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Macromolecular Chemistry and Physics

Aqueous Emulsion Polymerization of Substituted Acetylenes: Effects of Organic Solvent and Analysis of Blue Shifts and Emulsion Polymerization Mechanism
Bo Chen, Xuan Liu, Chuqi Xu, Ci Song, Xiaofeng Luo, Wantai Yang, Jianping Deng*
A series of optically active nanoparticles composed of helical substituted polyacetylene is prepared via emulsion polymerization. A specic organic solvent is required for solid substituted acetylene monomers to undergo emulsion polymerization. The effects of this organic solvent are investigated. Its amount is found to be decisive for obtaining stable polymer emulsions. The helical conformations of the substituted polyacetylenes in nanoparticle state are identied with the help of CD and UV-vis spectra. A blue shift occurs in CD and UV-vis spectra of some of the polyacetylene emulsions. The underlying driving force for the blue shift is discussed, and an emulsion polymerization mechanism is proposed.

1. Introduction
Conjugated polymers have attracted a great deal of interest because of the unique structures and the remarkably potential applications, in particular, as novel optical and electrical materials. The recent progress in polymer chemistry afforded the easy synthesis of (composite) nanoparticles (NPs) constituted by conjugated polymers, for instance, polyaniline,[1] polypyrrole,[2] polythiophene,[3] and so forth. However, for polyacetylene and the derivatives, even though large achievements have been made in this intriguing research eld,[4] only few studies have been found focusing on the preparation of NPs derived from them,[5] to which Mecking and co-workers[6] have made remarkable contribution.
B. Chen, X. Liu, C. Song, X. Luo, Prof. W. Yang, Prof. J. Deng State Key Laboratory of Chemical Resource Engineering, College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China E-mail: dengjp@mail.buct.edu.cn C. Xu Xiamen Sunrui Ship Coatings Co. Ltd., China Shipbuilding industry Co., Xiamen 361101, China
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We have performed a series of emulsion polymerizations of acetylene derivatives, providing a variety of NPs composed of substituted polyacetylenes.[7] Such emulsion polymerizations were performed to circumvent to some degree the limitations frequently observed in substituted polyacetylenes, that is, low solubility, low processability, and low stability against heat and oxygen, as mentioned earlier.[7c] We further revealed that the formation of NPs little affected the polymers secondary structures. In more detail, the substituted polyacetylenes constituting NPs can adopt helical conformations, just like in the state of polymer solution. More interestingly, emulsion polymerization is favorable for the substituted polyacetylenes to adopt helical structures. Based on these investigations, we further prepared core/shell structured and hollow twolayered hybrid NPs composed of helical substituted polyacetylenes.[8] The structural distinction and the potential applications of such NPs encourage us to deepen the investigations. Some key factors affecting the emulsion polymerizations mentioned above were investigated in detail, by which the formula for polymerizations was optimized.[7] Nevertheless, for solid substituted acetylene monomers, how to effectively charge them into the aqueous

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polymerization system is still an open question. For this purpose, we utilized a specic solvent which can both solubilize the hydrophobic monomer and dissolve in water. We found that the content of this specic solvent is one of the key factors determining the formation of stable polymer emulsions. In the present study, we thus investigated in detail the effects of this special solvent on emulsion polymerization. In addition, we also found that some polymer emulsions show a blue shift in both circular dichroism (CD) and UV-vis spectra (compared with the corresponding polymer solution), whereas others did not show this phenomenon. Therefore, the present article also discusses the occurrence of blue shift. Finally, based on the present investigation and the earlier ones,[7,8] we propose an aqueous catalytic emulsion polymerization mechanism of substituted acetylene monomers. We are convinced that the present article will be helpful for our understanding more deeply the unique type of emulsion polymerization and will be useful for further designing and preparing advanced conjugated materials.

with deionized water before measurement. Number-average molecular weight ( Mn) and molecular weight distributions ( Mw/ Mn) of the polymers were determined by gel permeation chromatography (GPC, Waters 515-2410 system) calibrated by using polystyrenes as standard and tetrahydrofuran (THF) as eluent. Transmission electron microscopy (TEM) images were taken on a Hitachi H-800 electron microscope. Before measuring TEM and CD spectra, the original polymer emulsions were diluted with water to a suitable concentration. Specic rotations were measured on a Jasco P-1020 digital polarimeter with a sodium lamp as the light source at room temperature.

