Structural modifications and fibre processing of hydroxy-functionalised mesogenic polyazomethines

Abstract

A number of semiflexible homopolyazomethines and copolyazomethines based on hydroxy-functionalised mesogenic cores have been synthesised and characterised. The reported polymers include structural modifications such as an alteration of the coaxiality, shortening of the flexible spacers or copolymerisation to attain materials with reduced melting temperatures and suitable processability. These structural alterations have been introduced by condensing different α,ω-bis-[(4-formyl-3-hydroxyphenyl)oxy]alkanes with 2-methyl-1,4-phenylenediamine and/or 4-methyl-1,3-phenylenediamine. Fibres have been melt extruded from those nematic polyazomethines with the most favourable thermal properties. As-spun and tension-annealed fibres have been investigated by thermal analysis (TGA and DSC), X-ray diffraction and SEM microscopy in an attempt to infer a relationship between microstructure and tensile properties. From the results presented here, copolymerisation incorporating flexible spacers of different lengths seems to be the best strategy to balance ease of processing and tensile properties. Some of the fibres have improved mechanical properties compared with those previously reported for this class of semiflexible polyazomethine. A nematic polyazomethine with a decamethylenic spacer has also been modified with low percentages of several metal ions [Fe(III), Zn(II), V(IV) and Ni(II)] in order to establish a comparison with previously reported Cu(II)-modified fibres.