Skip to main content
SpringerLink
Log in

Fluorinated Colorless Polyimides with High Heat-resistance and Low Birefringence

  • Research Article
  • Published:
Chinese Journal of Polymer Science Aims and scope Submit manuscript

Abstract

The development of optical films with high transparency, high thermal resistance and low birefringence remains a challenge in the flexible display industry. In this work, we designed and synthesized a series of fluorinated colorless polyimides (CPIs) materials using 2,5-substituted m-phenylenediamine diamine monomers and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (CHDA). We systematically studied the effects of fluorinated group substitutions on the thermal, mechanical, optical and dielectric properties of CPI films. The introduction of alicyclic CHDA dianhydride affords high transparency and low yellowness, while the 2,5-substituted m-phenylenediamine diamines offer the CPIs with quite low birefringence as well as high glass transition temperatures. A particular CHDA/o3FBDA film with simple chemical structure stands out, exhibiting well-balanced overall properties.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

References

  1. Tominaka, S.; Nishizeko, H.; Mizuno, J. Osaka, T. Bendable fuel cells: on-chip fuel cell on a flexible polymer substrate. Energy Environ. Sci. 2009, 2, 1074–1077.

    Article  CAS  Google Scholar 

  2. Sheraw, C. D.; Zhou, L.; Huang, J. R.; Gundlach, D. J.; Jackson, T. N.; Kane, M. G.; Hill, I. G.; Hammond, M. S.; Campi, J.; Greening, B. K.; Francl, J. West, J. Organic thin-film transistor-driven polymer-dispersed liquid crystal displays on flexible polymeric substrates. Appl. Phys. Lett. 2002, 80, 1088–1090.

    Article  CAS  Google Scholar 

  3. Villani, F.; Vacca, P.; Nenna, G.; Valentino, O.; Burrasca, G.; Fasolino, T.; Minarini, C.; della Sala, D. Inkjet printed polymer layer on flexible substrate for OLED applications. J. Phys. Chem. C 2009, 113, 13398–13402.

    Article  CAS  Google Scholar 

  4. Li, H.; Ma, Y. Huang, Y. Material innovation and mechanics design for substrates and encapsulation of flexible electronics: a review. Mater. Horiz. 2021, 8, 383–400.

    Article  CAS  PubMed  Google Scholar 

  5. Sroog, C. Polyimides. Prog. Polym. Sci. 1991, 16, 561–694.

    Article  CAS  Google Scholar 

  6. Ding, M. Isomeric polyimides. Prog. Polym. Sci. 2007, 32, 623–668.

    Article  CAS  Google Scholar 

  7. Liaw, D. J.; Wang, K. L.; Huang, Y. C.; Lee, K. R.; Lai, J. Y.; Ha, C. S. Advanced polyimide materials: syntheses, physical properties and applications. Prog. Polym. Sci. 2012, 37, 907–974.

    Article  CAS  Google Scholar 

  8. Dhara, MG. Banerjee, S. Fluorinated high-performance polymers: poly(arylene ether)s and aromatic polyimides containing trifluoromethyl groups. Prog. Polym. Sci. 2010, 35, 1022–1077.

    Article  CAS  Google Scholar 

  9. Yi, C.; Li, W.; Shi, S.; He, K.; Ma, P.; Chen, M.; Yang, C. High-temperature-resistant and colorless polyimide: preparations, properties, and applications. Sol. Energy. 2020, 195, 340–354.

    Article  CAS  Google Scholar 

  10. Ni, H. J.; Liu, J. G.; Wang, Z. H.; Yang, S. Y. A review on colorless and optically transparent polyimide films: chemistry, process and engineering applications. J. Ind. Eng. Chem. 2015, 28, 16–27.

    Article  CAS  Google Scholar 

  11. Zhuang, Y.; Seong, J. G.; Lee, Y. M. Polyimides containing aliphatic/alicyclic segments in the main chains. Prog. Polym. Sci. 2019, 92, 35–88.

    Article  CAS  Google Scholar 

  12. Ding, M. Polyimides: relationship between chemistry, structure, and performance and their materials. Senond Ed. Beijing, Science Press, 2012.

    Google Scholar 

  13. Abadie, M. J. M. High performance polymers-polyimides based-from chemistry to applications. Rijeka: IntechOpen; 2012.

