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Anionic polymerization of butyl cyanoacrylate by tetrabutylammonium salts, 2. Propagation rate constants by Eromosele, Ighodalo Clement ;Pepper, David Charles is a Chemistry article available to read on EtoBox.

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Anionic polymerizations of butyl cyanoacrylate were initiated in tetrahydrofuran (plus a few experiments in 1,2-dimethoxyethane) by the salts tetrabutylammonium hydroxide, bromide, acetate and three substituted acetates. The hydroxide gives near-ideal 'living polymerization' kinetics, with k, close to lo6 I . mol-' . s -' at 20°C. The kinetics of the reactions initiated by the acetates and bromide are analysed by the slow-initiation-no-termination theory, using values of the initiation rate constants evaluated in Part 1. The k, values derived are in the same range as those from the OH-initiated reactions and those of the zwitterionic polymerizations initiated with covalent bases, i.e., tertiary phosphines and amines. A ca. 4-fold variation of k, with concentration of active species is given a speculative analysis in terms of dissociation from paired to free ions, yielding tentative estimates for k: --lo5 and k;-= lo7 1 . mol-I . s -' in THF at 20°C. Molecular weights were all high, a,,

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Author

Eromosele, Ighodalo Clement ;Pepper, David Charles

Publisher

Wiley (John Wiley & Sons); Wiley (ISSN 0025-116X)

Published

1989

Language

EN

Field

Chemistry (Physical Sciences)