Article Cite This: Macromolecules XXXX, XXX, XXX−XXX
Supramolecular Interfacial Polymerization of Miscible Monomers: Fabricating Supramolecular Polymers with Tailor-Made Structures Bo Qin, Shuai Zhang, Zehuan Huang, Jiang-Fei Xu,* and Xi Zhang* Key Lab of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China S Supporting Information *
ABSTRACT: We have fabricated a series of supramolecular polymers with tailor-made structures and properties through supramolecular interfacial polymerization of miscible monomers. Compared with homogeneous solution polymerization, supramolecular interfacial polymerization is advantageous for fabricating supramolecular polymers with higher molecular weights. Their higher molecular weights are attributed to the higher effective concentration of monomers at the interface than in solutions and diffusion-limited characteristic of supramolecular interfacial polymerization. Moreover, the glass transition temperatures of supramolecular polymers are well tuned by tuning the monomer structures and supramolecular interfacial copolymerization. It is anticipated that this research will further enrich the methodology for fabricating supramolecular polymers with controlled structures and properties through supramolecular interfacial polymerization. polymers with higher molecular weights.47−49 Therefore, it is feasible to extend this advantage to supramolecular interfacial polymerization of miscible monomers, thus fabricating supramolecular polymers with higher molecular weights and controllable properties. To this end, we prepared a bifunctional supramonomer (UPy-NCO)2 bearing two ureidopyrimidinone (UPy) units flanked by two isocyanate end groups, which can be only dissolved in organic solvents such as chloroform. This oilsoluble supramonomer was connected by quadruple hydrogen bonding between two UPy units, thus endowing obtained polymers with dynamic nature.50−52 By the isocyanate−amine reaction, this supramonomer can be polymerized at the water− oil interface with various diamines with different types and lengths of linkers (Scheme 1). Since these diamine monomers can be dissolved in both water and oil phase, both of the solution and interfacial polymerization can be employed. Compared with solution polymerization, we envisioned that supramolecular interfacial polymerization may produce supramolecular polymers with higher molecular weights. In addition, the chain structures and properties of supramolecular polymers could be modulated by simply using different diamine monomers or copolymerizing them.
1. INTRODUCTION Supramolecular polymers refer to polymeric arrays whose monomers are connected together through highly directional and reversible noncovalent interactions, such as multiple hydrogen bonding,1−7 host−guest interaction,8−15 π−π interaction,16−23 and metal coordination.24,25 Based on the dynamic nature of noncovalent interactions, supramolecular polymers exhibit many fascinating characteristics including easy processability, reversibility, self-healing, and stimuli-responsiveness.26−40 Conventionally, supramolecular polymers are mostly prepared in the homogeneous solution.41−43 One essential requirement is that all the monomers should be dissolved in one solvent. However, when the monomers are immiscible and cannot be dissolved in the same solvent, conventional homogeneous solution polymerization cannot work. To address this problem, we have developed a new method of preparing supramolecular polymers through interfacial polymerization of supramonomers at the water−oil interface.44 In this regard, the construction of supramolecular polymers is successfully transferred from homogeneous solutions to water−oil interfaces. If two monomers are miscible, it can be imagined that both solution polymerization and supramolecular interfacial polymerization can be employed to prepare supramolecular polymers. However, by homogeneous solution polymerization of AA and BB type monomers,45 high molecular weight polymers can only be obtained when stoichiometry of two ditopic monomers is strictly 1:1 and conversion rate of reaction is close to 100%.46 As is known, one advantage of interfacial polymerization is to avoid these strict requirements and prepare © XXXX American Chemical Society
Received: February 7, 2018
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DOI: 10.1021/acs.macromol.8b00289 Macromolecules XXXX, XXX, XXX−XXX
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into a 20 mL screw vials with an inner diameter of 28 mm. Then, an aqueous solution of diamine monomers (12.5 mmol L−1, 2.0 mL) was carefully poured over the chloroform phase without disturbing the interface. After 4 h, the water and oil phase were carefully removed with a dropper, and the solid films were rinsed with CHCl3 for 4 times to remove residual monomers and dried in a vacuum oven for 12 h for further characterization. Preparation of Supramolecular Polymers through Solution Polymerization. For comparison, solution polymerization of miscible monomers was performed in chloroform. Both diamine monomer and supramonomer (UPy-NCO)2 were dissolved in chloroform at the concentration of 25.0 mmol L−1. 2.0 mL of hexamethylenediamine solution was slowly added into supramonomer (UPy-NCO)2 (25.0 mmol L−1, 2.0 mL) within 2 min. Large amounts of precipitates appeared in the solution in 5 min. After 4 h, the precipitates were filtered and washed with chloroform for 4 times and dried in a vacuum oven for 12 h.
Scheme 1. Schematic Representations of (a) Molecular Structures of Supramonomer (UPy-NCO)2 (ChloroformSoluble) and Two Sets of Diamine Monomers (Noted as CnNH2 and EGn-NH2, Water-Soluble) and (b) Supramolecular Interfacial Polymerization by Isocyanate−Amine Reaction at the Water−Oil Interface
3. RESULTS AND DISCUSSION Reaction of Isocyanate and Amine at the Water−Oil Interface. We explored whether the supramonomer (UPyNCO)2 and diamine monomer could undergo the isocyanate− amine reaction at the water−oil interface. Typically, an aqueous solution of hexamethylendiamine was slowly added onto the surface of a solution of supramonomer (UPy-NCO)2 in chloroform. After a few minutes, a white-colored film formed at the water−oil interface. Owing to dynamic nature of quadruple hydrogen bonds, this white film of supramolecular polymers can be dissolved in DMSO-d6 by disassociating their hydrogen bonds. Thus, 1H NMR was first employed to study the obtained film. As shown in Figure 1, the CH2 protons (a)
2. EXPERIMENTAL SECTION Materials and Methods. All reagents were obtained from commercial suppliers and were used without further purification. All of the 1H NMR spectra were recorded using a JEOL JNM-ECA400 spectrometer (400 MHz). All of the solid-state NMR spectra were measured on a JEOL JNM-ECZ600R spectrometer (600 MHz). The experiments of solid-state NMR were carried out using a commercial JEOL 1.0 mm MAS probe with the spinning frequency of 60 kHz. Solid-state 1H MAS NMR spectra were recorded with a single pulse excitation, a 90° pulse length of 1.0 μs, and a recycle delay of 5.0 s. All spectra were referenced to solid glycine and were collected at room temperature. Pendant drop tests were performed on a drop shape analyzer (DSA30S, KRUSS, GmbH). All of the DSC measurements were carried out using a TA Instruments Discovery 250 equipped with an RCS90 cooling accessory operating at a heating/cooling rate of 10 °C/min in the range −30 to 150 °C. Data from the second heating cycle were reported unless indicated otherwise. Scanning electron microscopy (SEM) investigations were carried out on a Hitachi FESEM SU8000 instrument. The ESI-MS was collected on a LTQ LC/ MS apparatus. The FT-IR spectrum of the supramolecular polymer was conducted on a Perkin Elemer spectrum GX FT-IR system at room temperature. The elastic moduli of the supramolecular polymers were measured by using a commercial AFM (Cypher VRS AFM, Oxford Instruments). A tip (AC160) with a stiffness of 26 N/m was used in the indentation tests. All recorded curves were fitted and analyzed according to the Hertz model to yield the elastic modulus. All measurements were carried out in an ambient atmosphere at a temperature of 22 °C and a relative humidity of about 10%. Synthesis of UPy-NCO. UPy-NCO was prepared according to a modified literature procedure (Scheme S1):53 a solution of 2-amino-4hydroxy-6-methylpyrimidine (0.88 g, 7.0 mmol) in hexamethylene diisocyanate (7.07 g, 42.0 mmol) was heated at 100 °C for 18 h. Then the solution was cooled to room temperature and was added into 400 mL of petroleum ether. The resulting precipitates were filtered and washed with petroleum ether. The powder was dried at 50 °C under reduced pressure to yield 2.05 g of product as a white solid. Yield: 97%. The supramonomer (UPy-NCO)2 was formed by dissolving UPy-NCO in chloroform. 1H NMR (CDCl3, 400 MHz): 13.11 (s, 2 H), 11.86 (s, 2 H), 10.18 (s, 2 H), 5.82 (s, 2 H), 3.29 (m, 8 H), 2.23 (s, 6 H), 1.62 (m, 8H), 1.40 (m, 8 H). ESI-MS calcd for [(UPyNCO)2 + H]+ C26H38N10O6, 587.31; found 587.30. Preparation of Supramolecular Polymers through Supramolecular Interfacial Polymerization. A chloroform solution of the supramonomer (UPy-NCO)2 (25.0 mmol L−1, 2.0 mL) was added
Figure 1. 1H NMR spectra of (a) the diamine monomer C6-NH2, (b) the product at the water−oil interface, and (c) the oil-soluble monomer UPy-NCO (400 MHz, DMSO-d6).
next to isocyanate groups disappeared. Meanwhile, a new peak (δ = 3.0 ppm) ascribed to the addition product of isocyanate and amine appeared in the spectrum (Figure 1b), indicating that the reaction between two monomers can indeed happen at the water−oil interface. Furthermore, the product of interfacial reaction between isocyanate and amine groups was also characterized by ESI-MS (Figure S5). A molecular ion peak with a mass-to-charge ratio of 703.45 was detected, which is in good accordance with calculated molecular weight of the product with one positive charge. It is noteworthy that hydrolysis of isocyanate was not significant when water was added onto the surface of a chloroform solution of (UPyNCO)2. After 4 h, no hydrolyzed products were clearly observed in the 1H NMR (Figure S3) and ESI-MS (Figure S4) B
DOI: 10.1021/acs.macromol.8b00289 Macromolecules XXXX, XXX, XXX−XXX
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Macromolecules spectrum. Therefore, these results indicate that linear supramolecular polymers are prepared through the reaction between monomers at the water−oil interface. Characterization of Hydrogen Bonds in the Solid State. To determine whether the quadruple hydrogen bonds existed in the obtained films, FT-IR and solid-state 1H NMR were conducted for characterization. The N−H stretching vibration bands occurred at 3220 and 3145 cm−1 (Figure S6) in the FT-IR spectrum, which suggests existence of hydrogen bonds in the film. Then, high-resolution solid-state 1H NMR further provided solid evidence for the presence of quadruple hydrogen bonds.54 Owing to its high spinning frequency and magic-angle spinning (MAS), three different amide proton peaks ascribed to hydrogen bonds in the range of 10.0−14.0 ppm as well as the peaks of aromatic and aliphatic groups were clearly resolved (Figure 2). These results indicate that the solid films prepared at the interface consist of supramolecular polymers linked through quadruple hydrogen bonds between two UPy units.
Figure 3. (a) DP of supramolecular polymers prepared through interfacial polymerization and solution polymerization versus reaction time. (b) DSC traces of supramolecular polymers produced by interfacial polymerization and solution polymerization while keeping reaction time of 4 h.
Supramolecular polymers prepared by interfacial polymerization and solution polymerization were further characterized by DSC to determine their glass transition temperature (Tg). As shown in Figure 3b, at the reaction time of 4 h, Tg of supramolecular polymers fabricated by supramolecular interfacial polymerization was measured to be 113.7 °C, while that of supramolecular polymers prepared by solution polymerization was 110.5 °C. Based on Flory−Fox equation,56 Tg of polymers increases upon growth of their molecular weights. Therefore, the rise in Tg values can be ascribed to higher DP of the supramolecular polymers constructed by supramolecular interfacial polymerization. To further investigate morphologies of the obtained supramolecular polymers, SEM was used to characterize supramolecular polymers prepared by two methods. As shown in Figure S10a, the SEM image of the films prepared through supramolecular interfacial polymerization showed fiber-like structures, which may be related to entanglement of linear supramolecular polymers with high molecular weights.57 For the supramolecular polymers prepared by solution polymerization, spherical structures were observed (Figure S10b), which may be related to aggregation of the lowmolecular-weight supramolecular polymers. Plausible Reasons Behind Formation of Supramolecular Polymers with Higher Molecular Weights by Supramolecular Interfacial Polymerization. There may be two factors that can lead to formation of supramolecular polymers with higher molecular weights by supramolecular interfacial polymerization. One is the higher effective concentration of monomers at the water−chloroform interface, and the other is diffusion-limited characteristic of interfacial
Figure 2. Solid-state 1H NMR spectrum of the solid films (600 MHz, spinning frequency of 60 kHz).
Comparison between Solution Polymerization and Supramolecular Interfacial Polymerization. We wondered if supramolecular polymers fabricated by supramolecular interfacial polymerization exhibited higher degree of polymerization (DP) than supramolecular polymers fabricated by solution polymerization. To answer this question, solution polymerization in chloroform and supramolecular interfacial polymerization were utilized to fabricate supramolecular polymers, respectively, and DP of supramolecular polymers was calculated through end-group analysis by 1H NMR. As shown in Figures S8 and S9, the peak at 2.75 ppm is ascribed to Ha of UPy-monoamine as stoppers (denoted as UPy-C6-NH2, Figure S7a).55 Only the peaks of UPy-C6-NH2 as chain stoppers appeared in the 1H NMR (Figures S8 and S9), possibly because supramolecular polymers containing two UPyC6-NH2 as stoppers tended to precipitate in solution and at the interface. Then, the ratio of bifunctional monomers and chain stoppers UPy-C6-NH2 was used to determine the DP of supramolecular polymers. As shown in Figure 3a, DP of the supramolecular polymer fabricated by supramolecular interfacial polymerization was about 17 at the reaction time of 4 h. By comparison, DP of supramolecular polymers prepared by solution polymerization was about 6 under the same conditions. As a result, compared with solution polymerization, supramolecular polymers with higher molecular weights can be obtained through supramolecular interfacial polymerization of miscible monomers. C
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Macromolecules polymerization. To study the effective concentration of monomers at the water−chloroform interface, pendant drop tests was employed. As shown in Figure S11, the interface energy between pure chloroform and water was measured to be 31.33 mN m−1. By titrating a chloroform solution of (UPyNCO)2 into water, their interface energy was decreased to be 27.18 mN m−1. Similarly, by titrating pure chloroform into an aqueous solution of C6-NH2, their interface energy was also reduced to be 25.12 mN m−1. The decrease of interface energy indicates that the monomers in two phases tend to accumulate at the water−chloroform interface. In other words, effective concentrations of monomers at the interface are higher than that in solutions, thus leading to production of supramolecular polymers with higher molecular weights. To further investigate the diffusion-limited characteristic of supramolecular interfacial polymerization, kinetics of solution and interfacial polymerization was monitored by 1H NMR under different reaction times. As shown in Figure 3a, it is found that DP of the supramolecular polymers prepared by interfacial polymerization increased from 6 to 17 with increase of reaction time from 20 min to 4 h. However, DP of the supramolecular polymers prepared by solution polymerization reached 5 at the reaction time of 15 min, and it remained nearly unchanged with extension of the reaction time from 15 min to 4 h. The growth of supramolecular polymer chains during supramolecular interfacial polymerization could result from its diffusion-limited characteristic. Furthermore, the growth of supramolecular polymers was supported by kinetics study of the isocyanate−amine reaction. As shown in Figure S15, the conversion rate of this reaction in supramolecular interfacial polymerization was increased from 60% to 82% as the time evolved from 20 min to 4 h, while that in solution polymerization quickly reached 94% within 15 min under same conditions. It is clear that the reaction rate of solution polymerization is remarkably higher than that of supramolecular interfacial polymerization. Considering the higher effective concentrations of monomers at the interface, kinetics of supramolecular interfacial polymerization should be limited by diffusion of monomers, which agrees well with typical characteristics of conventional interfacial polymerization. Owing to fast isocyanate−amine reactions in the process of supramolecular interfacial polymerization, monomers may tend to react with ends of the growing polymer chain before they could penetrate through polymer films to start the growth of new chains.46 Therefore, in comparison with solution polymerization, higher effective concentrations of monomers and diffusion-limited characteristic can be responsible for the formation of supramolecular polymers with higher molecular weights by supramolecular interfacial polymerization. Tuning Chain Structures and Properties of Supramolecular Polymers. To understand if chain structures of supramolecular polymers could be controlled through supramolecular interfacial polymerization by changing monomer structures, we constructed a series of supramolecular polymers using different diamine monomers. Two kinds of diamine monomers bearing alkyl (Cn, n = 4, 6, 8, 10) or ethylene glycol (EGn, n = 0, 1, 2, 3) units were successfully employed to fabricate tailor-made supramolecular polymers through supramolecular interfacial polymerization. Then, Tg of these supramolecular polymers was determined by DSC as shown in Figure 4. By increasing the length of alkyl units from 4 to 10, their Tg decreased from 117.9 to 101.3 °C (Figure 4a). It is possible that such decrease of Tg should be resulted from the
Figure 4. DSC traces and Tg of supramolecular polymers prepared with various diamine monomers, including different length of alkyl chain (a) and different ethylene glycol units (b).
increasing flexibility of supramolecular polymers with increasing length of alkyl chains. Since this modulation is not significant enough, we further introduced another series of diamine monomers bearing different length of ethylene glycol units. As shown in Figure 4b, Tg of these supramolecular polymers remarkably decreased from 108.7 to 63.3 °C along with the increasing number of ethylene glycol units from 0 to 3. Thus, these results indicate that increasing length of ethylene glycol units will result in more dramatic decrease of Tg than that of alkyl chains. The reason behind it can be rationalized that the ethylene glycol units can endow the obtained supramolecular polymers with higher flexibility than the alkyl chains. Therefore, we have successfully demonstrated that supramolecular polymers constructed by supramolecular interfacial polymerization can be easily diversified, and their properties can be also effectively tuned by altering monomer structures. The mechanical properties of supramolecular polymers were investigated through indentation measurements by AFM. Typically, we chose supramolecular polymers fabricated by C6-NH2 and EG1-NH2 monomers for demonstration. As shown in Figure S16, the elastic modulus of supramolecular polymers prepared by C6-NH2 monomer was determined to be 1.0 ± 0.5 GPa, and the elastic modulus of supramolecular polymers fabricated by EG1-NH2 monomer was about 3.1 ± 0.7 GPa. Therefore, these results indicate that the elastic modulus of supramolecular polymers at room temperature is in the range of glassy polymers, which agrees well with the above DSC results. Supramolecular Interfacial Copolymerization. We wondered if interfacial copolymerization could be utilized to further diversify chain structures and properties of supramolecular polymers. To answer this question, two diamine monomers (EG1-NH2 and C8-NH2) in different molar ratios in D
DOI: 10.1021/acs.macromol.8b00289 Macromolecules XXXX, XXX, XXX−XXX
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the water phase were copolymerized with supramonomers (UPy-NCO) 2 to construct a series of supramolecular copolymers. As shown in Figure 5, by varying the molar ratio
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of China (21434004, 21704056). We thank Yang Jiao and Lingda Zeng at Tsinghua University for their constructive discussion. We also thank Zhen Wang at Renmin University of China for his assistance on pendant drop test as well as Meng Zhou and Dr. Haijun Yang at Tsinghua University for their help on solid-state NMR measurements.
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Figure 5. DSC traces and Tg of supramolecular polymers prepared by supramolecular interfacial copolymerization of C8-NH2 and EG1-NH2 in different molar ratios.
of C8-NH2 from 0.0 to 1.0, Tg of supramolecular polymers was easily controlled from 91.1 to 108.3 °C. It should be noted that the increase of Tg is not linear with the increase of the molar ratio. This may be because C8-NH2 monomers can diffuse from the water phase to chloroform phase faster than EG1-NH2 monomers. Therefore, these results illustrate that supramolecular interfacial copolymerization offers a simple and effective method for regulating the properties of supramolecular polymers.
4. CONCLUSION In summary, comparative study indicates that supramolecular polymers with higher molecular weights can be obtained through supramolecular interfacial polymerization than solution polymerization. Based on supramolecular interfacial polymerization, structures and properties of supramolecular polymers can be well tuned by changing monomer structures and copolymerization of different monomers. In addition to linear supramolecular polymers, supramolecular polymers with crosslinked and branched topological structures are expected to be produced with similar methodology. We anticipate that this line of research will further enrich the methodology of supramolecular polymerization for fabricating supramolecular polymeric materials with tailor-made architectures and functions.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.8b00289. NMR spectra, ESI-MS spectra, FT-IR spectra, pendant drop tests, SEM images, and AFM measurements (PDF)
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REFERENCES
AUTHOR INFORMATION
Corresponding Authors
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[email protected]. ORCID
Xi Zhang: 0000-0002-4823-9120 E
DOI: 10.1021/acs.macromol.8b00289 Macromolecules XXXX, XXX, XXX−XXX
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Macromolecules
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DOI: 10.1021/acs.macromol.8b00289 Macromolecules XXXX, XXX, XXX−XXX
