Synthesis of novel liquid crystalline and fire retardant molecules based on six-armed cyclotriphosphazene core containing Schiff base and amide linking units

Abstract

Nucleophilic substitution reaction between 4-hydroxybenzaldehyde and hexachlorocyclotriphosphazene, HCCP formed hexakis(4-formlyphenoxy)cyclotriphosphazene, 1. Intermediates 2a–e was formed from the alkylation reaction of methyl 4-hydroxybenzoate with alkyl bromide which further reduced to form benzoic acid intermediates. Further reaction of 2a–e and other substituted benzoic acid formed 3a–h, which then reduced to give subsequent amines, 4a–h. Other similar reaction was used to synthesis 4i. Condensation reaction between 1 and 4a–i yielded hexasubstituted cyclotriphosphazene compounds, 5a–i having Schiff base and amide linking units, and these compounds consist of different terminal substituents such as heptyl, nonyl, decyl, dodecyl, tetradecyl, hydroxy, carboxy, chloro, and nitro groups, respectively. Compound 5j with amino substituent at terminal end was formed from the reduction of 5i. All the intermediates and compounds were characterized using Fourier Transform Infrared (FT-IR), Nuclear Magnetic Resonance (NMR) and CHN elemental analysis. Mesophase texture of these compounds were determined using Polarized Optical Microscope (POM) and their mesophase transition were further confirmed using Differential Scanning Calorimetry (DSC). Only compounds 5a–e with alkoxy chains exhibited smectic A phase while other intermediates (1, 2a–e, 3a–h, and 4a–i) and final compounds (5f–j) are found to be non-mesogenic with no liquid crystal behaviour. The confirmation of the identity of the SmA phase was determined using XRD analysis. The study on the structure–properties relationship was conducted in order to determine the effect of the terminal group, length of the chains and linking units to the mesophase behaviour of the compounds. Moreover, the fire retardant properties of these compounds were determined using Limiting Oxygen Index (LOI) testing. Polyester resin with LOI value of 22.53% was used as matrix for moulding in the study. The LOI value increased to 24.71% when this polyester resin incorporated with 1 wt% of HCCP. Generally, all the final compounds showed a positive results with LOI value above 27% and the highest LOI value was belonged to compound 5i with 28.53%. The high thermal stability of the Schiff base molecules and the electron withdrawing group of the amide bonds and nitro group enhanced the fire retardant properties of this compound.