Citation: Ting Xu, Kexiang Chen, Zhiyuan He, Chuanzhen Zhang, Xiaoyu Li, Ziyan Zhang, Wenbo Fan, Zhishen Ge, Chenhui Cui, Yanfeng Zhang. 4D printing of reprocessable thiocyanate covalent adaptable networks with reconfigurable shape memory ability[J]. Chinese Chemical Letters, ;2026, 37(2): 111959. doi: 10.1016/j.cclet.2025.111959 shu

4D printing of reprocessable thiocyanate covalent adaptable networks with reconfigurable shape memory ability

School of Chemistry, State Key Laboratory of Fluorine & Nitrogen Chemicals, Institute of New Concept Sensors and Molecular Materials (INCSMM), Engineering Research Center of Energy Storage Materials and Devices, Ministry of Education, Xi’an Key Laboratory of Sustainable Polymer Materials, Xi’an Jiaotong University, Xi’an 710049, China

cuichenhui@xjtu.edu.cn

yanfengzhang@mail.xjtu.edu.cn

Received Date: 13 June 2025
Revised Date: 6 October 2025
Accepted Date: 13 October 2025
Available Online: 15 October 2025

Figures(5)

Shape memory polymers used in 4D printing only had one permanent shape after molding, which limited their applications in requiring multiple reconstructions and multifunctional shapes. Furthermore, the inherent stability of the triazine ring structure within cyanate ester (CE) crosslinked networks after molding posed significant challenges for both recycling, repairing, and degradation of resin. To address these obstacles, dynamic thiocyanate ester (TCE) bonds and photocurable group were incorporated into CE, obtaining the recyclable and 3D printable CE covalent adaptable networks (CANs), denoted as PTCE1.5. This material exhibits a Young’s modulus of 810 MPa and a tensile strength of 50.8 MPa. Notably, damaged printed PTCE1.5 objects can be readily repaired through reprinting and interface rejoining by thermal treatment. Leveraging the solid-state plasticity, PTCE1.5 also demonstrated attractive shape memory ability and permanent shape reconfigurability, enabling its reconfigurable 4D printing. The printed PTCE1.5 hinges and a main body were assembled into a deployable and retractable satellite model, validating its potential application as a controllable component in the aerospace field. Moreover, printed PTCE1.5 can be fully degraded into thiol-modified intermediate products. Overall, this material not only enriches the application range of CE resin, but also provides a reliable approach to addressing environmental issue.
- 4D Printing,
- Dynamic thiocyanate ester bonds,
- Covalent adaptable networks,
- Cyanate ester resin,
- Shape memory
1. [1]
  J. Yang, Y.X. Cheng, X. Gong, et al., Chin. Chem. Lett. 33 (2022) 2231–2242. doi: 10.1016/j.cclet.2021.08.105
2. [2]
  A.K. Zhang, F. Wang, L. Chen, et al., Chin. Chem. Lett. 32 (2021) 2923–2932. doi: 10.1016/j.cclet.2021.03.073
3. [3]
  M.N. He, Y. Zhao, Y.Q. Liu, D.C. Wei, Chin. Chem. Lett. 31 (2020) 826–830. doi: 10.1016/j.cclet.2019.06.003
4. [4]
  J. Zhang, M.K. Xu, N. Zhang, et al., Small 20 (2024) 2406358.
5. [5]
  Y.Y. Li, J.Q. You, H.X. Lv, et al., Chem. Eng. J. 489 (2024) 151205. doi: 10.1016/j.cej.2024.151205
6. [6]
