

FOLLOWUS
a.School of Materials and Energy, Guangdong University of Technology (GDUT), Guangzhou 510640, China
b.Guangzhou Liangyue Materials Technology Co., Ltd., Guangzhou 510663, China
tanwanyi@gdut.edu.cn (W.Y.T.)
cuitt@gdut.edu.cn (T.T.C.)
ygmin@gdut.edu.cn (Y.G.M.)
Received:18 January 2025,
Revised:04 March 2025,
Accepted:12 March 2025,
Published Online:14 May 2025,
Published:01 July 2025
Scan QR Code
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
Hui Zhang, Hui-Shan Hu, Zhi-Yu Lu, et al. Intrinsically Low Dielectric Constant and Low Dielectric Loss Polyimides Enabled by Rigid-Soft Structure[J]. Chinese journal of polymer science, 2025, 43(7): 1222-1230.
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 DOI: 10.1007/s10118-025-3338-2.
Hui Zhang, Hui-Shan Hu, Zhi-Yu Lu, et al. Intrinsically Low Dielectric Constant and Low Dielectric Loss Polyimides Enabled by Rigid-Soft Structure[J]. Chinese journal of polymer science, 2025, 43(7): 1222-1230. DOI: 10.1007/s10118-025-3338-2.
Develop an effective strategy to achieve low
D
k
/
D
f
at high frequency by endowing MPIs with rigid-soft structures based on a naphthalene-alkyl-based diamine.
Modified polyimides (MPIs) possess excellent thermal stability
chemical stability
and mechanical properties
and are considered to be a kind of dielectric material for high-frequency communication. Enhancing the rigidity of the polymer chains and intermolecular interactions can ensure low
D
k
/
D
f
at high frequency
which is attributed to the effective restriction of dipole orientations. However
it is difficult to achieve tight chain packing in an overly rigid polymer chain
whereas an overly flexible polymer chain might be insufficient to restrain small-scale molecular motions below
T
g
. To balance the trade-off between the rigidity of the polymer chains and tight chain packing
MPI was developed with a rigid-soft structure based on a naphthalene-alkyl-based diamine. On the one hand
incorporating the soft unit can enhance the movability of polymer chains to achieve dense chain packing for polyimides (PIs). On the other hand
the p
resence of rigid aromatic units can enhance intermolecular interactions and further restrict the motion of polar imide groups below
T
g
. As a result
the resultant MPI can prevent small-scale molecular motion below
T
g
. In contrast to the reference PI-TFMB-6FDA
D
k
/
D
f
is significantly reduced from 2.72/0.0075 to 2.73/0.005 at a high frequency of 10 GHz. Furthermore
the rigid-soft structure endows PIs with good thermoplasticity owing to the good chain flexibility above
T
g
. In addition
PIs based on rigid-soft structures can preserve favorable thermal stability.
Zhang, C.; He, X.; Lu, Q. High-frequency low-dielectric-loss in linear-backbone-structured polyimides with ester groups and ether bonds. Commun. Mater. 2024 , 5 , 1−11..
Qin, Y.; Yin, Q.; Lyu, J.; Wang, X.; Liu, X. Tuning the persistence lengths of main chain towards colorless and transparent polyimide with low dielectric loss and excellent general properties. Polymer 2024 , 298 , 126853..
Li, H.; Wei, P.; Wang, Y.; Zhu, Q.; Wang, X.; Gao, W.; Tao, L.; Ma, K.; Hu, Z.; Chen, W. High-frequency 5G substrate: Low dielectric biphenyl polyimide with low CTE and high thermal stability. Mater. Today Adv. 2024 , 23 , 100514..
Zhang, C.; He, X.; Lu, Q. Polyimide films with ultralow dielectric loss for 5G applications: Influence and mechanism of ester groups in molecular chains. Eur. Polym. J. 2023 , 200 , 112544..
Peng, Z.; Ye, A.; Zhang, L.; Li, X.; Lian, C.; Li, C. Micro-crosslinked polyimide nanocomposites with low dielectric constant and low dielectric loss for microwave antenna with molecular dynamics. Compos. Commun. 2024 , 46 , 101804..
Li, H.; Bao, F.; Li, S.; Li, Y.; Li, X.; Mu, K.; Wang, M.; Zhu, C.; Xu, J. Preparation of fluorinated polyimides with low dielectric constants and low dielectric losses by combining ester groups and triphenyl pyridine structures. Polym. Chem. 2024 , 15 , 22−29..
Qu, C.; Shan, L.; Zhang, G.; Sun, R. Preparation and dielectric properties research of a novel kind of intrinsic silane-containing polyimide. Polymer 2023 , 285 , 126361..
Nagella, S. R.; Park, S. S.; Chitumalla, R. K.; Jang, J.; Ha, C. S. Intrinsic low-dielectric-constant polyimides based on a novel diamine having −CF 3 groups and kinkable 1,4-diisopropylbenzene units. Polymer. Int. 2023 , 73 (3), 238−247..
