Caprolactam, nylon 6 from

Camphor, molecular model of, 129 specific rotation of, 296 Cannizzaro, Stanislao, 724 Cannizzaro reaction. 724 mechanism of, 724 Caprolactam, nylon 6 from, 1213 Capsaicin, structure of. 78 -curbahlehyde, aldehyde name ending, 696... 

Nylons are classified into two categories AB and AABB polymers. Molecules of the AB type consist of repeat units that contain a single amide group, such as nylon 6, which is illustrated in Fig. 23.2 a). Molecules of the AABB type consist of repeat units that contain two amide groups, such as nylon 66 (pronounced nylon six six ), which is illustrated in Fig. 23.2 b). Type AB nylons are made from a single monomer, such as caprolactam, which is shown in Fig. 23,3 a). We make type AABB nylons from diamines and diacids, such as adipic acid and hexamethylene diamine, which are shown in Fig. 23.3 b) and c), respectively. 

Figure 23.6 Principal reactions during the of the polymerization of nylon 6, a type A8 nylon, from caprolactam ...

PNC [Photonitrosation of cyclohexane] A photochemical process for making caprolactam (a precursor for nylon) from cyclohexane, nitrosyl chloride, and hydrogen chloride. The first photochemical product is cyclohexanone oxime ... 

NH3 or RNH2 or R2NH Amide formation from carboxylic acid derivatives (mild) or from carboxylic acids (A technical synthesis of nylon-6,6) transamidation [caprolactame — - nylon-6 (perlon)] Peptide synthesis (Section 6.4.3)... 

Nylon. In 1939 the DuPont Company introduced the first truly synthetic textile fiber. Dr. Wallace Carothers invented nylon as a result of his basic research into polymer science. Chemically, nylon is a polyamide fiber. The two major types of nylon polymer are used in textiles type 6,6 which is made by using hexam-ethylene glycol and adipic acid, and type 6, which is made by polymerizing e-caprolactam. Nylon fibers are made by melt-spinning the molten polymer. The result is a continuous filament fiber of indeterminate length. It is spun in many deniers, with its diameter varying from 10 to 50 microns. The cross-section usually is round, trilobal, or square with hollow channels when used as carpet fiber. 

In the anionic polymerization to form nylon block copolymer, the acyllactam Initiates caprolactam polymerization from the ends of the prepolymer. 

The first industrial production of caprolactam dates from 1938, when BASF started manufacturing perion (BASF nylon-6). The starting material was phenol. Other processes have been developed since then, using the same intermediate but also cyclohexane and toluene. 

Collision induced dissociation (B/E) mass spectra of (a) ion at m/z 71 from Nylon 3 pyrolysis (b) acrylamide (c) caprolactam. (Reprinted from Ref. 46, Copyright 1986, with permission from Elsevier Science.)... 

Perlon Generic name for polyamides from caprolactam (nylon 6) —... 

On the other hand, BASF in Germany developed another method of producing nylon from just one monomer (a homopolymer version of nylon), which was later called nylon-6. This competing version is derived from caprolactam as seen in Figure 5.8. 

C, b.p. 81"C. Manufactured by the reduction of benzene with hydrogen in the presence of a nickel catalyst and recovered from natural gase.s. It is inflammable. Used as an intermediate in the preparation of nylon [6] and [66] via caprolactam and as a solvent for oils, fats and waxes, and also as a paint remover. For stereochemistry of cyclohexane see conformation. U.S. production 1980 1 megatonne. 

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. 

Adiponitnle (hexanedinitnle, dicyanobutane, ADN), NC(CH2)4CN, is manufactured principally for use as an intermediate for hexamethylenediarnine (1,6-diaminohexane), which is a principal ingredient for nylon-6,6. However, in 1996, BASF aimounced the development of a process to make caprolactam from adiponitrile (44,45). Caprolactam is used to produce nylon-6. The implementation of this technology could increase the demand for adiponitrile dramatically. 

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. 

Enzymatic hydrolysis is also used for the preparation of L-amino acids. Racemic D- and L-amino acids and their acyl-derivatives obtained chemically can be resolved enzymatically to yield their natural L-forms. Aminoacylases such as that from Pispergillus OTj e specifically hydrolyze L-enantiomers of acyl-DL-amino acids. The resulting L-amino acid can be separated readily from the unchanged acyl-D form which is racemized and subjected to further hydrolysis. Several L-amino acids, eg, methionine [63-68-3], phenylalanine [63-91-2], tryptophan [73-22-3], and valine [72-18-4] have been manufactured by this process in Japan and production costs have been reduced by 40% through the appHcation of immobilized cell technology (75). Cyclohexane chloride, which is a by-product in nylon manufacture, is chemically converted to DL-amino-S-caprolactam [105-60-2] (23) which is resolved and/or racemized to (24)... 

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. 

Nylon-6 [25038-54-4] was first made in 1899 by heating 6-aminohexanoic acid (143), but its commercially feasible synthesis from caprolactam was discovered by Paul Schlack at 1. G. Farbenindustrie in 1938. Like nylon-6,6, it is a tough, white translucent, semicrystalline sofld, but melts at a lower temperature (T = 230° C. The physical properties and primary producers of nylon-6 are Hsted in Tables 9 and 10, respectively. 

Ingredients. Nylon-6 is produced commercially from caprolactam [105-60-2] which is the most important lactam industrially. AH industrial production processes for caprolactam are multistep and produce ammonium sulfate [7783-20-2] or other by-products. Approximately 95% of the world s caprolactam is produced from cyclohexanone oxime [100-64-1] via the Beckmann rearrangement (144). The starting material for cyclohexanone can be... 

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