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Molecular design, synthesis and characterization of intrinsically black polyimide films with high thermal stability and good electrical properties

Journal of Polymer Research volume 26, Article number: 171 (2019) Cite this article

Abstract

A series of intrinsically black polyimide (PI) films have been designed and synthesized by the copolymerization of pyromellitic dianhydride (PMDA), 4,4′-oxydianiline (ODA) and 4,4′-diaminodiphenylamine (NDA) via a two-step polycondensation procedure, followed by the high temperature imidization reaction of the poly(amic acid) (PAA) intermediates. Incorporation of the electron-rich NDA diamine apparently enhanced the formation of charge transfer complex (CTC) between the electron-donating diamine units and the electron-accepting dianhydride moiety; thus greatly absorbing the visible light and endowing the derived PI films deep colors. PI-5 with the 100% molar ratio of NDA in the diamines exhibited a cutoff wavelength value of 555 nm, which was 127 nm higher than that of PI-1 without NDA component. The PI films were nearly totally opaque at the wavelength of 500 nm when the molar ratio of NDA exceeded 80% in the diamines. PI-5 showed International Commission on Illumination (CIE) lab color parameters of 23.36 for L*, 46.43 for a*, and 40.26 for b*, indicating the essentially black plus red color instead of the yellow plus blue color for PI-1 film (L* = 89.93, a* = −11.09, and b* = 84.23). In addition, introduction of NDA into the copolymer films increased the high temperature dimensional stability of the films. PI-5 exhibited a glass transition temperature (Tg) and coefficient of thermal expansion (CTE) of 431.6 °C and 18.8 × 10−6 /K, respectively, which were superior to those of the PI-1 film (Tg = 418.8 °C, CTE = 29.5 × 10−6 /K). At last, incorporation of NDA components somewhat decreased the tensile properties and thermal decomposition temperatures of the PI films.

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Acknowledgements

Financial support from the Fundamental Research Funds of China University of Geosciences (No. 2652017345) is gratefully acknowledged.

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Authors and Affiliations

  1. Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing, 100083, China

    Yan Zhang, Yao-yao Tan, Jin-gang Liu, Xin-xin Zhi, Meng-ge Huangfu, Gang-lan Jiang & Xiao Wu

  2. School of Electrical Engineering, Beijing Jiaotong University, Beijing, 100044, China

    Xiumin Zhang

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  1. Yan Zhang
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  2. Yao-yao Tan
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  3. Jin-gang Liu
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  4. Xin-xin Zhi
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  7. Xiao Wu
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Correspondence to Jin-gang Liu or Xiumin Zhang.

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Zhang, Y., Tan, Yy., Liu, Jg. et al. Molecular design, synthesis and characterization of intrinsically black polyimide films with high thermal stability and good electrical properties. J Polym Res 26, 171 (2019). https://doi.org/10.1007/s10965-019-1835-0

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  • DOI: https://doi.org/10.1007/s10965-019-1835-0

Keywords

  • Polyimide
  • Blackness
  • Charge transfer complex
  • Optical properties
  • Thermal properties