ISSN:
0887-624X
Keywords:
2,4-ionene
;
poly(quaternary ammonium)salt
;
cobalt(II) phthalocyaninetetra-carboxylic acid
;
cobalt(II) phthalocyanineoctacarboxylic acid
;
mercaptoethanol
;
autoxi-dation
;
catalysis
;
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The promoting effects of 2,4-ionene on the cobalt(II) phthalocyaninetetracarboxylic acid-[CoPc(COOH)4] and cobalt(II) phthalocyanineoctacarboxylic acid-[CoPc(COOH)8] cata-lyzed autoxidation of 2-mercaptoethanol were studied. Dimerization of the CoPc(COOH)4 catalyst, combined with the disappearance of the catalytically inactive μ-peroxo complex and the appearance of substrate enrichment in the presence of 2,4-ionene, results in a 40-fold enhancement of the oxidation rate as compared with the polymer-free system. UV-VIS spectroscopy indicates that CoPc(COOH)8 is incapable of forming μ-peroxo complexes or 2,4-ionene-induced dimeric catalyst species under normal reaction conditions. Thus, it was possible to study exclusively the ionene-induced effect of substrate enrichment. Addition of 2,4-ionene to an aqueous CoPc(COOH)8 solution results in an activity enhancement by a factor of 2-3, which can be ascribed to substrate enrichment. Additionally, using mono-disperse ionene oligomers showed a molecular weight dependence of 2,4-ionene on the catalytic activity of CoPc(COOH)8, as was observed for the conventional 2,4-ionene/cobalt phthalocyaninetetrasodiumsulfonate system. The optimal polycation/catalyst ratios of both systems decrease with increasing chain length of 2,4-ionene, until a constant value is reached. This leads to the conclusion that the optimal polymer/catalyst ratios are predominantly determined by substrate enrichment. © 1995 John Wiley & Sons, Inc.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pola.1995.080331111
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