Skip to main content
SpringerLink
Log in

Physio- and chemo-dual crosslinking toward thermoand photo-response of azobenzene-containing liquid crystalline polyester

物理、化学双重交联偶氮液晶聚合物的合成及其光热双重响应性能

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Combining the stability of chemical crosslinking and the processability of physical crosslinking is a well-established strategy to design new materials with desirable stimuli–responsive properties. Herein, a series of azobenzenebased thermotropic liquid crystalline polyesters were synthesized by introducing mesogenic dial named 4,4ʹ-bis(6-hydroxyhexyloxy) azobenzene (BHHAB), 2-phenylsuccinic acid (PSA), and different contents of 1,2,3-propanetricarboxylic acid (PTA) as the chemical crosslinker. All these polyesters showed good thermal stability and smectic liquid crystalline phase. Wide-angel X-ray diffraction (WAXD) and the fluorescence emission spectra confirmed the existence of π–π stacking interactions as the physical crosslinking in the polymer chains, particularly at the lower content of PTA. However, when the PTA content increased, the chemical crosslinking changed the chain conformation, and thus the intensity of physical crosslinking slackened gradually. Combining the physical and chemical crosslinking, these polyesters showed the thermoplastic processability, thermal shape memory, heat-assisted healing and photo responsive behaviors. Taking advantages of these features, these multiple stimuli–responsive polymers can bring more chances for smart materials such as soft actuator.

摘要

结合化学交联提供的稳定性和物理交联提供的可热塑加工性可设计得到具有多种刺激响应行为的新材料. 本文以偶氮苯二氧己醇 (BHHAB) 为液晶基元, 与苯基丁二酸(PSA) 和丙三羧酸(PTA) 本体聚合得到一系列液晶聚合物PBHPS-x%PTA, 其中PTA作为化学交 联, 而取代苯基与介晶基元之间的π–π相互作用可提供物理交联. 热分析结果显示这些聚合物具有高的热稳定性并表现出近晶型液晶行 为. 广角X射线衍射(WAXD) 和荧光光谱证实了分子间具有可作为物理交联点的π–π相互作用; 并且随着PTA含量的增加, 化学交联会逐 渐影响分子链构象, 最终破坏物理交联作用. 轻度的化学交联保留了液晶聚合物的可热塑加工性, 而在物理交联与化学交联的共同作用下, 液晶聚合物具有可逆光致形变, 热致形状记忆及自修复性能, 在智能高分子材料领域表现出一定的应用前景.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Warner M, Terentjev E. Liquid Crystal Elastomers. Oxford: Oxford University Press, 2003

    Google Scholar 

  2. de Jeu WH. Liquid Crystal Elastomers: Materials and Applications. Heidelberg: Springer, 2012, pp. V–VI

    Book  Google Scholar 

  3. Huang WM, Zhao Y, Wang CC, et al. Thermo/chemo-responsive shape memory effect in polymers: a sketch of working mechanisms, fundamentals and optimization. J Polym Res, 2012, 19: 9952

    Article  Google Scholar 

  4. Ohm C, Brehmer M, Zentel R. Liquid crystalline elastomers as actuators and sensors. Adv Mater, 2010, 22: 3366–3387

    Article  Google Scholar 

  5. Degennes PG. One type of nematic polymers. C R Hebd Sean Acad Sci Ser B, 1975, 281: 101–103

    Google Scholar 

  6. Burke KA, Rousseau IA, Mather PT. Reversible actuation in mainchain liquid crystalline elastomers with varying crosslink densities. Polymer, 2014, 55: 5897–5907

    Article  Google Scholar 

  7. García-Márquez AR, Heinrich B, Beyer N, et al. Mesomorphism and shape-memory behavior of main-chain liquid-crystalline coelastomers: modulation by the chemical composition. Macromolecules, 2014, 47: 5198–5210

    Article  Google Scholar 

  8. Ahn S, Deshmukh P, Gopinadhan M, et al. Side-chain liquid crystalline polymer networks: exploiting nanoscale smectic polymorphism to design shape-memory polymers. ACS Nano, 2011, 5: 3085–3095

    Article  Google Scholar 

  9. Ahn S, Kasi RM. Exploiting microphase-separated morphologies of side-chain liquid crystalline polymer networks for triple shape memory properties. Adv Funct Mater, 2011, 21: 4543–4549

    Article  Google Scholar 

  10. Burke KA, Mather PT. Crosslinkable liquid crystalline copolymers with variable isotropization temperature. J Mater Chem, 2012, 22: 14518–14530

    Article  Google Scholar 

  11. Wen Z, Zhang T, Hui Y, et al. Elaborate fabrication of well-defined side-chain liquid crystalline polyurethane networks with tripleshape memory capacity. J Mater Chem A, 2015, 3: 13435–13444

    Article  Google Scholar 

  12. Finkelmann H, Nishikawa E, Pereira GG, et al. A new opto-mechanical effect in solids. Phys Rev Lett, 2001, 87: 015501

