Oxidation unsaturated groups

Overoxidation with permanganate is always a problem, but the relative reaction rates are very much a function of the pH of the reaction mixture and, in basic solution, potassium permanganate oxidizes unsaturated groups more rapidly than it oxidizes alcohols ... 

In modem manufacturing methods the oil is sometimes reacted directly with the glycerol to form a monoglyceride and this is then reacted with the acid to form the alkyd resin. When the resulting surface coating is applied to the substrate the molecules are substantially linear. However, in the presence of certain driers such as lead soaps there is oxidative cross-linking via the unsaturated group in the side chain and the resin hardens. 

Free radicals can be generated on the cellulose chain by hydrogen abstraction, oxidation, the ceric ion method, diazotization, introduction of unsaturated groups, or by y-irradiation. 

Development of the third class, i.e. unsaturated polyester resins, remained rather slow until the late 1930s, but after commercial production of maleic anhydride by catalytic oxidation of benzene began in 1933, maleic anhydride and fumaric acid rapidly became the most important sources of unsaturated groups in polyesters. The mechanism of drying of these resins on their own and with the addition of drying oils (i.e. unsaturated compounds such as linseed oil) was... 

A PP macromonomer with a methacryloyl end group was synthesized, and was used to prepare PMMA-g-PP graft copolymers by conventional free radical copolymerization [104]. Vinylidene-terminated PP (Mn = 1000) was converted into terminally hydroxylated PP (PP-OH) by a combination of the hydroboration reaction of the unsaturated group and oxidation reaction. Resulting PP-OH was reacted with methacryloylchloride to synthesize termi-... 

The unsaturated dibasic acids bear the same relation to the saturated dibasic acids, just considered, as the unsaturated mono-basic acids, acrylic acid, crotonic acid, etc. (p. 172), do to the saturated monobasic acids, acetic acid, etc. They are also the oxidation products of the unsaturated hydrocarbons, alcohols, and aldehydes just as oxalic and succinic acids are of the corresponding saturated compounds. As the simplest dibasic acid containing an ethylene unsaturated group will contain two carboxyl groups and also two doubly linked carbon atoms there must be at least four carbons in the compound. This compound will therefore correspond to succinic acid of the saturated series. Now succinic acid may be derived from either butane by oxidation or from ethane by substitution. Similarly the corresponding unsaturated acid may be derived from butene by oxidation or from ethene by substitution. All of these general relationships may be represented as follows ... 

The results of the oxidation of C2—C5 olefins over copper(i) oxide, silver, and gold catalysts are summarized in Table 1. We have excluded data from studies where additives have been deliberately included in the catalyst, or process gas stream, in order to improve the performance. Where several studies have been carried out we have quoted the best selectively obtained. While copper(i) oxide and gold give unsaturated aldehydes as the major product of partial oxidation, silver gives the epoxide. Copperfii) oxide is not a selective catalyst for olefin oxidation. The difference in behaviour between copper(i) and copper(ii) oxides is in line with the general trend in oxide catalysis. The selective catalysts tend to be those with either a full or an empty tZ-shell, i.e. the oxides of Groups IVA, VA, and VIA, and IB, IIB, IVB, VB, and VIB. ... 

Now, if an oxidant is added, the methyl group can further be dehydrogenated to an a,P-unsaturated group within the molecule. Gamma-Al203 was one of several acid catalysts that possessed catalytic activity for this reaction. The results in Table 9 are typical but not optimized. The combined methylation selectivity is,... 

Commercial polymers are believed to contain reactive groups such as hydroperoxide, carbonyl, and unsaturated groups. These groups often play important roles for the thermal oxidation processes of the polymers (1,2,9,10,43,44). Therefore, one may consider also the effects of the oxidation products originating from these reactive groups at the very beginning of the oxidation, when the mechanism of the copper-catalyzed oxidation of the polymer was discussed. Further experiments on the effects of various oxidation products on the thermal oxidation of the polymer will be published. 

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