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Amphiphilic Dendrimer-like Copolymers with High Chain Density by Living Anionic Polymerization

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Abstract

We report here a method for the preparation of amphiphilic dendrimer-like copolymers with dendritic polystyrene (PS) core and protonated poly(2-vinyl pyridine) (P2VP) or poly(methacrylic acid) (PMAA) shell. The method employed the efficient coupling reaction of anionic living polymer chains and chlorosilane. The synthesis started from a functionalized 3rd generation dendritic polystyrene, G3PS-g-SiCl, used as the precursor. The dendrimer-like copolymer of styrene and 2-vinyl pyridine, G3PS-g-P2VP, was synthesized by direct coupling of living P2VPLi to the precursor. The dendrimer-like copolymer of styrene and tert-butyl methacrylate, G3PS-g-PtBMA, was synthesized by an indirect procedure in which a living polymer containing mainly PtBMA segment was attached to the precursor. Both methods resulted in the formation of dendrimer-like copolymers with the high molecular weights (up to 8.5 × 106 Da), large molecular sizes (diameter up to 73 nm), and dense shells (number of arms up to 1300). These products, G3PS-g-P2VP and G3PS-g-PtBMA, were protonated with trifluoroacetic acid and acidic hydrolyzed, respectively. After transformation, amphiphilic dendrimer-like copolymers, G3PS-g-P2VPH+ and G3PS-g-PMAA, were obtained. Preliminary results on the solution properties of the amphiphilic products were presented.

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References

  1. Taton, D.; Feng, X.; Gnanou, Y. Dendrimer-like polymers: A new class of structurally precise dendrimers with macromolecular generations. New J. Chem. 2007, 31, 1097–1110.

    Article  CAS  Google Scholar 

  2. Taton, D.; Gnanou, Y.; Matmour, R.; Angot, S.; Hou, S.; Francis, R.; Lepoittevin, B.; Moinard, D.; Babin, J. Controlled polymerizations as tools for the design of star-like and dendrimer-like polymers. Polym. Int. 2006, 55, 1138–1145.

    Article  CAS  Google Scholar 

  3. Polymeropoulos, G.; Zapsas, G.; Ntetsikas, K.; Bilalis, P.; Gnanou, Y.; Hadjichristidis, N. 50th Anniversary perspective: Polymers with complex architectures. Macromolecules 2017, 50, 1253–1290.

    Article  CAS  Google Scholar 

  4. Hirao, A.; Goseki, R.; Ishizone, T. Advances in living anionic polymerization: From functional monomers, polymerization systems, to macromolecular architectures. Macromolecules 2014, 47, 1883–1905.

    Article  CAS  Google Scholar 

  5. Hirao, A.; Yoo, H. S. Dendrimer-like star-branched polymers: Novel structurally well-defined hyperbranched polymers. Polym. J. 2011, 43, 2–17.

    Article  CAS  Google Scholar 

  6. Hirao, A.; Sugiyama, K.; Matsuo, A.; Tsunoda, Y.; Watanabe, T. Synthesis of well-defined dendritic hyperbranched polymers by iterative methodologies using living/controlled polymerizations. Polym. Int. 2008, 57, 554–570.

    Article  CAS  Google Scholar 

  7. Hirao, A.; Sugiyama, K.; Tsunoda, Y.; Matsuo, A.; Watanabe, T. Precise synthesis of well-defined dendrimer-like star-branched polymers by iterative methodology based on living anionic polymerization. J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 6659–6687.

    Article  CAS  Google Scholar 

  8. Konkolewicz, D.; Monteiro, M. J.; Perrier, S. Dendritic and hyperbranched polymers from macromolecular units: Elegant approaches to the synthesis of functional polymers. Macromolecules 2011, 44, 7067–7087.

    Article  CAS  Google Scholar 

  9. Grayson, S. M.; Fréchet, J. M. J. Convergent dendrons and dendrimers: From synthesis to applications. Chem. Rev. 2001, 101, 3819–3867.

