基于5-乙烯基间苯二甲酸和烷基链的甲壳型液晶高分子的设计、合成及相行为

郑军峰; 吴雅婷; 徐鹏; 任相魁; 陈尔强

doi:10.11777/j.issn1000-3304.2025.25078

您当前的位置：

首页 >

文章列表页 >

基于5-乙烯基间苯二甲酸和烷基链的甲壳型液晶高分子的设计、合成及相行为

研究论文 | 更新时间：2025-05-19

- 基于5-乙烯基间苯二甲酸和烷基链的甲壳型液晶高分子的设计、合成及相行为
- Design, Synthesis, and Phase Behavior of Mesogen-Jacketed Liquid Crystalline Polymers Based on 5-Vinylisophthalic Acid and Alkyl Chains
- 高分子学报 2025年页码：1-12
- 作者机构：
  
  1.南京林业大学化学工程学院应用化学系南京 210037
  2.天津大学化工学院高分子科学与工程系天津 300350
  3.北京大学化学与分子工程学院高分子科学与工程系北京 100871
- 作者简介：
  
  E-mail: zjfphd@163.com
  xupeng@njfu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25078
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7407
- 收稿日期：2025-03-25，
  
  录用日期：2025-04-29，
  
  网络出版日期：2025-05-19，
- 稿件说明：
移动端阅览
郑军峰, 吴雅婷, 徐鹏, 任相魁, 陈尔强. 基于5-乙烯基间苯二甲酸和烷基链的甲壳型液晶高分子的设计、合成及相行为. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25078

Zheng, J. F.; Wu, Y. T.; Xu, P.; Ren, X. K.; Chen, E. Q. Design, synthesis, and phase behavior of mesogen-jacketed liquid crystalline polymers based on 5-vinylisophthalic acid and alkyl chains. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25078
郑军峰, 吴雅婷, 徐鹏, 任相魁, 陈尔强. 基于5-乙烯基间苯二甲酸和烷基链的甲壳型液晶高分子的设计、合成及相行为. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25078 DOI： CSTR： 32057.14.GFZXB.2025.7407.

Zheng, J. F.; Wu, Y. T.; Xu, P.; Ren, X. K.; Chen, E. Q. Design, synthesis, and phase behavior of mesogen-jacketed liquid crystalline polymers based on 5-vinylisophthalic acid and alkyl chains. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25078 DOI： CSTR： 32057.14.GFZXB.2025.7407.

摘要

在液晶高分子的设计中，人们通常把“去偶效应”和“甲壳效应”分割开来，即基于前者设计传统侧链液晶高分子(SCLCPs)，基于后者设计甲壳型液晶高分子(MJLCPs). 此外，研究最为广泛的MJLCPs是基于2-乙烯基对苯二甲酸的家族，但2-乙烯基对苯二甲酸的合成起始于原料2

4-二甲基苯甲酸的选择性氧化，步骤多，产率低. 针对这两个问题，本项目拟利用“去偶效应”与“甲壳效应”的协同，发展基于5-乙烯基间苯二甲酸的MJLCPs新体系. 我们合成了聚(5-乙烯基间苯二甲酸二烷基酯)(P

′-

，

为烷基链的碳原子数，

= 4

6)).烷基链的末端为叔丁基，叔丁基与酯基与之间为―(CH

)

― (

= 0

2). 在P

′-

的设计中，把叔丁基假定为大位阻的刚性基团，把―(CH

)

