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Autoxidation of thiols with cobalt (II) phthalocyanine-tetra-sodium sulfonate, attached to poly(vinylamine)

1. pH and viscometric effects

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Summary

The oxidation of 2-mercaptoethanol with molecular oxygen in water with cobalt(II)phthalocyanine-tetra-sodium sulfonate attached to poly(vinylamine) has been investigated.

Specially attention was paid to the effect of pH and chain dimensions on polymer activity. The polymer catalyst possesses a large conformational freedom at neutral pH, but at higher pH a shrinkage of the polymer coil occurs and diffusion limitations cannot be excluded. The catalyst shows an enzyme-like behaviour in the autoxidation of thiol. Overall activation energies appear to decrease with increasing pH. At pH = 7.4, Ea = 61 KJ mole−1; at pH = 9.5, Ea = 3 KJ mole−1.

Electrostatic effects are of major importance in the chemical reactivity since they affect the local thiol-anion concentration in the close vicinity of the polymer attached oxidation sites.

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Authors and Affiliations

  1. Laboratory of Polymer Chemistry, Eindhoven University of Technology, Postbox 513, NL-5600, MB Eindhoven, The Netherlands

    W. M. Brouwer, P. Piet & A. L. German

Authors
  1. W. M. Brouwer
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  2. P. Piet
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  3. A. L. German
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Brouwer, W.M., Piet, P. & German, A.L. Autoxidation of thiols with cobalt (II) phthalocyanine-tetra-sodium sulfonate, attached to poly(vinylamine). Polymer Bulletin 8, 245–251 (1982). https://doi.org/10.1007/BF00700285

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  • DOI: https://doi.org/10.1007/BF00700285

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