Next Article in Journal
Acknowledgement to Reviewers of Polymers in 2017
Next Article in Special Issue
Fluorinated Polymers as Smart Materials for Advanced Biomedical Applications
Previous Article in Journal
The Influence of Chemically Modified Potato Maltodextrins on Stability and Rheological Properties of Model Oil-in-Water Emulsions
Previous Article in Special Issue
Solubility, Emulsification and Surface Properties of Maleic Anhydride, Perfluorooctyl and Alkyl Meth-Acrylate Terpolymers
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Polymers
Volume 10
Issue 1
10.3390/polym10010068
polymers-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Photoinduced Cu(II)-Mediated RDRP to P(VDF-co-CTFE)-g-PAN

by
Xin Hu
1,4,
Guopeng Cui
2,4,
Ning Zhu
2,4,
Jinglin Zhai
2,4 and
Kai Guo
2,3,4,*
1
College of Materials Science and Engineering, Nanjing Tech University, Nanjing 211800, China
2
College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211800, China
3
State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211800, China
4
Jiangsu National Synergetic Innovation Centre for Advance Materials, Nanjing Tech University, Nanjing 211800, China
*
Author to whom correspondence should be addressed.
Polymers 2018, 10(1), 68; https://doi.org/10.3390/polym10010068
Submission received: 12 December 2017 / Revised: 4 January 2018 / Accepted: 10 January 2018 / Published: 13 January 2018
(This article belongs to the Special Issue Fluorinated Polymers)
Browse Figures
Versions Notes

Abstract

:
Photoinduced Cu(II)-mediated reversible deactivation radical polymerization (RDRP) was employed to synthesize poly(vinylidene fluoride-co-chlorotrifluoroethylene)-graft-polyacrylonitrile (P(VDF-co-CTFE)-g-PAN). The concentration of copper catalyst (CuCl2) loading was as low as 1/64 equivalent to chlorine atom in the presence of Me6-Tren under UV irradiation. The light-responsive nature of graft polymerization was confirmed by “off-on” impulsive irradiation experiments. Temporal control of the polymerization process and varied graft contents were achieved via this photoinduced Cu(II)-mediated RDRP.

Graphical Abstract

1. Introduction

Atom transfer radical polymerization (ATRP) [1,2,3,4] has been one of the most powerful reversible deactivation radical polymerization (RDRP) methodologies for the synthesis of well-defined polymers [5,6,7,8]. The original ATRP was conducted with a high concentration of Cu(I) catalyst (equivalent to alkyl halide initiator) in order to compensate for unavoidable radical termination reactions. A series of ATRP variants have been developed to reduce the catalyst loading. Activators regenerated by electron transfer (ARGET) ATRP [9], initiators for continuous activator regeneration (ICAR) ATRP [10], electrochemically-mediated ATRP (eATRP) [11], and Cu(0)-mediated RDRP [12,13,14,15] have been proposed to decrease the copper concentration below 100 ppm.
Photopolymerization has become increasingly popular thanks to its unique advantages in temporal and spatial control [16,17,18,19,20]. Photoinduced Cu(II)-mediated RDRP achieved remarkable progress in tailor-made polymer synthesis [21,22,23,24]. The combination of low-concentration CuBr2 and excess tris[2-(dimethylamino)ethyl]amine (Me6-Tren) exhibited outstanding efficiency in acrylate polymerizations [25,26]. Well-defined homopolymers, telechelic block copolymers, brush polymers, and sequence controlled polymers were obtained via photoinduced Cu(II)-mediated RDRP [27,28,29,30,31,32,33,34,35]. Iridium [36,37,38,39] and ruthenium [40] complexes were also found to be effective photocatalysts to mediate visible light-induced ATRP. Recently, organocatalyzed ATRP (OATRP) was established to generate metal-free polymers by using photoredox catalyst [41,42,43,44,45,46,47,48,49,50,51]. This young yet rapidly growing research area would attract broad interest from both academia and industry.
Poly(vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-co-CTFE)) is one of the most used high-performance fluoropolymers with various applications [52]. Several kinds of chemical and physical modification strategies have been presented to improve the functionality and compatibility of fluoropolymers. ATRP was also employed to synthesize P(VDF-co-CTFE)-g-polystyrene (PS) and P(VDF-co-CTFE)-g-polyacrylates [53,54,55]. The dielectric and energy storage properties were enhanced by the introduction of graft chains, which could reduce the remnant polarization of the fluoropolymer [54]. This Cu(I)-mediated process required relative high catalyst loading and elevated reaction temperature to initiate the less active C–Cl bond in P(VDF-co-CTFE) backbone, which resulted in unexpected chain transfer reactions and dehydrochlorination reactions [56]. Cu(0)-mediated RDRP of acrylonitrile (AN) and methyl methacrylate (MMA) in the presence of P(VDF-co-CTFE) allowed colorless and purer P(VDF-co-CTFE)-g-PAN and P(VDF-co-CTFE)-g-PMMA copolymers for its mild reaction conditions and lower catalyst concentration [57,58,59]. Improvements were achieved by transferring the polymerization from a batch reactor to a copper tubular reactor, such as diminished inconsistent induction time, suppressed “hot spot” effect, and decreased copper and ligand concentration [60].
Herein, photoinduced Cu(II)-mediated RDRP was utilized for the graft modification of P(VDF-co-CTFE) (Scheme 1). Polymerizations of acrylonitrile in the presence of CuCl2/Me6-Tren under UV irradiation was investigated to evaluate its effect on the preparation of P(VDF-co-CTFE)-g-PAN with low catalyst concentration and temporal control of the polymerization process.

