Maleic acid epoxide

R, R -Tartaric (racemic) acid is obtained synthetically by epoxidation of maleic acid with hydrogen peroxide in the presence of a catalyst followed... 

The methylated maleic acid adduct of phthalic anhydride, known as methyl nadic anhydride VI, is somewhat more useful. Heat distortion temperatures as high as 202°C have been quoted whilst cured systems, with bis-phenol epoxides, have very good heat stability as measured by weight loss over a period of time at elevated temperatures. The other advantage of this hardener is that it is a liquid easily incorporated into the resin. About 80 phr are used but curing cycles are rather long. A typical schedule is 16 hours at 120°C and 1 hour at 180°C. 

In industry many selective oxidations are carried out in a homogeneously catalyzed process. Heterogeneous catalysts are also applied in a number of processes, e.g. total combustion for emission control, oxidative coupling of methane, the synthesis of maleic acid from butanes, the epoxidation of ethylene. Here we focus upon heterogeneous catalysis and of the many examples we have selected one. We will illustrate the characteristics of catalytic oxidation on the basis of the epoxidation of ethylene. It has been chosen because it illustrates well the underlying chemistry in many selective oxidation processes. 

The hydrolysis of cw-epoxysuccinic acid (the initial product in the hydroxyla-tion reaction of maleic acid by hydrogen peroxide) by H2O2 is accelerated by the epoxidation catalyst sodium tungstate. The reaction is first-order within respect to the concentrations of the catalyst and the epoxide and end-product inhibition was observed. ... 

Tartaric acid (pKi = 2.98 pK2 = 4.34) has a rough , hard sour taste. It is used for the acidification of wine, in fruit juice drinks, sour candies, ice cream, and because of its formation of metal complexes, as a synergist for antioxidants. The production of (2R,3R)-tartaric acid is achieved from wine yeast, pomace, and cask tartar, which contain a mixture of potassium hy-drogentartrate and calcium tartrate. This mixture is first converted entirely to calcium tartrate, from which tartaric acid is hberated by using sulfuric acid. Racemic tartaric acid is obtained by cis-epoxidation of maleic acid, followed by hydrolysis ... 

The double bond in MA and derivatives can be epoxidized to yield epoxysuccinic acid derivatives 92. So far, the primary use of this reaction has been for the synthesis of tartaric acid 93 (R = H). Epoxysuccinic acid can also be made by the hypochlorite reaction of maleic acid. The final product, dl-trans-a,p-epoxysuccinic acid 92 (R = H) is isolated in a 75% yield. 

Halogenation, maleic acid derivatives, 60 Hammett equation, 138, 139 Hammett sigma values, 372 Hantzsch ester hyrogen donor, 43 MA reduction, 43 Heat of copolymerization MA-allyl chloride pair, 405 MA-yV-butyl vinyl ether pair, 405 MA-isopropenyl acetate pair, 333 MA-a-methylstyrene pair, 404, 405 MA-styrene pair, 404, 405 MA-vinyl acetate pair, 333, 405 polyester-styrene mixtures, 487 vinyl acetate with maleates and fumarates, 333 Heat of polymerization MA-epoxide reactions, 482 MA monomer, 244... 

MA copolymerization, 660 Hypochlorite reaction, epoxidation of maleic acid, 69... 

The first example in Table 2.5 was made from a partly epoxidized butadiene resin by reaction with dimethylamine followed by acrylic acid. The second example was again a reaction product of polybutadiene with maleic acid, followed by treatment with N,N-dimethylaminopropyl-amine. This polyamine was mixed with a novolac resin containing sites of unsaturation, an example of which is shown in Fig. 2.10. 

