Nylon adipic acid

Colourless liquid with a strong peppermintlike odour b.p. 155" C. Manufactured by passing cyclohexanol vapour over a heated copper catalyst. Volatile in steam. Oxidized to adipic acid. Used in the manufacture of caprolactam. Nylon, adipic acid, nitrocellulose lacquers, celluloid, artificial leather and printing inks. 

Ammonia is used in the production of several chemicals to make nylon adipic acid, hexa-methylene diamine, and caprolactam. It is used to treat metals in annealing, nitriding, and descaling. Ammonia is an excellent fungicide that is used to treat citric fruit. It is also used to increase the nitrogen content of crops used as feed for livestock. Ammonia dissolves readily in water to produce aqueous ammonia or ammonium hydroxide NH + 2 < > NH4+(a(i) + OH (ahydroxide ions shows that ammonia acts as a base in aqueous solution. Concentrated aqueous solutions contain 35% ammonia. Household ammonia cleaners contain between 5% and 10% ammonia. 

The concentration of nitrous oxide (N2O) in the atmosphere is increasing. This is a concern, since N2O has been identified as a greenhouse gas and as a source of ozoneconsuming NO in the stratosphere. A significant source of N2O to the atmosphere is production of adipic acid (AA), which is used in the production of nylon. Adipic acid is formed from reaction of cyclohexanol with nitric acid (HNO3) according to the scheme in Fig. 13.13. 

Polyamides. The first commercially produced synthetic polyamides were made from dibasic acids and diamines exemplified by polyhexameth-ylene adipamide (6,6-nylon). Adipic acid was first commercially produced by osdation of cyclohexanone produced from phenol, but today it is largely produced by oxidation of cyclohexane derived from either benzene or petroleum. Sebacic acid, another important nylon intermediate, is produced by caustic oxidation of ricinoleic acid from castor oil. 

Uses Solvent for cellulose ethers, fats, oils, waxes, inks, lacquers, resins, coatings paint and varnish remover extraction solvent for essential oils glass substitutes laboratory reagent chemical intermediate in fungicidal formulations mfg. of nylon, adipic acid, benzene, cyclohexanone, etc. mfg. of solid fuel for camp stoves diluent in food colorants solvent in cosmetics, pharmaceutical orals in food-pkg. adhesives defoamer in food-contact paper coatings... 

Bio-nylon Adipic acid Hexamethylene diamine (HMDA)... 

Although most of this product (about 60%) is used in the manufacture of polyamide 6,6, which is formed by a reaction with hexamethylenediamine, the growth in the use of adipic acid during the last 20 years is also attributable to the expansion of polyurethane and polyester resins. After nylon, these product sectors, together with PVC plasticizers and synthetic lubricants, consume most of the extra-nylon adipic acid produced today. 

C, b.p. 16UC. Manufactured by heating phenol with hydrogen under pressure in the presence of suitable catalysts. Oxidized to adipic acid (main use as intermediate for nylon production) dehydrogenated to cyclohexanone. 

H2N (CH2)a NH2- Colourless solid when pure m.p. 4LC, b.p. 204 C. Manufactured by the electrochemical combination of two molecules of acrylonitrile to adiponitrile followed by catalytic reduction, or by a series of steps from cyclohexanone via adipic acid. Used in the production of Nylon [6, 6]. 

Nylon A class of synthetic fibres and plastics, polyamides. Manufactured by condensation polymerization of ct, oj-aminomonocarboxylic acids or of aliphatic diamines with aliphatic dicarboxylic acids. Also rormed specifically, e.g. from caprolactam. The different Nylons are identified by reference to the carbon numbers of the diacid and diamine (e.g. Nylon 66 is from hexamethylene diamine and adipic acid). Thermoplastic materials with high m.p., insolubility, toughness, impact resistance, low friction. Used in monofilaments, textiles, cables, insulation and in packing materials. U.S. production 1983 11 megatonnes. 

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 ... 

Add 40 ml. of ethyl alcohol to 21 -5 g. of 70 per cent, ethylenediamine solution (0 -25 mol) dissolve 36 -5 g. of adipic acid (0 -25 mol) in 50 ml. of a 6 1 mixture of ethyl alcohol and water. Mix the two solutions, stir and cool. Filter off the resulting salt and recrystalliae it from 60 ml. of a 6 1 ethyl alcohol - water mixture, and dry the salt in the air. Heat the salt in an atmosphere of oxygen-free nitrogen or of carbon dioxide in an oil bath until it melts (ca. 160°) the product will sohdify after a short time. Reduce the pressure to 15 mm. of mercury or less and raise the temperature of the oil bath until the product remelts (about 290°) and continue the heating for 4r-5 hours. Upon coohng, a nylon type polymer is obtained. 

X,9. DEPOLYMERISATION OF A HEXAMETHYLENE-DIAMINE-ADIPIC ACID POLYMER (NYLON 66 )... 

