1.大连理工大学,化工学院智能材料前沿科学中心精细化工国家重点实验室,大连 116024
2.大连理工大学,大连理工大学高分子科学与材料系 大连 116024
3.辽宁省高性能树脂材料技术创新中心,大连 116012
E-mail: zongls@dlut.edu.cn
E-mail:wangjinyan@dlut.edu.cn
收稿:2026-04-23,
录用:2026-06-06,
网络首发:2026-07-13,
纸质出版:2026-08-20
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杨志超, 宗立率, 王锦艳, 蹇锡高. 非对称喹噁啉诱导主链扭曲制备高频低损耗聚芳醚. 高分子学报, 2026, 57(8), 1777-1785.
Yang, Z. C.; Zong, L. S.; Wang, J. Y.; Jian, X. G. Asymmetric quinoxaline-induced main-chain twisting for high-frequency low-loss poly(aryl ether)s. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1777-1785.
杨志超, 宗立率, 王锦艳, 蹇锡高. 非对称喹噁啉诱导主链扭曲制备高频低损耗聚芳醚. 高分子学报, 2026, 57(8), 1777-1785. DOI: 10.11777/j.issn1000-3304.2026.26099. CSTR: 32057.14.GFZXB.2026.7622.
Yang, Z. C.; Zong, L. S.; Wang, J. Y.; Jian, X. G. Asymmetric quinoxaline-induced main-chain twisting for high-frequency low-loss poly(aryl ether)s. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1777-1785. DOI: 10.11777/j.issn1000-3304.2026.26099. CSTR: 32057.14.GFZXB.2026.7622.
为满足高频通信技术对低介电聚合物电介质的迫切需求,本研究提出了一种通过分子主链工程调控链构象以降低介电常数(
D
k
)与介电损耗(
D
f
)的新策略. 不同于传统的增强刚性或引入柔性基团的方法,我们致力于在保持主链刚性的前提下引入可控的分子扭曲,以同步增大自由体积和限制偶极运动. 为此,设计并合成了2种具有不同连接键角的新型非对称单喹噁啉双卤单体,并与含氟双酚6F-BPA共聚,成功制备了主链扭曲程度具有差异的聚芳醚P6FEQA与P6FEQD. 作为对照,合成了基于对称双喹噁啉单体的线性聚合物P6FEQ. 系统研究表明,主链扭曲度的增加能通过降低材料堆积密度有效削弱宏观极化响应,并通过构象锁定有效抑制偶极弛豫. 其中,具有最大扭曲度的P6FEQD在15 G
Hz下展现出最优异的介电性能:介电常数低至2.385,介电损耗仅为0.00344,比商用聚醚醚酮(PEEK)在GHz频段的典型损耗值低近一个数量级,且所用单体易于合成. 本工作为通过“刚性扭曲”分子设计实现高频介电性能的优化提供了明确的范例.
To address the urgent demand for low-dielectric-constant polymer dielectrics in high-frequency communication technologies
this study proposes a new strategy for modulating chain conformation through main-chain engineering to reduce the dielectric constant (
D
k
) and dielectric loss (
D
f
). Distinct from conventional approaches that enhance rigidity or introduce flexible segments
we aimed to introduce controlled molecular twists while maintaining main-chain rigidity
thereby simultaneously increasing free volume and restricting dipole motion. To this end
two novel asymmetric single-quinoxaline-based difluoro monomers with different bond angles were designed and synthesized
and copolymerized with the fluorinated bisphenol 6F-BPA to successfully prepare poly(aryl ether)s
namely P6FEQA and P6FEQD
with varying degrees of main-chain twisting. For comparison
a linear polymer
P6FEQ
was synthesized using a symmetric bis-quinoxaline
monomer. Systematic investigations revealed that increasing the degree of main-chain twist effectively attenuates the macroscopic polarization response by reducing packing density and strongly suppresses dipole relaxation through conformational locking. Among the obtained polymers
P6FEQD
which exhibited the highest degree of twisting
demonstrated the most outstanding dielectric performance at 15 GHz
with a
D
k
as low as 2.385 and a
D
f
of only 0.00344
which was nearly an order of magnitude lower than the typical loss values of commercial poly(ether ether ketone) (PEEK) in the GHz frequency range. Notably
the monomers employed are readily synthesizable. This work provides a clear paradigm and mechanistic elucidation for achieving high-frequency dielectric performance optimization through "rigid-twist" molecular design.
