Preparation and Properties of Polybenzoxazole Copolymers Bearing Pendants and Imide Ring in the Main Chain

A series of aromatic poly(hydroxyamide)s (PHAs) containing varying oligo(oxyethylene) substituents and 1,3-phenylene imide ring unit in the main chain were synthesized by the direct polycondensation reaction. The inherent viscosities of the PHAs exhibited in the range of 0.89~1.12 dL/g in DMAc or DMAc/LiCl solution. The PH-2~5 copolymers were easily soluble in strong aprotic solvents: DMAc, NMP, DMSO etc. and the PH-5 copolymer was soluble in less polar solvents such as m-creasol and pyridine with LiCl salt on heating. However, all PBOs were quite insoluble in other solvents, but only partially soluble in sulfuric acid. All copolymers (PH-2~5) could afford the flexible and tough films by solution casting. We identified that the PHAs were converted to the PBOs by the thermal cyclization reaction in the range of $200{\sim}380^{\circ}C$. The 10% weight loss temperatures and char yields of the PBOs were recorded in the range of $382{\sim}647^{\circ}C$ and 38.7~73.1% values at $900^{\circ}C$. The tensile strength and initial modulus of the PH-5 in the copolmers showed the highest values of 2.46 GPa and 49.55 MPa, respectively. The LOI values of the PHAs were in the range 26.6~29.0%, and increased with increasing 1,3-phenylene imide ring unit.