2. Experimental Section

2.1. Materials

P(VDF-co-CTFE) was provided by Solvay Solex (Brussels, Belgium) (Dyneon 31008, with the [VDF]:[CTFE] = 94:6, containing 0.89 mmol chlorine atom per gram). Acrylonitrile (AN) (J&K, Beijing, China, 99%) was washed by 5 wt % aqueous sodium hydroxide solution three times, and was subsequently rinsed with deionized water until neutralization. The resultant solution was dried overnight with anhydrous MgSO4, then distilled under reduced pressure to remove extant inhibitor and stored under N2 at −20 °C. Dimethyl sulfoxide (DMSO) (Xilong Chemical, Shenzhen, China, AR) was distilled under vacuum from CaH2. Other reagents were used as received. The source of the UV light (Shany Cosmetics Company, New York, NY, US) setup was a commercially available UV nail gel curing lamp with four 9 W bulbs (36 W, λmax ~365 nm, item model number: SH-KD-UVLAMP36W).

2.2. Synthesis Procedure

Polymerizations were conducted by using a Schlenk technique [57]. First, 0.500 g of P(VDF-co-CTFE) (VDF:CTFE = 94:6) (containing 0.445 mmol Cl atom) was dissolved in 10 mL DMSO with stirring before CuCl2·2H2O (2.4 mg, 0.0140 mmol) and Me6-Tren (19.2 mg, 0.0834 mmol) were added under N2 atmosphere. After adding 0.88 mL AN (13.35 mmol), the reactant mixture ([Cl]:[Cu]:[Me6-Tren]:[AN] = 1:(1/32):(6/32):30) was put into the ultraviolet light (λmax ~ 365 nm) while cooling with a hair dryer. Samples were taken at regular time intervals followed by precipitation in H2O/CH3OH (v:v = 1:1) mixture, washed three times with ethyl alcohol, and dried overnight under reduced pressure. The resultant graft copolymer was obtained for characterization.

2.3. Characterization

Nuclear magnetic resonance (NMR) spectra were recorded on a Bruker (Rheinstetten, Germany) (Advance III) 400 MHz instrument for solutions in DMSO-d6 containing tetramethylsilane (TMS) as internal standard. Fourier transform infrared (FTIR) spectroscopy of polymer films was performed on a Nicolet iS5 (Thermo Scientific, Madison, WI, US). Differential scanning calorimetric (DSC) analysis was conducted on a Discovery DSC 250 (TA instruments, New Castle, DE, US). After rapid heating and cooling cycles (at a rate of 20 °C/min) to remove the thermal history, the sample was heated at a rate of 10 °C/min under nitrogen atmosphere. Thermogravimetric analysis (TGA) (TA instruments, New Castle, DE, US) results were recorded on Netzsch STA 449 F3 Jupiter (Selb, Germany) in nitrogen atmosphere at a heating rate of 10 °C/min.