2.3. Monomer Synthesis and Emulsion Polymerization

Monomer 1 (M1 in Scheme 1) was synthesized following a previously reported method.[10] The emulsion polymerization process was introduced in detail earlier.[7] Taking H2O/DMF = 9/12 v/v as an example (Table 1), a typical procedure is stated as the following: a 50 mL glass reactor equipped with a reux condenser, a stirrer, an N2 inlet, and a dropping funnel was rst deaerated by purging N2 for 30 min. A predetermined amount of Triton X-100 (1.52 g, 2.4 mmol) and a given amount of deionized water (9 mL) were added in the reactor. The water used for polymerization was also deaerated for 30 min in advance. The aqueous solution was stirred under a stirring rate of 350 rpm at 30 C for 15 min to allow the Triton X-100 to dissolve completely. During this process and the subsequent polymerization, N2 bubbling was maintained all the time. A certain amount of M1 (0.09 g, 0.33 mmol) was dissolved in DMF (6 mL) in advance. The solution was purged with N2 to exclude the dissolved oxygen. Afterward, this solution was added dropwise into the reactor containing the emulsier solution. The solution was stirred at 350 rpm under nitrogen gas at 30 C for 10 min. By the end of this stage, homogeneous and clear emulsion was obtained. It indicates that the hydrophobic monomer molecules diffused inside the micelles formed by the emulsier. Next, a predetermined amount of catalyst (0.0038 g, 7.4 mol) was dissolved in DMF (6 mL) beforehand and the solution was bubbled with nitrogen. This solution was added dropwise in the above reactor like the monomer/DMF solution. The dropping

2. Experimental Section
2.1. Materials
The solvents were distilled under reduced pressure in advance. 1S-(+)-10-Camphorsulfonyl chloride, phenylacetylene, propargylamine, pyridine, poly(ethylene glycol) tert-octylphenyl ether (Triton X-100), and sodium dodecylsulfate (SDS) were purchased from Aldrich and used as received without further purication. (nbd)Rh+B(C6H5)4 was prepared as reported.[9]

2.2. Measurements
Circular dichroism and UV-vis absorption spectra were recorded on a Jasco 810 spectropolarimeter equipped with a JULABO heating immersion circulator. For emulsions, they were diluted

Table 1. Emulsion polymerization results of M1 with varied H2O/DMF ratio (Monomer: 0.33 mmol, catalyst: 7.4 mol, monomer/Triton X-100 = 1:7.3 (mol mol1), temperature: 30 C, polymerization time: 1.5 h).

H2O/DMF v/v 18/3

e) e)

Molecular weight of polymer Mna) 9900 10 180 Mw /Mna) 1.31 1.27 2.80

Particle diameterb) [nm] 89.7 89.1 90

c) [] 847 851

Polymerizationd)

precipitation precipitation emulsion emulsion solution solution

15/6 12/9 9/12 6/15

e) f)

Monomer 2
d)

25 700

by GPC (polystyrenes as standard, THF as eluent); b)Obtained according to TEM; c)Obtained from the obtained emulsions; The appearance of the product after polymerization; e)Stable emulsion could not be obtained; f)Monomer 2 is liquid; concentration 5 102 M, catalyst concentration 103 M, monomer/SDS = 1/5 mol/mol, temperature 30 C, polymerization time 3 h.

a)Determined

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Aqueous Emulsion Polymerization of Substituted Acetylenes . . .

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speed was about 40 drops per minute. After the complete catalyst solution had been added, the stirring speed was slowed to about 300 rpm to make the emulsion particles grow, and the polymerization proceeded under N2 at 30 C for 1.5 h. At the beginning of polymerization, the solution was colorless and transparent; with the occurrence of polymerization, the color of the solution changed slowly to yellow-green. After polymerization, rotary evaporator was used to remove the water and DMF in the obtained emulsion, providing a mixture of emulsier and polymer. Afterward, the product was placed in water and stirred at room temperature for at least 5 min to make the emulsier dissolve completely. Eventually, CHCl3 solution was ltered, collected, and concentrated to provide the pure polymer.

