Effect of Diamine Addition on Structural Features and Physical Properties of Polyamide 6 Synthesized by Anionic Ring-Opening Polymerization of ε-Caprolactam

Synthesis of ε-caprolactam in a twin screw extruder by anionic ring-opening polymerization was successfully carried out to prepare a novel nylon 6 (polyamide 6 (PA6)) containing a small amount of diamine moiety. The produced PA6 shows a remarkable improvement of the physical properties (mechanical properties as well as rheological properties). Added diamine molecules led to some structural changes in the synthesized PA6. The molar ratio of the additive (diamine) to the initiator appeared to be optimum at ca. 0.1. Although the molar mass of the PA6 has not changed significantly, less than twice the PA6 molar mass, the physical properties of the polymers produced have been markedly improved. The zero shear rate viscosity of the PA6 at the optimum diamine concentration appeared to be increased by almost 30 times that of the pure PA6. We have attributed this remarkable increase in viscosity to structural changes (branching formation during synthesis) and increased molar mass. The storage modulus at a low shear rate increased more than 100 times that of the pure PA6, but the loss modulus increased only 10-fold. This indicates that the elastic properties dominated due to the enhanced chain entanglements. In addition, the mechanical properties were significantly improved at the optimal amount of diamine reagent concentration. The elongation at break for the sample with optimum diamine addition was increased to twice that of neat PA6, whereby the tensile toughness was also doubled. Produced PA6 has a merit of processibility in the extrusion process such as a blow molding process in which stability against sagging under gravity is required and other processes in which elongational properties dominate.