    Article  Google Scholar 

  13. Yu Y, Nakano M, Ikeda T. Directed bending of a polymer film by light. Nature, 2003, 425: 145–145

    Article  Google Scholar 

  14. van Oosten CL, Bastiaansen CWM, Broer DJ. Printed artificial cilia from liquid-crystal network actuators modularly driven by light. Nat Mater, 2009, 8: 677–682

    Article  Google Scholar 

  15. Cheng F, Yin R, Zhang Y, et al. Fully plastic microrobots which manipulate objects using only visible light. Soft Matter, 2010, 6: 3447–3449

    Article  Google Scholar 

  16. Lee KM, Smith ML, Koerner H, et al. Photodriven, flexural-torsional oscillation of glassy azobenzene liquid crystal polymer networks. Adv Funct Mater, 2011, 21: 2913–2918

    Article  Google Scholar 

  17. Ware TH, McConney ME, Wie JJ, et al. Voxelated liquid crystal elastomers. Science, 2015, 347: 982–984

    Article  Google Scholar 

  18. Sun L, Huang WM, Ding Z, et al. Stimulus-responsive shape memory materials: A review. Mater Des, 2012, 33: 577–640

    Article  Google Scholar 

  19. Liu C, Qin H, Mather PT. Review of progress in shape-memory polymers. J Mater Chem, 2007, 17: 1543–1558

    Article  Google Scholar 

  20. Zhao Q, Qi HJ, Xie T. Recent progress in shape memory polymer: New behavior, enabling materials, and mechanistic understanding. Prog Polymer Sci, 2015, 49-50: 79–120

    Article  Google Scholar 

  21. Salvekar AV, Zhou Y, Huang WM, et al. Shape/temperature memory phenomena in un-crosslinked poly—caprolactone (PCL). Eur Polymer J, 2015, 72: 282–295

    Article  Google Scholar 

  22. Küpfer J, Finkelmann H. Macromol Chem Rapid Commun, 1991, 12: 717–726

    Article  Google Scholar 

  23. Broer DJ, Boven J, Mol GN, et al. In stiu photopolymerization of oriented liquid-crystalline acrylates 3. Oriented polymer networks from a mesogenic diacrylate. Macromol Chem Phys, 1989, 190: 2255–2268

    Google Scholar 

  24. Pei Z, Yang Y, Chen Q, et al. Mouldable liquid-crystalline elastomer actuators with exchangeable covalent bonds. Nat Mater, 2014, 13: 36–41

    Article  Google Scholar 

  25. Li Y, Rios O, Keum JK, et al. Photoresponsive liquid crystalline epoxy networks with shape memory behavior and dynamic ester bonds. ACS Appl Mater Interfaces, 2016, 8: 15750–15757

    Article  Google Scholar 

  26. Michal BT, McKenzie BM, Felder SE, et al. Metallo-, thermo-, and photoresponsive shape memory and actuating liquid crystalline elastomers. Macromolecules, 2015, 48: 3239–3246

    Article  Google Scholar 

  27. Qin C, Feng Y, Luo W, et al. A supramolecular assembly of crosslinked azobenzene/polymers for a high-performance light-driven actuator. J Mater Chem A, 2015, 3: 16453–16460

    Article  Google Scholar 

  28. Lv JA, Liu Y, Wei J, et al. Photocontrol of fluid slugs in liquid crystal polymer microactuators. Nature, 2016, 537: 179–184

    Article  Google Scholar 

  29. Lv J, Wang W, Wu W, et al. A reactive azobenzene liquid-crystalline block copolymer as a promising material for practical application of light-driven soft actuators. J Mater Chem C, 2015, 3: 6621–6626

    Article  Google Scholar 

  30. Mamiya J, Yoshitake A, Kondo M, et al. Is chemical crosslinking necessary for the photoinduced bending of polymer films? J Mater Chem, 2008, 18: 63–65

    Article  Google Scholar 

  31. Fang L, Zhang H, Li Z, et al. Synthesis of reactive azobenzene main-chain liquid crystalline polymers via michael addition polymerization and photomechanical effects of their supramolecular hydrogen-bonded fibers. Macromolecules, 2013, 46: 7650–7660

    Article  Google Scholar 

  32. Zhao R, Zhao T, Jiang X, et al. Thermoplastic high strain multi-shape memory polymer: side-chain polynorbornene with columnar liquid crystalline phase. Adv Mater, 2017, 29: 1605908

    Article  Google Scholar 

  33. Yang R, Chen L, Ruan C, et al. Chain folding in main-chain liquid crystalline polyesters: from p–p stacking toward shape memory. J Mater Chem C, 2014, 2: 6155–6164

    Article  Google Scholar 

  34. Meng ZY, Chen L, Zhong HY, et al. The effect of carbon nanotube plus graphene on the shape memory behavior and tensile properties of a liquid crystalline polyester. Acta Polym Sin, 2016, 12: 1758–1762

    Google Scholar 

  35. Meng ZY, Chen L, Zhong HY, et al. Effect of different dimensional carbon nanoparticles on the shape memory behavior of thermotropic liquid crystalline polymer. Composites Sci Tech, 2017, 138: 8–14