Li, K.; Yang, L.; Yang, L.; He, L.; Du, J.; Li, X. Low dielectric polyimide microsphere/polyimide composite films based on porous polyimide microsphere. Polym. Eng. Sci. 2024 , 64 , 5166−5175..
Sun, W.; Yang, M.; Peng, K.; Fu, Y. All-organic hyper-crosslinked polymer/polyimide composite films with ultralow high-frequency dielectric constant. Macromol. Rapid Commun. 2023 , 44 , 2200956..
Li, Y.; Ma, B.; Zhang, R.; Luo, X. Mechanically strong, thermal-insulated, and ultralow dielectric polyimide aerogels with adjustable crosslinking methods. Polymer 2022 , 253 , 125035..
Kim, S.; Son, J.; Park, H.; Jeong, E.; Nam, K. H.; Bae, J. S. Polymer concentration and liquid-liquid demixing time correlation with porous structure of low dielectric polyimide in diffusion-driven phase separation. Polymers 2022 , 14 , 1425..
Zhang, P.; Zhang, L.; Zhang, K.; Zhao, J.; Li, Y. Preparation of polyimide films with ultra-low dielectric constant by phase inversion. Crystals 2021 , 11 , 1383..
Kourakata, Y.; Onodera, T.; Kasai, H.; Jinnai, H.; Oikawa, H. Ultra-low dielectric properties of porous polyimide thin films fabricated by using the two kinds of templates with different particle sizes. Polymer 2021 , 212 , 123115..
Zou, B. Y.; Qiu, L. H.; Lei, H. Y.; Liu, J. M.; Peng, W. F.; Zhao, H. Q.; Bao, F.; Huang, M. J. Fluorinated colorless polyimides with high heat-resistance and low birefringence. Chinese J. Polym. Sci. 2023 , 41 , 1599−1608..
Fan, H.; Xie, T.; Wang, C.; Zhang, Y.; Pan, S.; Li, J.; Zhang, Y.; Guan, S.; Yao, H. Low-dielectric polyimide constructed by integrated strategy containing main-chain and crosslinking network engineering. Polymer 2023 , 279 , 126035..
Peng, W.; Lei, H.; Qiu, L.; Bao, F.; Huang, M. Pe rfluorocyclobutyl-containing transparent polyimides with low dielectric constant and low dielectric loss. Polym. Chem. 2022 , 13 , 3949−3955..
He, X.; Zhang, S.; Zhou, Y.; Zheng, F.; Lu, Q. The “fluorine impact” on dielectric constant of polyimides: a molecular simulation study. Polymer 2022 , 254 , 125073..
Wu, X.; Cai, J.; Cheng, Y. Synthesis and characterization of high fluorine-containing polyimides with low-dielectric constant. J. Appl. Polym. Sci. 2021 , 139 , 51972..
Tao, L.; Yang, H.; Liu, J.; Fan, L.; Yang, S. Synthesis and characterization of highly optical transparent and low dielectric constant fluorinated polyimides. Polymer 2009 , 50 , 6009−6018..
Sawada, R.; Ando, S. Polarization analysis and humidity dependence of dielectric properties of aromatic and semialicyclic polyimides measured at 10 GHz. J. Phys. Chem. C 2024 , 128 , 6979−6990..
He, J.; Wu, X.; Cheng, Y. Low dielectric post-cured benzocyclobutene-functionalized fluorine-containing polyimide material. Eur. Polym. J. 2023 , 196 , 112334..
Bei, R.; Qian, C.; Zhang, Y.; Chi, Z.; Liu, S.; Chen, X.; Xu, J.; Aldred, M. P. Intrinsic low dielectric constant polyimides: relationship between molecular structure and dielectric properties. J. Mater. Chem. C 2017 , 5 , 12807−12815..
Li, H.; Lan, X.; Bao, F.; Li, S.; Zhu, H.; Zhu, Z.; Li, Y.; Wang, M.; Zhu, C.; Xu, J. Preparation of triphenylamine polyimides with low dielectric constants with different side group sizes based on β -relaxation theory. Eur. Polym. J. 2024 , 211 , 112969..
Jiang, S.; Zhou, Z.; Zhang, J.; Yi, N.; Wang, J.; Zhao, J.; Fan, L.; Wu, Y.; Gan, F. Fabrication of high-performance polyimide films by tailoring coordination bondand chain rigidity. Eur. Polym. J. 2024 , 214 , 113161..
Chen, Y.; Chen, X.; Wang, Y.; Nie, Z.; Wang, X.; Tan, J.; Zhuang, Y.; Liu, X.; Wang, X. Increasing twist rigidity to prepare polyimides with low dielectric constants and dissipation factors over a wide temperature range. Macromolecules 2023 , 56 , 9379−9388..
Qin, Y.; Yin, Q.; Lyu, J.; Wang, X.; Liu, X. Preparation of polyimide films with ultralow dielectric loss at high frequency by reducing intermolecular friction. Polymer 2024 , 309 , 127432..
