Synthesis and characterization of novel optically active and flame-retardant heterocyclic polyimides

• Published in: Journal of applied polymer science Vol. 76; no. 2; pp. 240 - 248
• Main Authors: Mallakpour, Shadpour E., Hajipour, Abdol-Reza, Mahdavian, Ali-Reza, Khoee, Sepideh
• Format: Journal Article
• Language: English
• Published: New York John Wiley & Sons, Inc 11.04.2000; Wiley
• Subjects: 4-phenyl-1; 4-triazoline-3; 4‐phenyl‐1,2,4‐triazoline‐3,5‐diones, bistriazolinediones, inherent viscosity, diastereoselectivity; 5-diones; Applied sciences; bistriazolinediones; diastereoselectivity; Diels-Alder-ene polymerization; Exact sciences and technology; fire-resistant polymers; inherent viscosity; N-(tetrachlorophthaloyl)-L-leucine acid chloride; optically active polymers; Organic polymers; Physicochemistry of polymers; Polymers with particular properties; Preparation, kinetics, thermodynamics, mechanism and catalysts; Triazole derivative copolymer; Cyclopolymerization; Flame retardant; Diels Alder addition; Chlorine containing copolymer; Experimental study; Polyaddition; Functional polymer; Thermal stability; Thermal properties; Optically active copolymer; Cyclopolymer; Ene reaction; Preparation; Reaction mechanism; Triazole derivatives; Model reaction; Imide copolymer
• ISSN: 0021-8995; 1097-4628
• DOI: 10.1002/(SICI)1097-4628(20000411)76:2<240::AID-APP13>3.0.CO;2-A

Tetrachlorophthalic anhydride (1) was reacted with L‐leucine (2) in toluene solution at refluxing temperature in the presence of triethylamine and the resulting imide‐acid (4) was obtained in quantitative yield. The compound (4) was converted to the N‐(tetrachlorophthaloyl)‐L‐leucine acid chloride (5) by reaction with thionyl chloride. The reaction of this acid chloride (5) with isoeugenol (6) was carried out in chloroform and novel optically active isoeugenol ester derivative (7) as a chiral monomer was obtained in high yield. The compound (7) was characterized by 1H‐NMR, IR, Mass and elemental analysis, and then was used for the preparation of model compound (10) and polymerization reactions. 4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione, PhTD (8) was allowed to react with compound (7). The reaction is very fast, and gives only one diastereomer of (10) via Diels–Alder and ene pathways in excellent yield. The polymerization reactions of novel monomer (7) with bistriazolinediones [bis‐(p‐3,5‐dioxo‐1,2,4‐triazolin‐4‐ylphenyl)methane (11) and 1,6‐bis‐(3,5‐dioxo‐1,2,4‐triazolin‐4‐yl)hexane] (12) were carried out in N,N‐dimethylacetamide (DMAc) at room temperature. The reactions are exothermic, fast, and give novel optically active polymers (13) and (14) via repetitive Diels–Alder‐ene polyaddition reactions. The resulting polymers are optically active, thermally stable, and flame resistant. All of the above compounds were fully characterized by IR, 1H‐NMR, elemental analysis, and specific rotation. Some structural characterization and physical properties of these novel heterocyclic polyimides are reported. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 240–248, 2000