Enhancing Processability of Phenylethynyl-terminated Imide Oligomers and Properties of Cured Polyimides <italic style="font-style: italic">via</italic> ―CF<sub>3</sub> Incorporation

Xiao-Ying Xing; Xin-Er Liu; Zun-Chu Liu; Chu-Ying Li; Xue-Yi Yu; Ye Zhang; Xin-Zheng Huang; Ruo-Peng Liu; Si-Wei Liu; Yi Zhang

doi:10.1007/s10118-026-3716-4

Your Location：

Home >

Browse articles >

Enhancing Processability of Phenylethynyl-terminated Imide Oligomers and Properties of Cured Polyimides via ―CF₃ Incorporation

RESEARCH ARTICLE | Updated：2026-08-31

- Enhancing Processability of Phenylethynyl-terminated Imide Oligomers and Properties of Cured Polyimides via ―CF₃ Incorporation
- Chinese Journal of Polymer Science Vol. 44, Issue 9, Pages: 3002-3016(2026)
- Affiliations：
  
  a.PCFM Lab, GD HPPC Lab, Guangdong Engineering Technology Research Centre for High-performance Organic and Polymer Photoelectric Functional Films, GBRCE for Functional Molecular Engineering, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry, IGCME, Sun Yat-sen University, Guangzhou 510275, China
  b.Shenzhen Kuang-Chi Cutting-edge Technology Co., Ltd., Shenzhen 518057, China
- Author bio：
  
  ruopeng.liu@kuang-chi.com (R.P.L.)
  ceszy@mail.sysu.edu.cn (Y.Z.)
- Funds：
- DOI：10.1007/s10118-026-3716-4
  CLC：
- Received：16 April 2026，
  
  Accepted：16 May 2026，
  
  Online First：07 August 2026，
  
  Published：05 September 2026
- Accepted：
Scan QR Code
Xing, X. Y.; Liu, X. E.; Liu, Z. C.; Li, C. Y.; Yu, X. Y.; Zhang, Y.; Huang, X. Z.; Liu, R. P.; Liu, S. W.; Zhang, Y. Enhancing processability of phenylethynyl-terminated imide oligomers and properties of cured polyimides via ―CF₃ incorporation. Chinese J. Polym. Sci. 2026, 44, 3002–3016 DOI: 10.1007/s10118-026-3716-4.

Xiao-Ying Xing, Xin-Er Liu, Zun-Chu Liu, et al. Enhancing Processability of Phenylethynyl-terminated Imide Oligomers and Properties of Cured Polyimides via ―CF₃ Incorporation[J]. Chinese Journal of Polymer Science, 2026, 44(9): 3002-3016. DOI: 10.1007/s10118-026-3716-4.
Xing, X. Y.; Liu, X. E.; Liu, Z. C.; Li, C. Y.; Yu, X. Y.; Zhang, Y.; Huang, X. Z.; Liu, R. P.; Liu, S. W.; Zhang, Y. Enhancing processability of phenylethynyl-terminated imide oligomers and properties of cured polyimides via ―CF₃ incorporation. Chinese J. Polym. Sci. 2026, 44, 3002–3016 DOI: 10.1007/s10118-026-3716-4. DOI：

Xiao-Ying Xing, Xin-Er Liu, Zun-Chu Liu, et al. Enhancing Processability of Phenylethynyl-terminated Imide Oligomers and Properties of Cured Polyimides via ―CF₃ Incorporation[J]. Chinese Journal of Polymer Science, 2026, 44(9): 3002-3016. DOI: 10.1007/s10118-026-3716-4. DOI：

摘要

This study demonstrates the incorporation of ―CF

enhances the processability of phenylethynyl-terminated imide (PETI) oligomers

maintains thermal and mechanical properties

and reduces high-frequency

and

of the cured polyimides.

Abstract

Advanced aerospace technologies demand polymer-based wave-transparent materials with low dielectric constant (

)

low dissipation factor (

)

and high heat resistance for hypersonic vehicles. Thermosetting polyimides (PIs) from phenylethynyl-terminated imide (PETI) oligomers are promising candidates due to their excellent thermal stability; however

their application is limited by high

and

at high frequencies and processing difficulties. Here

a series of PETI oligomers were designed and synthesized by polycondensation of 9

9-bis(3

4-dicarboxyphenyl)fluorene dianhydride containing a Cardo structure

and six diamine monomers

respectively. The diamines were divided into three pairs by backbone flexibility

with each pair comprising a non-fluorinated diamine and its trifluoromethyl (―CF

) substituted analog. The effec

ts of chain segment flexibility and ―CF

substitution on the processability of the oligomers and the properties of the cured PIs were systematically investigated. Results show that oligomers with ―CF

groups exhibit enhanced solubility and improved viscosity stability at 270 °C compared to their non-fluorinated counterparts. Moreover

the corresponding cured resins show lower

and

values while maintaining good thermal stability and mechanical properties. Notably

the BPAF-FA system exhibits favorable properties: an oligomer solubility of 40 wt% in NMP

and a minimum melt viscosity of 5.61 Pa·s;

