Skip to main content
Log in

Synthesis and optical properties of semi-fluorinated poly(ether imide)s derived from non-fluorinated 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA) and trifluoromethyl-substituted diamines

  • Article
  • Published:
Journal of Materials Research Aims and scope Submit manuscript

Abstract

A series of optically transparent and colorless semi-fluorinated poly(ether imide)s (PEIs) (III) were prepared from non-fluorinated 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA) with various trifluoromethyl-substituted diamines. The III series showed more colorless and higher optical transparency with a cutoff absorption wavelength (λ0) below 370 nm than the IV series based on the corresponding non-fluorinated analogues and V series derived from CF3-free pyromellitic dianhydride (PMDA). Compared with the fluorinated VI series based on fluorinated 4,4′-hexafluoroisopropylidenediphthalic anhydride (6FDA), the semi-fluorinated III series not only exhibited much better optical transparency, but also had better mechanical and thermal properties. The III series had a tensile strength of 79.8–109.5 MPa, modulus of elasticity of 3.0–7.7 GPa and elongation at break of 14.2–26.7%, together with glass-transition temperatures (Tg) ranging from 214.3 to 265.1 °C and temperatures of 5% weight loss (T5%) beyond 530 °C. Meanwhile, the novel semi-fluorinated PEI IIIb was optically transparent and colorless with a λ0 of 367 nm coupled with dielectric constants below 3.2 and contact angles against water over 112°. In particular, the optically transparent IIIa exhibited the best tensile strength of 109.5 MPa when compared with already reported counterparts.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6

Similar content being viewed by others

References

  1. J.A. Spechler, T.W. Koh, J.T. Herb, B.P. Rand, and C.B. Arnold: A transparent, smooth, thermally robust, conductive polyimide for flexible electronics. Adv. Funct. Mater. 25, 7428 (2015).

    Article  Google Scholar 

  2. J. Kim, J. Kwon, M. Kim, J. Do, D. Lee, and H. Han: Low-dielectric-constant polyimide aerogel composite films with low water uptake. Polym. J. 134, 48 (2016).

    Google Scholar 

  3. J.W. Zha, B.H. Fan, Z.M. Dang, and S.T. Li: Microstructure and electrical properties in three-component (Al2O3–TiO2)/polyimide nanocomposite films. J. Mater. Res. 25, 2384 (2010).

    Article  CAS  Google Scholar 

  4. C.Y. Lin, D.H. Kuo, F.R. Sie, J.Y. Cheng, and G.S. Liou: Preparation and characterization of organosoluble polyimide/BaTiO3 composite films with mechanical-and chemical-treated ceramic fillers. Polym. J. 44, 1131 (2012).

    Article  CAS  Google Scholar 

  5. L.S. Li, Y. Xu, J.F. Che, X. Su, C.R. Song, and X.P. Ma: Transparent fluorinated poly(imide siloxane) copolymers with good adhesivity. Macromol. Res. 25, 1076 (2017).

    Article  CAS  Google Scholar 

  6. H.J. Ni, J.G. Liu, Z.H. Wang, and S.Y. Yang: A review on colorless and optically transparent polyimide films: Chemistry, process and engineering applications. J. Ind. Eng. Chem. 28, 16 (2015).

    Article  CAS  Google Scholar 

  7. S. Ando, T. Matsuura, and S. Sasaki: Coloration of aromatic polyimides and electronic properties of their source materials. Polym. J. 29, 69 (1997).

    Article  CAS  Google Scholar 

  8. M. Hasegawa, D. Hirano, M. Fujii, M. Haga, E. Takezawa, S. Yamaguchi, A. Ishikawa, and T. Kagayama: Solution-processable colorless polyimides derived from hydrogenated pyromellitic dianhydride with controlled steric structure. J. Polym. Sci., Part A: Polym. Chem. 51, 575 (2013).

    Article  CAS  Google Scholar 

  9. F.Y. Ke, N.H. Song, D.H. Liang, and H.Y. Xu: A method to break charge transfer complex of polyimide: A study on solution behavior. J. Appl. Polym. Sci. 127, 797 (2013).

    Article  CAS  Google Scholar 

  10. Y.W. Liu, Y. Zhang, Q. Lan, S.W. Liu, Z.X. Qin, L.H. Chen, C.Y. Zhao, Z.G. Chi, J.R. Xu, and J. Economy: High-performance functional polyimides containing rigid nonplanar conjugated triphenylethylene moieties. Chem. Mater. 24, 1212 (2012).

    Article  CAS  Google Scholar 

  11. A.S. Mathews, I. Kim, and C.S. Ha: Synthesis, characterization, and properties of fully aliphatic polyimides and their derivatives for microelectronics and optoelectronics applications. Macromol. Res. 15, 114 (2007).

    Article  CAS  Google Scholar 

  12. Y.G. Hou, G.F. Chen, X.L. Pei, and X.Z. Fang: Synthesis and characterization of novel optically transparent and organosoluble polyimides based on diamines containing cyclohexane moiety. J. Polym. Res. 19, 9955 (2012).

