Partial phase diagrams and microstructures were investigated in a one-phase microemulsion region of sodium oleate/monoalkyl poly (oxyalkylene) ethers/water ternary systems by conductivity, freezefracture electron microscopy and pulsed field gradient spin-echo (PGSE) NMR measurements. The influence of n-decane and glycerol trioleate on the ternary phase diagrams was also examined. Monomethyl, ethyl and butyl poly (oxyethylene) ethers and monobutyl ethers having both ethylene oxide (EO) and propylene oxide (PO) groups with different alkylene oxide chain length were used for this purpose. Although similar one phase microemulsion regions appeared in the monobutyl poly (oxyethylene) ether ternary systems, the microemulsion regions shrunk on increasing EO chain length by adding n-decane and glycerol trioleate. The introduction of PO groups at the terminal position of ethers had a spreading effect on the one phase region even in quaternary systems. Transition from water-in-oil to oil-in-water microemulsions through bicontinuous structures was found to occur with increase in water content.
8- or 9- [2- (perfluorooctyl) ethoxy] -tricyclo [5. 2. 1.02' 6] deca- 3- en (1) was synthesized by the reaction of 2- (perfluorooctyl) ethanol with dicyclopentadiene in the presence of boron trifluo-ride- ethyl ether complex. The reaction rate exceeded that of the linear hydrocarbon alcohol with dicyclopentadiene. At the start of liquid phase oxygen oxidation, radicals were formed by the abstraction of hydrogen at the allyl position of (1) in the presence of azobis (isobutyronitrile), and peroxy radicals were subsequently produced by oxygen attack. The peroxy radical produced hydroperoxide by hydrogen abstraction in an intermolecular manner. At above a concentration of 10 % hydroperoxide, was converted to the corresponding hydroxide and ketone. The activation energy of hydroperoxide formation in neat was 20.6 kcal mol-1. Neither the addition of the peroxy radical to a double bond nor its coupling could be detected.
A study was made of the liquid phase oxygen oxidation of 8- or 9- [2- (perfluorooctyl) ethoxy] -tricyclo [5. 2. 1.02, 6] deca-3-en, active catalytic species, reaction behavior and components of products. The catalysts used were radical forming type : azobis (isobutyronitrile) and benzoyl peroxide, and transition metal salt type : Co-naphthenate and Mn- naphthenate. All reactions were carried out with oxygen bubbling in a xylene solution. Using radical forming catalysis, practically hydroperoxide alone was produced upto about a 10 % conversion, followed by the production of the corresponding hydroxide and ketone. On using the transition metal salt type, these three components were formed at the start of the reaction ; the hydroperoxide formation ratio was comparatively smaller and production of oligomer, larger. With radical forming catalysts, hydrogen abstraction led to the smooth formation of peroxy radicals and production of hydroperoxide. Hydroperoxide gradually decomposed with the transition metal salt type, excess amount of alkoxy and peroxy radicals were produced at the start of the reaction.
Assessment was made of the stabilization of fish oil, rich in highly unsaturated fatty acids, by several antioxidants at 5, 20, and 60°C. Antioxidants used were a mixed tocopherols concentrate (m-Toc), L-ascorbyl palmitate (Ap), dibutylhydroxytoluene (BHT), propyl gallate (PG), t-butylhydroquinone (TBHQ) and m-Toc combined with one or two of the others. Their added amounts were 0.1 and 0.2 % for m-Toc and 100 ppm for the others. In storage at 5°C, TBHQ markedly suppressed rapid increase in peroxide and carbonyl in fish oil. Antioxidant activity decreased in the order of TBHQ>PG>BHT>AP>m-Toc. m-Toc in combination with other antioxidants enhanced antioxidant activity. The most effective combination was that with TBHQ, followed by AP and PG. In storage at 20°C, the order of antioxidant activity was the same as at 5°C. Antioxidant effectiveness decreased with increase in storage temperature. Owing to the rapid rate of oxidation, no significant antioxidant activity could be seen at 60°C.