    Book  Google Scholar 

  14. Liu, Y. Y.; Wang, Y. K.; Wu, D. Y. Synthetic strategies for highly transparent and colorless polyimide film. J. Appl. Polym. Sci. 2022, 139, e52604.

    Article  CAS  Google Scholar 

  15. Hu, X.; Yan, J.; Wang, Y.; Mu, H.; Wang, Z.; Cheng, H.; Zhao, F.; Wang, Z. Colorless polyimides derived from 2R, 5R, 7S, 10S-naph-thanetetracarboxylic dianhydride. Polym. Chem. 2017, 8, 6165–6172.

    Article  CAS  Google Scholar 

  16. Ozawa, H.; Ishiguro, E.; Kyoya, Y.; Kikuchi, Y.; Matsumoto, T. Colorless polyimides derived from an alicyclic tetracarboxylic dianhydride, CpODA. Polymers 2021, 13, 2824.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  17. Peng, W.; Lei, H.; Qiu, L.; Bao, F.; Huang, M. Perfluorocyclobutyl-containing transparent polyimides with low dielectric constant and low dielectric loss. Polym. Chem. 2022, 13, 3949–3955.

    Article  CAS  Google Scholar 

  18. Matsuura, T.; Hasuda, Y.; Nishi, S.; Yamada, N. Polyimide derived from 2,2’-bis(trifluoromethyl)-4,4’-diaminobiphenyl. 1. Synthesis and characterization of polyimides prepared with 2,2’-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or pyromellitic dianhydride. Macromolecules. 1991, 24, 5001–5005.

    Article  CAS  Google Scholar 

  19. Peng, W. F.; Lei, H. Y.; Zhang, X. X.; Qiu, L. H.; Huang, M. J. Fluorine substitution effect on the material properties in transparent aromatic polyimides. Chinese J. Polym. Sci. 2022, 40, 781–788.

    Article  CAS  Google Scholar 

  20. Zuo, H. T.; Gan, F.; Dong, J.; Zhang, P.; Zhao, X.; Zhang, Q. H. Highly transparent and colorless polyimide film with low dielectric constant by introducing meta-substituted structure and trifluoromethyl groups. Chinese J. Polym. Sci. 2021, 39, 455–464.

    Article  CAS  Google Scholar 

  21. Lin, S. H.; Li, F. M.; Cheng, S. Z. D.; Harris, F. W. Organo-soluble polyimides: Synthesis and polymerization of 2,2’-bis(trifluoromethyl)-4,4’,5,5’-biphenyltetracarboxylic dianhydride. Macromolecules 1998, 31, 2080–2086.

    Article  CAS  Google Scholar 

  22. Feiring, A. E.; Auman, B. C.; Wonchoba, E. R. Synthesis and properties of fluorinated polyimides from novel 2,2’-bis(fluoroalkoxy) benzidines. Macromolecules 1993, 26, 2779–2784.

    Article  CAS  Google Scholar 

  23. Song, G.; Chen, C.; Wang, X.; Yao, J. Synthesis and properties of polyimides derived from 2,2’-dichloro-4, 4’, 5, 5’-biphenyl-tetracarboxylic dianhydride. Polymer 2019, 183, 121862.

    Article  CAS  Google Scholar 

  24. Li, F. M.; Ge, J. J.; Honigfort, P. S.; Fang, S.; Chen, J. C.; Harris, F. W.; Cheng, S. Z. D. Dianhydride architectural effects on the relaxation behaviors and thermal and optical properties of organo-soluble aromatic polyimide films. Polymer 1999, 40, 4987–5002.

    Article  CAS  Google Scholar 

  25. Hougham, G.; Tesoro, G.; Shaw, J. Synthesis and properties of highly fluorinated polyimides. Macromolecules 1994, 27, 3642–3649.

    Article  CAS  Google Scholar 

  26. Xiao, P.; He, X.; Zheng, F.; Lu, Q. Super-heat resistant, transparent and low dielectric polyimides based on spirocyclic bisbenzoxazole diamines with Tg > 450 °C. Polym. Chem. 2022, 13, 3660–3669.

    Article  CAS  Google Scholar 

  27. Zhang, M.; Miao, J.; Xu, Y.; Wang, Z.; Yan, J. Colorless polyimides from fluorinated ladder diamines containing norbornyl benzocyclobutene segments. Macromolecules 2022, DOI: https://doi.org/10.1021/acs.macromol.2c00894.

