Adipic acid, preparation

The unrecrystallized adipic acid, prepared as described on page 9, may be used. 

Adipic acid is conveiiiently prepared by the oxidation of cyc/ohexanol (or cyclohexanone) with concentrated or with 50 per cent, nitric acid ... 

Polyamides from diamines and dibasic acids. The polyamides formed from abphatic diamines (ethylene- to decamethylene-diamine) and abphatic dibasic acids (oxabc to sebacic acid) possess the unusual property of forming strong fibres. By suitable treatment, the fibres may be obtained quite elastic and tough, and retain a high wet strength. These prpperties render them important from the commercial point of view polyamides of this type are cabed nylons The Nylon of commerce (a 66 Nylon, named after number of carbon atoms in the two components) is prepared by heating adipic acid and hexamethylenediamine in an autoclave ... 

Plasticizers. About 2.5% of U.S. adipic acid consumed in 1988 was used in two basic types of adipic ester based plasticizers (195). Simple adipate esters prepared from Cg—alcohols are used especially as PVC plasticizers (qv). Eor special appHcations requiring low volatility or extraction resistance, polyester derivatives of diols or polyols are preferred. 

Isophorone usually contains 2—5% of the isomer P-isophorone [471-01-2] (3,5,5-trimethyl-3-cyclohexen-l-one). The term a-isophorone is sometimes used ia referring to the a,P-unsaturated ketone, whereas P-isophorone connotes the unconjugated derivative. P-lsophorone (bp 186°C) is lower boiling than isophorone and can be converted to isophorone by distilling at reduced pressure ia the presence of -toluenesulfonic acid (188). Isophorone can be converted to P-isophorone by treatment with adipic acid (189) or H on(Ill) acetylacetoate (190). P-lsophorone can also be prepared from 4-bromoisophorone by reduction with chromous acetate (191). P-lsophorone can be used as an iatermediate ia the synthesis of carotenoids (192). 

Tetraacylates have been prepared ia this way from stearic, ben2oic, cinnamic, and other acids, as well as from diacids such as succinic and adipic acids (14) (129). In some cases, TiCl may also be used. 

Diesters. Many of the diester derivatives are commercially important. The diesters are important plasticizers, polymer intermediates, and synthetic lubricants. The diesters of azelaic and sebacic acids are useflil as monomeric plasticizing agents these perform weU at low temperatures and are less water-soluble and less volatile than are diesters of adipic acid. Azelate diesters, eg, di- -hexyl, di(2-ethylhexyl), and dibutyl, are useflil plasticizing agents for poly(vinyl chloride), synthetic mbbers, nitroceUulose, and other derivatized ceUuloses (104). The di-hexyl azelates and dibutyl sebacate are sanctioned by the U.S. Food and Dmg Administration for use in poly(vinyl chloride) films and in other plastics with direct contact to food. The di(2-ethylhexyl) and dibenzyl sebacates are also valuable plasticizers. Monomeric plasticizers have also been prepared from other diacids, notably dodecanedioic, brassyflc, and 8-eth5lhexadecanedioic (88), but these have not enjoyed the commercialization of the sebacic and azelaic diesters. 

Azelaic, sebacic, dodecanedioic, and brassyhc acids may be used in copolyetheresteramides (111). Two patents describe additional apphcations for the C-9—C-40 diacids for the preparation of polyester carbonates (112), and the copolymerization of epoxides and carbon dioxide by reaction of either glutaric or adipic acids with zinc oxide (113). 

Seb cic Acid. Sebacic acid [111-20-6] C QH gO, is an important intermediate in the manufacture of polyamide resins (see Polyamides). It has an estimated demand worldwide of approximately 20,000 t/yr. The alkaline hydrolysis of castor oil (qv), which historically has shown some wide fluctuations in price, is the conventional method of preparation. Because of these price fluctuations, there have been years of considerable interest in an electrochemical route to sebacic acid based on adipic acid [124-04-9] (qv) as the starting material. The electrochemical step involves the Kolbn-type or Brown-Walker reaction where anodic coupling of the monomethyl ester of adipic acid forms dimethyl sebacate [106-79-6]. The three steps in the reaction sequence from adipic acid to sebacic acid are as follows ... 

Glutaric acid is easily and cheaply prepared by oxidation of cyclopentanone cf. Adipic Acid, Coll. Vol. i, 18. The oxidation needs careful control—if it gets out of hand succinic acid results. 

Hexamethylenediamine may be conveniently prepared from adipic acid via adiponitrile... 

In a typical process adiponitrile is formed by the interaction of adipic acid and gaseous ammonia in the presence of a boron phosphate catalyst at 305-350°C. The adiponitrile is purified and then subjected to continuous hydrogenation at 130°C and 4000 Ibf/in (28 MPa) pressure in the presence of excess ammonia and a cobalt catalyst. By-products such as hexamethyleneimine are formed but the quantity produced is minimized by the use of excess ammonia. Pure hexamethylenediamine (boiling point 90-92°C at 14mmHg pressure, melting point 39°C) is obtained by distillation, Hexamethylenediamine is also prepared commercially from butadience. The butadiene feedstock is of relatively low cost but it does use substantial quantities of hydrogen cyanide. The process developed by Du Pont may be given schematically as ... 

