Methyl methacrylate-chloroprene copolymerization: an evaluation of copolymerization models

doi:10.1016/0032-3861(84)90221-0

Polymer

Volume 25, Issue 4, April 1984, Pages 569-573

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Abstract

The composition and triad fraction data of Ebdon (Polymer 1974, 15, 782) for the copolymerization of methyl methacrylate with chloroprene have been re-evaluated using non-linear least squares curve-fitting procedures and statistical testing of conclusions. Using the compositions and triad fractions separately, best estimates of reactivity ratios together with the joint confidence intervals for these parameters for terminal and penultimate models have been calculated. It has been shown that the terminal model cannot describe adequately the experimental compositions or triad fractions. While the allowance of a penultimate effect for methyl methacrylate chain end radicals provides a significant improvement over the fit of the terminal model to the copolymer compositions, there is only a small probability that both the triad fraction and the composition data can be described adequately by one set of penultimate reactivity ratios.

References (14)

J.R. Ebdon
Polymer
(1974)
D. Braun et al.
Eur. Polym. J.
(1973)
K.W. Doak et al.
J. Am. Chem. Soc.
(1951)
R. Chujo et al.
Polym. J.
(1972)
I. Motoc et al.
J. Polym. Sci., Polym. Chem. Ed.
(1978)
P.W. Tidwell et al.
J. Macromol. Sci., Rev. Macromol. Chem.
(1970)
R.C. McFarlane et al.
J. Polym. Sci., Polym. Chem. Ed.
(1980)

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Polymer paperMethyl methacrylate-chloroprene copolymerization: an evaluation of copolymerization models

Abstract

Polymer

Eur. Polym. J.

J. Am. Chem. Soc.

Polym. J.

J. Polym. Sci., Polym. Chem. Ed.

J. Macromol. Sci., Rev. Macromol. Chem.

J. Polym. Sci., Polym. Chem. Ed.

Polymer paper
Methyl methacrylate-chloroprene copolymerization: an evaluation of copolymerization models