Synthesis and Characterisation of Side‐Chain Liquid Crystalline Poly[1‐({[(4‐cyano‐4′‐biphenyl)oxy]alkyl}oxy)‐2,3‐epoxypropane

Abstract

AbstractSummary: A new series of side‐chain liquid‐crystal polymers, the poly[1‐({[(4‐cyano‐4′‐biphenyl)oxy]alkyl}oxy)‐2,3‐epoxypropane], has been synthesized in which the spacer length is varied from 2 to 8 methylene units. The synthesis used for the chemical modification of polyepichlorohydrin (PECH) involved the phase transfer catalyzed etherification of the chloromethyl groups with sodium 4‐cyano‐4′‐biphenoxide and lithium n‐(4‐cyano‐4′‐oxybiphenyl)‐alkanoates. All the resulting polymers (except polymers 7 and 8), including that without spacer, characterized by 1H NMR, and IR, exhibit thermotropic liquid crystalline mesomophism. The thermal behavior of the polymers has been characterized using differential scanning calorimetry (DSC) and polarized light microscopy (POM) equipped with hot‐stage. A more pronounced odd‐even effect in the clearing temperatures is observed on increasing the spacer length in which the odd members display slightly higher values, which were also dependent on the substitution degree of PECH. The flexible PECH chain assists nematic LC formation compared with other more rigid backbone polymers where a smectic phase is often encountered with the same mesogen. A comparison of the thermal properties of the cyanobiphenyl based series reported here. Polyacrylate (PA) and poly(methacrylate)‐based (PMA) SCLCPs containing 4‐cyanobiphenyl as the mesogenic unit are consistent with the general rule that increasing backbone flexibility for a given mesogenic unit and spacer length enhance the clearing temperature. This was not found from the PECH‐based series, which show the lower clearing temperature than the PMA and PA series, even though they have more flexible backbone than PA and PMA series. So the clearing temperature is not solely determined by the flexibility of the backbone.Schlieren textures of PECHOC2‐B taken at 110 °C (cooling from isotropic phase after annealing 1 h).magnified imageSchlieren textures of PECHOC2‐B taken at 110 °C (cooling from isotropic phase after annealing 1 h).