Some specific recent applications of the GC-MS technique to various types of polymers include the following PE [49,50], poly(l-octene) [51], poly(l-decene) [51], poly(l-dodecene) [51], 1-octene-l-decene-l-dodecene terpolymer [51], chlorinated polyethylene [52], polyolefins [53, 54], acrylic acid methacrylic acid copolymers [55], polyacrylates [56], styrene-butadiene and other rubbers [57-59], nitrile rubber [60], natural rubbers [61, 62], chlorinated natural rubber [63, 64], polychloroprene [65], PVC [66-68], silicones [69, 70], polycarbonates [71], styrene-isoprene copolymers [72], substituted PS [73], polypropylene carbonate [74], ethylene-vinyl acetate copolymers [75], Nylon [76], polyisopropenyl cyclohexane a-methyl styrene copolymers [77], m-cresol-novolac epoxy resins [78], polymeric flame retardants [79], poly(4-N-alkyl styrenes) [80], polyvinyl pyrrolidone [81], vinyl pyrrolidone-methyl acryloxysilicone copolymers [82], polybutylcyanoacrylate [83], polysulfide copolymers [84], poly(diethyl-2-methacryloxy)ethyl phosphate [85], ethane-carbon monoxide copolymers [86], polyetherimide [87], bisphenol A [88], ethyl styrene [89], styrene-isoprene block copolymer [89], polyvinyl alcohol-co-vinyl acetate [90], epoxide thiol [91], maleic acid-propylene copolymer [92], P-hydroxy butyrate-P-hydroxy valerate copolymer [93], polycaprolactams [39,94], PS [95,96], polypyrrole [95,96], polyhydroxy alkanoates [97], poly(p-chloromethyl) styrene [81], polybenzooxazines and siloxy substituted polyoxadisila-pentanylenes [98,99] poly benzyl methacrylates [100], polyolefin blends after ageing in soil [101] and polystyrene peroxide [43]. 

Acrylic acid, methacrylic acid, or maleic acid ring opening of epoxidized PBD give access to hydroxyl esters with an a,p-unsaturated double bond next to a carbonyl group. The acrylic derivatives are much more reactive in radical polymerizations than the double bonds of PBD. Peroxide-initiated copolymerization of PBD with acrylic esters and styrene proceeds readily to give hard and tough resins... 

The corresponding monohydroxy[ C]methyl derivatives, accessible through reaction of equimolar amounts of H CHO and alkyl cyanoacetates or dialkyl malonates readily eliminate water to give alkyl 2-cyano[3- C]acrylates till. =CN) and dialkyl [ " C]-methylenemalonates till. R = COOR ), respectively, which are highly valuable intermediates in Michael additions, Diels—Alder reactions and epoxidations. Unfortunately, carbon-14-labeled acrylates are unstable towards radiation induced polymerization. In order to circumvent this undesirable side effect, it has been recommended to run the formation in the presence of anthracene in order to trap the [ Clacrylates in situ as stable Diels-Alder adducts 112. These can be purified and stored briefly. Their subsequent thermolysis in the presence of maleic acid anhydride re-generates the acrylates 111 for immediate use in further reactions. ... 

Y = 2-bicycloheptene 9,10-epoxy stearate Octyl 9>10-epoxy stearate Maleic acid halfester R = thiol acid and alkyl R = aryl and alkyl epoxide... 

With regard to the use of tungsten-based systems, Payne and Williams reported on the selective epoxidation of maleic, fumaric, and crotonic acids with a catalytic amount of sodium tungstate (2mol%) in combination with aqueous hydrogen... 

The preferred catalysts are salts of inorganic and organic acids as well as tertiary amines. Phthalic anhydride, succinic anhydride and maleic anhydride are typical acid anhydrides, while ethylene oxide, propylene oxide, epichlorohydrin and phenyl glycidyl ether are typical epoxides. The synthesis of a ladder polymer was carried out by using bisanhydrides264. ... 

Isomerization has been observed with many a,j3-unsaturated carboxylic acids such as w-cinnamic 10), angelic, maleic, and itaconic acids (94). The possibility of catalyzing the interconversion of, for example, 2-ethyl-butadiene and 3-methylpenta-l,3-diene has not apparently been explored. The cobalt cyanide hydride will also catalyze the isomerization of epoxides to ketones (even terminal epoxides give ketones, not aldehydes) as well as their reduction to alcohols. Since the yield of ketone increases with pH, it was suggested that reduction involved reaction with the hydride [Co" (CN)jH] and isomerization reaction with [Co (CN)j] 103). A related reaction is the decomposition of 2-bromoethanol to acetaldehyde... 

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