The nylon 66 salt is prepared by reacting the hexamethylenediamine and adipic acid in boiling methanol, the comparatively insoluble salt (melting point 190-191°C) precipitating out. 

The starting point in the prepration of these rubbers is a polyester prepared by reacting a glycol such as ethylene or propylene glycol with adipic acid. This is then reacted with an excess of a bulky di-isocyanate such as 1,5-naphthylene di-isoyanate (Figure 27.3). 

Putrescine dihydrochloride has been prepared by the Hofmann degradation of adipamide 3.. s by the Curtius degradation of adipyl hydrazide through the urethane by the Curtius degradation of adipyl azide obtained from adipyl chloride and sodium azide by the Schmidt degradation of adipic acid with hydrogen azide by the reduction of succinonitrile, succinaldoxime, or 7-phthalimidobutyronitrile with sodium and from N-ben-zoyl-7-iodobutylamine ... 

Ketals bearing the double bond at the 4,5-position are prepared by reaction with glycol in the presence of weak acids such as adipic acid. In this case ketal formation proceeds via the intermediate 2,4-dien-3-ol ether. Hemithioketals (71) of A -3-ketones are prepared by reaction with mer-... 

Furfural is a natural monomer obtained by the steam acid digestion of corncobs, bagasse, rice husks, oat hulls, or similar materials. It acts as the precursor for the preparation of two important monomers (Scheme 1), adipic acid and hexamethylene diamine, used in the... 

The main use of acrolein is to produce acrylic acid and its esters. Acrolein is also an intermediate in the synthesis of pharmaceuticals and herhicides. It may also he used to produce glycerol hy reaction with isopropanol (discussed later in this chapter). 2-Hexanedial, which could he a precursor for adipic acid and hexamethylene-diamine, may he prepared from acrolein Tail to tail dimenization of acrolein using ruthenium catalyst produces trans-2-hexanedial. The trimer, trans-6-hydroxy-5-formyl-2,7-octadienal is coproduced. Acrolein, may also he a precursor for 1,3-propanediol. Hydrolysis of acrolein produces 3-hydroxypropionalde-hyde which could he hydrogenated to 1,3-propanediol. ... 

The best known step-growth polymers are the polyamides, or nylons, first prepared by Wallace Carothers at the DuPont Company by heating a diamine with a diacid. Por example, nylon 66 is prepared by reaction of adipic acid (hexanedioic acid) with hexamethylenediamine (.1.,6-hexanediamine) at 280 °C. The designation "66" tells the number of carbon atoms in the diamine (the first 6) and the diacid (the second 6). 

Docosanedioic acid has been prepared by Wolff-Kishner reduction of 6,17-diketodocosanedioic acid, formed by reaction of the half-ester acid chloride of adipic acid with the a,co-cadmium derivative of decane (%26 overall yield).3 Reduction of Wolff-Kishner method, followed by simultaneous reduction and desulfurization with Raney nickel of the 2,5-bis(co-carboxyoctyl)thiophene pro-... 

This dicarboxy-terminated oligomer is prepared by reacting excess adipic acid with 1,2-edianediol in die bulk until hydroxyl group conversion is complete (Scheme 2.47). The molar mass of final polymer depends on the initial molar ratio of monomers (procedure similar to that described in ref. 401). 

The most important AA-BB-type polymer is PA-6,6. It is a semicrystalline material and has a high melting temperature (265°C). PA-6,6 is prepared from 1,6 hexamethylenediamine and adipic acid (Eq. 3.27) ... 

PA-4,6 salt is prepared from adipic acid and 1,4-tetramethylenediamine as described for the PA-6,6 salt (Example la). PA-4,6 salt (20 g), 2 mL water, and 0.2 mL 1,4-tetramethylenediamine (2.1 mol % excess) are added to a 100-mL glass container in an autoclave. The autoclave is flushed with nitrogen, closed, and given a starting nitrogen pressure of 5 bar. The autoclave is heated over a period of 60 min to 180° C and maintained at that temperature for 100 min, when the pressure is increased to about 8 bar. The pressure is then gradually released, the reaction mass cooled, and the material removed from the autoclave. The prepolymer is crushed into small particles (0.1—0.2 mm) (see Example lb). This prepolymer has a relative viscosity (r]rd) of 1.3 as measured in 96% sulfuric acid (1% solution at 25° C). 

The starting materials were low molecular weight polymers prepared by reacting 1,4 diaminobutane and adipic acid for two hours at 220 C in a capsule in an autoclave 10). The low molecular weight material was powdered by crushing and ballmilling. 

Step polymerisations tend to be carried out using two different bifunctional molecules so that these give rise to molecules which are essentially copolymers. For example, nylon 6,6 is prepared from hexamethylenediamine and adipic acid it thus consists of alternating residues along the polymer chain and may be thought of as an alternating copolymer. 

Most of the hexamethylenediamine produced is used for the manufacture of Type 66 nylon by polymerization with adipic acid. A minor use is for the preparation of hexamethylene diisocyanate used in light-stable polyurethane coatings. 

You are the Production Manager for a plant producing adipic acid by the nitric acid oxidation of a mixture of cyclohexanone and cyclohexanol. Your company is preparing for ISO 14001 registration. 

C04-0063. One starting material for the preparation of nylon is adipic acid. Adipic acid is produced from the oxidation of cyclohexane ... 

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