  28. Lei, H.; Bao, F.; Peng, W.; Qiu, L.; Zou, B.; Huang, M. Torsion effect of the imide ring on the performance of transparent polyimide films with methyl-substituted phenylenediamine. Polym. Chem. 2022, 13, 6606–6613.

    Article  CAS  Google Scholar 

  29. Liu, H.; Zhai, L.; Bai, L.; He, M.; Wang, C.; Mo, S. Fan, L. Synthesis and characterization of optically transparent semi-aromatic polyimide films with low fluorine content. Polymer 2019, 163, 106–114.

    Article  CAS  Google Scholar 

  30. Tapaswi, P. K.; Ha, C. S. Recent trends on transparent colorless polyimides with balanced thermal and optical properties: design and synthesis. Macromol. Chem. Phys. 2019, 220, 1800313.

    Article  Google Scholar 

  31. Hasegawa, M. Development of solution-processable, optically transparent polyimides with ultra-low linear coefficients of thermal expansion. Polymers 2017, 9, 520.

    Article  PubMed  PubMed Central  Google Scholar 

  32. Liu, J.; Nakamura, Y.; Shibasaki, Y.; Ando, S.; Ueda, M. Synthesis and characterization of highly refractive polyimides from 4,4’-thiobis(p-phenylenesulfanyl)aniline and various aromatic tetracarboxylic dianhydrides. J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 5606–5617.

    Article  CAS  Google Scholar 

  33. Uchiyama, A.; Ono, Y.; Ikeda, Y.; Shuto, H.; Yahata, K. Copolycarbonate optical films developed using birefringence dispersion control. Polym. J. 2012, 44, 995–1008.

    Article  CAS  Google Scholar 

  34. Bao, F.; Lei, H.; Zou, B.; Peng, W.; Qiu, L.; Ye, F.; Song, Y.; Qi, F.; Qiu, X.; Huang, M. Colorless polyimides derived from rigid trifluoromethyl-substituted triphenylenediamines. Polymer 2023, 273.

  35. Li, F. M.; Kim, K. H.; Savitski, E. P.; Chen, J. C.; Harris, F. W.; Cheng, S. Z. D. Molecular weight and film thickness effects on linear optical anisotropy of 6FDA-PFMB polyimides. Polymer 1997, 38, 3223–3227.

    Article  CAS  Google Scholar 

  36. Ge, J. J.; Li, B. F.; Harris, F. W.; Cheng, S. Z. D. Novel polymer wide viewing angle compensation films for liquid crystal displays (LCDs). Chinese J. Polym. Sci. 2003, 21, 223–230.

    CAS  Google Scholar 

  37. Li, X.; Wang, M.; Mushtaq, N.; Chen, G.; Li, G.; Fang, X.; Zhang, A. Colorless polyimide films with low birefringence and retardation: synthesis and characterization. Polymer 2023, 265, 125579.

    Article  CAS  Google Scholar 

  38. Ando, S.; Sawada, T.; Sasaki, S. A rod-like fluorinated polyimide as an in-plane birefringent optical material. 2. Control of optical retardation using spontaneous molecular orientation. Polym. Adv. Technol. 1999, 10, 169–178.

    Article  CAS  Google Scholar 

  39. Jung, Y.; Jeong, B.; Yang, Y.; Kim, T.; Kwon, S. Correlation of stress and optical properties in highly transparent polyimides for future flexible display. Macromol. Res. 2017, 25, 971–975.

    Article  CAS  Google Scholar 

  40. Nakabayashi, K.; Imai, T.; Fu, M. C.; Ando, S.; Higashihara, T.; Ueda, M. Poly(phenylene thioether) s with fluorene-based cardo structure toward high transparency, high refractive index, and low birefringence. Macromolecules 2016, 49, 5849–5856.

    Article  CAS  Google Scholar 

  41. Min, X.; Wu, T.; Han, X.; An, M.; Yu, W.; Li, L. Zero-zero birefringence cellulose acetate-based optical films by benzoylation. ACS Appl. Polym. Mater. 2022, 4, 6255–6264.

    Article  Google Scholar 

  42. Wen, P.; He, R.; Li, X. D.; Lee, M. H. Syntheses and characterizations of high refractive index and low birefringence polyimides containing spirobifluorene in the side chain. Polymer 2017, 117, 76–83.