―假定为柔性间隔基. 偏光显微镜(PLM)和一维X-射线(1D XRD)分析表明，P

′-4和P

′-6为无定形高分子，而P

′-5从室温到样品分解前都具有稳定的六方柱状液晶相(

)，表现出典型的MJLCPs的液晶性质. 我们认为，与P

′-4相比，P

′-5中的隔基―CH

―提高了叔丁基的运动能力，进而提高了对主链的“甲壳效应”，即熵贡献的“甲壳效应”. 因而，P

′-5超分子柱的形成源于“去偶效应”与“甲壳效应”的协同. 2D XRD实验表明一维剪切的P

′-5呈现三维取向的

，具有优异的加工取向能力. XRD和分子模拟的结果表明P

′-5形成单链柱，与前期合成的P

不同. P

(

= 8

⁓

18)含有线形烷基链，形成双链柱. P

′-5的分子设计思想体现了“去偶效应”与“甲壳效应”有机统一；P

′-5基于易合成的5-乙烯基间苯二甲酸，化学结构简单，加工取向性能优异；P

′-

与P

仅仅是烷基链的构造不同，其超分子柱的链数却不同. 因而，本工作为MJLCPs的设计、MJLCPs的工业化应用、超分子柱链数的调控三个方面提供了新的思考.

Abstract

In designing of liquid crystalline polymers

"decoupling effect" and "jacketing effect" are usually considered as two converse directions. Generally

the former is used in designing traditional side-chain liquid crystalline polymers (SCLCPs)

while the latter is followed to obtain mesogen-jacketed liquid crystalline polymers (MJLCPs). The well-studied MJLCPs are based on 2-vinylterephthalic acid. However

the synthesis of 2-vinylterephthalic acid starts from the selective oxidation of 2

4-dimethylbenzoic acid and thus needs multi-step organic reactions with an overall low yield. With the two problems in mind

using the synergic effect of "decoupling effect" and "jacketing effect"

we plan to develop new MJLCPs based on 5-vinylisophthalic acid in this work. We synthesized poly[di(alkyl) 5-vinylisophthalates

]

′-

m denotes the number of carbon atoms of each alkyl chain). The tail of the alkyl chain is tert-butyl

and (CH

)

(

2) is located between the tert-butyl and ester group. In the design of P

′-

the tert-butyl group is assumed to be the rigid and highly steric group

while the ―(CH

)

― is used as the flexible spacer. Experimental results of polarized light microscope (PLM) and one-dimensional X-ray diffraction (1D XRD) demonstrate that P

′-4 and P

′-6 are amorphous

while P

′-5 exhibits hexagonal columnar liquid crystalline phase (

) before thermal decomposition. We consider that

compared to P

′-4

the spacer of ―CH

― in P

′-5 leads to stronger motions

hence enlarging "jacketing effect" of tert-butyl groups to the main-chain

namely entropy-contributed "jacketing effect". In other words

the formation of the spuramocular column of P

′-5 originates from the synergic effect of "decoupling effect" and "jacketing effect". 2D XRD results reveal that P

′-5 renders three-dimensionally ordering upon being subjected to 1D mechanically shearin

indicative of wonderful ability of processing ordering. Combined XRD and molecular simulation results indicate that P

′-5 renders "single-chain column"

different from that of P

(

=8-18) with "double-chain column"

which were synthesized previously by our group. This work offers new insights into the molecular design and industrial applications of MJLCPs

and into the manipulation of the chain-number of supermolecular columns of columnar polymers.

关键词

Keywords

references

赵瑞颖 , 蒋旭强 , 郑军峰 , 刘小青 , 徐艳双 , 杨爽 , 陈尔强 . 基于"多链超分子柱"的侧链液晶高分子柱状相 . 高分子学报 , 2018 , 49 ( 8 ), 973 - 986 . doi: 10.11777/j.issn1000-3304.2018.18065 http://dx.doi.org/10.11777/j.issn1000-3304.2018.18065

范祎宁 , 杨子凡 , 吴佳慧 , 赵凌 , 夏玮 , 张龙龙 , 王婕 , 陈季俞 , 孙铭鹤 , 栗佳骅 , 杨爽 , 陈尔强 . 柱状侧链高分子体系的结构、黏弹性及功能应用 . 高分子学报 , 2023 , 54 ( 10 ), 1468 - 1485 .