Volksen W. ; Miller R. D. ; Dubois G. Low dielectric constant materials . Chem. Rev. , 2010 , 110 ( 1 ), 56 - 110 . doi: 10.1021/cr9002819 http://dx.doi.org/10.1021/cr9002819
Maex K. ; Baklanov M. R. ; Shamiryan D. ; Lacopi F. ; Brongersma S. H. ; Yanovitskaya Z. S. Low dielectric constant materials for microelectronics . J. Appl. Phys. , 2003 , 93 ( 11 ), 8793 - 8841 . doi: 10.1063/1.1567460 http://dx.doi.org/10.1063/1.1567460
Zheng H. ; Zheng Z. J. ; Gong D. R. ; Tian C. ; Wen Y. ; Wang Z. ; Yan J. L. Synthesis and characterization of fluorinated poly(aryl ether)s with excellent dielectric properties . Polym. Chem. , 2024 , 15 ( 19 ), 1947 - 1954 . doi: 10.1039/d4py00119b http://dx.doi.org/10.1039/d4py00119b
Hergenrother P. M. The use, design, synthesis, and properties of high performance/high temperature polymers: an overview . High Perform. Polym. , 2003 , 15 ( 1 ), 3 - 45 . doi: 10.1177/095400830301500101 http://dx.doi.org/10.1177/095400830301500101
Simpson J. O. ; St Clair A. K. Fundamental insight on developing low dielectric constant polyimides . Thin Solid Films , 1997 , 308 , 480 - 485 . doi: 10.1016/s0040-6090(97)00481-1 http://dx.doi.org/10.1016/s0040-6090(97)00481-1
Hougham G. ; Tesoro G. ; Viehbeck A. ; Chapple-Sokol J. D. Polarization effects of fluorine on the relative permittivity in polyimides . Macromolecules , 1994 , 27 ( 21 ), 5964 - 5971 . doi: 10.1021/ma00099a006 http://dx.doi.org/10.1021/ma00099a006
Zahidul Islam M. ; Fu Y. Q. ; Deb H. ; Khalid Hasan M. ; Dong Y. B. ; Shi S. D. Polymer-based low dielectric constant and loss materials for high-speed communication network: dielectric constants and challenges . Eur. Polym. J. , 2023 , 200 , 112543 . doi: 10.1016/j.eurpolymj.2023.112543 http://dx.doi.org/10.1016/j.eurpolymj.2023.112543
Liu Y. Q. ; Hu T. J. ; Sun J. ; Fang Q. A facile method for preparing fluorinated Poly(aryl ether)s toward high-frequency low dielectric materials . Macromol. Rapid Commun. , 2025 , 46 ( 12 ), 2401017 . doi: 10.1002/marc.202401017 http://dx.doi.org/10.1002/marc.202401017
Petković Benazzouz M. M. ; Rakić A. A. ; Trišović N. P. ; Zarić B. L. ; Janjić G. V. Supramolecular perspective of coordination effects on fluorine interactions . Cryst. Growth Des. , 2021 , 21 ( 11 ), 6129 - 6142 . doi: 10.1021/acs.cgd.1c00584 http://dx.doi.org/10.1021/acs.cgd.1c00584
Wang Z. Y. ; Jiang B. ; Zhang Y. H. ; Li X. F. ; Wang Y. P. ; Shang Y. S. ; Zhang H. B. Influence of crosslink density on thermal, mechanical and dielectric properties of cross-linked fluorinated poly(aryl ether)s . Eur. Polym. J. , 2022 , 172 , 111244 . doi: 10.1016/j.eurpolymj.2022.111244 http://dx.doi.org/10.1016/j.eurpolymj.2022.111244