3. Results and Discussion

3.1. Effects of DMF on Emulsion Polymerization In the present study, M1 and M2 (shown in Scheme 1) are utilized to perform emulsion polymerization, providing polymer 1 emulsion and polymer 2 emulsion from M1 and M2, respectively. M1 and M2 are used because both of them are hydrophobic, and M1 is a chiral solid monomer, whereas M2 is an achiral liquid monomer. The emulsion of polymer 1 was found to demonstrate optical activity, because of the formation of helical structures of predominant screw sense in polymer 1. In addition, polymer 1 emulsion and polymer 2 emulsion differ largely with respect to blue shifts in CD and UV-vis spectra, as to be discussed later. For performing emulsion polymerization in aqueous media, solid monomer 1 (M1) should be dissolved rst in a suitable organic solvent, which was then added in emulsier (Triton X-100)/H2O aqueous system. This organic solvent should be soluble in water and simultaneously can solubilize M1. DMF was proved to be a good choice for this specic requirement. In the course of our experiments, we found that the content of DMF played a large role in the emulsion polymerization under investigation.

Accordingly, we investigated the inuence of DMF content on the emulsion polymerization. The relevant polymerization results are listed in Table 1. When the concentration of DMF was lower (H2O/DMF = 18/3 and 15/6 v/v in Table 1), M1 could indeed undergo polymerization; however, the polymer emulsion was unstable, since observable precipitation occurred in these two cases. This indicates that DMF was not enough in amount to transfer all the monomer molecules into the emulsier micelles. It further means that DMF diffuses too quickly in water before the monomer molecules (and/ or Rh-catalyst) were all transferred inside the emulsier micelles and some polymerization took place outside the micelles. Thus, the polymerization systems are not stable enough. Table 1 shows that when the amount of DMF is increased (H2O/DMF = 12/9 and 9/12 v/v), the formed polymer emulsions became quite stable, without noticeable precipitation occurring. The emulsions can be stored for at least half a year, without noticeable change. The emulsions were characterized by TEM, CD, and UV-vis spectroscopy techniques. These measurements will be discussed in detail later on. The pure polymer from monomer 1 (with H2O/DMF = 12/9 v/v) was subjected to FTIR and 1H NMR measurements, and the obtained spectra are shown in Figures S1 and S2 (see Supporting Information). When DMF was further increased to H2O/DMF = 6/15 v/v, M1 underwent solution polymerization rather than emulsion polymerization. This assumption was made according to the TEM images (to be discussed later) in which no particles can be found. In addition, the polymerization product seems more transparent than the others, as illustrated in Figure 1. The photographs of polymerization product obtained with varied H2O/DMF ratio are all presented in Figure 1 for a clear visual comparison. Among the ve polymer samples, the rst two (A and B) contained precipitation at the bottom of the bottle, whereas C and D are similar to the earlier ones with SDS as emulsier for the monomers emulsion polymerization.[7] For the last one (E), it seems the most transparent, indicating to some degree its solution nature

Scheme 1. The structures of monomers 1 and 2.

Figure 1. Photographs of polymer 1 emulsions prepared using varying H2O/DMF ratios: (A) 18/3, (B) 15/6, (C) 12/9, (D) 9/12, (E) 6/15 v/v (for detailed polymerization conditions, see Table 1).

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Figure 2. TEM images of polymer 1 emulsions prepared using different H2O/DMF ratios: (A) 18/3; (B) 15/6; (C) 12/9; (D) 9/12 v/v (for polymerization conditions, see Table 1).

rather than emulsion. The differences among the ve samples are considered as being originated from the varied amount of DMF, as discussed earlier. The TEM images in Figure 2 also provide further support for our consideration above. In the TEM images of A and B, no regular spherical particles can be observed, demonstrating the formation of precipitation in these two systems. For C and D, regular NPs are clearly observed. The NPs are of 80 nm in diameter. For the last sample with H2O/DMF ratio being 6/15 v/v, nothing can be observed in the TEM image (the image thus not shown). These observations veried our conclusions made on the effects of DMF on emulsion polymerization. The above consideration is illustratively presented in Scheme 2. Briey, DMF is required to transfer solid M1 and Rh-based catalyst inside the micelles in aqueous media. However, only DMF in an appropriate amount is favorable for the monomer to undergo emulsion polymerization, providing stable polymer emulsion. This nding is helpful for us to continue our research dealing with emulsion polymerization of substituted acetylene monomers. 3.2. Emulsion Polymerization Mechanism Initially, we thought that the catalytic emulsion polymerization stated above should be considered as microemulsion polymerization.[7] Nevertheless, the

