Improved methods of estimating monomer reactivity ratios in copolymerization by considering experimental errors in both variables

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Abstract
Existing methods of calculating monomer reactivity ratios in copolymerization are reviewed briefly, evaluated, and classified according to their mathematical and computational similarities. More attention is paid to procedures based on the integrated copolymer equation with which calculation of r values is performed most often by electronic computer. Unfortunately, until now all procedures have shown shortcomings because the real‐error structure of the observations has not been taken into account. A new algorithm that does account correctly for measurement errors in both variables is described. A computational method is illustrated for copolymerization data obtained from quantitative gas chromatographic analysis of the monomer feed throughout the reaction. It is shown that the actual error structure of the variables corresponds to the assumed error structure. Reliability of the estimates is substantially increased, compared with the existing methods. Standard deviations of the monomer reactivity ratios are given and appear to be in good agreement with reality.

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