    Article  CAS  Google Scholar 

  13. H.S. Liu and S.C. Jeng: Liquid crystal alignment by polyhedral oligomeric silsesquioxane (POSS)-polyimide nanocomposites. Opt. Mater. 35, 1418 (2013).

    Article  CAS  Google Scholar 

  14. S. Bong, H. Yeo, M. Goh, B.C. Ku, Y.Y. Kim, P.H. Bong, B. Park, and N.H. You: Synthesis and characterization of colorless polyimides derived from 4-(4-aminophenoxy)-2,6-dimethylaniline. Macromol. Res. 12, 1091 (2016).

    Article  CAS  Google Scholar 

  15. L. Yi, C.Y. Li, W. Huang, and D.Y. Yan: Soluble and transparent polyimides with high Tg from a new diamine containing tert-butyl and fluorene units. J. Polym. Sci., Part A: Polym. Chem. 54, 976 (2016).

    Article  CAS  Google Scholar 

  16. G.F. Chen, Y. Zhou, K. Ma, W. Wang, and X.Z. Fang: Synthesis and properties of transparent polyimides derived from 1,4-cyclohexylene bis(trimellitate anhydride). High Perform. Polym. 29, 627 (2017).

    Article  CAS  Google Scholar 

  17. B. Jarzabek, E. Schab-Balcerzak, T. Chamenko, D. Sek, J. Cisowski, and A. Volozhin: Optical properties of new aliphatic—aromatic co-polyimides. J. Non-Cryst. Solids 299, 1057 (2002).

    Article  Google Scholar 

  18. A.S. Mathews, I. Kim, and C.S. Ha: Fully aliphatic polyimides from adamantane-based diamines for enhanced thermal stability, solubility, transparency, and low dielectric constant. J. Appl. Polym. Sci. 102, 3316 (2006).

    Article  CAS  Google Scholar 

  19. Y. Guo, D. Shen, H. Ni, J. Liu, and S. Yang: Organosoluble semi-alicyclic polyimides derived from 3,4-dicarboxy-1,2,3,4-tetrahydro-6-tert-butyl-1-naphthalene succinic dianhydride and aromatic diamines: Synthesis, characterization and thermal degradation investigation. Prog. Org. Coat. 76, 768 (2013).

    Article  CAS  Google Scholar 

  20. S.D. Kim, S.Y. Kim, and I.S. Chung: Soluble and transparent polyimides from unsymmetrical diamine containing two trifluoromethyl groups. J. Polym. Sci., Part A: Polym. Chem. 51, 4413 (2013).

    Article  CAS  Google Scholar 

  21. I.H. Choi, B. Sohn, and J.H. Chang: Synthesis and characterization of transparent copolyimide films containing CF3 groups: Comparison with copolyimide nanocomposites. Appl. Clay Sci. 48, 117 (2010).

    Article  CAS  Google Scholar 

  22. M.D. Damaceanu, C.P. Constantin, A. Nicolescu, M. Bruma, N. Belomonia, and R.S. Begunov: Highly transparent and hydrophobic fluorinated polyimide films with ortho-kink structure. Eur. Polym. J. 50, 200 (2014).

    Article  CAS  Google Scholar 

  23. Y.C. Chen and S.H. Hsiao: Optically transparent and organosoluble poly(ether imide)s based on a bis(ether anhydride) with bulky 3,3′,5,5′-tetramethylbiphenyl moiety and various fluorinated bis(ether amine)s. High Perform. Polym. 30, 47 (2018).

    Article  CAS  Google Scholar 

  24. P.K. Tapaswi, M.C. Choi, S. Nagappan, and C.S. Ha: Synthesis and characterization of highly transparent and hydrophobic fluorinated polyimides derived from perfluorodecylthio substituted diamines monomers. J. Polym. Sci., Part A: Polym. Chem. 53, 479 (2015).

    Article  CAS  Google Scholar 

  25. M. Ghaemy, F.R. Berenjestanaki, and M. Bazzar: Organosoluble, thermally stable and low dielectric constant fluorinated polyimides containing 2,4,5-triphenylimidazole moiety in the main chains. Des. Monomers Polym. 17, 101 (2014).

    Article  CAS  Google Scholar 

  26. C.L. Chung, C.P. Yang, and S.H. Hsiao: Organosoluble and colorless fluorinated poly(ether imide)s from 1,2-bis(3,4-dicarboxyphenoxy)benzene dianhydride and trifluoromethyl-substituted aromatic bis(ether amine)s. J. Polym. Sci., Part A: Polym. Chem. 44, 3092 (2006).

    Article  CAS  Google Scholar 

  27. W.B. Jang, D. Shin, S. Choi, S. Park, and H. Han: Effects of internal linkage groups of fluorinated diamine on the optical and dielectric properties of polyimide thin films. Polymer 48, 2130 (2007).

    Article  CAS  Google Scholar 

  28. Y.C. Chen, S.H. Hsiao, and Y.Y. Su: Organosoluble and colorless fluorinated poly(ether imide)s derived from a highly contorted biphenyl-2,2′-diol bis(ether anhydride) and aromatic bis(ether amine)s with trifluoromethyl substituents. J. Polym. Res. 24, 87 (2017).

