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    Polymerisation of vinyl monomers in continuous-flow reactors. An experimental study, which includes digital computer modelling, of the homopolymerisation of styrene and methylmethacrylate by anionic and free radical mechanisms respectively in continuous flow-stirred-tank reactors.

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    Publication date
    2009-10-28T15:27:01Z
    Author
    Bourikas, N.
    Supervisor
    Johnson, A.F.
    Keyword
    Polymerisation
    Vinyl monomers
    Continuous flow-stirred-tank reactors
    Computer modelling
    Homopolymerisation
    Styrene
    Methylmethacrylate
    Free radical mechanisms
    Rights
    Creative Commons License
    The University of Bradford theses are licenced under a Creative Commons Licence.
    Institution
    University of Bradford
    Department
    Postgraduate School of Studies in Polymer Science.
    Awarded
    1976
    
    Metadata
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    Abstract
    An introduction is given to the background theory and scientific literature of the major subject areas of interest in this thesis, namely the chemistry of free radical and anionic polymerisation, molecular weight control in each type of polymerisation, polymerisation reactors, computer simulation of polymerisation processes and polymer characterisation by gel permeation chromatography. A novel computer model has been devised, based on the analysis of the polymerisation process in terms of the reaction extent of each reactant and the use of generation functions to describe the concentration of living and dead polymeric species, for the free radical, solution polymerisation of methylmethacrylate in a CSTR. Both heat and mass balance expressions have been described. Conversion, Mn and Mw were monitored. To test the model a reactor was designed and constructed. A detailed description of the reactor and the experimental conditions used for the validation of the model are given. The results of these studies are presented and excellent agreement is shown between model predictions and experiments up to 30% conversion for Mn w and % conversion. A similar study is described for the anionic polymerisation of styrene in tetrahydrofuran as solvent, in a CSTR. In this work the computer model becomes 'stiff' when realistic rate constants are introduced in the kinetic expressions. Experimental difficulties were encountered in obtaining reproducible results in the anionic work. A new approach of using 'scavengers' as protecting agents for the living chains is described. A scavenger was successfully employed in the preparation of block copolymers using a tubular reactor. Block copolymerisation, in addition to providing a means of checking the number of the 'living' chains inside the reactor, is of interest in its own right. All the experimental findings are discussed in relation to the currently accepted views found in the scientific literature.
    URI
    http://hdl.handle.net/10454/3792
    Type
    Thesis
    Qualification name
    PhD
    Collections
    Theses

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