3. Results and Discussion

Poly(acrylonitrile) (PAN) and its copolymers have been widely used as precursors for novel carbon materials with outstanding properties and performances [43]. P(VDF-co-CTFE)-g-PAN copolymers could be synthesized via Cu(0)-mediated reversible deactivation radical polymerization (RDRP) in batch and flow reactors [57,60]. Comparing with traditional ATRP protocol, copper catalyst loading was as low as about 1/4 equivalent to the chlorine atoms in the batch reactor. Copper catalyst, however, is highly desirable to decrease in order to reduce the amount of metal residue, which would potentially influence the application of final material. Inspired by the work about photoinduced Cu(II)-mediated RDRP [25,26], CuCl2/Me6-Tren was employed to promote the polymerizations of AN with P(VDF-co-CTFE) as macroinitiator. The polymerization results are listed in Table 1. After 6 h of UV irradiation (λ ~ 365 nm, 36 W) while cooling with a hair dryer, P(VDF-co-CTFE)-g-PAN (graft content = 20.8 mol %) was obtained with a low copper concentration ([Cl]:[Cu]:[L]:[AN] = 1:(1/32):(6/32):30) (Table 1, run 5) according to NMR analysis [57]. A 13.4 mol % graft content was achieved, even upon reducing the catalyst feed ratio into 1/64 (Table 1, run 7). This would be favorable for the applications of resultant graft copolymers in dielectric devices.
Controlled experiments in the absence of light source or any reagent were conducted. P(VDF-co-CTFE) with no PAN graft chains was obtained by the removal of UV irradiation (Table 1, run 1). To further illustrate the light-responsive nature of the polymerization, a series of polymerizations were tested by introducing an “off-on” sequence ([Cl]:[Cu]:[L]:[AN] = 1:(1/32):(6/32):30). In Figure 1, the graft content reached 2.1 mol % after 30 min and stayed almost unchanged during 30 min dark. The re-exposure to UV enabled the polymerization to start again. These cycles were repeated several times. The omission of P(VDF-co-CTFE) afforded no product (Table 1, run 2), which indicated that autopolymerization of AN did not occur under the current condition. In the absence of catalyst/ligand, no graft content was observed (Table 1, run 3), which elucidated the control of activation/deactivation equilibrium by CuCl2/Me6-Tren.
The influence of [Cu]:[L] on graft polymerization was investigated. It was supposed that 1:6 would be better to yield a higher graft content (Table 1, runs 4, 5, and 6), which was consistent with previous reports [25,26]. Kinetics study showed a linear dependence between −ln(1-conversion) and reaction time. This confirmed that the polymerization rate was first-order with respect to the monomer concentration (Figure 2). Under the optimized reaction conditions, polymerizations with different monomer feed ratio were carried out to fabricate P(VDF-co-CTFE)-g-PAN with varied graft contents (Table 1, runs 8 and 9). A chain extension experiment was conducted. The resultant P(VDF-co-CTFE)-g-PAN (graft content = 20.8 mol %) was used as macroinitiator to initiate polymerization of AN ([Cl]:[Cu]:[L]:[AN] = 1:(1/32):(6/32):(30), UV (λmax = 365 nm)). The graft content was increased into 30.2 mol % upon another 6 h exposure.
The chemical structure of P(VDF-co-CTFE)-g-PAN was characterized by FTIR, 1H NMR, and 19F NMR. In Figure 3, the characteristic absorption peak at 2247 cm−1 (–CN) indicated the presence of PAN segments in the copolymer. The 1H NMR spectrum (Figure 4) displayed two multiple peaks of head-head and head-tail connections of VDF units (2.2–2.4 ppm and 2.7–3.2 ppm). The shoulder peak at 3.0–3.3 ppm corresponded to the proton signal of VDF adjacent to CTFE (–CF2CH2CFClCF2–). A new peak appearing around 1.9–2.1ppm was attributed to the proton on the methylene group of the AN unit (–CH2-CHCN–). Another new peak appeared at 3.0–3.3 ppm and overlapped with the proton signals of head-to-tail connections of VDF in P(VDF-co-CTFE), which was assigned to the methine proton (–CH2CHCN–). The signals of –CH2CHFCF2– from hydrogenation of CTFE unites and –CH=CFlCF2– from elimination of HCl from main chains were not observed. This indicated that the typical side reactions did not happen in this photoinduced Cu(II)-mediated RDRP process. The 19F NMR spectrum provided more information about the structure of graft copolymers. In Figure 5, the new peak appearing at 112.3 ppm was attributed to the AN units inserting into the C–Cl bond, where the C–C bond took the place of the C–Cl bond, which was consistent with the previous report [57]. No other new peaks were observed, which illustrated that the typical side reactions in traditional ATRP were avoided in this process.
The thermal properties of P(VDF-co-CTFE)-g-PAN was explored by using DSC and TGA. In Figure 6, one endothermic peak was observed on each curve below 180 °C, which was assigned to the melting of the crystalline fluoropolymers. The melting temperature decreased from 149 to 137 °C with the increase of PAN graft content. This suggested that the crystalline degree of P(VDF-co-CTFE) and the crystal domain size were influenced by the introduction of PAN graft segments. The TGA (Figure 7) showed that the pristine P(VDF-co-CTFE) began to decompose at about 400 °C, and about 40 wt % remained at 500 °C. Meanwhile, two polymer degradation stages were observed for the P(VDF-co-CTFE)-g-PAN copolymers. The first stage started from about 300 °C, which corresponded to the decomposition of PAN segment. The second stage began from about 450 °C, which was attributed to the degradation of P(VDF-co-CTFE) backbone chain. It was noteworthy that the weight remaining over 500 °C was enhanced with the increase of PAN content. It was supposed that the PAN was carbonized to carbon material with higher thermal stability.

4. Conclusions

In summary, poly(vinylidene fluoride-co-chlorotrifluoroethylene)-graft-polyacrylonitrile (P(VDF-co-CTFE)-g-PAN) with varied graft contents were prepared via photoinduced Cu(II)-mediated reversible deactivation radical polymerization (RDRP). Upon UV irradiation, CuCl2/Me6-Tren enabled low catalyst loading and temporal control of the polymerization process. This protocol might have potential application in the area of novel dielectric materials.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (21604037 and 21522604).

