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Title: Comonomer composition distribution in free radically initiated solution copolymerisation
Author: Austen, Robert C.
Awarding Body: University of Bradford
Current Institution: University of Bradford
Date of Award: 1980
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New and published equations are presented for the prediction of copolymerisation behaviour in binary and multi-component comonomer systems. Equations for transposing between molar and weight composition ratios or fractions in the feed or copolymer are reviewed and new ones given. Predictions for the binary copolymer case are demonstrated with a computer program, which from only one input card outputs either molar or weight calculation results or graphs of various sequence or copolymerisation parameters or a comprehensive sequence distribution analysis. The literature is reviewed for both differential and integral calculation methods for the determination of binary copolymerisation reactivity ratios. Two new calculation methods are presented including the "Reciprocal Kelen-Tudos" method, which obtains the same solutions as the Kelen-Tudos method but more simply. The computer calculation and graphical presentation of four published differential calculation methods with error analyses is given. A new computer method is described for the conversion of feed composition analysis data into useful copolymerisation parameters. New single line equations are given for each of these parameters applicable to either GLC or spectroscopic analysis of liquid and / or gaseous mixtures. Copolymerisation rate behaviour is reviewed for binary and multi-component systems. Least squares curve fitting by rational polynomials of monomer-time curves is demonstrated. Methods for the prediction of monomer addition schedules to obtain homogeneous binary copolymer are presented. These are simplified and extended to the case of mixed homogeneous-heterogeneous copolymer. Fundamental differences in the literature are shown for the definitions of various copolymer sequence distributions. A comprehensive review of binary copolymer structure theory is presented. New equations for the number of symmetric, asymmetric and observable sequences are given. The literature is reviewed and many new equations are given for indices, which indicate the degree of structural or compositional heterogeneity in binary or multi-component copolymers and which may be used to relate the properties of copolymers prepared by batch, continuous or controlled semi-batch monomer addition processes. The methods of analysing copolymer composition in binary and multi-component copolymers are reviewed, in particular Size Exclusion sion Chromatography (S.E.C. or G.P.C.). New more accurate equations are given for binary copolymer composition obtained by S.E.C. instruments fitted with a single spectroscopic detector, for the case when both comonomers absorb at the same wavelength. An on-line simultaneous automatic data acquisition computer program with automatic analysis of composition and heterogeneity indices is applied to the case of Spectroscopic Size Exclusion Chromatography.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Chemistry, general