Citation: Rui-ying Zhao, Xu-qiang Jiang, Jun-feng Zheng, Xiao-qing Liu, Yan-shuang Xu, Shuang Yang, Er-qiang Chen. Columnar Phase of Side-chain Liquid Crystalline Polymers Based on “Multi-chain Column”[J]. Acta Polymerica Sinica, ;2018, 0(8): 973-986. doi: 10.11777/j.issn1000-3304.2018.18065 shu

Columnar Phase of Side-chain Liquid Crystalline Polymers Based on “Multi-chain Column”

1.
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, Center for Soft Mater Science and Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871
2.
Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871
3.
College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037

Corresponding author: Er-qiang Chen, eqchen@pku.edu.cn
Received Date: 23 February 2018
Revised Date: 26 March 2018

Side-chain liquid crystalline polymer (SCLCP) can form columnar liquid crystalline (LC) phases, in addition to the conventional nematic and smectic phase. For the SCLCP containing the discotic mesogenic group attached to the main-chain through a flexible spacer, the columnar phase relies on the assembly of the discotic mesogens. On the other hand, the SCLCP with extended conformation, such as mesogen-jacketed LC polymers and dendronized polymers, can exhibit the columnar phase based on the parallel packing of the cylindrical chains. In this case, " single chain column” is considered to be the building block of the columnar phase in general. Recently, our work on hemiphasmid SCLCP demonstrates that the " multi-chain column” is also important for the columnar phases of SCLCP. Hemiphasmid SCLCP possesses the hemiphasmid side-chain composed of a rod-like mesogen linked with a half-disk end group. It can readily self-organize into columnar phases with a pretty lager lattice parameter (e.g., 5 – 10 nm). It is found that the number of repeating units (Z_rep) packed in a column stratum with a thickness of ~ 0.4 nm is surprisingly large. As an example, for the hexagonal columnar phase with the a parameter of ~ 6 nm, the value of Z_rep is ~ 10. Squeezing a chain segment with 10 repeating units into the 0.4 nm-thick column stratum is physically unreasonable. The " unusual Z_rep” indicates the existence of " multi-chain column” that consists of a bundle of chains (e.g., 4 – 5 chains) laterally associated together. We synthesized a series of hemiphasmid SCLCPs with different chemical structures. Various main-chains have been employed, including polystyrene, poly(methacrylate), polyacetylene, and polynorbornene. The hemiphasmid moieties can invoke different rod-like mesogens, and can be attached to the main-chain directly or via a flexible spacer. For all the samples obtained, we have verified that the " multi-chain column” is applicable. The formation of " multi-chain column” can be understood from the nano-segregation among the main-chain, the rod-like mesogen and the flexible tails. Theoretical analysis indicates that the " multi-chain column” is a structure of thermodynamic equilibrium. The number of chains in the column is dependent on the volume fraction of the rigid component of the SCLCP. We propose that the chains in the column can interlock and intertwine, resulting in the intra-column entanglement. This hypothesis is supported by the study of hemiphasmid side-chain polynorbornene, which illustrates that the intra-column entanglement can endow the polymer with properties of thermoplastic elastomer. Moreover, the polymer can further exhibit excellent multi-shape memory effect at high strain. We anticipate that the further study of the " multi-chain column”, which has been overlooked for years, will deepen our understanding of some fundamental issues of the structure and dynamics of polymers, and will also help to explore the new properties and applications of SCLCPs.