=2.953

=0.0098 (at 50% RH)

=403 °C. Mechanistic analysis indicates that these improvements result from the synergistic effects of the intrinsic characteristics of ―CF

groups (steric hindrance

electron-withdrawing effect

low polarizability

and hydrophobicity) and their role in influencing chain flexibility

symmetry

and molecular packing. These findings provide valuable guidance for the design of high-temperature-resistant

low-dielectric wave-transparent composite materials.

关键词

Keywords

references

Nag, A.; Rao, R. R.; Panda, P. K. High temperature ceramic radomes (HTCR) – a review. Ceram. Int. 2021 , 47 , 20793−20806..

Tang, L.; Zhang, J. L.; Tang, Y. S.; Kong, J.; Liu, T. X.; Gu, J. W. Polymer matrix wave-transparent composites: a review. J. Mater. Sci. Technol. 2021 , 75 , 225−251..

[Gu, J. W.; Tang, Y. S.; Kong, J.; Dang, J., in Polymer matrix wave-transparent composites , Wiley-VCH GmbH, Weinheim Germany, 2024, p. 1.

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..

Connell, J. W.; Smith, J. G.; Hergenrother, P. M. Oligomers and polymers containing phenylethynyl groups. J. Macromol. Sci., Polym. Rev. 2000 , 40 , 207−230..

Kim, M.; Kim, K.; Lee, J. H.; Jeon, E.; Song, J.; Choi, J.; Yeo, H.; Nam, K. H. Phenylethynyl-terminated imide oligomer-based thermoset resins. Polymers 2024 , 16 , 2947−2973..

Zhang, H. Y.; Yuan, L. L.; Hong, W. J.; Yang, S. Y. Improved m elt processabilities of thermosetting polyimide matrix resins for high temperature carbon fiber composite applications. Polymers 2022 , 14 , 965−980..

Hong, W. J.; Yuan, L. L.; Yang, S. Y. High temperature phenylethynyl-terminated imide oligomers derived from asymmetric diphenyl ether diamines for resin transfer molding. Polymer 2023 , 269 , 125635−125647..

Meng, X. S.; Wen, Y.; Wang, X. W.; Shen, D. L.; Yan, J. L.; Wang, Z. High performance imide oligomers and thermosets derived from 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. Polymer 2023 , 281 , 126086−126094..

Li, X.; Liu, T.; Jiao, Y.; Dong, J.; Gan, F.; Zhao, X.; Zhang, Q. Novel high-performance poly(benzoxazole-co-imide) resins with low dielectric constants and superior thermal stabilities derived from thermal rearrangement of ortho-hydroxy polyimide oligomers. Chem. Eng. J. 2019 , 359 , 641−651..

Li, X.; Zhang, P.; Dong, J.; Gan, F.; Zhao, X.; Zhang, Q. Preparation of low-κ polyimide resin with outstanding stability of dielectric properties versus temperature by adding a reactive Cardo-containing diluent. Compos. Part B: Eng. 2019 , 177 , 107401−107411..

Bei, R. X.; Chen, K. J.; Liu, Q.; He, Y. W.; Li, C. Y.; Huang, H. T.; Guo, Q.; Chi, Z. G.; Xu, J. R.; Chen, Z. Q.; Liu, S. W.; Zhang, Y. Relationship among the water adsorption, polymer structure, and high-frequency dissipation factor: precise analysis of water adsorption of low-dielectric constant polyimide films. Macromolecules 2024 , 57 , 2142−2153..

Li, Y. H.; Sun, G. H.; Zhou, Y.; Liu, G. M.; Wang, J.; Han, S. H. Progress in low dielectric polyimide film — a review. Prog. Org. Coat. 2022 , 172 , 107103−107121..

[Abraham, M. J.; Murtola, T.; Schulz, R.; Páll, S.; Smith, J. C.; Hess, B.; Lindahl, E. GROMACS: high performance molecular simulations through multi-level parallelism from laptops to supercomputers. SoftwareX 2015, 1-2 , 19–25..

[Lu, T.; Sobtop Version 1.0 (dev2). [accessed on 16th January, 2026]http://sobereva.com/soft/Sobtop.

Lu, T.; Chen, F. W. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 2012 , 33 , 580−592 ..

Humphrey, W.; Dalke, A.; Schulten, K. VMD: visual molecular dynamics. J. Mol. Graphics 1996 , 14 , 33−38..