Jiang L. M. ; Liu H. R. ; Yuan K. Y. ; Zhang G. S. ; Xiao C. H. ; Wang C. H. ; Zong L. S. ; Wang J. Y. ; Jian X. G. Construction of fluorinated hyperbranched polyaryletherketone-based UV-cured films with low dielectric and enhanced mechanical properties . Polymer , 2024 , 299 , 126902 . doi: 10.1016/j.polymer.2024.126902 http://dx.doi.org/10.1016/j.polymer.2024.126902
Hou W. H. ; Zong L. S. ; Zhu L. Y. ; Wang J. M. ; Zhang Y. B. ; Li Z. S. ; Wang J. Y. ; Jian X. G. Design and synthesis of low-dieclectric polyaryl ethers containing bulky tetraphenyl vinyl pendant group . Polym. Adv. Technol. , 2024 , 35 ( 4 ), e 6357 . doi: 10.1002/pat.6357 http://dx.doi.org/10.1002/pat.6357
Alegria A. ; Colmenero J. Dielectric relaxation of polymers: segmental dynamics under structural constraints . Soft Matter , 2016 , 12 ( 37 ), 7709 - 7725 . doi: 10.1039/c6sm01298a http://dx.doi.org/10.1039/c6sm01298a
Tang L. ; Jia M. S. ; He M. K. ; Liu Q. Q. ; Lin Y. H. ; Yi Y. T. ; Liu X. L. ; Liu X. ; Tang Y. S. ; Gu J. W. Fabrication, applications, and prospects for poly(p-phenylene benzobisoxazole) nanofibers . SusMat , 2024 , 4 ( 6 ), e 245 . doi: 10.1002/sus2.245 http://dx.doi.org/10.1002/sus2.245
Lin Y. H. ; Tang L. ; Cheng L. ; Zeng X. X. ; Zhang J. L. ; Tang Y. S. ; Kong J. ; Gu J. W. Mechanically strong PBO wave-transparent composite papers with excellent UV resistance and ultra-low dielectric constant . J. Mater. Sci. Technol. , 2025 , 225 , 151 - 158 . doi: 10.1016/j.jmst.2024.12.006 http://dx.doi.org/10.1016/j.jmst.2024.12.006
Zhu L. Y. ; Zong L. S. ; Wang C. H. ; Liu X. L. ; Yuan B. ; Wang J. Y. ; Jian X. G. Effect of di-halogen monomers embraced in main chain of low-dielectric colorless fluorene-based poly(aryl ether)s on their performance . Polym. Adv. Technol. , 2022 , 33 ( 6 ), 1846 - 1854 . doi: 10.1002/pat.5639 http://dx.doi.org/10.1002/pat.5639
Jiang J. W. ; Sun Y. L. ; Wang Z. P. Low dielectric constant and dielectric loss quinoxaline-based poly (aryl ether)s with excellent solubility, hydrophobic and thermal properties . Eur. Polym. J. , 2024 , 215 , 113156 . doi: 10.1016/j.eurpolymj.2024.113156 http://dx.doi.org/10.1016/j.eurpolymj.2024.113156
Zhang R. M. ; Yang K. R. ; Liu X. Q. ; Lu X. X. ; Xu L. P. ; Chang T. Y. ; Cui H. L. ; Wei D. S. Terahertz spectroscopy studies on dielectric and thermal stability properties of polymer resins . J. Opt. Soc. Am. B , 2025 , 42 ( 8 ), 1723 . doi: 10.1364/josab.564930 http://dx.doi.org/10.1364/josab.564930
Hedrick J. L. ; Labadie J. W. Poly(aryl ether phenylquinoxalines) . Macromolecules , 1990 , 23 ( 6 ), 1561 - 1568 . doi: 10.1021/ma00208a001 http://dx.doi.org/10.1021/ma00208a001
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