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  • 1975-1979  (12)
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Year
  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 83 (1979), S. 3290-3293 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    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 14 (1976), S. 2575-2585 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Irradiation of sodium allylsulfonate in aqueous solution at high pressure (up to 9000 kg/cm2) gave a deliquescent white powder which is insoluble in organic solvent. The product was addition polymer of allylsulfonate from the high-resolution NMR and infrared spectra. The rate of polymerization was proportional to the third and second powers of monomer concentration in the initial and later stages, respectively. From the high dependence of the rate on monomer concentration, the reaction was deduced to proceed in an associated monomer or micelle. The rate of polymerization was increased by addition of sodium chloride. The G value for monomer consumption was about 104 at high pressure, which suggests that the degradative chain transfer is not important in the polymerization. Overall activation volumes were -7 and -5 ml/mole in the initial and later stages, respectively.
    Additional Material: 12 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 2607-2616 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of radiation on polystyrene was studied in the presence and absence of silica gel by molecular weight measurement with GPC. Polystyrene crosslinked under vacuum in the absence of silica gel, but it either crosslinked or degraded by radiation, depending on the molecular weight of the polymer in the presence of silica gel. Part of the deposited polymer bonded to silica gel by radiation; the G value for graft-chain formation is in the range of 0.01-0.1. Irradiation of polystyrene grafted on silica gel resulted in degradation of the graft chain because of the transfer of energy from silica gel. The G value for main chain scission was about 2 when graft polymer was irradiated in the absence of homopolymer. The degradation of graft polymer was suppressed when the polymer was irradiated in the presence of homopolymer, and the amount of unextractable polymer from silica gel increased with increasing irradiation. This adds evidence to the estimation that an increase in grafting percent coupled with a slight decrease in molecular weight at a later stage of radiation-induced polymerization of styrene adsorbed on silica gel is due to a secondary effect of radiation on the polymer.
    Additional Material: 7 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 393-404 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of dose rate on the rate of polymerization and molecular weight distribution of radiation-induced polymerization of styrene adsorbed on silica gel was studied in a wide dose rate range of 4.4 × 104 to 3 × 108 rad/hr by γ rays of 60Co and electron beams with a Cockcroft-Walton-type accelerator. Dose rate dependence on the initial rate of polymerization was about 1 below 3 × 107 rad/hr, and it decreased gradually at high dose rates. Throughout the dose rate range, graft polymerizations and homopolymerizations by cationic and radical mechanisms proceeded simultaneously. Dose rate dependence of the cationic polymerization was 1 below 3 × 107 rad/hr, while dose rate dependence of the radical polymerization was 0.65 below 3 × 107 rad/hr. At high dose rates, molecular weight and fraction of graft polymer decreased, and fraction of cationic polymerization increased. A very high-molecular-weight graft polymer was formed above 4.4 × 105 rad/hr at the initial stage of the polymerization. The dose rate dependence of this polymerization was larger than 1 and decreased with increase in dose rate. The polymerization seems to be related to an excitation of monomer or growing chain.
    Additional Material: 5 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 405-414 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of amount of monomer on radiation-induced polymerization of styrene adsorbed on silica gel was investigated with the monomer amounting from less than monolayer adsorption to more than the equilibrium adsorption. The rate of graft polymerization and the molecular weight of the polymer changed with the amount of monomer adsorbed on silica gel. Maximum grafting efficiency was obtained at monolayer adsorption. The molecular weight of graft polymer was higher than that of homopolymer in both radical and cationic polymerizations, and the ratio in molecular weight of graft polymer to that of homopolymer tends to be unity with increasing amount of adsorbed monomer. These results can mainly be explained in terms of the number of initiating species (radical and cation) that change in relation to the amount of adsorbed monomer. Propagation and termination change with amount of adsorbed monomer in relation to the molecular mobility of adsorbed monomer. A very high-molecular-weight graft polymer is formed only with a small amount of adsorbed monomer in the initial stage. The grafting percent with a large amount of adsorbed monomer increased after most of the monomer has been polymerized. Secondary effect of radiation on the graft and homopolymers due to energy transfer from silica gel is suggested from the complicated phenomena in the later stage of the reaction.