Cho, D.; Drzal, L. T. Characterization, properties, and processing of LaRC™ PETI-5 as a high-temperature sizing material. I. FTIR studies on imidization and phenylethynyl end-group reaction behavior. J. Appl. Polym. Sci. 2000 , 76 , 190−200..

Chen, J. S.; Qu, X. M.; Liu, J. G.; Yang, H. X.; Fan, L.; Yang, S. Y. Novel phenylethynyl-endcapped polyimide oligomers: synthesis and characterization. Polym. Eng. Sci. 2008 , 48 , 918−924..

Gong, C. J.; Huang, X. H.; Lv, S. K.; Li, J. X.; Tang, J. K.; Huang, F. R. Poly(silylene arylacetylene)s containing hexafluoroisopropylidene with attractive mechanical properties and dielectric performance for wave-transparent composites. Mater. Chem. Front. 2023 , 7 , 5015−5027..

Fang, X. M.; Xie, X. Q.; Simone, C. D.; Stevens, M. P.; Scola, D. A. A solid-state 13C NMR study of the cure of 13C-labeled phenylethynyl end-capped polyimides. Macromolecules 2000 , 33 , 1671−1681..

Kim, M.; Khim, S.; Lee, J. H.; Jeon, E.; Song, J.; Choi, J.; Yeo, H.; Nam, K. H. Curing kinetics of ultrahigh-temperature thermosetting polyimides based on phenylethynyl-terminated imide oligomers with different backbone conformations. ACS Appl. Polym. Mater. 2024 , 6 , 13401−13412..

Mohammadi, M.; Davoodi, J.; Javanbakht, M.; Rezaei, H. Glass transition temperature of PMMA/modified alumina nanocomposite: molecular dynamic study. Mater. Res. Express 2018 , 6 , 035309−035315..

Wang, X. M.; Liu, F.; Lai, J. C.; Fu, Z. Q.; You, X. Z. Comparative investigations on the effects of pendent trifluoromethyl group to the properties of the polyimides containing diphenyl-substituted cyclopentyl Cardo-structure. J. Fluorine Chem. 2014 , 164 , 27−37..

Yan, S. Y.; Chen, W. Q.; Yang, X. J.; Chen, C.; Huang, M. F.; Xu, Z. S.; Yeung, K. W. K.; Yi, C. F. Soluble polyimides based on a novel pyridine-containing diamine m,p-PAPP and various aromatic dianhydrides. Polym. Bull. 2010 , 66 , 1191−1206..

Miyauchi , M.; Ishida, Y.; Ogasawara, T.; Yokota, R. Synthesis and characterization of soluble phenylethynyl-terminated imide oligomers derived from pyromellitic dianhydride and 2-phenyl-4,4′-diaminodiphenyl ether. React. Funct. Polym. 2013 , 73 , 340−345..

Meng, X. S.; Lu, G. W.; Liu, X. J.; Meng, Q. J.; Shi, J. W.; Yuan, H.; Ke, H. J.; Wang, X. W.; Fan, W. F.; Liu, J. F.; Yan, J. L.; Wang, Z. Highly soluble phenylethynyl-terminated imide oligomers and thermosetting polyimides based on 2,2′,3,3′-biphenyltetracarboxylic dianhydride. Chem. Res. Chin. Univ. 2019 , 35 , 530−536..

Miyauchi, M.; Ishida, Y.; Ogasawara, T.; Yokota, R. Novel phenylethynyl-terminated PMDA-type polyimides based on KAPTON backbone structures derived from 2-phenyl-4,4′-diaminodiphenyl ether. Polym. J. 2012 , 44 , 959−965..

Simone, C. D.; Scola, D. A. Phenylethynyl end-capped polyimides derived from 4,4′-(2,2,2-trifluoro-1-phenylethylidene) diphthalic anhydride, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, and 3,3′,4,4′-biphenylene dianhydride: structure−viscosity relationship. Macromolecules 2003 , 36 , 6780−6790..

Kuroki, T.; Shibuya, A.; Toriida, M.; Tamai, S. Melt-processable thermosetting polyimide: Synthesis, characterization, fusibility, and property. J. Polym. Sci., Part A: Polym. Chem. 2004 , 42 , 2395−2404..

Hong, W. J.; Yuan, L. L.; Ma, Y. P.; Cui, C.; Zhang, H. Y.; Yang, S. Y.; Sun, W. H. Resin transfer moldable fluorinated phenylethynyl-terminated imide oligomers with high Tg: structure–melt stability relationship. Polymers 2021 , 13 , 903−925..

Li, L. S.; Xu, Y.; Che, J. F.; Liu, X. H.; Zhao, W.; Ye, Z. F. Effects of diamines on the optical properties of poly(ether imide)s derived from 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl ] propane dianhydride (BPADA). Macromol. Res. 2019 , 27 , 843−849..