Rosen B. M. ; Wilson C. J. ; Wilson D. A. ; Peterca M. ; Imam M. R. ; Percec V. Dendron-mediated self-assembly, disassembly, and self-organization of complex systems . Chem. Rev. , 2009 , 109 ( 11 ), 6275 - 6540 . doi: 10.1021/cr900157q http://dx.doi.org/10.1021/cr900157q

Rudick J. G. ; Percec V. Induced helical backbone conformations of self-organizable dendronized polymers . Acc. Chem. Res. , 2008 , 41 ( 12 ), 1641 - 1652 . doi: 10.1021/ar800086w http://dx.doi.org/10.1021/ar800086w

Yang Z. F. ; Li J. H. ; Chen X. ; Fan Y. N. ; Huang J. ; Yu H. F. ; Yang S. ; Chen E. Q. Precisely controllable artificial muscle with continuous morphing based on "breathing" of supramolecular columns . Adv. Mater. , 2023 , 35 ( 14 ), 2211648 . doi: 10.1002/adma.202211648 http://dx.doi.org/10.1002/adma.202211648

Zhao R. Y. ; Zhao T. P. ; Jiang X. Q. ; Liu X. ; Shi D. ; Liu C. Y. ; Yang S. ; Chen E. Q. Thermoplastic high strain multishape memory polymer: side-chain polynorbornene with columnar liquid crystalline phase . Adv. Mater. , 2017 , 29 ( 12 ), 1605908 . doi: 10.1002/adma.201605908 http://dx.doi.org/10.1002/adma.201605908

Donald A. M. ; Windle A. H. ; Hanna S. Liquid Crystalline Polymers, 2 nd ed . Cambridge University Press : Cambridge, U.K. , 2005 . doi: 10.1017/cbo9780511616044.009 http://dx.doi.org/10.1017/cbo9780511616044.009

Cotton J. P. ; Hardouin F. Chain conformation of liquid-crystalline polymers studied by small-angle neutron scattering . Prog. Polym. Sci. , 1997 , 22 ( 4 ), 795 - 828 . doi: 10.1016/s0079-6700(97)00007-5 http://dx.doi.org/10.1016/s0079-6700(97)00007-5

Wang R. ; Wang Z. G. Theory of side-chain liquid crystal polymers: bulk behavior and chain conformation . Macromolecules , 2010 , 43 ( 23 ), 10096 - 10106 . doi: 10.1021/ma101805d http://dx.doi.org/10.1021/ma101805d

Finkelmann, H.; Wendorff, H. J. Structure of Nematic Side Chain Polymers . In Polymeric Liquid Crystals. Blumstein, A., Ed. Plenum Press: New York , 1985 . doi: 10.1007/978-1-4899-2299-1_17 http://dx.doi.org/10.1007/978-1-4899-2299-1_17

Zhou Q. F. ; Li H. M. ; Feng X. D. Synthesis of liquid-crystalline polyacrylates with laterally substituted mesogens . Macromolecules , 1987 , 20 ( 1 ), 233 - 234 . doi: 10.1021/ma00167a042 http://dx.doi.org/10.1021/ma00167a042

Zhou Q. F. ; Zhu X. L. ; Wen Z. Q. Liquid-crystalline side-chain polymers without flexible spacer . Macromolecules , 1989 , 22 ( 1 ), 491 - 493 . doi: 10.1021/ma00191a094 http://dx.doi.org/10.1021/ma00191a094

Chen X. F. ; Shen Z. H. ; Wan X. H. ; Fan X. H. ; Chen E. Q. ; Ma Y. G. ; Zhou Q. F. Mesogen-jacketed liquid crystalline polymers . Chem. Soc. Rev. , 2010 , 39 ( 8 ), 3072 - 3101 . doi: 10.1039/b814540g http://dx.doi.org/10.1039/b814540g