    Article  CAS  Google Scholar 

  29. C.P. Yang, Y.Y. Su, and Y.Y. Chen: Colorless poly(ether-imide)s deriving from 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride(BPADA) and aromatic bis(ether amine)s bearing pendent trifluoromethyl groups. Eur. Polym. J. 42, 721 (2006).

    Article  CAS  Google Scholar 

  30. Y. Zhou, G.F. Chen, W. Wang, L.P. Song, and X.Z. Fang: Comparative study of transparent polyimides derived from bis(ether anhydride)s and bis(ester anhydride)s using 2,2′-bis(trifluoromethyl)biphenyl-4,4′-diamine. High Perform. Polym. 29, 218 (2017).

    Article  CAS  Google Scholar 

  31. C.P. Yang, Y.Y. Su, S.J. Wen, and S.H. Hsiao: Highly optically transparent/low color polyimide films prepared from hydroquinone- or resorcinol-based bis(ether anhydride) and trifluoromethyl-containing bis(ether amine)s. Polymer 47, 7021 (2006).

    Article  CAS  Google Scholar 

  32. I.H. Choi and J.H. Chang: Colorless polyimide nanocomposite films containing hexafluoroisopropylidene group. Polym. Adv. Technol. 22, 682 (2011).

    Article  CAS  Google Scholar 

  33. Y. Liu, Y. Xing, Y.H. Zhang, S.W. Guan, H.B. Zhang, Y. Wang, Y.P. Wang, and Z.H. Jiang: Novel soluble fluorinated poly(ether imide)s with different pendant groups: Synthesis, thermal, dielectric, and optical properties. J. Polym. Sci., Part A: Polym. Chem. 48, 3281 (2010).

    Article  CAS  Google Scholar 

  34. T.C. Xiao, X. Fang, and D.S. Fan: High thermal conductivity and low absorptivity/emissivity properties of transparent fluorinated polyimide films. Polym. Bull. 74, 4561 (2017).

    Article  CAS  Google Scholar 

  35. Z.Y. Ge, L. Fan, and S.Y. Yang: Synthesis and characterization of novel fluorinated polyimides derived from 1,1′-bis(4-aminophenyl)-1-(3-trifluoromethylphenyl)-2,2,2-trifluoroethane and aromatic dianhydrides. Eur. Polym. J. 44, 1252 (2008).

    Article  CAS  Google Scholar 

  36. H. Behniafar and N. Sefid-girandehi: Optical and thermal behavior of novel fluorinated polyimides capable of preparing colorless, transparent and flexible films. J. Fluorine Chem. 132, 878 (2011).

    Article  CAS  Google Scholar 

  37. B.M. Li, Z.Y. Wu, and L. Lin: Structure, thermal stability, electrochemical behaviors, and mechanical properties of organosoluble polyimide with pyrimidine ring in the main chain. J. Appl. Polym. Sci. 133, 43680 (2016).

    Google Scholar 

  38. M.A. Seyed, E. Soheila, T. Mehdi, and S. Zahed: Fabrication and characterization of novel high-performance fluorinated polyimides with xanthene pendent architecture: Study of thermal, photophysical, antibacterial and heavy metal ion adsorption behavior. J. Fluorine Chem. 192, 48 (2016).

    Article  CAS  Google Scholar 

  39. C.Y. Wang, S.J. Cao, W.T. Chen, C. Xu, X.Y. Zhao, J. Li, and Q. Ren: Synthesis and properties of fluorinated polyimides with multi-bulky pendant groups. RSC Adv. 7, 26420 (2017).

    Article  CAS  Google Scholar 

  40. M.A.B. Meador, E. McMillon, A. Sandberg, E. Barrios, N.G. Wilmoth, C.H. Mueller, and F.A. Miranda: Dielectric and other properties of polyimide aerogels containing fluorinated blocks. ACS Appl. Mater. Interfaces 6, 6062 (2014).

    Article  CAS  Google Scholar 

  41. T.T. Wu, J. Dong, F. Gan, Y.T. Fang, X. Zhao, and Q.H. Zhang: Low dielectric constant and moisture-resistant polyimide aerogels containing trifluoromethyl pendent groups. Appl. Surf. Sci. 440, 595 (2018).

    Article  CAS  Google Scholar 

  42. A.I. Wozniak, A.S. Yegorov, V.S. Ivanov, S.M. Igumnov, and K.V. Tcarkova: Recent progress in synthesis of fluorine containing monomers for polyimides. J. Fluorine Chem. 180, 45 (2015).

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors are grateful to the project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Yong Xu.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Xu, Y., Li, L., Che, J. et al. Synthesis and optical properties of semi-fluorinated poly(ether imide)s derived from non-fluorinated 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA) and trifluoromethyl-substituted diamines. Journal of Materials Research 34, 545–554 (2019). https://doi.org/10.1557/jmr.2018.440

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1557/jmr.2018.440

Navigation