Citation: Li Lan-Lan, Jiang Ru-Yi, Chen Jin-Xing, Wang Mo-Zhen, Ge Xue-Wu. One-step synthesis of self-healable hydrogels by the spontaneous phase separation of linear multi-block copolymers during the emulsion copolymerization[J]. Chinese Chemical Letters, ;2017, 28(4): 868-874. doi: 10.1016/j.cclet.2016.12.025 shu

One-step synthesis of self-healable hydrogels by the spontaneous phase separation of linear multi-block copolymers during the emulsion copolymerization

a.
CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China
b.
Petro China Company Limited, Beijing 100007, China

Corresponding author: Wang Mo-Zhen, pstwmz@ustc.edu.cn Ge Xue-Wu, xwge@ustc.edu.cn
Received Date: 11 November 2016
Revised Date: 30 November 2016
Accepted Date: 12 December 2016
Available Online: 7 April 2017

Figures(9)

Self-healable polyacrylamide-based hydrogels were prepared at room temperature via a one-step emulsion copolymerization of acrylamide (AM), dodecyl 2-methacrylate (DM), and 5-acetylaminopentyl acrylate (AAPA) using sodium dodecyl sulfonate (SDS) as the emulsifler and ammonium persulfate (APS) as the initiator.The produced linear multi-block copolymer chains are composed of randomly-linked hydrophilic polyacrylamide segments (PAM) and hydrophobic segments constituted by DM and AAPA units (P (DM-co-AAPA)).The P (DM-co-AAPA) segments will self-aggregate into hydrophobic micro-domains during the polymerization process driven by the hydrophobic interactions, and finally separate from water phase, acting as the crosslinks and leading to the formation of strong hydrogels with a storage modulus as high as 400 Pa.These hydrophobic microdomains will be dissolved in water when the temperature increases to 70 ℃, resulting in a temperature-responsive reversible sol-gel transition of the prepared hydrogels.Furthermore, the prepared hydrogels have excellent self-healing ability.The broken hydrogels can be automatically healed into a body with a same strength within 2-min's contact.This work provides a new simple way to prepare reversible physical crosslinked hydrogel with high strength and self-healing efficiency.
- Self-healing,
- 5-Acetylaminopentyl acrylate,
- Hydrogen bond,
- Emulsion copolymerization
1. [1]
  Billiet T., Vandenhaute M., Schelfhout J., S.Van Vlierberghe, Dubruel P. A review of trends and limitations in hydrogel-rapid prototyping for tissue engineering[J]. Biomaterials, 2012,33:6020-6041. doi: 10.1016/j.biomaterials.2012.04.050
2. [2]
  Hamidi M., Azadi A., Rafiei P. Hydrogel nanoparticles in drug delivery[J]. Adv. Drug Deliv.Rev., 2008,60:1638-1649. doi: 10.1016/j.addr.2008.08.002
3. [3]
  Wang Y., Chai Z.H., He H.Y., Jiang Y.Z., Fu G.Q. Polyacrylamide hydrogels with phenylboronic acid moieties for the imprinting of proteins[J]. Chin.Chem.Lett., 2010,21:1487-1489. doi: 10.1016/j.cclet.2010.06.005
4. [4]
  Brown H.R. A model of the fracture of double network gels[J]. Macromolecules, 2007,40:3815-3818. doi: 10.1021/ma062642y
5. [5]
  S. Mora, The kinetic approach to fracture in transient networks, Soft Matter 7 (2011)4908-4917.
6. [6]
  Cong H.P., Wang P., Yu S.H. Stretchable and self-healing graphene oxide-polymer composite hydrogels:a dual-network design[J]. Chem.Mater., 2013,25:3357-3362. doi: 10.1021/cm401919c
7. [7]
  D. L. Taylor, M. In Het Panhuis, Self-healing hydrogels, Adv. Mater. 28(2016) 9060-9093.
8. [8]
  Phadke A., Zhang C., Arman B.. Rapid self-healing hydrogels[J]. Proc.Natl. Acad.Sci.U.S.A., 2012,109:4383-4388. doi: 10.1073/pnas.1201122109
9. [9]