    Article  CAS  PubMed  Google Scholar 

  10. Bosman, A. W.; Janssen, H. M.; Meijer, E. W. About dendrimers: Structure, physical properties, and applications. Chem. Rev. 1999, 99, 1665–1688.

    Article  CAS  PubMed  Google Scholar 

  11. Six, J. L.; Gnanou, Y. From star-shaped to dendritic poly(ethylene oxide)s: Toward increasingly branched architectures by anionic polymerization. Macromol. Symp. 1995, 95, 137–150.

    Article  CAS  Google Scholar 

  12. Francis, R.; Taton, D.; Logan, J. L.; Masse, P.; Gnanou, Y.; Duran, R. S. Synthesis and surface properties of amphiphilic star-shaped and dendrimer-like copolymers based on polystyrene core and poly(ethylene oxide) corona. Macromolecules 2003, 36, 8253–8259.

    Article  CAS  Google Scholar 

  13. Feng, X.; Taton, D.; Borsali, R.; Chaikof, E. L.; Gnanou, Y. pH Responsiveness of dendrimer-like poly(ethylene oxide)s. J. Am. Chem. Soc. 2006, 128, 11551–11562.

    Article  CAS  PubMed  Google Scholar 

  14. Matmour, R.; Lepoittevin, B.; Joncheray, T. J.; El-khouri, R. J.; Taton, D.; Duran, R. S.; Gnanou, Y. Synthesis and investigation of surface properties of dendrimer-like copolymers based on polystyrene and poly(tert-butylacrylate). Macromolecules 2005, 38, 5459–5467.

    Article  CAS  Google Scholar 

  15. Feng, X.; Taton, D.; Chaikof, E. L.; Gnanou, Y. Fast access to dendrimer-like poly(ethylene oxide)s through anionic ring-opening polymerization of ethylene oxide and use of nonprotected glycidol as branching agent. Macromolecules 2009, 42, 7292–7298.

    Article  CAS  Google Scholar 

  16. Feng, X.; Taton, D.; Chaikof, E. L.; Gnanou, Y. Toward an easy access to dendrimer-like poly(ethylene oxide)s. J. Am. Chem. Soc. 2005, 127, 10956–10966.

    Article  CAS  PubMed  Google Scholar 

  17. Kong, L. Z.; Pan, C. Y. Preparation of dendrimer-like copolymers based on polystyrene and poly(L-lactide) and formation of hollow microspheres. Polymer 2008, 49, 200–210.

    Article  CAS  Google Scholar 

  18. Zhao, Y.; Shuai, X.; Chen, C.; Xi, F. Synthesis of star block co-polymers from dendrimer initiators by combining ring-opening polymerization and atom transfer radical polymerization. Macromolecules 2004, 37, 8854–8862.

    Article  CAS  Google Scholar 

  19. Teertstra, S. J.; Gauthier, M. Dendrigraft polymers: Macromolecular engineering on a mesoscopic scale. Prog. Polym. Sci. 2004, 29, 277–327.

    Article  CAS  Google Scholar 

  20. Trollsȧs, M.; Kelly, M. A.; Claesson, H.; Siemens, R.; Hedrick, J. L. Highly branched block copolymers: Design, synthesis, and morphology. Macromolecules 1999, 32, 4917–4924.

    Article  CAS  Google Scholar 

  21. Stancik, C. M.; Pople, J. A.; Trollsȧs, M.; Lindner, P.; Hedrick, J. L.; Gast, A. P. Impact of core architecture on solution properties of dendrimer-like star copolymers. Macromolecules 2003, 35, 5765–5775.