  D. Grinberg, S. Siddique, M.Q. Le, et al., J. Polym. Sci. B 57 (2019) 109–115. doi: 10.1002/polb.24763
7. [7]
  Y.L. Hu, Z.Y. Wang, D.D. Jin, et al., Adv. Funct. Mater. 30 (2020) 1907377. doi: 10.1002/adfm.201907377
8. [8]
  I. Choi, S. Jang, S. Jung, et al., Mater. Horizons 10 (2023) 3668–3679. doi: 10.1039/d3mh00521f
9. [9]
  C.Y. Deng, J.T. Qu, J.H. Dong, et al., Chem. Eng. J. 494 (2024) 152992. doi: 10.1016/j.cej.2024.152992
10. [10]
  R. El-Dabaa, I. Salem, Open House Int. 46 (2021) 376–390. doi: 10.1108/ohi-02-2021-0028
11. [11]
  Y. Wang, H.X. Xuan, L.Z. Zhang, et al., Adv. Mater. 36 (2024) 2313761. doi: 10.1002/adma.202313761
12. [12]
  M.C. Biswas, S. Chakraborty, A. Bhattacharjee, Z. Mohammed, Adv. Funct. Mater. 31 (2021) 2100257. doi: 10.1002/adfm.202100257
13. [13]
  Y.K. Zhang, L.Y. Xu, L. Zhao, et al., J. Mater. Sci. Technol. 167 (2023) 14–26. doi: 10.1117/12.2673406
14. [14]
  R. Wang, C. Yuan, J.X. Cheng, et al., Nat. Commun. 15 (2024) 758.
15. [15]
  X.X. Chen, R.Y. Wang, C.H. Cui, et al., Chem. Eng. J. 428 (2022) 131212. doi: 10.1016/j.cej.2021.131212
16. [16]
  X.X. Chen, Q.Y. Zhong, S.J. Wang, et al., Acta Polym. Sin. 5 (2019) 469–484.
17. [17]
  C.H. Cui, X.J. Zhao, X.Y. Wang, et al., Polym. Chem. 16 (2025) 1595–1602. doi: 10.1039/d4py01280a
18. [18]
  K.X. Chen, C.H. Cui, Z. Li, et al., ACS Macro Lett. 12 (2023) 543–548. doi: 10.1021/acsmacrolett.3c00165
19. [19]
  H.X. Lei, S.N. Wang, D.J. Liaw, et al., ACS Macro Lett. 8 (2019) 582–587. doi: 10.1021/acsmacrolett.9b00199
20. [20]
  W.Q. Ye, W.X. Fu, X.P. Liu, C. Yang, Z. Xu, Chin. Chem. Lett. 35 (2024) 108494.
21. [21]
  S.W. Feng, X.L. Peng, J.J. Cui, et al., Adv. Funct. Mater. 34 (2024) 2401431. doi: 10.1002/adfm.202401431
22. [22]
  H.G. Li, B. Zhang, H.T. Ye, et al., Sci. Adv. 10 (2024) eadl4387. doi: 10.1126/sciadv.adl4387
23. [23]
  F.Z. Wang, W.T. Gao, C.H. Li, Chin. Chem. Lett. 35 (2024) 109305. doi: 10.1016/j.cclet.2023.109305
24. [24]
  A. Inamdar, J. Cherukattu, A. Anand, B. Kandasubramanian, Ind. Eng. Chem. Res. 57 (2018) 4479–4504. doi: 10.1021/acs.iecr.7b05202
25. [25]
  C.F. Wang, Y.S. Tang, Y.X. Zhou, et al., Polym. Chem. 12 (2021) 3753–3761. doi: 10.1039/d1py00597a
26. [26]
  Z.L. Cao, X.R. Xu, F.Y. Sun, et al., Adv. Funct. Mater. 35 (2025) 2505979. doi: 10.1002/adfm.202505979
27. [27]
  Z.P. Lei, H.X. Chen, C.Q. Luo, et al., Nat. Chem. 14 (2022) 1399–1404. doi: 10.1038/s41557-022-01046-4
28. [28]
  Z.P. Lei, L.J. Wayment, J.R. Cahn, et al., J. Am. Chem. Soc. 144 (2022) 17737–17742. doi: 10.1021/jacs.2c00778
29. [29]
  Y.A. Zhao, Z.Q.S. Cai, X.W. Qiu, et al., J. Mater. Sci. 59 (2024) 9350–9360. doi: 10.1007/s10853-024-09789-w
30. [30]
  S. Chandrasekaran, E.B. Duoss, M.A. Worsley, J.P. Lewicki, J. Mater. Chem. A 6 (2018) 853–858. doi: 10.1039/c7ta09466c
31. [31]
  Z.X. Zhou, Y.W. Li, J. Zhong, et al., ACS Appl. Mater. Interfaces 12 (2020) 38682–38689. doi: 10.1021/acsami.0c10909
32. [32]
  C.H. Cui, L. An, Z.L. Zhang, et al., Adv. Funct. Mater. 32 (2022) 2203720. doi: 10.1002/adfm.202203720
33. [33]
