Polymerization in the crystalline state. X. Solid-state conversion of 6-aminocaproic acid to oriented nylon 6

• Published in: Journal of polymer science. Part A-1, Polymer chemistry Polymer chemistry, 1968-08, Vol.6 (8), p.2033-2049
• Main Authors: Macchi, E. M., Morosoff, N., Morawetz, H.
• Format: Article
• Language: English
• ISSN: 0449-296X; 1542-9350
• DOI: 10.1002/pol.1968.150060801

When single crystals of 6‐aminocaproic acid (ACA) are heated about 30°C below their melting point, polycondensation to nylon 6 takes place. The polymer crystallites are biaxially oriented towards each other and the relation between their orientation and that of the parent monomer crystal has been clarified. The kinetics of the process are characterized by three stages, ( a ) an induction period, ( b ) a stage in which monomer disappears at a constant rate while polymer of relatively low molecular weight is formed, and ( c ) a slow polycondensation of the polyamide chains after exhaustion of the monomer. Oligomer concentrations were below detectable limits at all stages of the process. Addition of monomer to the polyamide was retarded when ACA was kept from reaching its equilibrium vapor pressure (0.12 mm Hg at 170°C) by condensation on a cool surface or when an inert gas was admitted to the system. This was interpreted as suggesting that ACA is transported through the vapor phase to the propagating polyamide. A number of surfaces catalyzed the polycondensation of ACA vapor, but nylon 6 formed in this way on KCl crystals exhibited no preferred orientation. The linear dimer and trimer of ACA were also found to condense to nylon 6 in the crystalline state, although at a slower rate than the monomer. The solid‐state polycondensation of these oligomers was accelerated when they were exposed to the vapor of the monomer. Solid‐state polycondensation of single crystals of the linear dimer led also to biaxially oriented nylon 6.