Trimellitic anhydride

CeH3Me3. Liquid produced by catalytic cracking of methyl benzenes. Used to prepare trimellitic anhydride. 

A polyester-type fluorescent resin matrix (22) is made by heating trimellitic anhydride, propylene glycol, and phthaUc anhydride with catalytic amounts of sulfuric acid. Addition of Rhodamine BDC gives a bright bluish red fluorescent pigment soluble in DME and methanol. It has a softening point of 118°C. Exceptional heat resistance and color brilliance are claimed for products of this type, which are useful for coloring plastics. 

Of the three benzenetricarboxyhc acids, only trimellitic acid as the anhydride is commercially produced in large volume, by Hquid-phase air oxidation of either pseudocumene or dimethyl benzaldehyde. The pseudocumene oxidation is another variant of the cobalt—manganese—bromine catalyst in acetic acid solvent as described in the terephthaUc acid section. The acid is available as a laboratory chemical (99). The lUPAC name of trimellitic anhydride is 5-isobenzofurancarboxyhc acid (l,3-dihydro-l,3-dioxo). 

Physical and Chemical Properties. Trimellitic acid and trimellitic anhydride are odorless white crystalline soHds in their pure form. The acid is reasonably stable up to the melting point, where dehydration to the anhydride occurs. The anhydride reacts with atmopsheric moisture, even at room temperature, to revert to the acid. Physical properties of the acid and its anhydride are Hsted in Tables 29—31. 

Table 29. Physical Constants of Trimellitic Acid and Trimellitic Anhydride...

In 1991, Alusuisse Italia announced the constmction of a 20 x 10 t/yi" trimellitic anhydride unit at Bergamo, Italy (109) and commenced production in late 1994. A European patent appHcation (110) assigned to Alusuisse suggests that the process used is very similar to that of Amoco, that is, pseudocumene is air oxidized in the Hquid phase using heavy-metal catalysts and bromine. A number of other companies have shown interest in the production of trimellitic anhydride (111—113). 

Economic Aspects. When trimellitic anhydride was introduced in semicommercial quantities in 1962, it was priced at 1.19/kg. The price was reduced to 0.55/kg as it became available in commercial quantities in 1968. The mid-1994 price was quoted as 2.31/kg from Amoco, fob, the JoHet, Illinois plant. A price history is given in Table 32. Although trimellitic anhydride production and sales figures are not available, the pubUshed U.S. Tariff Commission s production data for trimeUitate esters provides data for the trimellitic anhydride demand trend in the United States, since the largest single use of trimellitic anhydride is for the trimeUitate esters (115). These data are given in Table 32. 

Table 32. U.S. Trimellitic Anhydride Prices and TrimeUitate Ester Production...

Year Trimellitic anhydride price, /kg TrimeUitate ester production, 10 t/vr... 

The freezing point of trimellitic anhydride, the maximum temperature reached during crystallization of a molten sample, is a measure of the product purity. Impurities and trimellitic acid formed by hydrolysis depress the freezing point. 

Polymers based on trimellitic anhydride are widely used in premium electromagnetic wire enamels requiring high temperature performance. Several types of trimellitic anhydride-derived polymers are used as wire enamels poly(amide—imide)s (133), poly(ester—imide)s (134), and poly(amide—imide— ester)s (135). Excellent performance characteristics are imparted by trimellitic anhydride-based polymers for wire enamel requirements of flexibiUty, snap, burnout, scrap resistance, heat shock, and dielectric strength. 

Derivatives. The dual functionaUty of trimellitic anhydride makes it possible to react either the anhydride group, the acid group, or both. Derivatives of trimellitic anhydride include ester, acid esters, acid chloride, amides, and amide—imides (136). Trimellitate esters are the most important derivatives, and physical properties of more significant esters are Hsted in Table 34. 

Manufacture. The only current U.S. manufacturer of trimesic acid is Amoco Chemical Co. It is produced by oxidation of mesitylene (1,3,5-trimethylbenzene) via the Hquid-phase oxidation in acetic acid using the cobalt— manganese—bromine catalyst system (138). This is a variant of the system used to produce terephthaUc and isophthaUc acids as well as trimellitic anhydride. American Bio-Synthetics Corp. did produce it by batch oxidation of mesitylene with potassium permanganate. 

Powder coatings are formulated from the reaction product of trimethylolpropane and IPDI, blocked with caprolactam, and polyester polyols. The saturated polyester polyols are based on aromatic acid diols, neopentyl glycol, and trimellitic anhydride for further branching. To avoid the release of caprolactam in the curing reaction, systems based on IPDI dimer diols are used. 

The polyester resins used in this technology are typically based on terephthaUc acid [100-21 -0] CgH O, or isophthaUc acid [121 -91 -5] CgH O, neopentyl glycol [126-30-7] branched using trimellitic anhydride (38). The most commonly used curing agents are adducts of isophorone... 

Polyamide Imides. Polyamide imides (PAIs) are formed from the condensation of trimellitic anhydride and aromatic diamines (33). The polymer is called amide—imide because the polymer chain comprises amide linkages alternating with imide linkages, with the general chemical stmcture ... 

Esters based on trimellitic anhydride, the trimellitates, have become very popular primary plasticisers for use at high temperatures or where a high level of resistance to aqueous extraction is required. Because of their frequency of use at elevated temperatures, they are usually supplied commercially containing an antioxidant. 

If trimellitic anhydride is used instead of pyromellitic dianhydride in the reaction illustrated in Figure 18.35 then a polyamide-imide is formed (Figure 18.37). The Torlon materials produced by Amoco Chemicals are of this type. 

In order to obtain cured products with higher heat distortion temperatures from bis-phenol epoxy resins, hardeners with higher functionality have been used, thus giving a higher degree of cross-linking. These include pyromellitic dianhydride IV, and trimellitic anhydride V. 

Triglycidyl-s-triazinetrione Triglycidyl iso-cyanurate Trimellitic anhydride, see Benzene-... 

As previously discussed, solvents that dissolve cellulose by derivatization may be employed for further functionahzation, e.g., esterification. Thus, cellulose has been dissolved in paraformaldehyde/DMSO and esterified, e.g., by acetic, butyric, and phthalic anhydride, as well as by unsaturated methacrylic and maleic anhydride, in the presence of pyridine, or an acetate catalyst. DS values from 0.2 to 2.0 were obtained, being higher, 2.5 for cellulose acetate. H and NMR spectroscopy have indicated that the hydroxyl group of the methy-lol chains are preferably esterified with the anhydrides. Treatment of celliflose with this solvent system, at 90 °C, with methylene diacetate or ethylene diacetate, in the presence of potassium acetate, led to cellulose acetate with a DS of 1.5. Interestingly, the reaction with acetyl chloride or activated acid is less convenient DMAc or DMF can be substituted for DMSO [215-219]. In another set of experiments, polymer with high o -celliflose content was esterified with trimethylacetic anhydride, 1,2,4-benzenetricarboylic anhydride, trimellitic anhydride, phthalic anhydride, and a pyridine catalyst. The esters were isolated after 8h of reaction at 80-100°C, or Ih at room temperature (trimellitic anhydride). These are versatile compounds with interesting elastomeric and thermoplastic properties, and can be cast as films and membranes [220]. 

Polymers with hetero-atoms in the chain are suitable for chemical recycling of waste materials. In addition to depolymerisation (nylon 6) and solvolysis (nylon 6,6, PETP, PU) the degradation of aliphatic polyamides with dicarboxylic acids, diamines and cyclic anhydrides, especially trimellitic anhydride, becomes more and more important. The utilisation of the obtained fragments is described. 

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