Synthesis and characterization of Thermally Rearranged (TR) polymers: influence of ortho-positioned functional groups of polyimide precursors on TR process and gas transport properties

摘要

Aromatic polyimides bearing various ortho-functional groups (i.e., acetate group and pivalic acetate group) were prepared via acetyiation of a poly(hydroxyimide) containing ortho-positioned hydroxy groups using acetic anhydride or pivalic anhydride. The completeness of acetyiation was confirmed by ~1H NMR and FTIR. Chemically derivatized polyimides were used as precursors for an imide-to-benzoxazole thermal rearrangement (TR) process. The influence of various ortho-functionalities on the TR process and gas transport properties of the resulting TR polymers was studied. Differing from the -OH groups in a poly(hydroxyimide), the acetate groups of acetylated polyimide precursors degrade at elevated temperatures, and the degradation process interplays with imide-to-benzoxazole conversion. The acidic degradation product, as detected by ~1H NMR, is suspected to have some catalytic effect on the TR process, which along with the protecting function of the acetate groups, resulted in a lower onset TR conversion temperature, the ability to conduct the TR process in air, and a higher TR conversion level. Gas permeation properties greatly depend on the ortho-functionality of polyimide precursors as well. The precursor films containing larger functional groups are much more permeable with comparable gas selectivities. Similarly, the resulting TR polymers formed from polyimides with larger leaving groups also showed much higher gas permeabilities despite similar degrees of TR conversion. The incorporation of bulkier functional groups in the TR precursors provides an effective way to significantly improve the gas transport performance, particularly the gas permeabilities of both the polyimide precursors and the resulting TR polymers.