- Side-chain liquid crystalline polymer,
- Hemiphasmid mesogen,
- Multi-chain column,
- Intra-column entanglement,
- Shape memory
1. [1]
2. [2]
  Donald A, Windle A, Hanna S. Liquid Crystalline Polymers, Cambridge: Cambridge University Press, 2006. 1-356
3. [3]
  Thünemann A F, Kubowicz S, Burger C, Watson M D, Tchebotareva N, Müllen K. J Am Chem Soc, 2003, 125: 352–356
4. [4]
  Laschat S, Baro A, Steinke N, Giesselmann F, Hägele C, Scalia G, Judele R, Kapatsina E, Sauer S, Schreivogel A, Tosoni M. Angew Chem Int Ed, 2007, 46: 4832–4887
5. [5]
  Mu B, Wu B, Pan S, Fang J, Chen D. Macromolecules, 2015, 48: 2388–2398
6. [6]
7. [7]
  Finkelmann H, Ringsdorf H, Wendorff J H. Makromol Chem, 1978, 179: 273–276
8. [8]
  Finkelmann H, Ringsdorf H, Siol W, Wendorff J H. Makromol Chem, 1978, 179: 829–832
9. [9]
  Finkelmann H, Happ M, Portugal M, Ringsdorf H. Makromol Chem, 1978, 179: 2541–2544
10. [10]
  Davidson P. Prog Polym Sci, 1996,21: 893–950
11. [11]
  Ungar G. Polymer, 1993, 34: 2050–2059
12. [12]
  Zhou Q F, Li H M, Feng X D. Macromolecules, 1987, 20: 233–234
13. [13]
14. [14]
  Chen X F, Shen Z H, Wan X H, Fan X H, Chen E Q, Ma Y G, Zhou Q F. Chem Soc Rev, 2010, 39: 3072–3101
15. [15]
16. [16]
  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. J Am Chem Soc, 2003, 125: 6854–6855
17. [17]
  Ye C, Zhang H, Huang Y, Chen E Q, Lu Y, Shen D, Wan X H, Shen Z H, Cheng S Z D, Zhou Q F. Macromolecules, 2004, 37: 7188–7196
18. [18]
  Tu H L, Wan X H, Liu Y X, Chen X F, Zhang D, Zhou Q F, Shen Z H, Ge J J, Jin S, Cheng S Z D. Macromolecules, 2000, 33: 6315–6320
19. [19]
20. [20]
  Rudick J G, Percec V. Acc Chem Res, 2008, 41: 1641–1652
21. [21]
  Percec V, Ahn C H, Cho W D, Jamieson A M, Kim J, Leman T, Schmidt M, Gerle M, Möller M, Prokhorova S A, Sheiko S S, Cheng S Z D, Zhang A, Ungar G, Yeardley D J P. J Am Chem Soc, 1998, 120: 8619–8631
22. [22]
  Percec V, Imam M R, Peterca M, Leowanawat P. J Am Chem Soc, 2012, 134: 4408–4420
23. [23]
  Rosen B M, Wilson D A, Wilson C J, Peterca M, Won B C, Huang C, Lipski L R, Zeng X, Ungar G, Heiney P A, Percec V. J Am Chem Soc, 2009, 131: 17500–17521
24. [24]
  Zheng J F, Liu X, Chen X F, Ren X K, Yang S, Chen E Q. ACS Macro Lett, 2012, 1: 641–645
25. [25]
  Liu X Q, Wang J, Yang S, Chen E Q. ACS Macro Lett, 2014, 3: 834–838
26. [26]
  Xu Y S, Shi D, Gu J, Lei Z, Xie H L, Zhao T P, Yang S, Chen E Q. Polym Chem, 2016, 7: 462–473
27. [27]
  Zhao R Y, Zhao T P, Jiang X Q, Liu X, Shi D, Liu C Y, Yang S, Chen E Q. Adv Mater, 2017, 29: 1605908
28. [28]
  Nguyen H T, Destrade C, Malthécte J. Adv Mater, 1997, 9: 375–388
29. [29]
  Levelut A M, Malthěte J, Destrade C, Tinh N H. Liq Cryst, 1987, 2: 877–888
30. [30]
  Gharbia M, Gharbi A, Nguyen H T, Malthête J. Curr Opin Colloid Interface Sci, 2002, 7: 312–325
31. [31]
  Hoag B P, Gin D L. Adv Mater, 1998, 10: 1546–1551
32. [32]
  Rosen B M, Wilson C J, Wilson D A, Peterca M, Imam M R, Percec V. Chem Rev, 2009, 109: 6275–6540
33. [33]
  Lin C, Ringsdorf H, Ebert M, Kleppinger R, Wendorff J H. Liq Cryst, 1989, 5: 1841–1847
34. [34]
  Percec V, Heck J. Polym Bull, 1990, 24: 255–262
35. [35]
  Percec V, Heck J. Polym Bull, 1991, 25: 55–62
36. [36]
  Percec V, Heck J. J Polym Sci, Part A: Polym Chem, 1991, 29: 591–597
37. [37]
  Percec V, Heck J. Polym Bull, 1991, 25: 431–438
38. [38]
  Percec V, Heck J, Ungar G. Macromolecules, 1991, 24: 4957–4962
39. [39]