Ye C. ; Zhang H.-L. ; Huang Y. ; Chen E.-Q. ; Lu Y. L. ; Shen D. Y. ; Wan X.-H. ; Shen Z. H. ; Cheng S. Z. D. ; Zhou Q. F. Molecular weight dependence of phase structures and transitions of mesogen-jacketed liquid crystalline polymers based on 2-vinylterephthalic acids . Macromolecules , 2004 , 37 ( 19 ), 7188 - 7196 . doi: 10.1021/ma049195b http://dx.doi.org/10.1021/ma049195b

Yin X. Y. ; Ye C. ; Ma X. ; Chen E. Q. ; Qi X. Y. ; Duan X. F. ; Wan X. H. ; Cheng S. Z. D. ; Zhou Q. F. Manipulating supramolecular self-assembly via tailoring pendant group size of linear vinyl polymers . J. Am. Chem. Soc. , 2003 , 125 ( 23 ), 6854 - 6855 . doi: 10.1021/ja034462z http://dx.doi.org/10.1021/ja034462z

Liu Y. X. ; Zhang D. ; Wan X. H. ; Zhou Q. F. Synthesis of a novel "mesogen-jacketed liquid crystal polymer" based on vinylterephthalic acid . Chinese J. Polym. Sci. , 1998 , 6 ( 13 ), 283 - 288 .

Zhang Y. F. ; Wang Y. C. ; Yu X. S. ; Zhao Y. ; Ren X. K. ; Zhao J. F. ; Wang J. ; Jiang X. Q. ; Chang W. Y. ; Zheng J. F. ; Yu Z. Q. ; Yang S. ; Chen E. Q. Isophthalate-based room temperature phosphorescence: from small molecule to side-chain jacketed liquid crystalline polymer . Macromolecules , 2019 , 52 ( 6 ), 2495 - 2503 . doi: 10.1021/acs.macromol.9b00171 http://dx.doi.org/10.1021/acs.macromol.9b00171

Zheng J. F. ; Yu K. L. ; Jiang X. Q. ; Tang T. ; Sun J. ; Ding L. L. ; Zhang R. ; Zhao Y. ; Ren X. K. ; Xu J. R. ; Zhang Y. F. ; Yu X. S. ; Yang S. ; Chen E. Q. Side-chain jacketed liquid crystalline polymer forming double-chain supramolecular column and hexagonal superlattice . Macromolecules , 2018 , 51 ( 17 ), 6949 - 6957 . doi: 10.1021/acs.macromol.8b00943 http://dx.doi.org/10.1021/acs.macromol.8b00943

Wang S. ; Hu D. P. ; Guan X. Y. ; Cai S. L. ; Shi G. ; Shuai Z. G. ; Zhang J. ; Peng Q. ; Wan X. H. Brightening up circularly polarized luminescence of monosubstituted polyacetylene by conformation control: mechanism, switching, and sensing . Angew. Chem. Int. Ed. , 2021 , 60 ( 40 ), 21918 - 21926 . doi: 10.1002/anie.202108010 http://dx.doi.org/10.1002/anie.202108010

Wunderlich, B. Macromolecular Physics . Academic Press : New York , 1973 ; Vol . I .

Liu X. B. ; Zhao Y. F. ; Chen E. Q. ; Ye C. ; Shen Z. H. ; Fan X. H. ; Cheng S. Z. D. ; Zhou Q. F. Lamella-to-lamella transition and effect of coil-stretching on crystallization in a rod-coil diblock copolymer containing poly(ε-caprolactone) . Macromolecules , 2008 , 41 ( 14 ), 5223 - 5229 . doi: 10.1021/ma800517k http://dx.doi.org/10.1021/ma800517k

刘宣伯 , 许佳儒 , 赵永峰 , 杨爽 , 范星河 , 陈尔强 . 基于甲壳型液晶高分子的刚-柔型二嵌段共聚物的层状相: 链伸展行为的研究 . 高分子学报 , 2017 , 48 ( 10 ), 1668 - 1679 .

Rubinstein M. ; Colby , R. H. Polymer Physics . Oxford University Press: Oxford, 2003 .

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

聚(乙烯基对苯二甲酸二烷基酯)的非寻常相转变