Maleic acid anhydride

For the manufacturing of sulfosuccinic acid esters, which belong to a special class of surfactants, maleic acid anhydride is needed. Maleic acid anhydride is an important intermediate chemical of the chemical industry. Its worldwide output amounts to about 800,000 tons (1990) [64]. Maleic acid is produced by catalytic vapor phase oxidation process of benzene or n-C4 hydrocarbons in fixed bed or fluidized bed reactors according the following reaction equations. The heat of reaction of the exothermic oxidation processes is very high. 

Using benzene as starting material the yield of maleic acid anhydride is about 70 mol %. Using n-C4 hydrocarbons only about 50 mol % yield is obtained. But due to the lower molecular weights of the C4 olefins the wt % values are about 90% in both cases. 

Butadiene has the advantage of a relatively low heat of reaction (995 kJ/ mol compared with 1875 kJ/mol in the oxidation of benzene), but the disadvantage of a relatively high price compared with the other -C4 hydrocarbons. Good prospects has the n-butane route. Keeping the n-butane conversion at about 15%, the yield of maleic acid anhydride amounts to 50-60 mol %. 

In 1990 50% of the maleic acid anhydride was produced by oxidation of benzene and the other 50% by oxidation of the different n-C4 hydrocarbons. 

These anionic surfactants are based on the petrochemically gained maleic acid anhydride. Sulfosuccinates are surface-active metal (mostly sodium) salts of either monoester or diesters of sulfosuccinic acid. 

These are two chemically different groups of products which have distinct application fields. Both product groups are obtained by reacting maleic acid anhydride (MA) with hydroxyl group(s)-carrying molecules, followed by sulfation of the intermediate product, an ester. Whereas the diester types are mainly made from a few different branched and unbranched alcohols, the monoester are derived from a wide variety of raw materials fatty alcohols, fatty acid alkanolamides, ethoxylated fatty alcohols, fatty acid alkanolamides, their etho-xylates, and others. All these raw materials—with the exception of the branched chains—may be obtained from natural renewable resources. 

The reaction partner of maleic acid anhydride can be changed. Instead of a hydroxyl group a primary or secondary amine can be used. Either monoamides or diamides can be obtained. Simple sulfation as mentioned above closes the reaction series. The variety of sulfosuccinamates (monoamides) and sulfosuccinamides (diamides) is smaller than that of sulfosuccinates. An important use lies in the field of technical applications (Fig. 2). 

In the sulfosuccinate esters a comparable hydrophobic part consists of the fatty chain plus the functionalities introduced by maleic acid anhydride function. The product variation would then be possible by changing the chain length and/or degree of saturation of the fatty alcohol. The fatty alcohol itself can be replaced by an ethoxylated fatty alcohol with different degrees of ethoxylation as another parameter to be varied. 

Other lipophilic groups possibly attached to the maleic acid anhydride are alkanolamides of fatty acids. In this case the variations could be chain length and/or saturation grade of the C chain, the type of alkanolamine (most common are isopropanolamine, monoethanolamine, and diglycolamine), or an etho-... 

TABLE 3 An Overview of Sulfosuccinate Monoester Types Defined by the Reaction Partner(s) of Maleic Acid Anhydride... 

Dioxane Maleic acid anhydride Sodium sulfate Sulfur dioxide... 

Most industrially desirahle oxidation processes target products of partial, not total oxidation. Well-investigated examples are the oxidation of propane or propene to acrolein, hutane to maleic acid anhydride, benzene to phenol, or the ammoxidation of propene to acrylonitrile. The mechanism of many reactions of this type is adequately described in terms of the Mars and van Krevelen modeE A molecule is chemisorbed at the surface of the oxide and reacts with one or more oxygen ions, lowering the electrochemical oxidation state of the metal ions in the process. After desorption of the product, the oxide reacts with O2, re-oxidizing the metal ions to their original oxidation state. The selectivity of the process is determined by the relative chances of... 

The first type is a standard polysoap derived from a polymerizable surfactant leading to poly(sodium 11-acryloyloxyundecane-l-sulfonate) PSl whereas the second polysoap is an alternating copolymer of maleic acid anhydride and acrylamide leading to a polymer with carboxylic acid groups and hydrophobic n-alkylamide groups PS2 (see Fig. 6.9). The organometaUic catalyst was not covalently bound to the polysoaps in the catalytic experiments. 

Synonyms AI3-24283 AIDS-189609 AIDS-189660 BRN 0106909 ds-Butenedioic anhydride CCRIS 2941 Dihydro-2,5-dioxofuran 2,5-Furanedione EINECS 203-571-6 Lytron 810 Lytron 820 MA Maleic acid anhydride NSC 9568 NSC 137651 NSC 137652 NSC 137653 RCRA waste number U147 Toxilic anhydride UN 2215. 

NHj 1 -Flnoro-2,4-dinitrobenzene Acetanhydride Bolton-Hunter reagent Dansylchloride Formaldehyde Maleic acid anhydride N-Snccinimidyl propionate Phenylisocyanate Sodium borohydride Succinic anhydride... 

SMANCS (Styrere-co-maleic acid/anhydride polymer bound to neocarzinostatin Neocarzinostatin (an antitumor protein) Amide bond between polymer carboxyl and protein amino None N/A SMANCS showed anticancer activity against many tumor cell lines, and had lower IC50 values than five other anticancer agents tested Liver tumors reduced more than 50% after 6 months in human subjects 15, 56, 57... 