Add 10 ml. of concentrated sulphuric acid cautiously to 45 ml. of water contained in a 200 ml. round-bottomed flask, introduce 3 g. of Nylon 66 polymer into the hot solution, and heat under reflux for 6 hours. Allow to stand for 1 hour and cool in ice for a further hour. Filter off the solid and keep the filtrate. Recrystalhse the sohd (adipic acid) from water m.p. 152°. 

The leader of DuPont s effort was Wallace H Carothers who reasoned that he could reproduce the properties of silk by constructing a polymer chain held together as is silk by amide bonds The neces sary amide bonds were formed by heating a dicar boxylic acid with a diamine Hexanedioic acid adipic acid) and 1 6 hexanediamme hexamethylenedi-amine) react to give a salt that when heated gives a polyamide called nylon 66 The amide bonds form by a condensation reaction and nylon 66 is an example of a condensation polymer... 

Amidation. Heating of the diammonium salt or reaction of the dimethyl ester with concentrated ammonium hydroxide gives adipamide [628-94-4] mp 228°C, which is relatively insoluble in cold water. Substituted amides are readily formed when amines are used. The most industrially significant reaction of adipic acid is its reaction with diamines, specifically 1,6-hexanediamine. A water-soluble polymeric salt is formed initially upon mixing solutions of the two materials then hea ting with removal of water produces the polyamide, nylon-6,6. This reaction has been studied extensively, and the hterature contains hundreds of references to it and to polyamide product properties (31). 

Since adipic acid has been produced in commercial quantities for almost 50 years, it is not surprising that many variations and improvements have been made to the basic cyclohexane process. In general, however, the commercially important processes stiU employ two major reaction stages. The first reaction stage is the production of the intermediates cyclohexanone [108-94-1] and cyclohexanol [108-93-0], usuaHy abbreviated as KA, KA oil, ol-one, or anone-anol. The KA (ketone, alcohol), after separation from unreacted cyclohexane (which is recycled) and reaction by-products, is then converted to adipic acid by oxidation with nitric acid. An important alternative to this use of KA is its use as an intermediate in the manufacture of caprolactam, the monomer for production of nylon-6 [25038-54-4]. The latter use of KA predominates by a substantial margin on a worldwide basis, but not in the United States. 

Adipic acid is a very large volume organic chemical. Worldwide production in 1986 reached 1.6 x 10 t (3.5 x 10 lb) (158) and in 1989 was estimated at more than 1.9 x 10 t (Table 7). It is one of the top fifty (159) chemicals produced in the United States in terms of volume, with 1989 production estimated at 745,000 t (160). Growth rate in demand in the United States for the period 1988—1993 is estimated at 2.5% per year based on 1987—1989 (160). Table 7 provides individual capacities for U.S. manufacturers. Western European capacity is essentially equivalent to that in the United States at 800,000 t/yr. Demand is highly cycHc (161), reflecting the automotive and housing markets especially. Prices usually foUow the variabiUty in cmde oil prices. Adipic acid for nylon takes about 60% of U.S. cyclohexane production the remainder goes to caprolactam for nylon-6, export, and miscellaneous uses (162). In 1989 about 88% of U.S. adipic acid production was used in nylon-6,6 (77% fiber and 11% resin), 3% in polyurethanes, 2.5% in plasticizers, 2.7% miscellaneous, and 4.5% exported (160). 

Because of projected nylon-6,6 growth of 4—10% (167) per year in the Far East, several companies have announced plans for that area. A Rhc ne-Poulenc/Oriental Chemical Industry joint venture (Kofran) announced a 1991 startup for a 50,000-t/yr plant in Onsan, South Korea (168,169). Asahi announced plans for a 15,000-t/yr expansion of adipic acid capacity at their Nobeoka complex in late 1989, accompanied by a 60,000-t/yr cyclohexanol plant at Mizushima based on their new cyclohexene hydration technology (170). In early 1990 the Du Pont Company announced plans for a major nylon-6,6 complex for Singapore, including a 90,000-t/yr adipic acid plant due to start up in 1993 (167). Plans or negotiations for other adipic acid capacity in the area include Formosa Plastics (Taiwan) (171) and BASF-Hyundai Petrochemical (South Korea) (167). Adipic acid is a truly worldwide... 

About 85% of U.S. adipic acid production is used captively by the producer, almost totally ia the manufacture of nylon-6,6 (194). The remaining 15% is sold ia the merchant market for a large number of appHcations. These have been developed as a result of the large scale availabihty of this synthetic petrochemical commodity. Prices for 1960—1989 for standard resia-grade material have parahed raw material and energy costs (petroleum and natural gas)... 

Polyamides. In 1988, 77% of U.S. demand for adipic acid was for nylon-6,6 fiber, while 11% was used in nyon-6,6 resins (195). In Western Europe only about 66% was for polyamide, because of the stronger competition from nylon-6. The fiber appHcations include carpets (67%), apparel (13%), tire cord (7%), and miscellaneous (13%). Nylon-6,6 resins were distributed between injection mol ding (85%) for such appHcations as automotive and electrical parts and for extmsion resins (15%) for strapping, film, and wire and cable. 

