14 Preparation and Chemistry of Nylon Plastics

PREPARATION OF NYLpN PLASTICS

Discussion of the synthetic routes to cornrnercial and candidate nylon plastics
logically begins with nylon-66 and nylon-6. Asthe cornrnercially most important
nylon plastics as well as fibers, they havereceived the most study. The methods
employed to synthesize the monomers (often referred to as intermediates
because of their mid-position between raw material s and polymers) and their
conversion into useful nylons are representative of synthetic methods and
polymerization techniques applicable to other nylons. The preparation of other
nylon plastics is subsequently reviewed, but excluded are somenylons that have
been mentioned as commercial possibilities such as nylons-3, 4, and -5 and
wholly aromatic nylons. Such nylons are fiber (1) but not plastic candidates
because they are melt unstable or have excessively high melt viscosities,
difficulties which can be overcome in fiber technology by solution spinning.
Intermediates for Nylon-66 and Nylon-6
The multiplicity of processes that lead to intermediates for nylon-66 and
nylon-6 is ilIustrated in Figure 2-1. Adipic acid is manufactured principally by
the nitric acid oxidation of a cyclohexanol/cyclohexanone mixture obtained by
the air oxidation of cyclohexane, althugh the oxidation of cyclohexanol
obtained by the hydrogenation of phenol isalsoused (2,3,4). Hexamethylenedi-
arnine is made by the hydrogenation of adiponitrile which can be derived from
adipic acid, butadiene, furfural, propylene, or acetylene. Receiving particular
attention in recent years is the propylene route because it affords low-cost
acrylonitrile which has been hydrodimerized electrolyticaIly to adiponitrile
(5,6,7). The reaction of butadiene and hydrogen cyanide in the presence of
selected catalysts has been described asanew route to adiponitrile (220).
Most processes for the manufacture of caprolactam involveasafinal step the
rearrangement of cyclohexanoneoxime to caprolactam (8):
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The oxime can be obtained by hydrogenation of nitrocyclohexane and by
treatment of cyclohexane with nitrosyl chloride in the presence of lght (9,10),
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