    Additional Material: 9 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 13 (1975), S. 369-375 
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 19 (1975), S. 1959-1969 
    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 physical state of the blends of radiation-polymerized polyethylene with high-density polyethylene was studied. Only one peak was observed in DSC heating curves of the blends quenched from the melt regardless of the each polymer content. In addition, transparency of the high-density polyethylene was improved by melt blending with radiation-polymerized polyethylene. This is a characteristic of high-density polyethylene and radiation-polymerized polyethylene blends different from high-density and low-density polyethylene blends. A new peak and/or a new shoulder, however, appeared in DSC heating curves of the blends with heat treatment at 110°, 120°, and 125°C. These results suggest that the physical state of the blends quenched from the melt is one where the crystallization of the radiation-polymerized polyethylene is high hindered by the presence of high-density polyethylene. The radiation-polymerized polyethylene may remain mainly in a physical state similar to the melt. The haze value of the blends increased with heat treatment. The increase in the haze is caused by change in physical states, such as growth of spherulites and formation of microcrystals and microvoids, by the heat treatment.
    Additional Material: 8 Ill.
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  • 8
    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-induced polymerization of ethylene using aqueous tert-butyl alcohol as medium was carried out in a large-scale pilot plant with a 50-liter central source-type reactor at a pressure of 105 to 395 kg/cm2, temperature of 30° to 80°C, mean dose rate of 4.5 × 104 to 1.9 × 105 rads/hr, ethylene feed rate of 5.5 to 23.5 kg/hr, and medium feed rate of 21 to 102 l./hr. The space-time yield and molecular weight of the polymer were in the range of 4.7 to 16.8 g/l.-hr and 1.3 × 104 to 8.9 × 104, respectively. The space-time yield and molecular weight increased with mean residence time at 30°C, whereas at 80°C they became almost independent of the time. The space-time yield increased with pressure and dose rate, slightly decreased with temperature, and was maximum at ethylene molar fraction of 0.5. The polymer molecular weight increased with pressure and ethylene molar fraction, and decreased with dose rate and temperature. The total amount of deposited polymer on the reactor wall, source case wall, and scraping blades was usually less than 1 kg, which was negligibly small for the analysis of polymerization. Continuous discharge of the polymer slurry and production of fine-powder polyethylene were successfully carried out. In the central source-type reactor, a dose rate of 1.9 × 105 rads/hr was obtained with a 60Co source of ca. 12 kCi.
    Additional Material: 13 Ill.
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  • 9
    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-induced polymerization of ethylene using tert-butyl alcohol aqueous solution as a medium was carried out in a pilot plant with 10 liter reactor at pressures of 100 to 400 kg/cm2, ethylene feed rates of 1.2 to 11.8 kg/hr, medium feed rates of 0 to 100 liter/hr, dose rates of 0.6 × 105 to 1.4 × 105 rad/hr, and at room temperature. The space-time yield and molecular weight of polymer were in the range of 1.2 to 16.7 g/liter hr and 6 × 103 to 2 × 105, respectively. The space-time yield and molecular weight increased with pressure and mean residence time. The space-time yield was the maximum at an ethylene molar fraction of 0.5. The produced polymer was continuously taken out from the high-pressure system as a slurry. The amount of deposited polymer to the reactor wall was markedly decreased, and five full days continuous operation was successfully performed with the space-time yield of 13.5 g/liter hr.
    Additional Material: 12 Ill.
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  • 10
    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-induced bulk polymerization of ethylene was carried out with use of a pilot plant with a 10 liter reactor at pressures of 225-400 kg/cm2, temperatures of 30-95°C, ethylene feed rates of 5-28 kg/hr, and dose rate of 3.8 × 105 rad/hr. Characteristics of the process are mild polymerization conditions and capability of producing medium density polyethylene in powder form. The spacetime yield and molecular weight of polymer were in the range of 3.5 to 13.1 g/liter hr and 2.2 × 104 to 14 × 104, respectively. The space-time yield increased with mean residence time and 2.4 powders of pressure, and decreased with temperature. Molecular weight changed similarly with the reaction conditions. These results were consistent with those of the bench plant experiment and the scale effect was small. Polymer deposit to the reactor wall limited a period of continuous operation of the plant. The amount of deposited polymer was increased with the square of reaction time. The rate of polymer deposit was proportional to polymer concentration and to the cube of pressure. The polymer deposit cannot be solved in the bulk process.
    Additional Material: 9 Ill.
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