Polyimides with alicyclic diamines. II. Hydrogen abstraction and photocrosslinking reactions of benzophenone‐type polyimides

Abstract

AbstractPhotosensitive polyimides with alicyclic diamines and benzophenone moiety were prepared by reactions of 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA) with diamines in aprotic solvents, followed by thermal or chemical imidizations. Among them the polyimide from BTDA and bis(4‐amino‐3‐methylcyclohexyl) methane (DMDHM) can be dissolved in several organic solvents such as dichloromethane, tetrachloroethane, and N‐methyl‐2‐pyrrolidone (NMP). In order to compare properties of the polyimides with alicyclic diamines with those of corresponding aromatic polyimides, the UV absorption spectra and fluorescence spectra of these polyimides and their model compounds were investigated. No occurrence of charge transfer at photoexcited states was ascertained for the polyimides with alicyclic diamines. The hydrogen abstraction and crosslinking during photoirradiation have been studied to learn the influence of the elimination of charge transfer process in these photosensitive polyimides. The quantum yield of hydrogen abstraction for the model compound of alicyclic polyimides is 0.56 in THF measured with HPLC. The quantum yield for the photocrosslinking reaction of the solvent‐soluble polyimide with alicyclic diamine, PI(BTDA/DMDHM), was determined to be 0.004 in air from gel permeation chromatography (GPC) measurement, which is four times higher than that for photosensitive polyimides with aromatic diamines. © 1994 John Wiley & Sons, Inc.