subsequent investigations seem not to approve this view. In more detail, we ever thought that DMF should play a role of co-emulsier for the substituted acetylene monomers to undergo microemulsion polymerization. But as far as a liquid monomer is concerned, such as M2 (phenylacetylene in Scheme 1) to be involved in detail later, it can undergo emulsion polymerization without using DMF as a co-emulsier or carrier. (The relevant data are presented in Table 1. The FTIR and 1H NMR spectra of the pure polymer derived from monomer 2 are illustrated in Figures S3 and S4 in Supporting Information.) In addition, we ever tried both hydrophobic [(nbd)Rh+B(C6H5)4] and hydrophilic [Rh(cod)2BF4] catalyst for performing emulsion polymerization, but only the former offered stable substituted polyacetylene emulsions.[7] Therefore, the present study together with the previous ones enables us to propose a mechanism on this novel type of catalytic emulsion polymerization in aqueous media. The proposed emulsion polymerization mechanism is outlined in Scheme 3. Even though a variety of emulsion polymerizations have been accomplished with substituted acetylene monomers in our laboratory, the involved polymerization mechanism has not yet been specically considered. On the basis of the present study and our earlier relevant studies, the underlying mechanism will be analyzed herein. Still taking M1 as representative, our consideration is schematically presented in Scheme 3. Emulsier (Triton X-100 or SDS) forms micelles in water rst, when the monomer solution (e.g., M1 in DMF) or liquid monomer (e.g., M2) is added in this

Scheme 2. Schematic illustration for polymerization of M1 with variying H2O/DMF ratios.

Scheme 3. Proposed emulsion polymerization mechanism to form helical substituted polyacetylene NPs.

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be assigned to the phenyl group in the emulsier Triton X-100. This strong absorption shields the absorption of the polymer in the emulsions. To explore the underlying reason for the blue shifts occurring in Figure 3, we further investigated M2 in a similar way for conducting emulsion polymerization of M1. M2 smoothly underwent emulsion polymerization, as evidenced by Figure 3. (A) CD and (B) UV-vis spectra of polymer 1 emulsions with varied H2O/DMF the TEM images (A) and photograph (B) ratio (for detailed polymerization conditions, see Table 1). For measuring CD and UV-vis in Figure 4. In this case, the NPs are regspectra, the original emulsions were diluted 1:20 with water (0.8 103 M by monomer ular, with 90 nm in diameter. Figure 4B unit). The spectra were recorded at 25 C. shows the yellowish color in polymer 2 emulsion, much different from the ones in Figure 1. We think that the difference in emulsion color aqueous system, the hydrophobic monomer molecules is originated in the different effective conjugation length disperse into the micelles. When the hydrophobic Rh of the polymer main chains. This will be involved again catalyst is added in, its molecules also disperse inside the below. The Mn and Mw/Mn of polymer 2 thus obtained micelles, in which Rh catalyst initiates the polymerization were 25 700 and 2.80, respectively. of monomer. Finally, substituted polyacetylene NPs emulFigure 5 presents the UV-vis absorption spectra of sions are generated. More interestingly, the polymers conpolymer 2 in the forms of both emulsion and solution (in stituting the NPs can adopt helical structures just like the CHCl3). The insert is an enlarged spectrum of polymer 2 corresponding polymer chains in solution. Such polymer in CHCl3 solution. From the spectra in Figure 5 and referemulsions exhibited considerable optical activity, as will ring to the reports,[7,8,11,13,14] we conclude that in the state be observed in polymer 1 emulsion. of NPs, polymer 2 also adopted helical conformations, just like polymer 1 discussed above. Nevertheless, polymer 2 3.3. Blue Shifts in CD and UV-vis Spectra in solution did not show CD effect, because there is no chiral factor in this polymer, and the helices formed in it With stable emulsions in hand, we further characterized are composed of both right- and left-handed screw sense the polymer emulsions with CD and UV-vis spectroscopy, in equal amount. For the same reason, polymer 2 emulaiming at elucidating the secondary structures of the subsion failed to show CD signal in CD spectra either. stituted polyacetylene forming the NPs. Herein, it should We can nd an interesting difference between the be stressed that CD and UV-vis spectroscopies have been spectra in Figure 3 and Figure 5. In more detail, both the proved highly efcient for exploring the helical conformaCD and UV-vis spectra of polymer 1 emulsion demontions of substituted polyacetylenes in solution,[7] NPs,[8,11] strated a remarkable blue shift when compared with the and (hydro)gel state.[12] For polymer 1 emulsions, the relecorresponding spectra of polymer 1 in solution (menvant spectra are presented in Figure 3A (CD) and 3B (UV-vis tioned above). However, such a blue shift is not observed in absorption spectra). polymer 2 emulsion (vs. polymer 2 solution). The blue shift For the two polymer emulsions, both of them showed was also found in emulsication of helical substituted polyintense CD signal around 300 nm (Figure 3A). According acetylenes, which was specically investigated earlier.[15] to our proceeding investigations and the specic optical The above-mentioned blue shift can be explained by rotations in Table 1, the CD spectra in Figure 3A demonScheme 4A. We considered that whether the blue shift strate the helical structures formed in the substituted polyacetylenes constituting the NPs. However, the CD spectra showed a considerable blue shift when compared with the corresponding CD spectra of the same polymer solution reported in our earlier article.[10] (In solution, the CD spectra appeared around 410 nm.[10]) It is important to point out that some of the helical substituted polyacetylenes did not show such a blue shift, for example, polymer 2, which will be discussed in detail in next section. The driving force for the blue shifts will also be considered below, taking polymers 1 and 2 as two representatives. In Figure 4 . (A) TEM image and (B) photograph of polymer 2 emulFigure 3B, the strong absorption around 275 nm should sion (for polymerization conditions, see Table 1).
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effective conjugation length of the polymer main chains, as reected by blue shifts in the CD and UV-vis spectra in Figure 3. This type of substituted polyacetylene is well exemplied by polymer 1 in the present study. On the other hand, for the polymers with relatively bulky or rigid pendent groups, when the polymers form NPs, the bulky pendent groups will prevent the polymer main chains from compacting so tightly as in the polymers with not-so-bulky pendent groups. Consequently, the effective conjugation length of the polymer backbones will change little in NPs state when compared with the same polymer in solution. This idea is schematically illustrated in Scheme 4B. Polymer 2 in the current study is such a substituted polyacetylene.

4. Conclusion
Monomers 1 and 2 smoothly underwent catalytic emulsion polymerization in aqueous media. A specic organic solvent (DMF in the current study) is required for introducing solid monomer 1 into the emusier micelles. The amount of this solvent played a crucial role for forming the stable polymer emulsion. The as-prepared emulsions exhibited considerable optical activity because of the substituted polyacetylene chains adopting helical structures with preferential screw sense. Blue shifts were observed in polymer 1 emulsion. For polymer 2 emulsion, no such a blue shift took place. The underlying driving force for the occurrence of blue shifts was put forward. According to the present study and the earlier related investigations, a polymerization mechanism was provided for the catalytic emulsion polymerizations of substituted acetylene monomers.

Figure 5. UV-vis spectra of polymer 2 emulsion and solution (insert). (For the conditions for emulsion polymerization, see Figure 4). The concentration for measuring UV-vis absorbance: emulsion after dilution with water by 250 times (0.2 103 M); solution, 0.1 103 M. Temperature, 25 C.

occurs or not predominantly depends on the substituent groups in the side chains of the polyacetylenes. For the polymers with relatively less bulky pendent groups, the polymer backbones can be compacted to some degree in the course of forming NPs. This leads to the shortened

Supporting Information
Supporting Information is available from the Wiley Online Library
or from the author. Acknowledgements: This work is supported by the National Natural Science Foundation of China (21174010, 20974007, 20574004), the Fundamental Research Funds for the Central Universities (ZZ1117), and the Project of Polymer Chemistry and Physics, Beijing Municipal Commission of Education. Received: November 3, 2011; Revised: December 14, 2011; Published online: March 2, 2012; DOI: 10.1002/macp.201100610 Keywords: blue shifts; chiral; emulsion polymerization; helical polymers; substituted polyacetylenes Scheme 4 . Illustration of blue shift occurring in helical substituted polyacetylene emulsion. (A) The substituted pendant groups are not bulky enough and in the formation of NPs, compacting of the polymer chains occurs, resulting in blue shifts in CD and UV-vis spectra. (B) The bulky pendant groups prevent the polymer chains from such a considerable compact.

[1] a) B. Davodi, M. S. Lashkenari, H. Eisazadeh, Synth. Met. 2011, 161, 1207; b) L. R. Nemzer, A. Schwartz, A. J. Epstein, Macromolecules 2010, 43, 4324; c) B. A. Deore, M. S. Freund, Macromolecules 2009, 42, 164.

