Autoxidation of 1-decanethiol catalyzed by cobalt phthalocyaninetetrasulfonate on cationic latexes
- Oklahoma State Univ., Stillwater (USA)
Cationic latexes 60 nm in diameter have been prepared by emulsion copolymerization of 2% of quaternary ammonium ion surfactant monomers and 1-5% of divinylbenzene with styrene. All of the surfactant monomers were bound to the product latexes, within experimental error. The cationic latexes bound cobalt phthalocyaninetetrasulfonate (CoPcTs) quantitatively from aqueous CoPcTsNa{sub 4}. The CoPcTs latexes catalyzed autoxidation of 1-decanethiol dispersed in water with zero-order consumption of dioxygen from a gas buret at 1 atm of pressure to at least 65% conversion of thiol. All reactions had an induction time before the start of oxygen consumption. Rates increased with pH in the range 7-9, and the following observations were made at pH 9. The zero-order rate constants with CoPcTs latexes were up to 14 times faster than with CoPcTsNa{sub 4} in aqueous solution. Hexadecyltrimethylammonium bromide and one of the surfactant monomers as micellar catalysts gave rate enhancements similar to those with latex catalysts. Rates of autoxidation in the three-phase mixtures of water, latex particles, and thiol droplets were not affected significantly by the method of mixing. The rate of latex-catalyzed oxidation increased with small amounts of added methanol and nonionic surfactant. Varied concentrations of dispersed 1-decanethiol in the range 1-4 {times} 10{sup {minus}2} M gave saturation kinetics. Increasing partial pressures of dioxygen in the range 0.25-1.0 atom gave small increases in rate.
- OSTI ID:
- 7196770
- Journal Information:
- Journal of Organic Chemistry; (USA), Vol. 54:13; ISSN 0022-3263
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
THIOLS
OXIDATION
CATALYSTS
COBALT COMPOUNDS
DATA ANALYSIS
EXPERIMENTAL DATA
LATEX
MEASURING INSTRUMENTS
MEASURING METHODS
CHEMICAL REACTIONS
DATA
ELASTOMERS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC POLYMERS
ORGANIC SULFUR COMPOUNDS
POLYMERS
RUBBERS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties