Terephthalic dimethyl ester

Preparation 211.—Dimethyl Terephthalate (Dimethyl ester of 1 4-benzenedicarboxylic acid). 

The first oxidation step proceeds under conditions that lead only to the reaction of one methyl group and the monoacid is formed. To convert the second methyl group as well, it is necessary to form the monoadd methyl ester in the next step. After the second oxidation step the terephthalic dimethyl ester is formed under the same esterification conditions by reaction with methanol. Terephthahc dimethyl ester is later reacted directly with ethylene glycol to form the PET polymer with liberation of methanol. The total process provides a yield in terephthalic acid dimethyl ester of 85% with respect to p-xylene. 

Ak2o has been iastmmental ia developiag a new process for the stereospecific synthesis of 1,4-cyclohexane diisocyanate [7517-76-2] (21). This process, based on the conversion of poly(ethylene terephthalate) [25038-59-9] circumvents the elaborate fractional crystallisation procedures required for the existing -phenylenediamine [108-45-2] approaches. The synthesis starts with poly(ethylene terephthalate) (PET) (32) or phthaUc acid, which is converted to the dimethyl ester and hydrogenated to yield the cyclohexane-based diester (33). Subsequent reaction of the ester with ammonia provides the desired bisamide (34). The synthesis of the amide is the key... 

Phthahc anhydride (1) is the commercial form of phthaUc acid (2). The worldwide production capacity for the anhydride was ca 3.5 x 10 metric tons ia 1993, and it was used ia the manufacture of plasticizers (qv), unsaturated polyesters, and alkyd resins (qv) (see Polyesters, unsaturated). Sales of terephthahc acid (3) and its dimethyl ester are by far the largest of any of the benzenepolycarboxyhc acids 14.3 x 10 t were produced in 1993. This is 80% of the total toimage of ah. commercial forms of the benzenepolycarboxyhc acids. Terephthahc acid is used almost exclusively for the manufacture of poly(ethylene terephthalate), which then is formed into textiles, films, containers, and molded articles. Isophthahc acid (4) and trimehitic anhydride (5) are commercial products, but their worldwide production capacities are an order of magnitude smaller than for terephthahc acid and its dimethyl ester. Isophthahc acid is used primarily in the production of unsaturated polyesters and as a comonomer in saturated polyesters. Trimehitic anhydride is used mainly to make esters for high performance poly(vinyl chloride) plasticizers. Trimesic acid (6), pyromehitic dianhydride (7), and hernimehitic acid (8) have specialized commercial apphcations. The rest of the benzenepolycarboxyhc acids are not available commercially. 

The oldest of these materials, a poly (trimethylhexamethylene terephthal-amide) was first marketed by Dynamit Nobel in the mid-1960s (Trogamid T). It is a condensation product of trimethylhexamethylenediamine and terephthalic acid (or its dimethyl ester) (Figure 18.25). In practice a 1 1 mixture of 2,2,4- and 2,4,4-trimethyldiamines is used, this being produced from acetone via iso-phorone, trimethyladipic acid and trimethyladiponitrile. 

Chemical Designations - Synonyms Terephthalic Acid, Dimethyl Ester Chemical Formula 1,4-CH3OOCC5H4COOCH3. 

Prior to polymerization, p-xylene is first oxidized to terephthalic acid (TA) or dimethyl terephtalate (DMT). These diacid or dimethyl ester monomers are then polymerized via a condensation reaction with ethylene glycol to form the polyester. Prior to the development of a method to purify TA to make purified terephtahc acid (PTA, >99% pure) by the Mid-Century Corporation in the 1950s [10], DMT was the primary way to obtain the purified dicarboxylate. The Amoco Oil Company, now part of BP International, made several improvements to the PTA process since its inception [11]. Since the advent of the availability of PTA, it has become the monomer of choice over DMT. PTA avoids the complications of including methanol to enable purification and handling the methanol evolved during the polymerization to polyester. 

Terephthalic Acid, Dimethyl Ester Tergitol 3-A-B Nonionic Tergitol Nonionic 45-S-10 Tergitol Nonionic 45-S-10 Tergitol Nonionic TMN Terpinene... 

