Maleic anhydride CAS

PA= phthalic anhydride MA = maleic anhydride CA = citraconic anhydride... 

Maleic anhydride CAS. 108-3I-6. til, maleic acid [CAS 110-16-7]. (2), and I umarie acid [CAS 110-17-81. i3) are multifunctional chemical intermediates that lind applications in nearly every Held id industrial chemistry. Each molecule contains two acid carbonyl groups and a double bond in the u. position. Maleic anhydride and maleic acid are important raw materials used in the manufacture of phthalic-type alkyd and polyester resins, surface coatings, lubricant additives, plasticizers. copolymers, and agricultural chemicals [see Alkyd Resins Polymers, and Lubricant). Both chemicals derive their common names from naturally occurring malic acid. 

When the proportion of one type of monomeric unit in a copolymer is small, the detection of the presence in the pyrolysis products of that component is sometimes more difficult. As an example, a sample of poly(ethylene-graft-maleic anhydride), CAS 106343-08-2, with 3% wt. maleic anhydride was pyrolyzed at 600° C in He with separation of a Carbowax column. The results are shown in the upper trace in Figure 6.1.14. 

Among the copolymers of styrene that have practical applications is poly(styrene-co-maleic anhydride) [71]. The pyrogram of a sample of poly(styrene-co-maleic anhydride), CAS 9011-13-6, with 7% wt maleic anhydride and = 224,000 is given in Figure 6.2.8. The pyrolysis was done at 600° C in He with separation of a Carbowax column and MS detection, similarly to other polymers discussed in this book (see Table 4.2.2). 

The results for a Py-GC/MS analysis of a sample of poly(ethylene-a/f-maleic anhydride) CAS 9006-26-2, with = 100,000-500,000 are shown in Figure 6.9.4. The pyrolysis was done at 600° C in He at a heating rate of 10° C/ms, TAT = 10 s, and the separation was done on a Carbowax column in identical conditions as for other examples previously discussed (see Table 4.2.2). The MS was operated in EI+ mode. The peak identification for the chromatogram shown in Figure 6.9.4 was done using MS spectral library searches only and is given in Table 6.9.3. 

A rather similar pyrogram is obtained and a similar path is followed during the pyrolysis of poly(isobutylene-a/f-maleic anhydride), CAS 26426-80-2. A sample of this polymer with M = 60,000 was pyrolyzed at 600 C in He in similar conditions as for poly(ethylene-a/f-maleic anhydride). The pyrogram is shown in Figure 6.9.5, and the peak identification obtained by MS spectral library searches only is given in Table 6.9.4. 

Physical Properties. Mahc acid crystallines from aqueous solutions as white, translucent, anhydrous crystal. The S(—) isomer melts at 100-103°C (1) and the R(+) isomer at 98-99°C (2). On heating, D,L-mahc acid decomposes at ca 180°C by forming fumaric acid and maleic anhydride. Under normal conditions, malic acid is stable under conditions of high humidity, it is hygroscopic. 

Low molecular weight (1000—5000) polyacrylates and copolymers of acryflc acid and AMPS are used as dispersants for weighted water-base muds (64). These materials, 40—50% of which is the active polymer, are usually provided in a Hquid form. They are particularly useful where high temperatures are encountered or in muds, which derive most of their viscosity from fine drill soHds, and polymers such as xanthan gum and polyacrylamide. Another high temperature polymer, a sulfonated styrene maleic—anhydride copolymer, is provided in powdered form (65,66). AH of these materials are used in relatively low (ca 0.2—0.7 kg/m (0.5—2 lb /bbl)) concentrations in the mud. 

Diallyl Isophthalate. DAIP polymerizes faster than DAP, undergoes less cyclization, and yields cured polymers of better heat resistance, eg, up to ca 200°C. Prepolymer molding materials such as Dapon M of EMC, are not sticky. Maleic anhydride accelerates polymerization, whereas vinyl isobutyl ether retards it and delays gelation in castings. Copolymers with maleic anhydride are exceptionally hard and tough and may scratch homopolymer surfaces. 

Styrene Copolymers. Acrylonitrile, butadiene, a-methylstyrene, acryUc acid, and maleic anhydride have been copolymerized with styrene to yield commercially significant copolymers. Acrylonitrile copolymer with styrene (SAN), the largest-volume styrenic copolymer, is used in appHcations requiring increased strength and chemical resistance over PS. Most of these polymers have been prepared at the cross-over or azeotropic composition, which is ca 24 wt % acrylonitrile (see Acrylonithile polya rs Copolyp rs). 

