Synthesis and Characterization of Soluble Polyimides Derived from 2,2*-Bis(3,4-dicarboxyphenoxy)-9,9*- spirobifluorene Dianhydride

The synthesis of aromatic poly(ether imide)s containing spirobifluorene units in the polymer backbone is described. 2,29-Bis(3,4-dicarboxyphenoxy)-9,99-spirobifluorene dianhydride, which was used as a new monomer, was synthesized with 2,29-dihydroxy-9,99-spirobifluorene as the starting material. In the spiro-segment, the rings of the connected bifluorene were orthogonally arranged. This bis(ether anhydride) monomer was employed in reactions with a variety of aromatic diamines to furnish poly(ether imide)s, involving an initial ring-opening polycondensation and subsequent chemically induced cyclodehydration. Excellent solubility in common organic solvents at room temperature, good optical transparency, and high thermal stability are the prominent characteristic features of these new polymers, which can be attributed to the presence of spiro-fused orthogonal bifluorene segments along the polymer chain. The glass-transition temperatures of the polyimides were 240–293 °C, and the 5% weightloss temperatures were greater than 500 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 262–268, 2002