  Zhu B.L., Jasinski N., Benitez A.. Hierarchical nacre mimetics with synergistic mechanical properties by control of molecular interactions in self-healing polymers[J]. Angew.Chem.Int.Ed., 2015,54:8653-8657. doi: 10.1002/anie.201502323
10. [10]
  Akay G., A.Hassan-Raeisi , Tuncaboylu D.C.. Self-healing hydrogels formed in catanionic surfactant solutions[J]. Soft Matter, 2013,9:2254-2261. doi: 10.1039/c2sm27515e
11. [11]
  X. Hao, H. Liu, Z. Lu, Y. J. Xie, H. Y. Yang, Endowing the conventional HMPAM hydrogel with pH-responsive and self-healing properties, J. Mater. Chem. A 1 (2013)6920-6927.
12. [12]
  Deng G.H., Li F.Y., Yu H.G.. Dynamic hydrogels with an environmental adaptive self-healing ability and dual responsive sol-gel transitions[J]. ACS Macro Lett., 2012,1:275-279. doi: 10.1021/mz200195n
13. [13]
  Zeng C., Seino H., Ren J., Hatanaka K., Yoshie N. Bio-based furan polymers with self-healing ability[J]. Macromolecules, 2013,46:1794-1802. doi: 10.1021/ma3023603
14. [14]
  Zhang Y.L., Yang B., Zhang X.Y.. A magnetic self-healing hydrogel[J]. Chem. Commun., 2012,48:9305-9307. doi: 10.1039/c2cc34745h
15. [15]
  J. J. Cash, T. Kubo, A. P. Bapat, B. S. Sumerlin, Room-temperature self-healing polymers based on dynamic-covalent boronic esters, Macromolecules 48 (2015)2098-2106.
16. [16]
  A. Harada, R. Kobayashi, Y. Takashima, A. Hashidzume, H. Yamaguchi, Macroscopic self-assembly through molecular recognition, Nat. Chem. 3 (2011)34-37.
17. [17]
  Wei Z.J., He J., Liang T.. Autonomous self-healing of poly (acrylic acid) hydrogels induced by the migration of ferric ions[J]. Polym.Chem., 2013,4:4601-4605. doi: 10.1039/c3py00692a
18. [18]
  Ahn B.K., Lee D.W., Israelachvili J.N., Waite J.H. Surface-initiated self-healing of polymers in aqueous media[J]. Nat.Mater., 2014,13:867-872. doi: 10.1038/nmat4037
19. [19]
  Dai X.Y., Zhang Y.Y., Gao L.N.. A mechanically strong highly stable, thermoplastic, and self-healable supramolecular polymer hydrogel[J]. Adv. Mater., 2015,27:3566-3571. doi: 10.1002/adma.v27.23
20. [20]
  Liu H., Xiong C.M., Tao Z.. Zwitterionic copolymer-based and hydrogen bonding-strengthened self-healing hydrogel[J]. RSC Adv., 2015,5:33083-33088. doi: 10.1039/C4RA15003A
21. [21]
  Tuncaboylu D.C., Sari M., Oppermann W., Okay O. Tough and self-healing hydrogels formed via hydrophobic interactions[J]. Macromolecules, 2011,44:4997-5005. doi: 10.1021/ma200579v
22. [22]
  Candau F., Selb J. Hydrophobically-modified polyacrylamides prepared by micellar polymerization[J]. Adv.Colloid Interface Sci., 1999,79:149-172. doi: 10.1016/S0001-8686(98)00077-3
23. [23]
  Regalado E.J., Selb J., Candau F. Viscoelastic behavior of semidilute solutions of multisticker polymer chains[J]. Macromolecules, 1999,32:8580-8588. doi: 10.1021/ma990999e
24. [24]
  Jeon I., Cui J.X., Illeperuma W.R.K., Aizenberg J., Vlassak J.J. Extremely stretchable and fast self-healing hydrogels[J]. Adv.Mater., 2016,28:4678-4683. doi: 10.1002/adma.v28.23
25. [25]
  Caputo M.R., Selb J., Candau F. Effect of temperature on the viscoelastic behaviour of entangled solutions of multisticker associating polyacrylamides[J]. Polymer, 2004,45:231-240. doi: 10.1016/j.polymer.2003.11.010
26. [26]
  A. Hill, F. Candau, J. Selb, Properties of hydrophobically associating polyacrylamides: influence of the method of synthesis, Macromolecules 26 (1993)4521-4532.
27. [27]
  Hao X., Zhou W.F., Yao R.C.. A new class of thermo-switchable hydrogel: application to the host-guest approach[J]. J.Mater.Chem.A, 2013,1:14612-14617. doi: 10.1039/c3ta13250a
28. [28]
  Y. L. Chen, Z. B. Guan, Multivalent hydrogen bonding block copolymers self-assemble into strong and tough self-healing materials, Chem. Commun. 50 (2014)10868-10870.
29. [29]
  Williams G.A., Ishige R., Cromwell O.R.. Mechanically robust and self-healable superlattice nanocomposites by self-assembly of single-component sticky polymer-grafted nanoparticles[J]. Adv.Mater., 2015,27:3934-3941. doi: 10.1002/adma.201500927
30. [30]
  Chambon F., Winter H.H. Linear viscoelasticity at the gel point of a crosslinking PDMS with imbalanced stoichiometry[J]. J.Rheol., 1987,31:683-697. doi: 10.1122/1.549955
31. [31]
  Winter H.H., Chambon F. Analysis of linear viscoelasticity of a crosslinking polymer at the gel point[J]. J.Rheol., 1986,30:367-382. doi: 10.1122/1.549853
32. [32]
  Bai T., Liu S.J., Sun F.. Zwitterionic fusion in hydrogels and spontaneous and time-independent self-healing under physiological conditions[J]. Biomaterials, 2014,35:3926-3933. doi: 10.1016/j.biomaterials.2014.01.077
33. [33]
  Tuncaboylu D.C., Sahin M., Argun A., Oppermann W., Okay O. Dynamics and large strain behavior of self-healing hydrogels with and without surfactants[J]. Macromolecules, 2012,45:1991-2000. doi: 10.1021/ma202672y
34. [34]
  Chen Y.L., Kushner A.M., Williams G.A., Guan Z.B. Multiphase design of autonomic self-healing thermoplastic elastomers[J]. Nat.Chem., 2012,4:467-472. doi: 10.1038/nchem.1314
1. [1]
  Salim Ullah , Jianliang Shen , Hong-Tao Xu . Innovative self-healing conductive organogel: Pioneering the future of electronics. Chinese Chemical Letters, 2025, 36(3): 110553-. doi: 10.1016/j.cclet.2024.110553
2. [2]
  Huiying Xu , Minghui Liang , Zhi Zhou , Hui Gao , Wei Yi . Application of Quantum Chemistry Computation and Visual Analysis in Teaching of Weak Interactions. University Chemistry, 2025, 40(3): 199-205. doi: 10.12461/PKU.DXHX202407011
3. [3]
  Supphachok Chanmungkalakul , Syed Ali Abbas Abedi , Federico J. Hernández , Jianwei Xu , Xiaogang Liu . The dark side of cyclooctatetraene (COT): Photophysics in the singlet states of “self-healing” dyes. Chinese Chemical Letters, 2024, 35(8): 109227-. doi: 10.1016/j.cclet.2023.109227
4. [4]
  Saadullah Khattak , Hong-Tao Xu , Jianliang Shen . Bio-electronic bandage: Self-powered performances to accelerate intestinal wound healing. Chinese Chemical Letters, 2024, 35(12): 110210-. doi: 10.1016/j.cclet.2024.110210
5. [5]
  Hailong He , Wenbing Wang , Wenmin Pang , Chen Zou , Dan Peng . Double stimulus-responsive palladium catalysts for ethylene polymerization and copolymerization. Chinese Chemical Letters, 2024, 35(7): 109534-. doi: 10.1016/j.cclet.2024.109534
6. [6]
  Yujuan Zhao , Zaiwang Zhao . Monolayer mesoporous nanosheets with surface asymmetry via a dual-emulsion-directed monomicelle assembly. Chinese Journal of Structural Chemistry, 2024, 43(2): 100238-100238. doi: 10.1016/j.cjsc.2024.100238
7. [7]
  Yan Zou , Yin-Shuang Hu , Deng-Hui Tian , Hong Wu , Xiaoshu Lv , Guangming Jiang , Yu-Xi Huang . Tuning the membrane rejection behavior by surface wettability engineering for an effective water-in-oil emulsion separation. Chinese Chemical Letters, 2024, 35(6): 109090-. doi: 10.1016/j.cclet.2023.109090
8. [8]
  Ke Wang , Jia Wu , Shuyi Zheng , Shibin Yin . NiCo Alloy Nanoparticles Anchored on Mesoporous Mo2N Nanosheets as Efficient Catalysts for 5-Hydroxymethylfurfural Electrooxidation and Hydrogen Generation. Chinese Journal of Structural Chemistry, 2023, 42(10): 100104-100104. doi: 10.1016/j.cjsc.2023.100104
9. [9]
  Yang Qin , Jiangtian Li , Xuehao Zhang , Kaixuan Wan , Heao Zhang , Feiyang Huang , Limei Wang , Hongxun Wang , Longjie Li , Xianjin Xiao . Toeless and reversible DNA strand displacement based on Hoogsteen-bond triplex. Chinese Chemical Letters, 2024, 35(5): 108826-. doi: 10.1016/j.cclet.2023.108826
10. [10]
  Ping Lu , Baoyin Du , Ke Liu , Ze Luo , Abiduweili Sikandaier , Lipeng Diao , Jin Sun , Luhua Jiang , Yukun Zhu . Heterostructured In2O3/In2S3 hollow fibers enable efficient visible-light driven photocatalytic hydrogen production and 5-hydroxymethylfurfural oxidation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100361-100361. doi: 10.1016/j.cjsc.2024.100361
11. [11]
  Linfang ZHANG , Wenzhu YIN , Gui YIN . A 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran-based near-infrared fluorescence probe for the detection of hydrogen sulfide and imaging of living cells. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 540-548. doi: 10.11862/CJIC.20240405
12. [12]
  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
13. [13]
  Yunkang Tong , Haiqiao Huang , Haolan Li , Mingle Li , Wen Sun , Jianjun Du , Jiangli Fan , Lei Wang , Bin Liu , Xiaoqiang Chen , Xiaojun Peng . Cooperative bond scission by HRP/H₂O₂ for targeted prodrug activation. Chinese Chemical Letters, 2024, 35(12): 109663-. doi: 10.1016/j.cclet.2024.109663
14. [14]
  Junmeng Luo , Qiongqiong Wan , Suming Chen . Chemistry-driven mass spectrometry for structural lipidomics at the C=C bond isomer level. Chinese Chemical Letters, 2025, 36(1): 109836-. doi: 10.1016/j.cclet.2024.109836
15. [15]
  Qiongqiong Wan , Yanan Xiao , Guifang Feng , Xin Dong , Wenjing Nie , Ming Gao , Qingtao Meng , Suming Chen . Visible-light-activated aziridination reaction enables simultaneous resolving of C=C bond location and the sn-position isomers in lipids. Chinese Chemical Letters, 2024, 35(4): 108775-. doi: 10.1016/j.cclet.2023.108775
16. [16]
  Yi Luo , Lin Dong . Multicomponent remote C(sp²)-H bond addition by Ru catalysis: An efficient access to the alkylarylation of 2H-imidazoles. Chinese Chemical Letters, 2024, 35(10): 109648-. doi: 10.1016/j.cclet.2024.109648
17. [17]
  Guoju Guo , Xufeng Li , Jie Ma , Yongjia Shi , Jian Lv , Daoshan Yang . Photocatalyst/metal-free sequential C–N/C–S bond formation: Synthesis of S-arylisothioureas via photoinduced EDA complex activation. Chinese Chemical Letters, 2024, 35(11): 110024-. doi: 10.1016/j.cclet.2024.110024
18. [18]
  Peng Wang , Jianjun Wang , Ni Song , Xin Zhou , Ming Li . Radical dehydroxymethylative fluorination of aliphatic primary alcohols and diverse functionalization of α-fluoroimides via BF₃·OEt₂-catalyzed C‒F bond activation. Chinese Chemical Letters, 2025, 36(1): 109748-. doi: 10.1016/j.cclet.2024.109748
19. [19]
  Yixia Zhang , Caili Xue , Yunpeng Zhang , Qi Zhang , Kai Zhang , Yulin Liu , Zhaohui Shan , Wu Qiu , Gang Chen , Na Li , Hulin Zhang , Jiang Zhao , Da-Peng Yang . Cocktail effect of ionic patch driven by triboelectric nanogenerator for diabetic wound healing. Chinese Chemical Letters, 2024, 35(8): 109196-. doi: 10.1016/j.cclet.2023.109196
20. [20]
  Jingwen Zhao , Jianpu Tang , Zhen Cui , Limin Liu , Dayong Yang , Chi Yao . A DNA micro-complex containing polyaptamer for exosome separation and wound healing. Chinese Chemical Letters, 2024, 35(9): 109303-. doi: 10.1016/j.cclet.2023.109303

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(729)
HTML views(43)

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