Alkyd resin synthesis. This synthesis consists of two steps. In the first step, a triglyceride oil is reacted at ca. 250°C with polyols, such as glycerol or pentaery-thritol, in tire presence of a basic catalyst to form a monoglyceride. In the second step, phthalic anhydride, with or without another dibasic acid such as maleic anhydride, is added to the reaction medium and reacted at high temperature. The resulting product is a branched polyester (Scheme 2.56). 

Although benzobarrelene has been used in a number of recent studies, the best available published synthesis" starts with the Diels-Alder reaction of j8-naphthol and maleic anhydride, affording benzobarrelene in ca. 1% yield after five further steps. Minor improvements allow small quantities of benzobarrelene to be prepared in an overall yield of ca. 10%. The reaction of benzyne with benzene is relatively inefficient, giving benzobarrelene in ca. 2% yield. When benzyne is generated by decomposition of benzenediazonium-2-carboxylate at high dilution in benzene, the yield of benzobarrelene is raised to 14%. The reactions of benzyne with other aromatic substrates are equally inefficient. 

Numerous examples involving the preparation of tetrahydrothiophenes via [3 + 2] cycloaddition of thiocarbonyl ylides with electron-poor alkenes have been reported. Thiobenzophenone (5)-methylide (16), generated from 2,5-dihydro-1,3,4-thiadiazole (15) and analogous compounds, react with maleic anhydride, N-substituted maleic imide, maleates, fumarates, and fumaronitrile at —45°C (28,91,93,98,128,129). Similar reactions with adamantanethione (5)-methylide (52) and 2,2,4,4-tetramethyl-3-thioxocyclobutanone (5)-methylide (69) occur at ca. +45°C and, generally, the products of type 70 were obtained in high yield (36,94,97,130) (Scheme 5.25). Reaction with ( )- and (Z)-configured dipolaro-philes stereospecifically afford trans and cis configured adducts. 

A variety of metal oxides (e.g. V2O5) have been employed for oxidation reactions, besides noble metals (e.g. Pt and Ag). Auto-exhaust catalysts employ metals such as Rh, Pd and Pt besides Ce02 and other oxides. The use of metal oxide catalysts for oxidation reactions has been discussed quite widely in the literature (Grasselli Brazdil, 1985). Perovskite oxides of the type CaMn03 and Laj A jM03 (A = Ca, Sr M = Co, Mn) are excellent candidates as oxidation catalysts. The 14-electron oxidation of butane to maleic anhydride is effectively carried out over phosphorus vanadium oxide catalysts of the type VOPO4 (Centi et al., 1988). 

BA BuE-PA BE-HET BE-HHPA BE-MA BE-PA BE-SA CA CHX DMA DMBA DY 062 GA HEB HHPA HMTA MA MTHPA NMA benzoic acid monobutylester of phthalic acid monobenzylester of hexachloroendomethylenetetrahydrophthalic acid monobenzylester of hexahydrophthalic acid monobenzylester of maleic acid monobenzylester of phthalic acid monobenzylester of succinic acid citraconic anhydride cyclohexanol N,N-dimethylaniline dimethylbenzylamine high boiling tertiary amine (Ciba Geigy AG) gjptaric anhydride 2-hydroxy-4-(2,3-epoxypropoxy)benzophenone hexahydrophthalic anhydride hexamethylenetetramine maleic anhydride methyltetrahydrophthalic anhydride nadic methyl anhydride (methylbicyclo[2.2.1]heptene-2,3-dicarboxylic anhydride isomers)... 

Ca->,POa, inhibition/dispersion, Ca Phosphonate control, Fe stabilization MA/EA/VA Maleic anhydride/ethyl acrylate/vinyl acrylate examples Belclene 283, Polycol 90... 

