Catalysis of polyvinylpyridine-supported Cu(II) during 2,6-Di-tert-butylphenol oxidation in the presence of inorganic base

Journal Article · Sun Nov 01 00:00:00 EST 1992 · Journal of Catalysis; (United States)

DOI:https://doi.org/10.1016/0021-9517(92)90004-2· OSTI ID:5650314

Takokoro, Hiroyuki; Nishiyama, Satoru; Tsuruya, Shigeru; Masai, Mitsuo ^[1]

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1. Kobe Univ., Nada (Japan)

The liquid-phase oxidation of 2,6-di-tert-butylphenol(BOH) was studied using a heterogeneous polymer-supported Cu(II) catalyst, basic Cu(II)-poly(4-vinylpyridine) (Cu(II)-PVP) catalyst. The only oxidation product was 3,3[prime],5,5[prime]-tetramethyl-4,4[prime]-diphenoquinone. The oxidation reaction of BOH did not proceed by the presence of only the Cu(II)-PVP catalyst itself, but was significantly promoted by adding an inorganic base such as KOH in the solvent. The added KOH was found to have the role of generating the corresponding phenolate anion by dissociating the BOH molecule. The turnover number (mole of absorbed O[sub 2] molecule per unit time and unit mole of Cu(II)) with the basic Cu(II)-PVP catalyst in the BOH oxidation passed through a maximum with the variation in the pyridine/Cu(II) mole ratios (ligand ratio). From the dependence of the reaction rate on the Cu(II) concentration of the Cu(II)-PVP catalyst, it was found that the reaction order of the Cu(II) concentration was changed from second- to first-order with an increase in the Cu(II) amount in the Cu(II)-PVP. On the basis of the kinetic results it is assumed that the rate-determining step in the BOH oxidation catalyzed by the basic Cu(II)-PVP changed from the reoxidation step of the dinuclear Cu(I) complex with an oxygen molecule to the BOH oxidation step by the mononuclear Cu(II) complex with an increase in the Cu(II) amount in the Cu(II)-PVP catalyst. Since the catalytic activity of the used Cu(II)-PVP catalyst almost remained intact, it was found possible to re-use the Cu(II)-PVP catalyst. 31 refs., 14 figs., 3 tabs.

• OSTI ID: 5650314
• Journal Information: Journal of Catalysis; (United States), Vol. 138:1; ISSN 0021-9517
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COPPER COMPLEXES
CATALYTIC EFFECTS
PHENOLS
OXIDATION
CATALYSIS
CATALYST SUPPORTS
CATALYSTS
CHEMICAL REACTION KINETICS
HETEROGENEOUS CATALYSIS
ORGANIC POLYMERS
PHENOLATES
POTASSIUM HYDROXIDES
PYRIDINES
QUINONES
SOLVENTS
ALKALI METAL COMPOUNDS
AROMATICS
AZINES
CHEMICAL REACTIONS
COMPLEXES
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
HYDROXIDES
HYDROXY COMPOUNDS
KINETICS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
POLYMERS
POTASSIUM COMPOUNDS
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties