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Polymer 54 (2013) 6929e6935

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Supramolecular polymer gel with multi stimuli responsive, selfhealing and erasable properties generated by hosteguest interactions
Fei Zeng a, Ying Han a, Zhi-Chao Yan b, Chen-Yang Liu b, Chuan-Feng Chen a, *
a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China b CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

a r t i c l e i n f o
Article history: Received 22 August 2013 Received in revised form 19 October 2013 Accepted 28 October 2013 Available online 1 November 2013 Keywords: Self-healing Hosteguest interaction Supramolecular polymer gel

a b s t r a c t
A supramolecular polymer gel formed between triptycene-based bis(crown ether) and copolymer containing dibenzylammonium (DBA) moieties by hosteguest interactions was described. We demonstrated the formation of the supramolecular polymer networks between the bis(crown ether) and the copolymer by the 1H NMR spectroscopy and solution viscometry, and we also obtained a colorless and transparent supramolecular polymer gel at high concentration. Moreover, the supramolecular polymer gel showed multi-stimuli reversible responsiveness, such as thermo-, acid/base-, and chemo- induced gelesol transitions. Furthermore, the result of rheological measurements showed the gel has an intrinsic selfhealing property, and the thixotropic process could be repeated at least three times. Interestingly, when doped with spiropyran molecules, the supramolecular polymer gel could also be employed as erasable materials. Thus, these results could be highly anticipated to benet for further construction of smart materials with high healing efciency, and ultimately be used in practical application. 2013 Elsevier Ltd. All rights reserved.

1. Introduction Materials with advanced functions have been widely used in contemporary technology and industry, and have a great impact on our daily life. Conventional polymer materials, which are held together by irreversible covalent bonds, are usually unable to selfrepaired under continuous sustaining damage and causing resources wasted and environment pollutions resulted by its nature. However, polymers with self-healing properties could signicantly extend the lifetimes of materials [1], which would thus cut the cost and correspondingly reduce demand on resources and environmental impact. During the past decades, scientists and engineers have paid more and more attentions to construct materials with selfhealing properties [2,3]. Most of the reported approaches required either an input of external energy in the form of heating [4e9] or light [10e13] to induce reformation of the covalent bonds between polymers after being damaged or healing agents [14e16] to form new polymeric materials in the destroyed area. Moreover, much of the reported materials needed long time to heal the materials [5,17] and the number of breaking and healing cycles was limited [14]. Although signicant progress has been made in this area, it is still urgently to develop a system with intrinsic self-healing properties.
* Corresponding author. E-mail address: cchen@iccas.ac.cn (C.-F. Chen). 0032-3861/$ e see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.polymer.2013.10.048

During the past decade, supramolecular chemistry has been attractive in materials science, especially on construction of the materials based on non-covalent interactions including hydrogen bonding [18e21], metaleligand interactions [22e28], ionic interactions [29e31] and pep interactions [8,9]. Owing to the inherent reversible properties of these weak interactions, materials linked by non-covalent bond not only exhibited responsiveness to external stimuli [32] but also retained stability and functionality similar to covalently bonded systems. Thus, non-covalent interactions could be considered as a good candidate to construct materials with intrinsic self-healing properties. Recently, Guan [33] and co-workers reported the use of hydrogen-bonding to prepare self-repairing polymers with good mechanical properties and requires no external input of energy or materials to heal. Because of the combination of multiple non-covalent bonds, hosteguest interactions have drawn considerable interest and being widely used in the construction of smart materials with stimuli-responsiveness [34e38] and shape-memory [39,40] properties for their diverse binding selectivity and reversible stimuli responsiveness. Especially, the construction of supramolecular polymer gels, which are precisely designed physical gels brought together by reversible secondary interactions to form three dimensional networks of melt macromolecules [41], has attracted considerable attention. However, most of them focused on their stimuli-responsiveness and few of them showed the self-healing property [42,43]. Moreover, the

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materials that showed both multi-stimuli reversible responsiveness and intrinsic fast self-healing properties had rarely been reported. Herein, we report the formation of supramolecular polymer gel by hosteguest interactions between a triptycene-based bis(crown ether) host 1 and copolymer 2 containing dibenzylammonium moieties (Fig. 1). We found that this gel showed multi-stimuli reversible responsiveness such as thermo-, pH-, and chemoinduced gelesol transitions. Especially, this material represented fast self-healing property without input of external energy or healing agents, and the breaking and healing cycles could maintain at least three times. Moreover, the supramolecular polymer gel doped with spiropyran molecules could also be used as an erasable material. It is highly anticipated that the results presented here would benet for the further construction of materials with high healing efciency and ultimately be used in practical application. 2. Experimental 2.1. Characterization methods H NMR and 13C NMR spectra were recorded on a Bruker DMX300 NMR spectrometer. The Mn and polydispersity index of copolymer 2 were determined by gel permeation chromatography (GPC) (Waters Co.) using polystyrene (PS) as standard and dimethylformamide (DMF) as eluent. The reduced viscosities of copolymer 2 with host 1 and copolymer 2 with DB24C8 at (25 0.05)  C were performed on the Ubbelohde viscometer. Field emission scanning electron micrography (FE-SEM, Hitachi S-4800) was used to observe the morphologies of the xerogels at an accelerating voltage of 10 kV. Before the experiment, samples were prepared by drop casting the suspension of free-dried gels on silicon substrates then coating with Pt. Rheological dates were obtained from an AR2000ex strain-controlled rheometer using 20 mm parallel plate geometry at 25  C and analyzed with rheology advantage data analysis software. The samples were placed between the para-plate and the platform with special care to avoid evaporation of solvents. The recovery properties of the samples in response to applied shear forces were followed the following programmed procedure (applied shear force, expressed in terms of strain; duration in parentheses): 0.1% (300 s) / 100% (300 s) / 0.1% (600 s) / 100% (300 s) / 0.1% (600 s) / 100% (300 s) / 0.1% (1200 s). 2.2. Synthesis of copolymer 2 The mixture of monomer 3 (0.74 g, 1.56 mmol), methyl acrylate (4.03 g, 46.8 mmol) and AIBN (15 mg, 0.09 mmol) were dissolved in DMF (6 mL) in a Schlenk tube, and the mixture solution was degassed by bubbling nitrogen for 20 min. Then, the Schlenk tube was sealed and heated in an oil bath set to 65  C for 12 h. After cooling to room temperature, the polymer was precipitation from cold diethyl ether as colorless viscous liquid. Discarding the upper uid, and then vacuum drying afforded the copolymer 2 as a colorless and transparent solid (3.10 g, 65%). 1H NMR (300 MHz, CDCl3, 295 K): d 7.99e7.34 (br, 9H, DBA aryl-H), 7.13e6.92 (br, 4H, St-H), 4.98 (br, 2H, St-CH2), 4.21 (br, 4H, DBA-CH2), 3.66e3.17 (br, 27H, ester-OCH3), 1.81e1.21 (br, 39H, polymer backbone). 3. Results and discussion 3.1. Synthesis and characterization of copolymer 2 The synthesis of copolymer 2 bearing pendant dibenzylammonium moiety was achieved by free-radical copolymerization of monomer 3 [36] and methyl acrylate in DMF in the presence of AIBN (Scheme 1). The molar ratio of DBA to ester moiety in the
1

copolymer estimated from the 1H NMR spectroscopy was 1:9. From the gel permeation chromatography (GPC) measurement, the number-average molecular weight (Mn) of the copolymer is 64.8 kDa, and the polydispersity index (PDI) value is 1.18 (Fig. S2, Supporting Information). 3.2. Self-assembly of host 1 and copolymer 2 In the previous work [44], we reported a novel triptycene-based bis(crown ether) host 1 incorporating two dibenzo-24-crown-8 ether moieties, and found that it could form a 1:2 complex with two molecules of dibenzy-lammonium (DBA) salt 4, and the complexation process was also well established. As copolymer 2 bearing dibenzylammonium moieties, complexation between host 1 and copolymer 2 could be occurred and 1H NMR spectroscopy was used to investigate the complexation process. As shown in Fig. 2, after the mixture of Host 1 and copolymer 2 at a 1:2 M ratio of host 1/ DBA units in CDCl3/CD3CN (1:1, v/v), the signals from protons H1, H2 and H3 of Host 1 shifted upeld, and the signals corresponding to the methylene protons H4 and H5 of copolymer 2 showed signicant downeld shift. These observations suggested that the secondary ammonium salt moiety of copolymer 2 was located in the center of the dibenzo-24-crown-8 ether of host 1, which could result in the formation of cross-linked supramolecular polymer networks ultimately. Moreover, it was also found that the protons of H1-5 showed two sets of signals, corresponding to the complexed and uncomplexed molecules, which indicated that the complexation between host 1 and the DBA units of copolymer 2 was a slow exchange process on the NMR spectroscopy timescales. These results are consistent with the complexation between host 1 and the dibenzylammonium salts as reported before [44]. Self-assembly of host 1 and copolymer 2 to form supramolecular polymer networks in solution was also studied by viscometry. As shown in Fig. 3, no obvious changes of reduced viscosity with varied concentrations of dibenzo-24-crown-8 (DB24C8) and copolymer 2 at a 1:1 M ratio of DB24C8/DBA in CHCl3/CH3CN were observed, indicating that no signicant physical entanglements occurred. However, the reduced viscosity of host 1 and copolymer 2 at a 1:2 M ratio of host 1/DBA units mixed in CHCl3/CH3CN increased exponentially with varied concentrations, which suggested the self-assembly process occurred and ultimately formed the cross-linked supramolecular polymer networks. Hence, it has been proved that the self-assembly of host 1 and the DBA units of copolymer 2 is undoubtedly dispensable for the formation of the cross-linked supramolecular polymer networks. 3.3. Gelation and multi-stimuli reversible responsivity of the supramolecular polymer gel Interestingly, it was found that a colorless and transparent organogel could be formed when host 1 and copolymer 2 were mixed in CHCl3/CH3CN (v/v 1:1) at high concentration (Fig. S3). Such phenomenon represents the direct support for the formation of supramolecular polymer networks and thereby entraps a large amount of solvent. Also, scanning electron microscope was used to investigate the microstructure of supramolecular gel, and the results showed that the porous structure could be observed, which conrmed the formation of supramolecular polymer networks (Fig. S4). Hosteguest interactions with multiple non-covalent bonding only require relatively low activation energy to be broken, which made the gel be sensitive to temperature. As expected, heating the supramolecular polymer gel in the vial above 60  C led to the formation of colorless uid solution. Subsequent cooling to the room temperature restored the gel state immediately (Fig. 4b). Thus, the

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Fig. 1. a) The proton designations of host 1 and formation of a 1:2 complex between host 1 and guest 4. b) Cartoon representations of copolymer 2 and host 1. c) Formation of supramolecular polymer gel between host 1 and copolymer 2.

Scheme 1. Synthesis of copolymer 2.

reversible gelesol transition induced by temperature could be achieved. It was known that the association and disassociation of the complex between DB24C8 and secondary ammonium salts could be chemically controlled by pH, which inspired us to further carried out the pH-induced reversible gelesol transition. As shown in Fig. 4d, the colorless uid solution was observed when 2.2 equiv (per host 1) of triethylamine (TEA) was added to the gel, owing to the deprotonation of the DBA salts and ultimately decomplexation of the complex. As soon as the addition of 2.4 equiv (per host 1) of triuoroacetic acid (TFA) to the above solution, the supramolecular polymer gel could be formed again due to the reformation of the supramolecular polymer networks after protonation of the secondary amine in the copolymer. The 1H NMR experiment also demonstrated this reversible process. Upon the addition of 2.2 equiv. (per host 1) of triethylamine (TEA) to the solution of host 1 and copolymer 2 in CDCl3/CD3CN, all the complexed signals disappeared. After 2.4 equiv. of triuoroacetic acid were added, the proton signals for complexation were observed again (Fig. S5). Furthermore, the reversible solegel transition could be trigged by chemical stimuli. Since DB24C8 showing higher binding afnity toward potassium cation K than secondary ammonium

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Fig. 2. Partial 1H NMR spectra (300 MHz, CDCl3:CD3CN 1:1, 295 K) of a) free host 1, b) host 1 and copolymer 2 (molar ratio 1:2 host 1/DBA units, c and uc denote complexed and uncomplexed moieties, respectively), and c) free copolymer 2. [1]0 4.0 mM.

salts [40], adding 4.0 equiv. (per host 1) of KPF6 to the supramolecular gel led to a transparent colorless solution. When 6.0 equiv. (per host 1) of 18-crown-6 was added, which could bind K more tightness than DB24C8, the reformation of the gel would appear (Fig. 4d). Protecting groups such as (Boc)2O are also used to investigate the reversible solegel transition. After addition of 4.0 equiv. (per host 1) of (Boc)2O and catalytic amount of DMAP to the gel, it resulted in the collapse of the supramolecular gel. The subsequent addition of acetic acid could restore the gel state. More interestingly, the reversible solegel transition could also be achieved by the competitive guest. The apparent association constant of host 1 and paraquat (Ka,exp 1.63 (0.3) 104 M1) was higher than the constant between host 1 and DBA (Kap,1 720 (180) M1 and Kap,2 77 (22) M1) [44]. Thus, adding of 1.0 equiv. (per host 1) of paraquat to the gel could cause gel collapse immediately, due to the formation of more

stable complex between host 1 and paraquat. When 2.0 equiv of host 1 was added, the supramolecular polymer gel could be reformed. The reversible solegel transition induced by competitive guest has rarely been reported, and it would be found potential applications in the cure of patients that could be suffered from the paraquat in the form of use the gel as drug delivery.

3.4. Rheological measurements and self-healing property of supramolecular gel Rheological experiments were further carried out to investigate the viscoelastic properties of supramolecular polymer gel. As shown in Fig. 5a, the oscillatory rheological measurements showed that at lower scanning frequency, G0 (storage modulus) is smaller than G00 (loss modulus), which suggested the viscous property of the gel. While at higher scanning frequency, G0 is larger than G00 , and the elastic property of the sample was demonstrated. As shown in Fig. 5b, strain amplitude sweeps of the samples demonstrated an elastic response typical of gel. The value of G0 rapidly decreases above the critical strain region (g 26.0%), indicating a collapse of the gel state to a quasi-liquid state. Moreover, the gel can fast recover its mechanical strength without either input of external energy or healing agents after destroyed by large-amplitude oscillatory, known as thixotropy. Once a large-amplitude oscillatory force was applied (g 100%), the value of G0 decreased from 1341 to 404 Pa (Pa), resulting in the collapse of the gel. The value of G0 immediately recovers to nearly 90% of its initial value once the high strain was canceled. Furthermore, the thixotropic process could be repeated several times (Fig. 5c). This excellent self-healing property of the supramolecular gel might be resulted from the introducing of hosteguest interactions to the materials. The resulted present here would provide an opportunity for the construction of materials with self-healing properties. The self-healing property of the supramolecular polymer gel can also be observed in sight. Considering the observation of the selfhealing property of the gel visually and directly, we placed the gel in the bottom of the vial and damaged it with a knife then turned it upside down. As shown in Fig. 6, it was found that the gel could repair itself in a short time after the destroyed.

300 250 200

copolymer 2+host 1 copolymer 2+DB24C8

red / ml g-1

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-1

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Fig. 3. Variation of reduced viscosities (CHCl3/CH3CN 1:1, 25  C) as a function of total concentrations obtained for supramolecular polymer networks of 1 and copolymer 2 (1:2 M ratio for host 1/DBA in 2), and the control mixture of DB24C8 and copolymer 2 (1:1 M ratio for DB24C8/DBA in 2).

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Fig. 4. Supramolecular polymer gel responding to external stimulus (16.37 mg host 1 and 40.4 mg copolymer 2 in 1.1 mL CHCl3/CH3CN 1/1). a) Guest-induced gelesol transition, b) thermo-induced gelesol transition, c) chemical-induced gelesol transition, d) K-induced gelesol transition, and e) acid/base-induced gelesol transition.

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Fig. 5. Rheological properties of the supramolecular polymer gel. (a) G0 and G00 values of the supramolecular polymer gel on frequency sweep. (b), (c) G0 and G00 values of the supramolecular gel on strain sweep (b) and in continuous step strain measurements (c). (d) G0 and G00 values of the supramolecular gel on frequency sweep after several damage test.

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Fig. 6. Photographs of the supramolecular gel with self-healing process.

3.5. Supramolecular polymer gel used as erasable material Spiropyran (SP) molecules [45] are an important class of photochromic compounds and have been investigated extensively for optical memories, switches, and displays [46,47], owing to the

reversible changes between open form and the closed form under visible or UV light irradiation. SP-functionalized macromolecular gels [48] and low-molecular-weight gelators (LMWGs) with the SP moiety have been reported [49e51]. However, they always have synthetic difculties encountered in the preparation of SP-

Fig. 7. a) Photochromic reactions of spiropyran molecule under UV and visible light irradiation. b) Photographs of the supramolecular gel recording of ICCAS characters by exposure to UV light (365 nm) for 5.0 min, and erasing the recorded pattern by exposure to visible light for 1.0 min c) The changes of maximum absorption (561 nm) of the spiropyran molecule between UV and Visible light.

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functionalized molecules. Here, we used the doping method (described in the Supporting Information) conveniently to prepared supramolecular polymer gel containing spiropyran molecules and showed well photochromic property. As shown in Fig. 7a, the colorless transparent gel was covered with a black paper engraved with the characters ICCAS and these characters turn into pink after exposure to UV light for 5.0 min. While under the visible light, the characters disappeared within 1.0 min. Moreover, these changes could also be monitored by the changes of the ultraviolet absorption spectrum of the supramolecular polymer gel. As shown in Fig. 7b, the absorbance of the supramolecular polymer gel decreased from 0.275 to 0.006 under visible light for 1.0 min, after exposure to the UV light for 5.0 min the value reached 0.27. Furthermore, this process could be repeated several times. Thus, we could draw a conclusion that our supramolecular gel could be used as a material to data writing or erasing. 4. Conclusion In summary, we have described the construct of supramolecular polymer gel by the self-assembly of triptycene-based bis(crown ether) host 1 and copolymer 2 containing DBA moieties via hoste guest interactions. Interestingly, it was found that the supramolecular polymer gel showed multi-stimuli reversible responsiveness such as thermo-, acid/base-, and chemo- induced gelesol transitions. Especially, the reversible solegel transition that induced by competitive guest has been reported and might provide an approach to use the gel as drug delivery to cure of patients that suffered from the paraquat. Moreover, this material exhibited intrinsic self-healing property and the thixotropic process could be repeated at least three times. Furthermore, it was found that the supramolecular polymer gel could be successfully employed as erasable material when it was doped with spiropyran molecule. The results presented here indicated our supramolecular gel could be an ideal candidate for the development of intelligent material with desired functionalities. Our future works will focus on expanding the application of the materials and using other novel triptycene-derived synthetic hosts with multiple cavities [52e54] to construct materials with desired functionalities and ultimately being used in practical, which is underway in our laboratory. Acknowledgment We thank the National Natural Science Foundation of China (21332008, 91127009), and the National Basic Research Program (2011CB932501) for nancial support. Appendix A. Supplementary data Supplementary data related to this article can be found online at http://dx.doi.org/10.1016/j.polymer.2013.10.048. References
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