Author Contributions

Xin Hu and Kai Guo conceived and designed the experiments; Xin Hu and Guopeng Cui performed the experiments; Xin Hu, Ning Zhu and Kai Guo analyzed the data; Ning Zhu and Jinglin Zhai. contributed reagents/materials/analysis tools; Xin Hu wrote the paper.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Wang, J.; Matyjaszewski, K. Atom transfer radical polymerization in the presence of transition-metal complexes. J. Am. Chem. Soc. 1995, 117, 5614–5615. [Google Scholar] [CrossRef]
  2. Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T. Polymerization of Methyl Methacrylate with the Carbon Tetrachloride/Dichlorotris-(triphenylphosphine)ruthenium(II)/Methylaluminum Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living Radical Polymerization. Macromolecules 1995, 28, 1721–1723. [Google Scholar] [CrossRef]
  3. Matyjaszewski, K.; Xia, J. Atom Transfer Radical Polymerization. Chem. Rev. 2001, 101, 2921–2990. [Google Scholar] [CrossRef] [PubMed]
  4. Matyjaszewski, K. Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives. Macromolecules 2012, 45, 4015–4039. [Google Scholar] [CrossRef]
  5. Chiefari, J.; Chong, Y.; Ercole, F.; Krstina, J.; Jeffery, J.; Le, T.P.; Mayadunne, R.T.; Meijs, G.F.; Moad, C.L.; Moad, G. Living Free-Radical Polymerization by Reversible Addition-Fragmentation Chain Transfer: The RAFT Process. Macromolecules 1998, 31, 5559–5562. [Google Scholar] [CrossRef]
  6. Boyer, C.; Bulmus, V.; Davis, T.P.; Ladmiral, V.; Liu, J.; Perrier, S. Bioapplications of RAFT Polymerization. Chem. Rev. 2009, 109, 5402–5436. [Google Scholar] [CrossRef] [PubMed]
  7. Benot, D.; Chaplinski, V.; Raslau, R.B.; Hawker, C.J. Development of a Universal Alkoxyamine for “Living” Free Radical Polymerizations. J. Am. Chem. Soc. 1999, 121, 3904–3920. [Google Scholar] [CrossRef]
  8. Hawker, C.J.; Bosman, A.W.; Harth, E. New Polymer Synthesis by Nitroxide Mediated Living Radical Polymerizations. Chem. Rev. 2001, 101, 3661–3688. [Google Scholar] [CrossRef] [PubMed]
  9. Min, K.; Gao, H.; Matyjaszewski, K. Use of Ascorbic Acid as Reducing Agent for Synthesis of Well-Defined Polymers by ARGET ATRP. Macromolecules 2007, 40, 1789–1791. [Google Scholar] [CrossRef]
  10. Matyjaszewski, K.; Jakubowski, W.; Min, K.; Tang, W.; Huang, J.Y.; Braunecker, W.A.; Tsarevsky, N.V. Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents. Proc. Natl. Acad. Sci. USA 2006, 103, 15309–15314. [Google Scholar] [CrossRef] [PubMed]
  11. Magenau, A.J.D.; Strandwitz, N.C.; Gennaro, A.; Matyjaszewski, K. Electrochemically Mediated Atom Transfer Radical Polymerization. Science 2011, 332, 81–84. [Google Scholar] [CrossRef] [PubMed]
  12. Zhang, Y.; Wang, Y.; Matyjaszewski, K. ATRP of Methyl Acrylate with Metallic Zinc, Magnesium, and Iron as Reducing Agents and Supplemental Activators. Macromolecules 2011, 44, 683–685. [Google Scholar] [CrossRef]
  13. Percec, V.; Guliashvili, T.; Ladislaw, J.S.; Wistrand, A.; Stjerndahl, A.; Sienkowska, M.J.; Monteiro, M.J.; Sahoo, S. Ultrafast Synthesis of Ultrahigh Molar Mass Polymers by Metal-Catalyzed Living Radical Polymerization of Acrylates, Methacrylates, and Vinyl Chloride Mediated by SET at 25 °C. J. Am. Chem. Soc. 2006, 128, 14156–14165. [Google Scholar] [CrossRef] [PubMed]
  14. Anastasaki, A.; Nikolaou, V.; Nurumbetov, G.; Wilson, P.; Kempe, K.; Quinn, J.F.; Davis, T.P.; Whittaker, M.R.; Haddleton, D.M. Cu(0)-Mediated Living Radical Polymerization: A Versatile Tool for Materials Synthesis. Chem. Rev. 2016, 116, 835–877. [Google Scholar] [CrossRef] [PubMed]
  15. Anastasaki, A.; Nikolaou, V.; Haddleton, D.M. Cu(0)-mediated living radical polymerization: recent highlights and applications; a perspective. Polym. Chem. 2016, 7, 1002–1026. [Google Scholar] [CrossRef]
  16. Shanmugam, S.; Boyer, C. Organic photocatalysts for cleaner polymer synthesis. Science 2016, 352, 1053–1054. [Google Scholar] [CrossRef] [PubMed]