  C.H. Cui, X.X. Chen, L. Ma, et al., ACS Appl. Mater. Interfaces 12 (2020) 47975–47983. doi: 10.1021/acsami.0c14189
34. [34]
  Q.J. Ma, L. Li, Y.F. Zhang, Y.P. Geng, J. Li, J. Funct. Polym. 37 (2024) 66–81.
35. [35]
  L. Pauling, Proc. Natl. Acad. Sci. U. S. A. 14 (1928) 359–362. doi: 10.1073/pnas.14.4.359
36. [36]
  L. Wu, Y.L. Song, Mater. Horiz. 12 (2025) 401–417. doi: 10.1039/d4mh01160k
37. [37]
  B. Zhang, H.G. Li, J.X. Cheng, et al., Adv. Mater. 33 (2021) 2101298. doi: 10.1002/adma.202101298
1. [1]
  Fangzhou Wang , Wentong Gao , Chenghui Li . A weak but inert hindered urethane bond for high-performance dynamic polyurethane polymers. Chinese Chemical Letters, 2024, 35(5): 109305-. doi: 10.1016/j.cclet.2023.109305
2. [2]
  Wenlei Yang , Lingyao Wang , Yuanbin Zhang . A shape-memory hydrogen-bonded organic framework for flue gas desulfurization. Chinese Journal of Structural Chemistry, 2025, 44(6): 100574-100574. doi: 10.1016/j.cjsc.2025.100574
3. [3]
  Chengyuan Yu , Huiyao Lin , Le Li , Ruirui Gu , Qi Zhang , Chenyu Shi , Chenchen Zhang , Fei Tong . Ion-cluster-optimized microphase separation in shape-memory polydisulfides for enhanced mechanical performance. Chinese Chemical Letters, 2026, 37(2): 111946-. doi: 10.1016/j.cclet.2025.111946
4. [4]
  Chong Liu , Ling Li , Jiahui Gao , Yanwei Li , Nazhen Zhang , Jing Zang , Cong Liu , Zhaopei Guo , Yanhui Li , Huayu Tian . The study of antibacterial activity of cationic poly(β-amino ester) regulating by amphiphilic balance. Chinese Chemical Letters, 2025, 36(2): 110118-. doi: 10.1016/j.cclet.2024.110118
5. [5]
  Brandon Bishop , Shaofeng Huang , Hongxuan Chen , Haijia Yu , Hai Long , Jingshi Shen , Wei Zhang . Artificial transmembrane channel constructed from shape-persistent covalent organic molecular cages capable of ion and small molecule transport. Chinese Chemical Letters, 2024, 35(11): 109966-. doi: 10.1016/j.cclet.2024.109966
6. [6]
  Shaonan Liu , Shuixing Dai , Minghua Huang . The impact of ester groups on 1,8-naphthalimide electron transport material in organic solar cells. Chinese Journal of Structural Chemistry, 2024, 43(6): 100277-100277. doi: 10.1016/j.cjsc.2024.100277
7. [7]
  Ruiyun Liu , Ping Wang , Xuefei Wang , Feng Chen , Huogen Yu . Work-function-engineered Mo 4d electronic structure modulation in Mo₂C MXene cocatalyst for efficient photocatalytic H₂ evolution. Acta Physico-Chimica Sinica, 2025, 41(11): 100137-0. doi: 10.1016/j.actphy.2025.100137
8. [8]
  Zhenjie Yang , Chenyang Hu , Xuan Pang , Xuesi Chen . Sequence design in terpolymerization of ε-caprolactone, CO₂ and cyclohexane oxide: Random ester-carbonate distributions lead to large-span tunability. Chinese Chemical Letters, 2024, 35(5): 109340-. doi: 10.1016/j.cclet.2023.109340
9. [9]
  Zhili Li , Qijun Wo , Dongdong Huang , Dezhong Zhou , Lei Guo , Yeqing Mao . Improving gene transfection efficiency of highly branched poly(β-amino ester)s through the in-situ conversion of inactive terminal groups. Chinese Chemical Letters, 2024, 35(8): 109737-. doi: 10.1016/j.cclet.2024.109737
10. [10]