  Percec V, Ahn C H, Ungar G, Yeardley D J P, Moller M, Sheiko S S. Nature, 1998, 391:161–164
40. [40]
  Wunderlich B. Macromolecular Physics, Vol. 1: Crystal Structure, Morphology, Defects. Academic Press, 1973. 62–85
41. [41]
  Watanabe J, Ono H, Uematsu I, Abe A. Macromolecules, 1985, 18: 2141–2148
42. [42]
  Yamagishi T, Fukuda T, Miyamoto T, Takashina Y, Yakoh Y, Watanabe J. Liq Cryst, 1991, 10: 467–473
43. [43]
  Stepanyan R, Subbotin A, Knaapila M, Ikkala O, Ten Brinke G. Macromolecules, 2003, 36: 3758–3763
44. [44]
  Fredrickson G H. Macromolecules, 1993, 26: 4351–4355
45. [45]
  Semenov A N, Sov Phys JETP, 1985, 61: 733–742
46. [46]
  Percec V, Aqad E, Peterca M, Rudick J G, Lemon L, Ronda J C, de B B, Heiney P A, Meijer E W. J Am Chem Soc, 2006, 128: 16365–16372
47. [47]
  Wang Y R, Li X J, Pan Y, Zheng Z H, Ding X B, Peng Y X. RSC Adv, 2014, 4: 17156–17160
48. [48]
  Zhang Y M, Wang Q H, Wang C, Wang T M. J Mater Chem, 2011, 21: 9073–9078
49. [49]
  Zheng N, Fang G Q, Cao Z L, Zhao Q, Xie T. Polym Chem, 2015, 6: 3046–3053
50. [50]
  Voit W, Ware T, Dasari R R, Smith P, Danz L, Simon D, Barlow S, Marder S R, Gall K. Adv Funct Mater, 2010, 20: 162–171
51. [51]
  Xie T, Xiao X C, Cheng Y T. Macromol Rapid Commun, 2009, 30: 1823–1827
52. [52]
  Barkley D A, Rokhlenko Y, Marine J E, David R, Sahoo D, Watson M D, Koga T, Osuji C O, Rudick J G. J Am Chem Soc, 2017, 139: 15977–15983
53. [53]
  Andreopoulou K A, Peterca M, Wilson D A, Partridge B E, Heiney P A, Percec V. Macromolecules, 2017, 50: 5271–5284
1. [1]
  Gengjia Chen , Junjie Ou . Application of the van Deemter Equation in Instrumental Analysis Teaching: A Case of Organic Polymer Monolithic Columns. University Chemistry, 2025, 40(11): 362-368. doi: 10.12461/PKU.DXHX202502003
2. [2]
  Yuxia Luo , Xiaoyu Xie , Fangfang Chen . 药物递送魔法师——分子印迹聚合物. University Chemistry, 2025, 40(8): 202-210. doi: 10.12461/PKU.DXHX202409129
3. [3]
  Yaping ZHANG , Tongchen WU , Yun ZHENG , Bizhou LIN . Z-scheme heterojunction β-Bi₂O₃ pillared CoAl layered double hydroxide nanohybrid: Fabrication and photocatalytic degradation property. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 531-539. doi: 10.11862/CJIC.20240256
4. [4]
  Fanpeng Meng , Fei Zhao , Jingkai Lin , Jinsheng Zhao , Huayang Zhang , Shaobin Wang . Optimizing interfacial electric fields in carbon nitride nanosheet/spherical conjugated polymer S-scheme heterojunction for hydrogen evolution. Acta Physico-Chimica Sinica, 2025, 41(8): 100095-0. doi: 10.1016/j.actphy.2025.100095
5. [5]
  Xingchao Zhao , Xiaoming Li , Ming Liu , Zijin Zhao , Kaixuan Yang , Pengtian Liu , Haolan Zhang , Jintai Li , Xiaoling Ma , Qi Yao , Yanming Sun , Fujun Zhang . Photomultiplication-Type All-Polymer Photodetectors and Their Applications in Photoplethysmography Sensor. Acta Physico-Chimica Sinica, 2025, 41(1): 100007-0. doi: 10.3866/PKU.WHXB202311021
6. [6]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
7. [7]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . Efficient Photocatalytic Production of H₂O₂ over ZnO/D-A Conjugated Polymer S-scheme Heterojunction and Charge Transfer Dynamics Investigation. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-0. doi: 10.3866/PKU.WHXB202406027
8. [8]
  Yue Zhang , Bao Li , Lixin Wu . GO-Assisted Supramolecular Framework Membrane for High-Performance Separation of Nanosized Oil-in-Water Emulsions. Acta Physico-Chimica Sinica, 2024, 40(5): 2305038-0. doi: 10.3866/PKU.WHXB202305038