  17. Dadashi-Silab, S.; Doran, S.; Yagci, Y. Photoinduced Electron Transfer Reactions for Macromolecular Syntheses. Chem. Rev. 2016, 116, 10212–10275. [Google Scholar] [CrossRef] [PubMed]
  18. Chen, M.; Zhong, M.; Johnson, J.A. Light-Controlled Radical Polymerization: Mechanisms, Methods, and Applications. Chem. Rev. 2016, 116, 10167–10211. [Google Scholar] [CrossRef] [PubMed]
  19. Zivic, N.; Bouzrati-Zerelli, M.; Kermagoret, A.; Dumur, F.; Fouassier, J.; Gigmes, D.; Lalevée, J. Photocatalysts in Polymerization Reactions. Chem. Cat. Chem. 2016, 8, 1617–1631. [Google Scholar] [CrossRef]
  20. Pan, X.; Tasdelen, M.A.; Laun, J.; Junkers, T.; Yagci, Y.; Matyjaszewski, K. Photomediated controlled radical polymerization. Prog. Polym. Sci. 2016, 62, 73–125. [Google Scholar] [CrossRef]
  21. Tasdelen, M.A.; Uygun, M.; Yagci, Y. Photoinduced Controlled Radical Polymerization in Methanol. Macromol. Chem. Phys. 2010, 211, 2271–2275. [Google Scholar] [CrossRef]
  22. Tasdelen, M.A.; Uygun, M.; Yagci, Y. Photoinduced Controlled Radical Polymerization. Macromol. Rapid Commun. 2011, 32, 58–62. [Google Scholar] [CrossRef] [PubMed]
  23. Konkolewicz, D.; Schroder, K.; Buback, J.; Bernhard, S.; Matyjaszewski, K. Visible Light and Sunlight Photoinduced ATRP with ppm of Cu Catalyst. ACS Macro Lett. 2012, 1, 1219–1223. [Google Scholar] [CrossRef]
  24. Ribelli, T.G.; Konkolewicz, D.; Bernhard, S.; Matyjaszewski, K. How are Radicals (Re)Generated in Photochemical ATRP? J. Am. Chem. Soc. 2014, 136, 13303–13312. [Google Scholar] [CrossRef] [PubMed]
  25. Anastasaki, A.; Nikolaou, V.; Zhang, Q.; Burns, J.; Samanta, S.R.; Wladron, C.; Haddleton, A.J.; McHale, R.; Fox, D.; Percec, V.; et al. Copper(II)/Tertiary Amine Synergy in Photoinduced Living Radical Polymerization: Accelerated Synthesis of ω-Functional and α,ω-Heterofunctional Poly(acrylates). J. Am. Chem. Soc. 2014, 136, 1141–1149. [Google Scholar] [CrossRef] [PubMed]
  26. Jones, G.R.; Whitfield, R.; Anastasaki, A.; Haddleton, D.M. Aqueous Copper(II) Photoinduced Polymerization of Acrylates: Low Copper Concentration and the Importance of Sodium Halide Salts. J. Am. Chem. Soc. 2016, 138, 7346–7352. [Google Scholar] [CrossRef] [PubMed]
  27. Anastasaki, A.; Nkkolaou, V.; McCaul, N.W.; Simular, A.; Godfrey, J.; Waldron, C.; Wilson, P.; Kempe, K.; Haddleton, D.M. Photoinduced Synthesis of α,ω-Telechelic Sequence-Controlled Multiblock Copolymers. Macromolecules 2015, 48, 1404–1411. [Google Scholar] [CrossRef]
  28. Anastasaki, A.; Nikolaou, V.; Simular, A.; Godfrey, J.; Li, M.; Nurumbetov, G.; Wilson, P.; Haddleton, D.M. Expanding the Scope of the Photoinduced Living Radical Polymerization of Acrylates in the Presence of CuBr2 and Me6-Tren. Macromolecules 2014, 47, 3852–3859. [Google Scholar] [CrossRef]
  29. Anastasaki, A.; Nikolaou, V.; Pappas, G.S.; Zhang, Q.; Wan, C.Y.; Wilson, P.; Davis, T.P.; Whittaker, M.R.; Haddleton, D.M. Photoinduced sequence-control via one pot living radical polymerization of acrylates. Chem. Sci. 2014, 5, 3536–3542. [Google Scholar] [CrossRef]
  30. Chuang, Y.M.; Ethirajan, A.; Junkers, T. Photoinduced Sequence-Controlled Copper-Mediated Polymerization: Synthesis of Decablock Copolymers. ACS Macro Lett. 2014, 3, 732–737. [Google Scholar] [CrossRef]
  31. Chuang, Y.M.; Wenn, B.; Gielen, S.; Ethirajan, A.; Junkers, T. Ligand switch in photoinduced copper-mediated polymerization: synthesis of methacrylate-acrylate block copolymers. Polym. Chem. 2015, 6, 6488–6497. [Google Scholar] [CrossRef]
  32. Vandenbergh, J.; Reekmans, G.; Adriaensens, P.; Junkers, T. Synthesis of sequence-defined acrylate oligomers via photo-induced copper-mediated radical monomer insertions. Chem. Sci. 2015, 6, 5753–5761. [Google Scholar] [CrossRef]
