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CT Fluorescence And Molecular Aggregation Of A Polyimide As Function Of Imidization Condition.

Published online by Cambridge University Press:  15 February 2011

M. Hasegawa
Affiliation:
Toho University
H. Arai
Affiliation:
Toho University
K. Horie
Affiliation:
The University of Tokyo
R. Yokota
Affiliation:
Institute of Space and Astronautical Science
I. Mita
Affiliation:
Dow Corning Japan, Ltd.
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Abstract

The emission mechanisms of solid PI(BPDA/PDA) derived from biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA) were examined with the absorption and fluorescence. spectra of model compounds (denoted by M). M(BPDA/CHA) (CHA: cyclohexyl amine) fluoresces at ca. 430 nm in hexafluoro-2-propanol(HFP) solution, while M(BPDA/AN) (AN: aniline) does not. PI(BPDA/PDA) film does not show the monomer fluorescence of biphenyldiimide unit, but shows only intermolecular CT fluorescence peaking at 530–540 nm. This suggests that for PI(BPDA/PDA) film and PI(BPDA/AN) in solution the local excited state of biphenyldiimide units is deactivated owing to intramolecular charge-transfer(CT).

The intermolecular CT fluorescence reflecting sensitively molecular packing of PI chains was used to monitor isothermal imidization process of poly(amic acid)(PAA) of BPDA/PDA. The fluorescence of PAA(BPDA/PDA) peaking at 490 nm decreases rapidly and disappears at 30–40% conversion, then the fluorescence of PI(BPDA/PDA) peaking at 540 nm increases gradually during isothermal imidization. The fluorescence intensity at 540 nm increases rapidly as imidization proceeds when imidized at higher temperature. A kinetic study on isothermal imidization shows that the vitrification is strongly related to the reorientation of polymer chains and the final PI structures.

Type
Research Article
Copyright
Copyright © Materials Research Society 1991

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References

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