    Article  Google Scholar 

  36. Zhong HY, Chen L, Yang R, et al. Azobenzene-containing liquid crystalline polyester with p–p interactions: diverse thermo-and photo-responsive behaviours. J Mater Chem C, 2017, 5: 3306–3314

    Article  Google Scholar 

  37. Zhong HY, Chen L, Liu XF, et al. Novel liquid crystalline copolyester containing amphi-mesogenic units toward multiple stimuliresponse behaviors. J Mater Chem C, 2017, 5: 9702–9711

    Article  Google Scholar 

  38. Yang R, Ding L, Chen W, et al. Chain folding in main-chain liquid crystalline polyester with strong p–p interaction: An efficient ß-nucleating agent for isotactic polypropylene. Macromolecules, 2017, 50: 1610–1617

    Article  Google Scholar 

  39. Montarnal D, Tournilhac F, Hidalgo M, et al. Epoxy-based networks combining chemical and supramolecular hydrogen-bonding crosslinks. J Polym Sci A Polym Chem, 2010, 48: 1133–1141

    Article  Google Scholar 

  40. Pan Y, Liu T, Li J, et al. High modulus ratio shape-memory polymers achieved by combining hydrogen bonding with controlled crosslinking. J Polym Sci B Polym Phys, 2011, 49: 1241–1245

    Article  Google Scholar 

  41. Chakraborty S, Rajput L, Desiraju GR. Designing ternary cocrystals with stacking interactions and weak hydrogen bonds. 4,4’-bis-hydroxyazobenzene. Cryst Growth Des, 2014, 14: 2571–2577

    Article  Google Scholar 

  42. Wool RP, O'Connor KM. A theory crack healing in polymers. J Appl Phys, 1981, 52: 5953–5963

    Article  Google Scholar 

  43. Ahn J, Park S, Lee JH, et al. Fluorescent hydrogels formed by CH–p and p–p interactions as the main driving forces: an approach toward understanding the relationship between fluorescence and structure. Chem Commun, 2013, 49: 2109–2111

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (51721091) and the Sichuan Province Youth Science and Technology Innovation Team (2017TD0006). The authors would also like to thank the Analysis and Testing Center of Sichuan University for the NMR measurement.

Author information

Authors and Affiliations

  1. Center for Degradable and Flame–Retardant Polymeric Materials, College of Chemistry, State Key Laboratory of Polymer Materials Engineering, National Engineering Laboratory of Eco–Friendly Polymeric Materials (Sichuan), Sichuan University, Chengdu, 610064, China

    Hai-Yi Zhong  (钟海艺), Li Chen  (陈力), Xiao-Min Ding  (丁晓敏) & Yu-Zhong Wang  (王玉忠)

  2. College of Pharmacy, Guangxi University of Chinese Medicine, Nanning, 530299, China

    Hai-Yi Zhong  (钟海艺)

  3. School of Materials Science and Engineering, Changzhou University, Changzhou, 213000, China

    Rong Yang  (杨荣)

Authors
  1. Hai-Yi Zhong  (钟海艺)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Li Chen  (陈力)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiao-Min Ding  (丁晓敏)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Rong Yang  (杨荣)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yu-Zhong Wang  (王玉忠)
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Li Chen  (陈力) or Yu-Zhong Wang  (王玉忠).

Additional information

Hi-Yi Zhong earned his PhD degree in Polymer Chemistry and Physics (2017) and BSc degree in Chemistry (2012) from Sichuan University under the supervision of Prof. Yu-Zhong Wang. His research interest is the stimuli responsive liquid crystalline polymers. He is currently a lecturer in the College of Pharmacy, Guangxi University of Chinese Medicine.

Li Chen is currently a full professor in the College of Chemistry, Sichuan University. He earned his PhD degree in Polymer Chemistry and Physics (2009) and MSc degree in Materials Science (2006) from Sichuan University, and BSc degree in Chemistry (2003) from Hunan University. In 2009, he joined Professor Yu-Zhong Wang’s group and his current research interests are focused on the synthesis, structure and properties of functional liquid crystalline polymers and flame-retardant materials.

Yu-Zhong Wang earned his PhD degree from Sichuan University in 1994, where he was promoted to a full Professor in 1995. He is the Director of the National Engineering Laboratory for Eco-Friendly Polymeric Materials (Sichuan). His research interests are focused on fire-retardant and functional polymeric materials, bio-based and biodegradable polymers. He has authored more than 460 publications in SCI journals and issued over 110 patents. He has been awarded eleven National and Provincial Science & Technology awards. In 2015, he was selected as an Academician of Chinese Academy of Engineering.

Electronic supplementary material

40843_2018_9247_MOESM0_ESM.pdf

Physio- and chemo-dual crosslinking toward thermoand photo-response of azobenzene-containing liquid crystalline polyester

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhong, HY., Chen, L., Ding, XM. et al. Physio- and chemo-dual crosslinking toward thermoand photo-response of azobenzene-containing liquid crystalline polyester. Sci. China Mater. 61, 1225–1236 (2018). https://doi.org/10.1007/s40843-018-9247-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-018-9247-6

Keywords

Search

Navigation