  33. Frick, E.; Anastasaki, A.; Haddleton, D.M.; Barner-Kowollik, C. Enlightening the Mechanism of Copper Mediated PhotoRDRP via High-Resolution Mass Spectrometry. J. Am. Chem. Soc. 2015, 137, 6889–6896. [Google Scholar] [CrossRef] [PubMed]
  34. Discekici, E.H.; Anastasaki, A.; Kaminker, R.; Willenbacher, J.; Truong, N.P.; Fleischmann, C.; Oschmann, B.; Lunn, D.J.; de Alaniz, J.R.; Davis, T.P.; et al. Light-Mediated Atom Transfer Radical Polymerization of Semi-Fluorinated (Meth)acrylates: Facile Access to Functional Materials. J. Am. Chem. Soc. 2017, 139, 5939–5945. [Google Scholar] [CrossRef] [PubMed]
  35. Laun, J.; Vorobii, M.; Pereira, A.D.; Pop-Georgievski, O.; Trouillet, V.; Welle, A.; Barner-Kowollik, C.; Rodriguez-Emmenegger, C.; Junkers, T. Surface Grafting via Photo-Induced Copper-Mediated Radical Polymerization at Extremely Low Catalyst Concentrations. Macromol. Rapid Commun. 2015, 36, 1681–1686. [Google Scholar] [CrossRef] [PubMed]
  36. Fors, B.P.; Hawker, C.J. Control of a Living Radical Polymerization of Methacrylates by Light. Angew. Chem. Int. Ed. 2012, 51, 8850–8853. [Google Scholar] [CrossRef] [PubMed]
  37. Treat, N.J.; Fors, B.P.; Kramer, J.W.; Christianson, M.; Chiu, C.; Alaniz, J.R.; Hawker, C.J. Controlled Radical Polymerization of Acrylates Regulated by Visible Light. ACS Macro Lett. 2014, 3, 580–584. [Google Scholar] [CrossRef]
  38. Poelma, J.E.; Fors, B.P.; Meyers, G.F.; Kramer, J.W.; Hawker, C.J. Fabrication of Complex Three-Dimensional Polymer Brush Nanostructures through Light-Mediated Living Radical Polymerization. Angew. Chem. Int. Ed. 2013, 52, 6844–6848. [Google Scholar] [CrossRef] [PubMed]
  39. Melker, A.; Fors, B.P.; Hawker, C.J.; Poelma, E.J. Continuous flow synthesis of poly(methyl methacrylate) via a light-mediated controlled radical polymerization. J. Polym. Sci. A 2015, 53, 2693–2698. [Google Scholar] [CrossRef]
  40. Zhang, G.; Song, I.Y.; Ahn, K.H.; Park, T.; Choi, W. Free Radical Polymerization Initiated and Controlled by Visible Light Photocatalysis at Ambient Temperature. Macromolecules 2011, 44, 7594–7599. [Google Scholar] [CrossRef]
  41. Treat, T.J.; Sprafke, H.; Kramer, J.W.; Clark, P.G.; Barton, B.E.; de Alaniz, J.R.; Fors, B.P.; Hawker, C.J. Metal-Free Atom Transfer Radical Polymerization. J. Am. Chem. Soc. 2014, 136, 16096–16101. [Google Scholar] [CrossRef] [PubMed]
  42. Miyake, G.M.; Theriot, J.C. Perylene as an Organic Photocatalyst for the Radical Polymerization of Functionalized Vinyl Monomers through Oxidative Quenching with Alkyl Bromides and Visible Light. Macromolecules 2014, 47, 8255–8261. [Google Scholar] [CrossRef]
  43. Pan, X.; Lamson, M.; Yan, J.; Matyjaszewski, K. Photoinduced Metal-Free Atom Transfer Radical Polymerization of Acrylonitrile. ACS Macro Lett. 2015, 4, 192–196. [Google Scholar] [CrossRef]
  44. Pan, X.; Fang, C.; Fantin, M.; Malhotra, N.; So, W.Y.; Peteanu, L.A.; Isse, A.A.; Gennaro, A.; Liu, P.; Matyjaszewski, K. Mechanism of Photoinduced Metal-Free Atom Transfer Radical Polymerization: Experimental and Computational Studies. J. Am. Chem. Soc. 2016, 138, 2411–2452. [Google Scholar] [CrossRef] [PubMed]
  45. Liu, X.; Zhang, L.; Cheng, Z.; Zhu, X. Metal-free photoinduced electron transfer-atom transfer radical polymerization (PET-ATRP) via a visible light organic photocatalyst. Polym. Chem. 2016, 7, 689–700. [Google Scholar] [CrossRef]
  46. Theriot, J.C.; Lim, C.; Yang, H.; Ryan, M.D.; Musgrave, C.B.; Miyake, G.M. Organocatalyzed atom transfer radical polymerization driven by visible light. Science 2016, 352, 1082–1086. [Google Scholar] [CrossRef] [PubMed]
  47. Pearson, R.M.; Lim, C.; McCarthy, B.G.; Musgrave, C.B.; Miyake, G.M. Organocatalyzed Atom Transfer Radical Polymerization Using N-Aryl Phenoxazines as Photoredox Catalysts. J. Am. Chem. Soc. 2016, 138, 11399–11407. [Google Scholar] [CrossRef] [PubMed]