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[2] a) K. Leonavicius, A. Ramanaviciene, A. Ramanavicius, Langmuir 2011, 27, 10970; b) S. S. Jeon, C. Kim, J. Ko, S. S. Im, J. Mater. Chem. 2011, 21, 8146. [3] a) Z. Wang, Y. Wang, D. Xu, E. S. W. Eric, Y. Zhang, Synth. Met. 2010, 160, 921; b) S. J. Lee, J. M. Lee, H. Z. Cho, W. G. Koh, I. W. Cheong, H. J. Kim, Macromolecules 2010, 43, 2484. [4] For some recent reviews: a) M. Goh, S. Matshshita, K. Akagi, Chem. Soc. Rev. 2010, 39, 2428; b) E. Yashima, K. Maeda, H. Iika, Y. Furusho, K. Nagai, Chem. Rev. 2009, 109, 6102; c) J. Liu, J. W. Y. Lam, B. Z. Tang, Chem. Rev. 2009, 109, 5799; d) G. R. Jonathan, V. Percec, Acc. Chem. Res. 2008, 41, 1641; e) T. Masuda, J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 165; f) M. G. Mayershofer, O. Nuyken, J. Polym. Sci., Part A: Polym. Chem. 2005, 43, 5723. [5] J. O. Krause, M. T. Zarka, U. Anders, R. Weberskirch, O. Nuyken, M. R. Buchmeiser, Angew. Chem. Int. Ed. 2003, 42, 5965. [6] a) J. Huber, S. Mecking, Angew. Chem. Int. Ed. 2006, 45, 6314; b) J. Huber, S. Mecking, Polym. Mater. Sci. Eng. 2007, 96, 306; c) V. Monteil, P. Wehrmann, S. Mecking, J. Am. Chem. Soc. 2005, 127, 14568. [7] a) X. F. Luo, J. P. Deng, W. T. Yang, Angew. Chem. Int. Ed. 2011, 50, 4909; b) X. F. Luo, L. Li, J. P. Deng, T. T. Guo, W. T. Yang, Chem. Commun. 2010, 46, 2745; c) J. P. Deng, B. Chen, X. F. Luo, W. T. Yang, Macromolecules 2009, 42, 933. [8] a) B. Chen, J. P. Deng, W. T. Yang, Adv. Funct. Mater. 2011, 21, 2345; b) L. Ding, Y. Y. Huang, Y. Y. Zhang, J. P. Deng,

[9] [10] [11] [12]

[13]

[14]

[15]

W. T. Yang, Macromolecules 2011, 44, 736; c) B. Chen, J. P. Deng, W. T. Yang, Colloid Polym. Sci. 2011, 289, 133; d) B. Chen, J. P. Deng, W. T. Yang, Macromolecules 2010, 43, 9613; e) X. F. Luo, X. Q. Liu, B. Chen, J. P. Deng, W. T. Yang, J. Polym. Sci., Part A: Polym. Chem. 2010, 48, 5611; f) B. Chen, J. P. Deng, X. Q. Liu, W. T. Yang, Macromolecules 2010, 43, 3177. R. R. Schrock, J. A. Osborn, Inorg. Chem. 1970, 9, 2339. Z. G. Zhang, J. P. Deng, W. G. Zhao, J. M. Wang, W. T. Yang, J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 500. K. Zhou, L. Y. Tong, J. P. Deng, W. T. Yang, J. Mater. Chem. 2010, 20, 781. a) L. Li, X. Y. Du, J. P. Deng, W. T. Yang, React. Funct. Polym. 2011, 71, 972; b) X. Y. Du, J. B. Liu, J. P. Deng, W. T. Yang, Polym. Chem. 2010, 1, 1030. a) J. P. Deng, J. Tabei, M. Shiotsuki, F. Sanda, T. Masuda, Macromolecules 2004, 37, 9715; b) J. P. Deng, J. Tabei, M. Shiotsuki, F. Sanda, T. Masuda, Macromolecules 2004, 37, 1891; c) R. Nomura, Y. Fukushima, H. Nakako, T. Masuda, J. Am. Chem. Soc. 2000, 122, 8830; d) E. Sidney, V. S. Pande, J. Phys. Chem. B 2001, 105, 482. a) V. Percec, J. G. Rudick, M. Peterca, P. A. Heiney, J. Am. Chem. Soc. 2008, 130, 7503; b) K. Maeda, K. Tanaka, K. Morino, E. Yashima, Macromolecules 2007, 40, 6783; c) T. Aoki, T. Fukuda, K. Shinohara, T. Kaneko, M. Teraguchi, M. Yagi, J. Polym. Sci., Part A: Polym. Chem. 2004, 42, 4502. Y. Y. Zhang, X. F. Luo, J. P. Deng, W. T. Yang, Macromol. Chem. Phys. 2011, 212, 353.

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