9. [9]
  Qianping Li , Hua Guan , Changfeng Wan , Yonghai Song , Jianwen Jiang . 大学有机化学复习课项目式教学——以“液晶化合物4-正戊基苯甲酸-4′-正戊基苯酯的合成路线设计与产品制备”为例. University Chemistry, 2025, 40(8): 100-116. doi: 10.12461/PKU.DXHX202410070
10. [10]
  Yukai Jiang , Yihan Wang , Yunkai Zhang , Yunping Wei , Ying Ma , Na Du . Characterization and Phase Diagram of Surfactant Lyotropic Liquid Crystal. University Chemistry, 2024, 39(4): 114-118. doi: 10.3866/PKU.DXHX202309033
11. [11]
  Xiaojun Liu , Lang Qin , Yanlei Yu . Dynamic Manipulation of Photonic Bandgaps in Cholesteric Liquid Crystal Microdroplets for Applications. Acta Physico-Chimica Sinica, 2024, 40(5): 2305018-0. doi: 10.3866/PKU.WHXB202305018
12. [12]
  Wendian XIE , Yuehua LONG , Jianyang XIE , Liqun XING , Shixiong SHE , Yan YANG , Zhihao HUANG . Preparation and ion separation performance of oligoether chains enriched covalent organic framework membrane. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1528-1536. doi: 10.11862/CJIC.20240050
13. [13]
  Zhongxin YU , Wei SONG , Yang LIU , Yuxue DING , Fanhao MENG , Shuju WANG , Lixin YOU . Fluorescence sensing on chlortetracycline of a Zn-coordination polymer based on mixed ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2415-2421. doi: 10.11862/CJIC.20240304
14. [14]
  Bao Jia , Yunzhe Ke , Shiyue Sun , Dongxue Yu , Ying Liu , Shuaishuai Ding . Innovative Experimental Teaching for the Preparation and Modification of Conductive Organic Polymer Thin Films in Undergraduate Courses. University Chemistry, 2024, 39(10): 271-282. doi: 10.12461/PKU.DXHX202404121
15. [15]
  Xiao SANG , Qi LIU , Jianping LANG . Synthesis, structure, and fluorescence properties of Zn(Ⅱ) coordination polymers containing tetra-alkenylpyridine ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2124-2132. doi: 10.11862/CJIC.20240158
16. [16]
  Xuefei Leng , Yanshai Wang , Hai Wang , Shengyang Tao . The In-Depth integration of “Industry-University-Research” in the Exploration and Practice of “Comprehensive Training in Polymer Engineering”. University Chemistry, 2025, 40(4): 66-71. doi: 10.12461/PKU.DXHX202405105
17. [17]
  Ruiying WANG , Hui WANG , Fenglan CHAI , Zhinan ZUO , Benlai WU . Three-dimensional homochiral Eu(Ⅲ) coordination polymer and its amino acid configuration recognition. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 877-884. doi: 10.11862/CJIC.20250052
18. [18]
  Ke Qiu , Fengmei Wang , Mochou Liao , Kerun Zhu , Jiawei Chen , Wei Zhang , Yongyao Xia , Xiaoli Dong , Fei Wang . A Fumed SiO₂-based Composite Hydrogel Polymer Electrolyte for Near-Neutral Zinc-Air Batteries. Acta Physico-Chimica Sinica, 2024, 40(3): 2304036-0. doi: 10.3866/PKU.WHXB202304036
19. [19]
  Minghui Wu , Markus Mühlinghaus , Xuechao Li , Chaojie Xu , Qiang Chen , Haiming Zhang , Klaus Müllen , Lifeng Chi . On-Surface Synthesis of Chevron-Shaped Conjugated Ladder Polymers Consisting of Benzo[a]azulene Units. Acta Physico-Chimica Sinica, 2024, 40(8): 2307024-0. doi: 10.3866/PKU.WHXB202307024
20. [20]
  Chunyuan Kang , Xiaoyu Li , Fan Yang , Bai Yang . Ionic-bond crosslinked carbonized polymer dots for tunable and enhanced room temperature phosphorescence. Acta Physico-Chimica Sinica, 2026, 42(1): 100156-0. doi: 10.1016/j.actphy.2025.100156

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(336)
HTML views(15)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142