  48. Lim, C.; Ryan, M.D.; McCarthy, B.G.; Theriot, J.C.; Sartor, S.M.; Damrauer, N.H.; Musgrave, C.B.; Miyake, G.M. Intramolecular Charge Transfer and Ion Pairing in N,N-Diaryl Dihydrophenazine Photoredox Catalysts for Efficient Organocatalyzed Atom Transfer Radical Polymerization. J. Am. Chem. Soc. 2017, 139, 348–355. [Google Scholar] [CrossRef] [PubMed]
  49. Dadashi-Silab, S.; Pan, X.; Matyjaszewski, K. Phenyl Benzo[b]phenothiazine as a Visible Light Photoredox Catalyst for Metal-Free Atom Transfer Radical Polymerization. Chem. Eur. J. 2017, 23, 5972–5977. [Google Scholar] [CrossRef] [PubMed]
  50. Ryan, M.D.; Pearson, R.M.; French, T.A.; Miyake, G.M. Impact of Light Intensity on Control in Photoinduced Organocatalyzed Atom Transfer Radical Polymerization. Macromolecules 2017, 50, 4616–4622. [Google Scholar] [CrossRef]
  51. Ramsey, B.L.; Pearson, R.M.; Beck, L.R.; Miyake, G.M. Photoinduced Organocatalyzed Atom Transfer Radical Polymerization Using Continuous Flow. Macromolecules 2017, 50, 2668–2674. [Google Scholar] [CrossRef] [PubMed]
  52. Chu, B.; Zhan, X.; Ren, K.; Neese, B.; Lin, M.; Wang, Q.; Bauer, F.; Zhang, Q. A Dielectric Polymer with High Electric Energy Density and Fast Discharge Speed. Science 2006, 313, 334–336. [Google Scholar] [CrossRef] [PubMed]
  53. Guan, F.; Pan, J.; Wang, J.; Wang, Q.; Zhu, L. Crystal Orientation Effect on Electric Energy Storage in Poly(vinylidene fluoride-co-hexafluoropropylene) Copolymers. Macromolecules 2010, 43, 384–392. [Google Scholar] [CrossRef]
  54. Li, J.; Hu, X.; Gao, G.; Ding, S.; Li, H.; Yang, L.; Zhang, Z. Tuning phase transition and ferroelectric properties of poly(vinylidene fluoride-co-trifluoroethylene) via grafting with desired poly(methacrylic ester)s as side chains. J. Mater. Chem. C 2013, 1, 1111–1121. [Google Scholar] [CrossRef]
  55. Li, J.; Tan, S.; Ding, S.; Li, H.; Yang, L.; Zhang, Z. High-field antiferroelectric behaviour and minimized energy loss in poly(vinylidene-co-trifluoroethylene)-graft-poly(ethyl methacrylate) for energy storage application. J. Mater. Chem. 2012, 22, 23468–23476. [Google Scholar] [CrossRef]
  56. Tan, S.; Liu, E.; Zhang, Q.; Zhang, Z. Controlled hydrogenation of P(VDF-co-CTFE) to prepare P(VDF-co-TrFE-co-CTFE) in the presence of CuX (X = Cl, Br) complexes. Chem. Commun. 2011, 47, 4544–4546. [Google Scholar] [CrossRef] [PubMed]
  57. Hu, X.; Li, J.; Li, H.; Zhang, Z. Synthesis and characterization of poly(vinylidene fluoride-co-chlorotrifluoroethylene)-grafted-poly(acrylonitrile) via single electron transfer-living radical polymerization process. J. Polym. Sci. A 2012, 50, 3126–3134. [Google Scholar] [CrossRef]
  58. Hu, X.; Li, J.; Li, H.; Zhang, Z. Cu(0)/2,6-bis(imino)pyridines catalyzed single-electron transfer-living radical polymerization of methyl methacrylate initiated with poly(vinylidene fluoride-co-chlorotrifluoroethylene). J. Polym. Sci. A 2013, 51, 4378–4388. [Google Scholar] [CrossRef]
  59. Hu, X.; Tan, S.; Gao, G.; Xie, Y.; Wang, Q.; Li, N.; Zhang, Z. ynthesis of unsaturation containing P(VDF-co-TrFE-co-CTFE) from P(VDF-co-CTFE) in one-pot catalyzed with Cu(0)-based single electron transfer living radical polymerization system. J. Polym. Sci. A 2014, 52, 3429–3440. [Google Scholar] [CrossRef]
  60. Zhu, N.; Hu, X.; Zhang, Y.; Zhang, K.; Li, Z.; Guo, K. Continuous flow SET-LRP in the presence of P(VDF-co-CTFE) as macroinitiator in a copper tubular reactor. Polym. Chem. 2016, 7, 474–480. [Google Scholar] [CrossRef]
Polymers 10 00068 sch001 550
Scheme 1. Photoinduced Cu(II)-mediated reversible deactivation radical polymerization (RDRP) to P(VDF-co-CTFE)-g-PAN. P(VDF-co-CTFE): poly(vinylidene fluoride-co-chlorotrifluoroethylene); PAN: poly(acrylonitrile).
Scheme 1. Photoinduced Cu(II)-mediated reversible deactivation radical polymerization (RDRP) to P(VDF-co-CTFE)-g-PAN. P(VDF-co-CTFE): poly(vinylidene fluoride-co-chlorotrifluoroethylene); PAN: poly(acrylonitrile).
Polymers 10 00068 sch001
Polymers 10 00068 g001 550