Cyclohexane. The LPO of cyclohexane [110-82-7] suppUes much of the raw materials needed for nylon-6 and nylon-6,6 production. Cyclohexanol (A) and cyclohexanone (K) maybe produced selectively by using alow conversion process with multiple stages (228—232). The reasons for low conversion and multiple stages (an approach to plug-flow operation) are apparent from Eigure 2. Several catalysts have been reported. The selectivity to A as well as the overall process efficiency can be improved by using boric acid (2,232,233). K/A mixtures are usually oxidized by nitric acid in a second step to adipic acid (233) (see Cyclohexanol and cyclohexanone). 

Until the 1960s, adipic acid [124-04-9] was virtually the sole intermediate for nylon-6,6. However, much hexamethylenediamine is now made by hydrodimerization of acrylonitrile (qv) or via hydrocyanation of butadiene (qv). Cyclohexane remains the basis for practically the entire world output of adipic acid. The U.S. capacity for adipic acid for 1993 was 0.97 X 10 t/yr (233). 

The United States accounts for about a third of the world s consumption of cyclohexane, or 3.785 x 10 m /yr (about 1 biUion gallons per year). U.S. producers and their 1990 capacities are Hsted in Table 13. Texaco has aimounced that it is leaving the cyclohexane business, but the timing is not yet certain. Over 90% of all cyclohexane goes to the production of nylon through either adipic acid (qv) or caprolactam (qv). The balance is used to produce 1,6-hexamethylenediamine [124-09-4] (HMD A) and for various solvent uses (see Diamines and higher amines, aliphatic Polyamides). 

Dilute nitric acid can be used to oxidize an aliphatic hydrocarbon. For example, a significant use for nitric acid is the oxidation of cyclohexanol and cyclohexanone (qv) to produce adipic acid (qv). Most adipic acid is used for the production of nylon-6,6. 

Some other phenol derivatives are somewhat local in appHcation. Eor example, aniline is produced from phenol at only two plants, one in Japan and one in the United States. Likewise, phenol is used in the production of nylon, via caprolactam (qv) or adipic acid (qv) by only one United States producer and one European producer. These markets, like the phenoHc resin and polycarbonate markets, are quite cycHcal. Thus, the entire phenol market tends to be cycHcal and closely tied to the housing and automotive markets. 

Ingredients. Nylon-6,6 is made from the reaction of adipic acid [124-04-9] and hexamethylenediamine [124-09-4]. The manufacture of intermediates for polyamides is extremely important not only is the quaUty of the polymer, such as color, degree of polymerization, and linearity, strongly dependent on the ingredient quaUty, but also the economic success of the producer is often determined by the yields and cost of manufacture of the ingredients. 

Adipic acid (qv) has a wide variety of commercial uses besides the manufacture of nylon-6,6, and thus is a common industrial chemical. Many routes to its manufacture have been developed over the years but most processes in commercial use proceed through a two-step oxidation of cyclohexane [110-83-8] or one of its derivatives. In the first step, cyclohexane is oxidized with air at elevated temperatures usually in the presence of a suitable catalyst to produce a mixture of cyclohexanone [108-94-1] and cyclohexanol [108-93-0] commonly abbreviated KA (ketone—alcohol) or KA oil ... 

Polymer Production. Three processes are used to produce nylon-6,6. Two of these start with nylon-6,6 salt, a combination of adipic acid and hexamethylenediamine in water they are the batch or autoclave process and the continuous polymerisation process. The third, the soHd-phase polymerisation process, starts with low molecular weight pellets usually made via the autoclave process, and continues to build the molecular weight of the polymer in a heated inert gas, the temperature of which never reaches the melting point of the polymer. 

The by-product of this process, pelargonic acid [112-05-0] is also an item of commerce. The usual source of sebacic acid [111-20-6] for nylon-6,10 [9008-66-6] is also from a natural product, ticinoleic acid [141-22-0] (12-hydroxyoleic acid), isolated from castor oil [8001-79-4]. The acid reacts with excess sodium or potassium hydroxide at high temperatures (250—275°C) to produce sebacic acid and 2-octanol [123-96-6] (166) by cleavage at the 9,10-unsaturated position. The manufacture of dodecanedioic acid [693-23-2] for nylon-6,12 begins with the catalytic trimerization of butadiene to make cyclododecatriene [4904-61-4] followed by reduction to cyclododecane [294-62-2] (see Butadiene). The cyclododecane is oxidatively cleaved to dodecanedioic acid in a process similar to that used in adipic acid production. 

Hexamethylenediamine [124-09-4] and adipic acid [124-04-9] are used in the commercial production of nylon-6,6 and S-caprolactam [105-60-2] is used for nylon-6 (see also Adipic acid Caprolactam). 

Nylon-4,6 [24936-71-8] introduced as Stanyl by Dutch State Mines, is synthesized from 1,4-tetramethylenediarnine and adipic acid (202). Stanyl has a high melting temperature (295°C), improved chemical resistance, better dimensional stabiUty, and higher modulus than nylon-6 and nylon-6,6 it is therefore highly suited for industrial yam appHcations, including tire cord. 

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