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
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沈阳化工大学材料科学与工程学院沈阳 110142