Figure 1. Graft contents vs. reaction time dependence for photoinduced Cu(II)-mediated RDRP of AN in DMSO with P(VDF-co-CTFE) as macroinitiator under “on-off” light sequence ([Cl]:[Cu]:[L]:[AN] = 1:(1/32):(6/32):30, UV (λmax = 365 nm)).
Figure 1. Graft contents vs. reaction time dependence for photoinduced Cu(II)-mediated RDRP of AN in DMSO with P(VDF-co-CTFE) as macroinitiator under “on-off” light sequence ([Cl]:[Cu]:[L]:[AN] = 1:(1/32):(6/32):30, UV (λmax = 365 nm)).
Polymers 10 00068 g001
Polymers 10 00068 g002 550
Figure 2. Semilogarithmic kinetic plots for photoinduced Cu(II)-mediated RDRP of AN in DMSO with P(VDF-co-CTFE) as macroinitiator ([Cl]:[Cu]:[L]:[AN] = 1:(1/32):(6/32):30, UV (λmax = 365 nm).
Figure 2. Semilogarithmic kinetic plots for photoinduced Cu(II)-mediated RDRP of AN in DMSO with P(VDF-co-CTFE) as macroinitiator ([Cl]:[Cu]:[L]:[AN] = 1:(1/32):(6/32):30, UV (λmax = 365 nm).
Polymers 10 00068 g002
Polymers 10 00068 g003 550
Figure 3. Fourier transform infrared (FTIR) spectrum of pristine P(VDF-co-CTFE) and P(VDF-co-CTFE)-g-PAN (Table 1, run 5).
Figure 3. Fourier transform infrared (FTIR) spectrum of pristine P(VDF-co-CTFE) and P(VDF-co-CTFE)-g-PAN (Table 1, run 5).
Polymers 10 00068 g003
Polymers 10 00068 g004 550
Figure 4. 1H NMR of pristine P(VDF-co-CTFE) and P(VDF-co-CTFE)-g-PAN (Table 1, run 5).
Figure 4. 1H NMR of pristine P(VDF-co-CTFE) and P(VDF-co-CTFE)-g-PAN (Table 1, run 5).
Polymers 10 00068 g004
Polymers 10 00068 g005 550
Figure 5. 19F NMR of pristine P(VDF-co-CTFE) and P(VDF-co-CTFE)-g-PAN (Table 1, run 5).
Figure 5. 19F NMR of pristine P(VDF-co-CTFE) and P(VDF-co-CTFE)-g-PAN (Table 1, run 5).
Polymers 10 00068 g005
Polymers 10 00068 g006 550
Figure 6. Differential scanning calorimetry (DSC) curves of pristine P(VDF-co-CTFE) and P(VDF-co-CTFE)-g-PAN with varied graft contents (Table 1, runs 7 and 9).
Figure 6. Differential scanning calorimetry (DSC) curves of pristine P(VDF-co-CTFE) and P(VDF-co-CTFE)-g-PAN with varied graft contents (Table 1, runs 7 and 9).
Polymers 10 00068 g006
Polymers 10 00068 g007 550
Figure 7. Thermogravimetric analysis (TGA) curves of pristine P(VDF-co-CTFE) and P(VDF-co-CTFE)-g-PAN copolymers with varied graft contents (Table 1, runs 7 and 9).
Figure 7. Thermogravimetric analysis (TGA) curves of pristine P(VDF-co-CTFE) and P(VDF-co-CTFE)-g-PAN copolymers with varied graft contents (Table 1, runs 7 and 9).
Polymers 10 00068 g007
Table
Table 1. Summary of photoinduced Cu(II)-mediated RDRP of AN in DMSO with P(VDF-co-CTFE) as macroinitiator under UV (λmax = 365 nm) irradiation for 6 h.
Table 1. Summary of photoinduced Cu(II)-mediated RDRP of AN in DMSO with P(VDF-co-CTFE) as macroinitiator under UV (λmax = 365 nm) irradiation for 6 h.
Run[Cl]:[Cu]:[L]:[AN]Conversion%Graft content [a]mol %Graft length [b]
1[c]1:(1/32):(6/32):30000
20:(1/32):(6/32):300--
31:(0):(0):30000
41:(1/32):(4/32):3010.017.22.9
51:(1/32):(6/32):3012.320.83.5
61:(1/32):(8/32):308.113.72.3
71:(1/64):(6/64):307.813.42.2
81:(1/32):(6/32):509.927.54.6
91:(1/32):(6/32):807.532.65.5
[a] Graft content was calculated by 1H NMR according to the literature [57]. [b] Graft length equaled graft content divided by 6%. [c] Polymerization was conducted without UV.

Share and Cite

MDPI and ACS Style

Hu, X.; Cui, G.; Zhu, N.; Zhai, J.; Guo, K. Photoinduced Cu(II)-Mediated RDRP to P(VDF-co-CTFE)-g-PAN. Polymers 2018, 10, 68. https://doi.org/10.3390/polym10010068

AMA Style

Hu X, Cui G, Zhu N, Zhai J, Guo K. Photoinduced Cu(II)-Mediated RDRP to P(VDF-co-CTFE)-g-PAN. Polymers. 2018; 10(1):68. https://doi.org/10.3390/polym10010068

Chicago/Turabian Style

Hu, Xin, Guopeng Cui, Ning Zhu, Jinglin Zhai, and Kai Guo. 2018. "Photoinduced Cu(II)-Mediated RDRP to P(VDF-co-CTFE)-g-PAN" Polymers 10, no. 1: 68. https://doi.org/10.3390/polym10010068

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop