Synthesis and properties of polyamides and copolyamides based on 2,6‐naphthalene dicarboxylic acid

Abstract

AbstractA number of polyamides based on 2,6‐naphthalene dicarboxylic acid (NDA) and various aromatic diamines were synthesized in N‐methyl pyrrolidone (NMP) containing lithium chloride (LiCl) or calcium chloride (CaCl2) by direct polycondensation using triphenyl phosphite and pyridine. The best reaction conditions for polycondensation were determined in terms of factors such as the amount of the solvency‐promoting reagent such as LiCl or CaCl2 and the initial reactant concentration. Thus, almost all polyamides were obtained with inherent viscosities above 1.0 and up to 3.28 dL/g. Similarly, high molecular weight copolyamides with inherent viscosities of 1.76–3.61 dL/g were prepared from 4,4′‐oxydianiline (ODA) and mixed dicarboxylic acids of NDA/terephthalic acid (TPA) or NDA/isophthalic acid (IPA). The solubility of NDA homopolyamides depended on the diamine components. The polyamides derived from meta‐, sulfone‐, or alkylene‐linked diamine showed increased solubility. Copolymerization of ODA with NDA/IPA led to a significant increase in solubility, whereas with NDA/TPA, it gave a limited improvement. All the homopolyamides and copolyamides showed an amorphous X‐ray diffraction pattern. Almost all the polymers soluble in aprotic solvents can be solution‐cast into strong and tough films. Glass transition shifts of some NDA polyamides can be observed in the differential scanning calorimetry (DSC) curves ranging from 243 to 345°C. Most NDA/IPA–ODA copolyamides also showed clear transitions in the range of 255–268°C. In nitrogen, all the polymers showed no significant weight loss up to 400°C, and their 10% weight loss temperatures were recorded in the range of 434–541°C. © 1994 John Wiley & Sons, Inc.