-16.0 l./mole-sec. The ratio kp/kt in this heterogeneous system was larger than that in homogeneous system by a factor of about 104-105.
    Additional Material: 9 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 16 (1978), S. 2875-2884 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation-induced graft polymerization of butadiene onto poly(vinyl chloride) powder was studied. By the kinetic treatment of elementary reactions the values of kp and kt[Z] of the graft polymerization were obtained. The activation energy of the propagation was calculated as 16.0 kcal mole-1. The value of kp was proportional of the 0.42 power of the dose rate and that of kt[Z] was proportional to the 0.84 power of the dose rate.
    Additional Material: 11 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 16 (1978), S. 179-187 
    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 styrene onto preirradiated poly(isobutylene oxide) was studied. An alkyl radical, —C(CH3)2—CH—O—, was mainly observed by the irradiation of preswelled poly(isobutylene oxide) in aerated methanol. Kinetic analysis of the graft copolymerization indicated that the preswelling influenced ktr and kt and did not influence of ∫0t Ridt and kp.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 13 (1975), S. 677-687 
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    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 14 (1976), S. 2365-2375 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Graft polymerization of styrene onto preirradiated poly(isobutylene oxide) was carried out at 25°C. The concentration of active sites for grafting was estimated by means of ESR and by the activation analysis of bromine atoms bound to the chain ends. Kinetic data such as differential amount of active sites (DACT), growth rate (GR), and average lifetime (τ) were obtained to calculate the molecular weight distribution of graft chains by the Monte Carlo simulation method. The number-average molecular weight of the graft chain was calculated from the equation, Mn = 2GRτ (mw), which agreed well with the observed value.
    Additional Material: 15 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 15 (1977), S. 1687-1696 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic studies of cografting reactions of styrene (St) and ethyl acrylate (EA) onto preirradiated polyethylene (PE) have been investigated by means of bromine labeling and infrared spectroscopy. Kinetic data obtained from these methods, that is, the percent grafting, the number of graft chains, and growing rates, were obtained at temperatures of 0, 20, 40, and 50°C. The graft percent was virtually influenced by the degree of swelling. At 0°C, the mixing ratio of ethyl acrylate and styrene monomer before the beginning of the reaction was equal to the existence ratio in the graft chains after the reaction. Therefore, this reaction is considered to be diffusion-controlled. On the contrary, at 20 and 40°C, the existence ratio in graft chains after the reaction. Therefore, this reaction is considered to be diffusion-controlled. On the contrary, at 20 and 40°C, the existence ratio in graft chains agreed with the theoretical curve calculated from monomer reactivity ratio. The number of active graft chains for given times were 3∼5 × 10-7 mole/g PE and it decreased with temperature; 0 〉 20 〉 50°C. While the total number of graft chains is 5∼15 × 10-7 mole/g PE and it increased with temperature; 0 〈 20 〈 50°C. The growing rate were 1∼5 monomer/site/sec for 0°C, 2∼15 for 20°C.
    Additional Material: 15 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1833-1842 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation-induced multiple-graft polymerization was studied by an ESR method. When methyl methacrylate vapor was introduced onto preirradiated polyethylene already grafted with styrene, the second step of grafting of methyl methacrylate occurred mainly in the polyethylene portion. The kinetic treatment proved that the termination rate constant kt of methyl methacrylate decreased with the amount of styrene grafted in advance. On the other hand, when styrene vapor was introduced onto polyethylene grafted with methyl methacrylate, only radicals of poly(methyl methacrylate) decreased. In this case, the second step of grafting of styrene occurred in the poly-(methyl methacrylate) portion which covered the whole surface of the polyethylene powder. When monomer vapors were alternately introduced onto preirradiated polyethylene powder, the second step of grafting occurred at the growing chain end of the first monomer.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 173-184 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: γ-Ray-induced polymerizations of ferrocenylmethyl methacrylate (FMMA) in crystalline and amorphous states were investigated with kinetical and ESR methods. In the crystalline state the polymerization of FMMA proceeded slowly and gave low-molecular-weight polymers, whereas in the amorphous state it proceeded rapidly and gave polymers of much higher molecular weight. Molecular weight distributions of these polymers were binodal. The temperature dependence and the dose-rate dependence of the polymerization rates were different between the two states. Wide-line nuclear magnetic resonance (NMR) spectra of the amorphous monomer suggested that the polymerization proceeded in a supercooled state. Electron spin resonance (ESR) spectra of γ-irradiated FMMA and 1,1′-ferrocenyl-di(methyl methacrylate) showed that ferrocene radicals and methacrylic radicals were formed simultaneously at low temperature; with increasing temperature the former radicals disappeared, whereas the latter changed into growing chain radicals. The yields of radicals were relatively low; this means that ferrocene groups in the monomers behave as a radiation energy absorber.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ferrocenylmethyl methacrylate (FMMA) was copolymerized with styrene (St), methyl methacrylate (MMA), and ethyl acrylate (EA) in benzene solution at 25°C by γ radiation. The reactions proceeded by a free radical mechanism, and monomer reactivity ratios were derived by the Tidwell-Mortimer method for St(M1)-FMMA(M2), r1 = 0.35 and r2 = 0.46; for MMA(M1-FMMA)(M2), r1 = 0.85 and r2 = 1.36; for EA(M1)-FMMA(M2), r1 = 0.36 and r2 = 3.03. The Q and e values of FMMA determined from copolymerization with St were 0.97 and 0.55, respectively. Terpolymerization of a MMA-FMMA-EA system based on the Alfrey-Goldfinger equations was studied. This is a typical terpolymerization system in which reactivities of the monomers obey the Q-e scheme. Comparing the results obtained here with those previously reported for other monomers, we concluded that FMMA is one of the most highly reactive monomers among alkyl methacrylates.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2167-2172 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal decomposition of polymer peroxide radicals formed in γ-irradiated polytetrafluoroethylene, ∼CF2CF(OO·)CF2∼ (radical I) and ∼CF2CF2(OO∼) (radical II), was studied by mass spectral analysis of the gas evolved in comparison with their photolysis with ultraviolet light. In the thermal decomposition of radicals I and II, CO2 was the most abundant component, with smaller amount of CO, CF2O, and gases present. In the photolysis, CO instead of CO2 was the most abundant in the case of radical I, while in the case of radical II, CO2 was again the main product. When a labeled polymer peroxide radical, ∼CF2CF(18O-18O·)CF2∼, was treated with heat or ultraviolet light, C18O16O was detected as a main component. In the treatment with ultraviolet light, a large amount of C18O comparable to that of C18O16O was also obtained. The mechanism of main-chain scission of radicals I and II is discussed.
    Additional Material: 1 Ill.
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