    Article  CAS  Google Scholar 

  43. Liu, Y.; Guo, J.; Wang, J.; Zhu, X.; Qi, D.; Li, W.; Shen, K. A novel family of optically transparent fluorinated hyperbranched polyimides with long linear backbones and bulky substituents. Eur. Polym. J. 2020, 125, 109526.

    Article  Google Scholar 

  44. Sun, Q.; Feng, Y.; Guo, J.; Wang, C. Achieving both low thermal expansion and low birefringence for polyimides by regulating chain structures. Eur. Polym. J. 2023, 189, 111986.

    Article  CAS  Google Scholar 

  45. Matsuura, T.; Ishizawa, M.; Hasuda, Y.; Nishi, S. Polyimides derived from 2,2’-bis(trifluoromethyl)-4,4’-diaminobiphenyl. 2. Synthesis and characterization of polyimides prepared from fluorinated benzenetetracarboxylic dianhydrides. Macromolecules 1992, 25, 3540–3545.

    Article  CAS  Google Scholar 

  46. Bao, F.; Qi, F.; Lei, H.; Luo, F.; Cai, Y.; Dai, X.; Dong, Z.; Qiu, X. Near-zero thermal expansion and high heat-resistance polyimide films based on a symmetric and rigid pyrazine structure. ACS Appl. Polym. Mater. 2022, 5, 672–679.

    Article  Google Scholar 

  47. Li, D.; Wang, C.; Yan, X.; Ma, S.; Lu, R.; Qian, G.; Zhou, H. Heat-resistant colorless polyimides from benzimidazole diamines: Synthesis and properties. Polymer 2022, 254, 125078.

    Article  CAS  Google Scholar 

  48. Hasegawa, M.; Fujii, M.; Ishii, J.; Yamaguchi, S.; Takezawa, E.; Kagayama, T. Ishikawa, A. Colorless polyimides derived from 1 S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride, self-orientation behavior during solution casting, and their optoelectronic applications. Polymer 2014, 55, 4693–4708.

    Article  CAS  Google Scholar 

  49. Wang, Z. H.; Chen, X.; Yang, H. X.; Zhao, J.; Yang, S. Y. The in-plane orientation and thermal mechanical properties of the chemically imidized polyimide films. Chinese J. Polym. Sci. 2019, 37, 268–278.

    Article  CAS  Google Scholar 

  50. Yin, Q.; Qin, Y.; Lv, J.; Wang, X.; Luo, L.; Liu, X. Reducing intermolecular friction work: preparation of polyimide films with ultralow dielectric loss from MHz to THz frequency. Ind. Eng. Chem. Res. 2022, 61, 17894–17903.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the Natural Science Foundation of Guangdong Province (No. 2022A1515010125), the Key-Area Research and Development Program of Guangdong Province (No. 2020B010182002), the Guangdong Basic and Applied Basic Research Foundation (No. 2022A1515110543), the R&D Program of Guangzhou (No. 2023A04J1577), the Major Program of National Natural Science Foundation of China (No. 51890871), the Recruitment Program of Guangdong (No. 2016ZT06C322), the 111 Project (No. B18023) and Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application at Soochow University. We thank Prof. Rongrong Hu and Dr. Guanfei Yao of South China University of Technology for the assistance in GPC measurement.

Author information

Authors and Affiliations

  1. South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou, 510640, China

    Bing-Yu Zou, Lu-Hao Qiu, Huan-Yu Lei, Jin-Ming Liu, Wei-Feng Peng, Hong-Qin Zhao, Feng Bao & Ming-Jun Huang

  2. Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, South China University of Technology, Guangzhou, 510640, China

    Ming-Jun Huang

Authors
  1. Bing-Yu Zou
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lu-Hao Qiu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Huan-Yu Lei
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jin-Ming Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Wei-Feng Peng
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Hong-Qin Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Feng Bao
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Ming-Jun Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Feng Bao or Ming-Jun Huang.

Ethics declarations

The authors declare no interest conflict.

Electronic Supplementary Information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zou, BY., Qiu, LH., Lei, HY. et al. Fluorinated Colorless Polyimides with High Heat-resistance and Low Birefringence. Chin J Polym Sci 41, 1599–1608 (2023). https://doi.org/10.1007/s10118-023-3011-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10118-023-3011-6

Keywords

Search

Navigation