Pyromellitates

Directions are provided for the determination of chloride in samples using CZE. The buffer solution includes pyromellitic acid which allows the indirect determination of chloride by monitoring absorbance at 250 nm. 

Aromatic polyimides are the first example we shall consider of polymers with a rather high degree of backbone ring character. This polymer is exemplified by the condensation product of pyromellitic dianhydride [Vll] and p-amino-aniline [Vlll] ... 

See also Pyromellitic acid.) [PHTTiALIC ACID AND OTTiERBENZENEPOLYCARBOXYLIC ACIDS] (Vol 18) Benzene-1,2,4,5-tetracarboxylic dianhydride-3-carboxylic acid [59025-58-0]... 

Pis commonly have been synthesized from reactions of pyromellitic dianhydride [26265-89-4] (PMD A) or 3,3H,4 -benzophenone tetracarboxyUc dianhydride [2421-28-5] (B IDA) with a number of diamines like 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-amino-3-methylphenyl)propane, I,I-bis(4-aminophenyl)-I-phenylethane, and 1,1-his(4-amino-3-methy1pheny1)-1-phenylethane (5). The PMDA-based Pis were thermally more stable than the corresponding Pis obtained from BTDA. 

Table 36. Physical Contants of Pyromellitic Acid and Pyromellitic Dianhydride...

The use of the Hquid-phase process in acetic acid with the cobalt— manganese—bromine system as explained in the tetephthaUc acid section is also possible (149). This process has been used by Amoco Chemical to produce pyromellitic acid, and facUities remain in place to do so again in the future. As with all hquid-phase oxidations of this type, yields ate high. A separate dehydration step would be needed to yield the dianhydtide. 

Mitsubishi Gas Chemical Co. in Japan produces pyromellitic dianhydtide in the same unit used for trimellitic anhydtide production (105). This process starts with pseudocumene, which is first carbonylated with carbon monoxide in the presence of boron trifluotide and hydrogen fluotide to form 2,4,5-trimethylbenzaldehyde. The Hquid-phase oxidation of the trimethylbenzaldehyde to pyromellitic acid and subsequent processing steps ate much the same as described for the Mitsubishi Gas Chemical process in the trimellitic acid section. The production of pyromellitic anhydtide is in conjunction with a joint venture agreement with Du Pont. 

Production, Storage, and Shipment. As noted above, AUco Chemical, Amoco Chemical, Mitsubishi Gas Chemical, and Hbls all produce either the acid or the anhydride using different production techniques. The relatively small production volumes of pyromellitic acid and dianhydride results in both storage and shipment in polyethylene-lined fiber dmms of 22—136-kg capacity. 

Health and Safety Factors. Both pyromellitic acid and its dianhydride irritate skin, eyes, and mucous membranes, and they cause skin sensitization (156). When it comes in contact with moist tissue the dianhydride converts to the acid. Direct contact with should be avoided and protective clothing should be worn in areas where it is used. The LD q for intergastric administration in rats is 2.2—2.6 g/kg (157). In 6-mo experiments, the maximum nontoxic dose was 0.07 mg/kg/d, and it affected the fiver, kidney, and reproductive tract. Precautions against fire and dust explosions as explained in the terephthafic acid section should be foUowed. 

Uses. Pyromellitic dianhydride imparts heat stabUity in applications where it is used. Its relatively high price limits its use to these applications. The principal commercial use is as a raw material for polyimide resins (see POLYIMIDES). These polypyromellitimides are condensation polymers of the dianhydride and aromatic diamines such as 4, -oxydianifine ... 

Because the heat distortion temperature of cured epoxy resins (qv) increases with the functionality of the curing agents, pyromellitic dianhydride is used to cross-link epoxy resins for elevated temperature service. The dianhydride may be added as a dispersion of micropulverized powder in liquid epoxy resin or as a glycol adduct (158). Such epoxies may be used as an insulating layer in printed circuit boards to improve heat resistance (159). Other uses include inhibition of corrosion (160,161), hot melt traffic paints (162), azo pigments (163), adhesives (164), and photoresist compounds (165). 

Hydroxyl number and molecular weight are normally determined by end-group analysis, by titration with acetic, phthaUc, or pyromellitic anhydride (264). Eor lower molecular weights (higher hydroxyl numbers), E- and C-nmr methods have been developed (265). Molecular weight deterrninations based on coUigative properties, eg, vapor-phase osmometry, or on molecular size, eg, size exclusion chromatography, are less useful because they do not measure the hydroxyl content. 

Polymerization by Transimidization Reaction. Exchange polymerization via equihbrium reactions is commonly practiced for the preparation of polyesters and polycarbonates. The two-step transimidization polymerization of polyimides was described in an early patent (65). The reaction of pyromellitic diimide with diamines in dipolar solvents resulted in poly(amic amide)s that were thermally converted to the polyimides. High molecular weight polyimides were obtained by employing a more reactive bisimide system (66). The intermediate poly(amic ethylcarboamide) was converted to the polyimide at 240°C. 

The pyromellitic dianhydride is itself obtained by vapour phase oxidation of durene (1,2,4,5-tetramethylbenzene), using a supported vanadium oxide catalyst. A number of amines have been investigated and it has been found that certain aromatic amines give polymers with a high degree of oxidative and thermal stability. Such amines include m-phenylenediamine, benzidine and di-(4-amino-phenyl) ether, the last of these being employed in the manufacture of Kapton (Du Pont). The structure of this material is shown in Figure 18.36. 

In order to prevent premature gelation the reaction mixture should be anhydrous, free from pyromellitic acid and reacted at temperatures not exceeding 50°C. 

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. 

Polyamide-imides may also be produced by reacting a diacid chloride with an excess of diamine to produce a low molecular mass polyamide with amine end groups. This may then be chain extended by reaction with pyromellitic dianhydride to produce imide linkages. Alternatively the dianhydride, diamine and diacid chloride may be reacted all together. 

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. 

Heat distortion temperatures of resins cured with pyromellitic dianhydride are often quoted at above 200°C. The high heat distortion is no doubt also associated with the rigid linkages formed between epoxy molecules because of the nature of the anhydride. The use of these two anhydrides has, however, been restricted because of difficulties in incorporating them into the resin. 

The thermal properties of the resin are dependent on the degree of cross-linking, the flexibility of the resin molecule and the flexibility of the hardener molecule. Consequently the rigid structures obtained by using cycloaliphatic resins or hardeners such as pyromellitic dianhydride will raise the heat distortion temperatures. 

A considerable number of non-cross-linked aromatic and heterocyclic polymers has been produced. These include polyaromatic ketones, aromatic and heterocyclic polyanhydrides, polythiazoles, polypyrazoles, polytriazoles, poly-quinoxalines, polyketoquinolines, polybenzimidazoles, polyhydantoins, and polyimides. Of these the last two have achieved some technical significance, and have already been considered in Chapters 21 and 18 respectively. The most important polyimides are obtained by reacting pyromellitic dianhydride with an aromatic diamine to give a product of general structure (Figure 29.17). 

Epichlorohydrin with bisphenol A. The curing agents may pose significant health hazards, e.g. amines (triethylamine, p-phenylenediamine, diethylenetriamine) or acid anhydrides (pyromellitic dianhydride)... 

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