  Chaochao Jin , Kai Li , Jiongpei Zhang , Zhihua Wang , Jiajing Tan . N,O-Bidentated difluoroboron complexes based on pyridine-ester enolates: Facile synthesis, post-complexation modification, optical properties, and applications. Chinese Chemical Letters, 2024, 35(9): 109532-. doi: 10.1016/j.cclet.2024.109532
11. [11]
  Tong Tong , Lezong Chen , Siying Wu , Zhong Cao , Yuanbin Song , Jun Wu . Establishment of a leucine-based poly(ester amide)s library with self-anticancer effect as nano-drug carrier for colorectal cancer treatment. Chinese Chemical Letters, 2024, 35(12): 109689-. doi: 10.1016/j.cclet.2024.109689
12. [12]
  Qiang Feng , Jindong Hao , Ya Hu , Rong Fu , Wei Wei , Dong Yi . Photocatalytic multi-component synthesis of ester-containing quinoxalin-2(1H)-ones using water as the hydrogen donor. Chinese Chemical Letters, 2025, 36(6): 110582-. doi: 10.1016/j.cclet.2024.110582
13. [13]
  Jingwen Wang , Peizhang Zhao , Mengmeng Li , Jun Li , Yunfeng Lin . Remedying infectious bone defects via 3D printing technology. Chinese Chemical Letters, 2025, 36(9): 110686-. doi: 10.1016/j.cclet.2024.110686
14. [14]
  Liying Ou , Zhenluan Xue , Bo Li , Zhiwei Jin , Jiaochan Zhong , Lixia Yang , Penghui Shao , Shenglian Luo . Nitrogen-containing linkage-bonds in covalent organic frameworks: Synthesis and applications. Chinese Chemical Letters, 2025, 36(6): 110294-. doi: 10.1016/j.cclet.2024.110294
15. [15]
  Hang Chen , Chengzhi Cui , Hebo Ye , Hanxun Zou , Lei You . Enhancing hydrolytic stability of dynamic imine bonds and polymers in acidic media with internal protecting groups. Chinese Chemical Letters, 2024, 35(5): 109145-. doi: 10.1016/j.cclet.2023.109145
16. [16]
  Jianye Kang , Xinyu Yang , Xuhao Yang , Jiahui Sun , Yuhang Liu , Shutao Wang , Wenlong Song . Carbon dots-enhanced pH-responsive lubricating hydrogel based on reversible dynamic covalent bondings. Chinese Chemical Letters, 2024, 35(5): 109297-. doi: 10.1016/j.cclet.2023.109297
17. [17]
  Xi Zhou , Shengyao Wang . Dynamic two-dimensional covalent organic frameworks via ‘wine rack' design. Chinese Journal of Structural Chemistry, 2025, 44(4): 100464-100464. doi: 10.1016/j.cjsc.2024.100464
18. [18]
  Qi Zhang , Bin Han , Yucheng Jin , Mingrun Li , Enhui Zhang , Jianzhuang Jiang . 2D and 3D phthalocyanine covalent organic frameworks for electrocatalytic carbon dioxide reduction. Chinese Chemical Letters, 2025, 36(9): 110330-. doi: 10.1016/j.cclet.2024.110330
19. [19]
  Yan Chen , Xinnan Wang , Yifan Lin , Chun Liu . Shape/dimension-controllable organic heterostructures from one monomer pair. Chinese Chemical Letters, 2025, 36(3): 109903-. doi: 10.1016/j.cclet.2024.109903
20. [20]
  Yi Zhu , Jingyan Zhang , Yuchao Zhang , Ying Chen , Guanghui An , Ren Liu . Designing unimolecular photoinitiator by installing NHPI esters along the TX backbone for acrylate photopolymerization and their applications in coatings and 3D printing. Chinese Chemical Letters, 2024, 35(7): 109573-. doi: 10.1016/j.cclet.2024.109573

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(10)
HTML views(1)

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