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  • 1
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Free radical homo- and copolymerisations of vinyl acetate and butyl acrylate were carried out in solution. Initial differences in data from homopolymerisation experiments lead us to investigate the influence of an eventual oxygen inhibition on the observed rate of polymerisation. A kinetic study at 70 °C was carried out both with and without a nitrogen purge. A decrease in the rate of polymerisation in the second instance was attributed to the presence of dissolved oxygen in the solution. Estimates of the apparent inhibition constant from different experiments are used to model both homopolymerisation and copolymerisation with vinyl acetate. The importance of taking this phenomenon into account during kinetic studies is demonstrated.
    Type of Medium: Electronic Resource
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  • 2
    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: An experimental investigation of mass transfer limitations on a single batch of high activity, heterogeneous catalysts used in the slurry polymerization of ethylene is presented. The viscosity of the continuous phase was varied, using trace amounts of inert copolymer in order to reduce the monomer diffusivity, and the activity levels were varied using hexene as an activator. These changes were intended to clearly identify situations in which the polymerization becomes mass-transfer-limited due to diffusion resistance in the pores of the catalyst. Increasing the observed activity of the catalyst from approximately 9000 to 40,000 grams of polymer per gram of catalyst per hour (g/g/h) revealed no evidence of mass transfer resistance, even when the diffusivity of the monomer in solution was reduced by a factor of six. Analysis of the molecular weight as a function of particle size supported this conclusion but did suggest that there might be slight chemical differences between large and small particles. © 1996 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 57 (1995), S. 371-384 
    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: This article begins by briefly reviewing the more important contributions to the area of modeling heat and mass transfer, and particle growth during the polymerization of olefins on Ziegler-Natta catalysts. It is shown that these models are capable of identifying the critical areas involved in heat and mass transfer, and of modeling polymerizations where the observed activity is less than approximately 5,000 g of polymer per gram of catalyst per hour (g/g/h). However, it is not possible to use these models “as-is” to model more modern catalysts whose activity levels can surpass the 50,000 g/g/h mark because they predict prohibitively large concentration gradients inside the growing particles during slurry polymerizations, and temperature gradients outside the particles during polymerization in the gas phase. An analysis of the mass and heat transfer Peclet numbers (Pe) reveals that certain simplifying assumptions may not always be valid. Pe values in the transition range suggest that convection inside the particles during polymerization in the liquid phase may help to explain why observed mass transfer rates are higher than the predicted rates. In an opposite vein, a Pe analysis shows that conductive heat transfer may play an important role at length scales characteristic of those in the early stages of polymerization. A new mechanism for heat transfer at reduced length scales is proposed. © 1995 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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