Abbreviations y x AFM AIBN BuMA Ca DCP DMA DMS DSC EGDMA EMA EPDM FT-IR HDPE HTV IPN LDPE LLDPE MA MAA MDI MMA PA PAC PB PBT PBuMA PDMS PDMS-NH2 interfacial tension viscosity ratio atomic force microscopy 2,2 -azobis(isobutyronitrile) butyl methacrylate capillary number dicumyl peroxide dynamic mechanical analysis dynamic mechanical spectroscopy differential scanning calorimetry ethylene glycol dimethacrylate ethyl methacrylate ethylene-propylene-diene rubber Fourier transform-infra-red high density polyethylene high temperature vulcanization interpenetrating polymer network low density polyethylene linear low density polyethylene maleic anhydride methacrylic acid 4,4 -diphenylmethanediisocyanate methyl methacrylate poly( amide) poly( acrylate) poly(butadiene) poly(butylene terephtalate) poly(butyl methacrylate) poly(dimethylsiloxane) amino-terminated poly(dimethylsiloxane)... 

As shown in Equation (4), the sensitized irradiation of a mixture of 4,6-dimethyl-2-pyrone and maleic anhydride, or of 4,6-dimethyl-5-ethoxycarbonyl-2-pyrone and maleimide, gives the mixed photoadducts (23) and (24) in ca. 20% yields (90BCJ3456, 92BCJ354). As with many other [2 + 2] cyclocondensation reactions involving heterocycles, these are thought to proceed via biradical intermediates. 

Process Economics Program Report SRI International. Menlo Park, CA, Isocyanates IE, Propylene Oxide 2E, Vinyl Chloride 5D, Terephthalic Acid and Dimethyl Terephthalate 9E, Phenol 22C, Xylene Separation 25C, BTX, Aromatics 30A, o-Xylene 34 A, m-Xylene 25 A, p-Xylene 93-3-4, Ethylbenzene/Styrene 33C, Phthalic Anhydride 34B, Glycerine and Intermediates 58, Aniline and Derivatives 76C, Bisphenol A and Phosgene 81, C1 Chlorinated Hydrocarbons 126, Chlorinated Solvent 48, Chlorofluorocarbon Alternatives 201, Reforming for BTX 129, Aromatics Processes 182 A, Propylene Oxide Derivatives 198, Acetaldehyde 24 A2, 91-1-3, Acetic Acid 37 B, Acetylene 16A, Adipic Acid 3 B, Ammonia 44 A, Caprolactam 7 C, Carbon Disulfide 171 A, Cumene 92-3-4, 22 B, 219, MDA 1 D, Ethanol 53 A, 85-2-4, Ethylene Dichloride/Vinyl Chloride 5 C, Formaldehyde 23 A, Hexamethylenediamine (HMDA) 31 B, Hydrogen Cyanide 76-3-4, Maleic Anhydride 46 C, Methane (Natural Gas) 191, Synthesis Gas 146, 148, 191 A, Methanol 148, 43 B, 93-2-2, Methyl Methacrylate 11 D, Nylon 6-41 B, Nylon 6,6-54 B, Ethylene/Propylene 29 A, Urea 56 A, Vinyl Acetate 15 A. 

Maleic anhydride (1.17 Mt/a world installed capacity) finds its major use in the synthesis of unsaturated polyester resins ca. 41%), with the remainder going to produce butanediol (14%), maleic copolymers (8%), tetrahydrofuran (7%),... 

In the first commercial process, introduced in 1933, maleic anhydride was produced by the catalytic oxidation of benzene with air. Although its appeal declined after the 1970s the benzene process is still operated, particularly where -butane is not available. The catalyst is a mixed oxide (70% V2O5 30% M0O3) deposited on a low surface area carrier to limit side reactions. Atom efficiency is inherently low, as implied by the stoichiometry of the oxidation in which two carbon atoms out of six are lost as CO2 (Equation B4). Molar yields however can be relatively high ca. 73%) and are generally higher than those in the -butane processes. 

The manufacture of phthalic anhydride (world installed capacity ca. 4.4 Mt/a) has several points of similarity to that of maleic anhydride in that there are two alternative feedstocks and a large amount of heat is released. The first process, introduced by BASF at the end of 19 century, was based on the liquid phase oxidation of naphthalene catalyzed by mercury salts. It was later replaced by the cleaner gas phase process, carried out over vanadium and molybdenum oxides. Naphthalene was supplied by coal tar distillation and was used exclusively until the end of 1950s when u-xylene, of petrochemical origin, became an abundantly available feedstock (Equation 36). A few production units however can use either feedstock, taking advantage of price fluctuations in coke plants (naphthalene) and in refineries (u-xylene). 

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