N 8.80% crysts (from ale), mp 78.5—79° sol in benz, toluene, dioxane acetone insol in w benzin. Its prepn was patented by C.J. Mighton [USP 2365717(1944) CA 39, 4627(1945)] thru heating of maleic acid anhydride 2-nitro-2-methyl-l-propanol in the presence of p-toluenesulfonic acid (Ref 2) It was found to be a suitable plasticizer of NC when It was desired to obtain flexihle solvendess rolled sheet propellants (Ref 3) Refs . 1) Beil 2, 19251 [Di( methylpropyl) maleate] 2) Beil 2, ]l925i [Di( 2-nitro-2-methylpropyl)-maleate] 3) Anon, Summary-TechRept of Div 8, NDRC, Vol -1(1946), pi 19... 

Economically, the oxidation of butenes is of importance mainly for the production of butadiene and maleic acid anhydride. 

Deeper oxidation products like furan and, particularly, maleic acid anhydride, can be produced by catalysts that have a stronger oxidative power than the above type-(a) catalysts, but, at the same time, have retained the capacity to transfer oxygen selectively to the organic molecule (a capacity which is absent in the type-(b) catalysts). Besides, a more acidic character of the catalyst surface is probably required to produce an acidic product like maleic anhydride effectively. The most interesting catalysts of this group are V2Os-based catalysts and certain molybdates and Mo03-based catalysts. 

Catalysts based on V2Os are particularly effective for the production of maleic acid anhydride. Pure V2Os, as well as several modified vanadium pentoxide catalysts, have been investigated. 

Pure V205 was investigated by Ai [9] using a flow reactor at 350°C. A maximum butadiene yield of 46% is reported, while furan and maleic acid anhydride can be produced (from butadiene and furan) with maximum selectivities of 72 and 60%, respectively. The depth of oxidation can be controlled by the oxygen pressure and the contact time. Isomerization reactions do not occur. Crotonaldehyde is formed as a by-product. The... 

Ai and Suzuki [5,9] investigated the combination V2Os—P2Os. The acidity was measured indirectly by the activity for dehydration of isopropanol and was shown to decrease with increasing P2Os content. The activity for the oxidation of butene-1 and butadiene to maleic acid anhydride decreased accordingly. It was shown that the adsorption equilibrium constant of the olefin on the catalyst also decreased in the same way. 

With tin vanadates, the selectivity for the formation of butadiene goes through a maximum at an atomic ratio Sn/V = 9. Below this ratio, the acidity is greater, leading to more maleic acid anhydride in the reaction products. Butadiene will adsorb more with increasing acidity and will have a greater opportunity to be oxidized. The resulting acid anhydride will desorb relatively easily from an acid catalyst. A basic catalyst will result in more combustion products. 

Infrared spectra of propene and isobutene on different catalysts were measured by Gorokhovatskii [143]. Copper oxide, which converts olefins to butadiene and aldehydes, shows adsorption complexes different from structures on a V2Os—P2Os catalyst which produces maleic acid anhydride. Differences also exist between selective oxidation catalysts and total oxidation catalysts. The latter show carbonate and formate bands, in contrast to selective oxides for which 7r-allylic species are indicated. A difficulty in this type of work is that only a few data are available under catalytic conditions most of them refer to a pre-catalysis situation. Therefore it is not certain that complexes observed are relevant for the catalytic action. 

Fig. 11.1 Structures of polysuccinic acid-maleic acid anhydride (A), polyvinyl pyrrolidone (B), and polyethyleneglycol (C).

Fig. 11. Fukugama s asymmetric synthesis of (-(-CP-263,114 intramolecular Diels—Alder reaction and formation of the maleic acid anhydride moiety. DBU = l,8-diazabicyclo[5.4.0]undec-7-ene, NIS = N-iodosuccinimide.

A recent addition to this field is the polymer-supported di(2-pyridyl)-methylamine-palladium dichloride complex covalently attached to a styrene-alt-maleic acid anhydride copolymer. Turnover numbers as high as 105 were reported and a couple of microwave-heated Suzuki-Miyaura reactions could be performed in neat water [134], 2-Pyridinealdoxime-based Pd(II)-... 

Styrene can be copolymerized with many monomers. The following monomers can be used along with styrene in the manufacture of food contact materials a-methylsty-rcne, vinyltoluene, divinylbenzene, acrylonitrile, ethyleneoxide, butadiene, fumaric and maleic acid esters of the mono functional saturated aliphatic alcohols C1-C8, acrylic acid ester and methacrylic acid, maleic acid anhydride, methylacrylamide-methylol ether, vinylmethyl ether, vinylisobutyl ether. Styrene and/or a-methylstyrene and/or vinyltoluene should be the main mixture component in every case. 

Soluble carriers include antibodies and soluble synthetic polymers such as poly(hydroxypropyl methacrylate), poly(lysine), poly(aspartic acid), polyvinylpyrrolidone), poly(N-vinyl-2-pyrrolidone-co-vinylamide) and poly (styrene co-maleic acid/anhydride). 

The cytotoxic neocarzinostatin (NCS) is a small protein (Mw 12 kD) associated with a low molecular weight chromophore. NCS is rapidly cleared by the kidney and its cytotoxicity is non-cell specific. To modify its disposition, two poly(styrene-co-maleic acid anhydride) copolymers (Mw 1,500) have been coupled to one molecule of NCS, to give styrene-maleic-anhydride-neocarcinostatin (SMANCS) systems. 

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