Zhang, H.; Hu, H. S.; Lu, Z. Y.; Liu, M. W.; Ge, H.; Yuan, H. B.; Song, J. J.; Tan, W. Y.; Cui, T. T.; Min, Y. G. Intrinsically low dielectric constant and low dielectric loss polyimides enabled by rigid-soft structure. Chinese J. Polym. Sci. 2025 , 43 , 1222−1230..

Bao, F.; Lei, H. Y.; Zou, B. Y.; Peng, W. F.; Qiu, L. H.; Ye, F.; Song, Y. H.; Qi, F. L.; Qiu, X. P.; Huang, M. J. Colorless polyimides derived from rigid trifluoromethyl-substituted triphenylenediamines. Polymer 2023 , 273 , 125883−125891..

Ruan, K. P.; Guo, Y. Q.; Gu, J. W. Liquid crystalline polyimide films with high intrinsic thermal conductivities and robust toughness. Macromolecules 2021 , 54 , 4934−4944..

Kang, X.; Liu, Z. C.; Xing, X. Y.; Li, C. Y.; Liang, L.; Wu, H. K.; Liu, Q. F.; Liu, S. W.; Zhang, Y. Influence of flexible aromatic ether diamine structures on aggregation state and high-frequency dielectric properties of polyimide films. ACS Appl. Polym. Mater. 2025 , 7 , 7460−7470..

Bei, R. X.; Chen, K. J.; He, Y. W.; Li, C. Y.; Chi, Z. G.; Liu, S. W.; Xu, J. R.; Zhang, Y. A systematic study of the relationship between the high-frequency dielectric dissipation factor and water adsorption of polyimide films. J. Mater. Chem. C 2023 , 11 , 10274−10281..

Gilormini, P.; Verdu, J. On the role of hydrogen bonding on water absorption in polymers. Polymer 2018 , 142 , 164−169..

[Chen, K. J.; Li, S. H.; Zheng, D. H.; Li, C. Y.; Liu, Z. C.; He, Y. W.; Lin, J. S.; Bei, R. X.; Meng, H. F.; Deng, B.; Su, X. X.; Huang, H. T.; Liu, S. W.; Zhang, Y. An umbrella shieldin g strategy enables low-water-absorption fluorine-free polyimide films with low-Dk/low-Df properties. CCS Chem . 2026 , doi: 10.31635/ccschem.026.202607439..

Kuo, C. C.; Lin, Y. C.; Chen, Y. C.; Wu, P. H.; Ando, S.; Ueda, M.; Chen, W. C. Correlating the molecular structure of polyimides with the dielectric constant and dissipation factor at a high frequency of 10 GHz. ACS Appl. Polym. Mater. 2020 , 3 , 362−371..

Yang, F. C.; Li, Y. F.; Ma, T.; Bu, Q. Q.; Zhang, S. J. Synthesis and characterization of fluorinated polyimides derived from novel unsymmetrical diamines. J. Fluorine Chem. 2010 , 131 , 767−775..

Dong, X. D.; Wan, B. Q.; Zha, J. W. Versatile landscape of low-k polyimide: theories, synthesis, synergistic properties, and industrial integration. Chem. Rev. 2024 , 124 , 7674−7711..

Dai, H. Y.; Zhang, Y.; Yang, Y.; Chen, J.; Li, C. Y.; Liu, H.; Liu, W. T.; Li, X.; Zhang, T. T.; Xue, R. Z.; Li, T. The influence of diamine structure on low dielectric constant and comprehensive properties of fluorinated polyimide films. Eur. Polym. J. 2025 , 222 , 113614−113624..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Topology-regulated Co-assembly of Single Chain Polymer Nanoparticles and Block Copolymers into Hierarchical Micelle@Vesicle Composite Structures

Energy Storage Performance of Supercapacitors with Polyelectrolyte Surface Coatings: Effects of Dielectric Contrast

A Paradigm for BF3 Co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature

2026-9 Contents

From Molecular Defect to Macroscopic Performance: Manipulating Dichroism and Mechanics in Iodine-doped Poly(vinyl alcohol) via Ethylene Incorporation

Related Author

Ye Zhang

Xin-Zheng Huang

Ruo-Peng Liu

Xiao-Ying Xing

Related Institution

Shenzhen Kuang-Chi Cutting-edge Technology Co., Ltd

⁰

Enhancing Processability of Phenylethynyl-terminated Imide Oligomers and Properties of Cured Polyimides via ―CF3 Incorporation

DOI：10.1007/s10118-026-3716-4

摘要

Abstract

关键词

Keywords

references

Enhancing Processability of Phenylethynyl-terminated Imide Oligomers and Properties of Cured Polyimides via ―CF₃ Incorporation