Optically transparent aromatic poly(ester imide)s with low coefficients of thermal expansion. 2: Effect of the introduction of alkyl‐substituted p ‐biphenylene units

A series of ester‐linked tetracarboxylic dianhydrides (TA‐X) were synthesized from trimellitic anhydride chloride and 4,4′‐biphenol analogs containing different numbers and positions of methyl substituents. Aromatic poly(ester imide)s (PEsIs) were polymerized from TA‐Xs and 2,2′‐bis(trifluoromethyl)benzidine to investigate the film properties systematically. A significant substituent effect on the target properties ( T g , optical transparency, the linear coefficient of thermal expansion (CTE) and ductility) was observed. A PEsI containing 2,2′,3,3′,5,5′‐hexamethyl‐substituted p ‐biphenylene units was chemically imidized in a homogeneous state. It was highly soluble at room temperature, even in less hygroscopic non‐amide solvents such as cyclopentanone (CPN), and provided a stable CPN solution with a high solid content. The CPN‐cast PEsI film was almost colorless as suggested from the rather low yellowness index (3.2), high light transmittance at 400 nm (71.5%) and very low haze (1.15%). This PEsI film also had a high T g (294 °C, determined by thermomechanical analysis) in addition to a low CTE (21.7 ppm K −1 ), moderate film ductility and very low water uptake. A structural modification of the PEsI by copolymerization with a tetracarboxylic dianhydride with a rigid/linear structure was effective in further reducing the CTE while maintaining the other excellent target properties. Thus, some of the PEsIs developed in this work are promising candidates as novel plastic substrates for use in image display devices. © 2017 Society of Chemical Industry