Calculation of Reactivity Ratios and Sequence Distributions in Copolymers from Monomers 13C-NMR Data |
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Authors: | John K. Borchardt |
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Affiliation: | 1. Research Center , Halliburton Services , Duncan, Oklahoma, 73536-0444;2. Shell Development Company, Westhollow Research Center , P.O. Box 1380, Houston, Texas, 77001 |
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Abstract: | A screening procedure has been developed to predict the average sequence distribution in vinyl copolymers from monomer 13C-NMR data. The 13C-NMR absorption frequencies of the carbon atoms of the polymerizable double bond are used to calculate the Alfrey-Price Q and e values as previously described by Borchardt and Dalrymple. These, in turn, are used to calculate the monomer reactivity ratios. Reactivity ratios for 54 copolymerizations were calculated by this procedure and compared to literature values. The copolymer sequence distribution may then be determined by means of a computer program written by Harwood. The sequence distribution in copolymers of methacrylic acid and dimethyl-aminoethyl methacrylate, acrylonitrile and methyl methacrylate, 1,1-dichloroethylene and methacrylonitrile, ethyl acrylate and n-butyl methacrylate, and acrylamide and sodium 2-acrylamido-2-methylpropane sulfonate were calculated from reactivity ratios derived from 13C-NMR data and compared to literature values. This procedure may be used to calculate the reactivity ratios from 13C-NMR spectra of monomers for which no Q and e values are known. By this method the average sequence distribution of such monomers in copolymers may be predicted, significantly reducing the number of copolymers to be synthesized and tested for use in various applications. |
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