ABA ABS ABS-PC ABS-PVC ACM ACS AES AMMA AN APET APP ASA BR BS CA CAB CAP CN CP CPE CPET CPP CPVC CR CTA DAM DAP DMT ECTFE EEA EMA EMAA EMAC EMPP EnBA EP EPM ESI EVA(C) EVOH FEP HDI HDPE HIPS HMDI IPI LDPE LLDPE MBS Acrylonitrile-butadiene-acrylate Acrylonitrile-butadiene-styrene copolymer Acrylonitrile-butadiene-styrene-polycarbonate alloy Acrylonitrile-butadiene-styrene-poly(vinyl chloride) alloy Acrylic acid ester rubber Acrylonitrile-chlorinated pe-styrene Acrylonitrile-ethylene-propylene-styrene Acrylonitrile-methyl methacrylate Acrylonitrile Amorphous polyethylene terephthalate Atactic polypropylene Acrylic-styrene-acrylonitrile Butadiene rubber Butadiene styrene rubber Cellulose acetate Cellulose acetate-butyrate Cellulose acetate-propionate Cellulose nitrate Cellulose propionate Chlorinated polyethylene Crystalline polyethylene terephthalate Cast polypropylene Chlorinated polyvinyl chloride Chloroprene rubber Cellulose triacetate Diallyl maleate Diallyl phthalate Terephthalic acid, dimethyl ester Ethylene-chlorotrifluoroethylene copolymer Ethylene-ethyl acrylate Ethylene-methyl acrylate Ethylene methacrylic acid Ethylene-methyl acrylate copolymer Elastomer modified polypropylene Ethylene normal butyl acrylate Epoxy resin, also ethylene-propylene Ethylene-propylene rubber Ethylene-styrene copolymers Polyethylene-vinyl acetate Polyethylene-vinyl alcohol copolymers Fluorinated ethylene-propylene copolymers Hexamethylene diisocyanate High-density polyethylene High-impact polystyrene Diisocyanato dicyclohexylmethane Isophorone diisocyanate Low-density polyethylene Linear low-density polyethylene Methacrylate-butadiene-styrene... 

Because of the difficulty encountered in removing the water that is produced when an acid reacts with an alcohol, PET is produced commercially by the reaction of dimethyl terephthalate, the dimethyl ester of terephthalic acid, with ethylene glycol in an ester interchange reaction. The methanol that is formed in this reaction is readily removed by distillation. 

On the other hand, although o-phthalic acid, or rather its anhydride, had long been produced in enormous amounts for use in the manufacture of alkyd resins, the para derivative was less well known and not available on a large scale. The synthesis is a straightforward one, however, from p-xylene, which is oxidized to terephthalic acid, either by means of nitric acid in the older process or by air (catalyzed) in the newer one. In the early years this compound then was converted to the easily purified dimethyl ester in order to obtain a colorless polymer adequate for the manufacture of commercially acceptable fibers. 

SYNS 1,4-BENZENE DICARBOXYLIC ACID DIMETHYL ESTER (9CI) DIMETHYL-1,4-BENZENE DICARBOXYLATE METHYL-4-CARBOMETHOXY BENZOATE NCI-C50055 TEREPHTHALIC ACID METHYL ESTER... 

The only practical means for ensuring the desired polymer quality is to use scrupulously pure monomers. Purification of a polymer after it is synthesized would be prohibitively expensive, because these materials are sparingly soluble and are often difficult or impossible to crystallize or free of solvent. The overall least expensive route to good quality polyfethylene terephthalate) was therefore through the dimethyl ester of terephthalic acid as shown in reaction (b). The byproduct methanol was recovered to generate more diester from the acid. In more recent years, methods have been developed to produce the diacid with satisfactory purity, and reaction (a) is now the preferred route to this polymer because the esterification step with methanol can be eliminated. Reactions (d), (e), and others, which the reader may be able to write, will be more expensive in the final analysis for the various reasons mentioned above. 

Dimethyl ester of terephthalic acid /a = 2-2 X Diethyl ester of terephthalic acid /x = 2-3 X... 

Other procedures to obtain the polymer include the use of terephthalic acid esterified to its dimethyl ester, which by a transesterification reaction with ethylene glycol generates the polymer. In addition to ethyleneglycol, other diols can be used in the esterification readion, such as 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, etc. 

Terephthalic acid is usually converted directly to the dimethyl ester for polymer synthesis. This is prepared by superficially conventional technology using methanol and a mineral acid under moderate conditions (Eq. 19.67). 

Terephthalic acid is almost insoluble in hot and cold water. It sublimes without melting. It can be identified most readily by converting it into its dimethyl ester as described below. 

The direct polyesterification reaction of diacids with glycols is the most important industrial synthetic route to polyester polyols. The second most important synthetic route is the transesterification reaction between dimethyl esters of dicarboxylic or dibasic acids (dimethyl adipate, dimethyl terephthalate, dimethyl carbonate or even polyethylene terephthalate) and glycols (reaction 8.2) [1, 3-8]. 

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