Self-association, compatibility, and strengthening behavior of liquid crystalline oligomers

• Main Author: Moilanen, A. (Anu)
• Format: Doctoral Thesis
• Language: English
• Published: University of Oulu 1998
• Subjects: liquid crystalline polymers; miscibility; polymer blends
• Online Access: http://urn.fi/urn:isbn:9514250915; http://nbn-resolving.de/urn:isbn:9514250915

Abstract Synthetic routes were developed for the preparation of 2-alkoxy-4-hydroxybenzoic acids and 2-alkoxyhydroquinones, and a large-scale synthesis was developed for the preparation of 2-thioalkoxyhydroquinones. The 2-alkoxy-4-hydroxybenzoic acids, which contained alkyl side chains of different length, were used in the synthesis of new main chain liquid crystalline (LC) homo-, random, and block co-oligomers. In addition, oligomers of terephthaloyl chloride and 2-thioalkoxyhydroquinones and oligomers of terephthaloyl chloride and 2-alkoxyhydroquinones were produced. All the oligomers were blended with aliphatic polyamide 11 (PA 11). The effect of alkyl side chain length on the compatibility behavior of the LC oligomers towards the aliphatic polymer was characterized by DSC and FTIR, and the effect of side chain length on the flexural properties of the blends was investigated with a three-point bending test. The miscibility studies showed variable interfacial adhesion between the blended compounds. The strongest adhesion was achieved between PA 11 and the homo-oligomers of 2-alkoxy-4-hydroxybenzoic acids with short or medium long substituents (C4-C10), but the interactions between PA 11 and the oligomer with long aliphatic side chain (C18) were poor, as were those between PA 11 and the wholly aromatic oligomer of 4-hydroxybenzoic acid. The compatibility between PA 11 and the co-oligomers of 2-alkoxy-4-hydroxybenzoic acids was slightly lower than the compatibility of the corresponding homo-oligomers. DSC and FTIR analyses of the blends of oligomers of terephthaloyl chloride and 2-thioalkoxyhydroquinones and oligomers of terephthaloyl chloride and 2-alkoxyhydroquinones with PA 11 implied that the interactions between the blended compounds were poor. FTIR spectra and viscosity measurements confirmed that all the oligomeric structures could self-associate, with effect on the final mechanical properties of the polyamide. The strength of PA 11 in a three-point bending test was increased by the addition of only 1% of LC oligomers to the matrix. The results also showed that the strengthening ability of the oligomers is directly proportional to the total amount of aliphatic carbons. The best strengthening results were obtained with unsubstituted oligomers, random co-oligomers of 2-alkoxy-4-hydroxybenzoic acids, and homo-oligomer of 2-butoxy-4-hydroxybenzoic acid. DSC investigations of a ternary blend of the oligomer of 2-decanyloxy-4-hydroxybenzoic acid, PA 11, and wholly aromatic commercial LC polymer showed the promising compatibilizing effect of the oligomer.