Meng, X.; Wen, Y.; Wang, X.; Shen, D.; Yan, J.; Wang, Z. High performance imide oligomers and thermosets derived from 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. Polymer 2023 , 281 , 126086..
Cheng, Y. C.; Chen, Y. C.; Lin, Y. C.; Kuo, C. C.; Chen, W. C. Exploring the cross-linking effect on decreasing the dielectric constant and dissipation factor of poly(ester imide)s at a high frequency of 10–40 GHz. ACS Appl. Polym. Mater. 2023 , 5 , 7907−7917..
Lee, J. S.; Yan, Y. Z.; Park, S. S.; Ahn, S. K.; Ha, C. S. A novel diamine containing ester and diphenylethane groups for colorless polyimide with a low dielectric constant and low water absorption. Polymers 2022 , 14 , 4504..
Zhu, T.; Yu, Q.; Zheng, W.; Bei, R.; Wang, W.; Wu, M.; Liu, S.; Chi, Z.; Zhang, Y.; Xu, J. Intrinsic high-k–low-loss dielectric polyimides containing ortho-position aromatic nitrile moieties: reconside ration on Clausius–Mossotti equation. Polym. Chem. 2021 , 12 , 2481−2489..
Zhou, Y.; Zhang, S.; Zheng, F.; Lu, Q. Intrinsically black polyimide with retained insulation and thermal properties: a black anthraquinone derivative capable of linear copolymerization. Macromolecules 2021 , 54 , 9307−9318..
Han, S.; Li, Y.; Hao, F.; Zhou, H.; Qi, S.; Tian, G.; Wu, D. Ultra-low dielectric constant polyimides: combined efforts of fluorination and micro-branched crosslink structure. Eur. Polym. J. 2021 , 143 , 110206..
Xiao, H.; Huang, J.; Wang, M.; Huang, W.; Li, M.; Jin, G. Unraveling molecular loss processes for dielectric polymers in the Terahertz frequency range: impact of polarity and chain rigidity. Polymer 2024 , 297 , 126855..
Jian, L. F.; Lu, Z. Y.; Zhang, J. Y.; Yuan, H. B.; Zhang, H.; Ge, H.; Tan, W. Y.; Cui, T. T.; Min, Y. G. Thermoplastic polyimide with low dielectric properties enabled by the 2,2′-spirobifluorene group. J. Appl. Polym. Sci. 2024 , 141 , 55686..
Tan, W. Y.; J ian, L. F.; Chen, W. P.; Zhang, Y. W.; Lu, X. C.; Huang, W. J.; Zhang, J. S.; Wu, J. W.; Feng, J. L.; Liu, Y. D.; et al. A facile strategy for intrinsic low- D k and low- D f polyimides enabled by spirobifluorene groups. Chinese J. Polym. Sci. 2022 , 41 , 288−296..
Zhang, L.; Liu, J.; Luo, L.; Liu, X.; Wang, X. All-organic polyimide/Cl-HBC composite film with high breakdown strength and ultra-low dielectric loss. Polymer 2022 , 245 , 124702..
Kim, S.; Lee, Y.; Park, J.; So, Y.; Jung, H. T.; Ko, M. J.; Won, J. C.; Jeong, S.; Kim, Y. H. Green and facile synthesis of hybrid composites with ultralow dielectric properties from water-soluble polyimide and dual-porous silica nanoparticles. ACS Appl. Mater. Interfaces 2022 , 15 , 4408−4418..
Li, X. T.; Zhu, X. M.; Dong, J.; Zhao, X.; Zhang, Q. H. Preparation of low-dielectric permittivity polyimide resins with high surface activity from chemically bonded hyperbranched polysiloxane. Chinese J. Polym. Sci. 2021 , 39 , 1200−1210..
Zhao, G.; Mu, X.; Ma, D.; Wang, S.; Pan, J.; Cui, J.; Qi, M. Dielectric and mechanical properties of TiO 2 /polyi mide composites with low dielectric constant. Polym. Eng. Sci. 2023 , 63 , 1953−1960..
Lu, Z.; Jian, L. F.; Zhang, J.; Du, Q.; Yuan, Z.; Tan, W.; Min, Y. Intrinsically microporous polyimides based on a rigid–soft structure for hydrogen separation. ACS Appl. Mater. Interfaces 2025 , 17 , 9786−9796..
Park, C. H.; Tocci, E.; Kim, S.; Kumar, A.; Lee, Y. M.; Drioli, E. A simulation study on OH-containing polyimide (HPI) and thermally rearranged polybenzoxazoles (TR-PBO): relationship between gas transport properties and free volume morphology. J. Phys. Chem. B 2014 , 118 , 2746−2757..
Rahmati, M.; Modarress, H.; Gooya, R. Molecular simulation study of polyurethane membranes. Polymer 2012 , 53 , 1939−1950..
0
Views
2
Downloads
0
CSCD
Publicity Resources
Related Articles
Related Author
Related Institution
京公网安备11010802024621