    Article  CAS  Google Scholar 

  22. Trollsȧs, M.; Hedrick, J. L. Dendrimer-like star polymers. J. Am. Chem. Soc. 1998, 120, 4644–4651.

    Article  Google Scholar 

  23. Hedrick, J. L.; Trollsȧs, M.; Hawker, C. J.; Atthoff, B.; Claesson, H.; Heise, A.; Miller, R. D. Dendrimer-like star block and amphiphilic copolymers by combination of ring opening and atom transfer radical polymerization. Macromolecules 1998, 31, 8691–8705.

    Article  CAS  Google Scholar 

  24. Percec, V.; Barboiu, B.; Grigoras, C.; Bera, T. K. Universal iterative strategy for the divergent synthesis of dendritic macromolecules from conventional monomers by a combination of living radical polymerization and irreversible TER minator multifunctional initiator (TERMINI). J. Am. Chem. Soc. 2003, 125, 6503–6516.

    Article  CAS  PubMed  Google Scholar 

  25. Matmour, R.; Gnanou, Y. Combination of an anionic terminator multifunctional initiator and divergent carbanionic polymerization: Application to the synthesis of dendrimer-like polymers and of asymmetric and miktoarm stars. J. Am. Chem. Soc. 2008, 130, 1350–1361.

    Article  CAS  PubMed  Google Scholar 

  26. Orfanou, K.; Iatrou, H.; Lohse, D. J.; Hadjichristidis, N. Synthesis of well-defined second (G-2) and third (G-3) generation dendritic polybutadienes. Macromolecules 2006, 39, 4361–4365.

    Article  CAS  Google Scholar 

  27. Bender, J. T.; Knauss, D. M. Dendritic polystyrene with hydroxyl-functionalized branch points by convergent living anionic polymerization. Macromolecules 2009, 42, 2411–2418.

    Article  CAS  Google Scholar 

  28. Hutchings, L. R.; Roberts-Bleming, S. J. DendriMacs. Well-defined dendritically branched polymers synthesized by an iterative convergent strategy involving the coupling reaction of AB2 macromonomers. Macromolecules 2006, 39, 2144–2152.

    Article  CAS  Google Scholar 

  29. Altintas, O.; Demirel, A. L.; Hizal, G.; Tunca, U. Dendrimer-like miktoarm star terpolymers: A3-(B-C)3 via click reaction strategy. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 5916–5928.

    Article  CAS  Google Scholar 

  30. Urbani, C. N.; Bell, C. A.; Whittaker, M. R.; Monteiro, M. J. Convergent synthesis of second generation AB-type miktoarm dendrimers using “click” chemistry catalyzed by copper wire. Macromolecules 2008, 41, 1057–1060.

    Article  CAS  Google Scholar 

  31. Bell, C. A.; Jia, Z.; Kulis, J.; Monteiro, M. J. Modulating two copper(I)-catalyzed orthogonal “click” reactions for the one-pot synthesis of highly branched polymer architectures at 25 °C. Macromolecules 2011, 44, 4814–4827.

    Article  CAS  Google Scholar 

  32. Matsuo, A.; Watanabe, T.; Hirao, A. Synthesis of well-defined dendrimer-like branched polymers and block copolymer by the iterative approach involving coupling reaction of living anionic polymer and functionalization. Macromolecules 2004, 37, 6283–6290.

    Article  CAS  Google Scholar 

  33. Hirao, A.; Matsuo, A.; Watanabe, T. Precise synthesis of dendrimer-like star-branched poly(methyl methacrylate)s up to seventh generation by an iterative divergent approach involving coupling and transformation reactions. Macromolecules 2005, 38, 8701–8711.

    Article  CAS  Google Scholar 

  34. Hirao, A.; Watanabe, T. Precise synthesis and characterization of fourth-generation dendrimer-like star-branched poly(methyl methacrylate)s and block copolymers by iterative methodology based on living anionic polymerization. Macromolecules 2009, 42, 682–693.

    Article  CAS  Google Scholar 

  35. Yoo, H. S.; Watanabe, T.; Matsunaga, Y.; Hirao, A. Precise synthesis of dendrimer-like star-branched poly(tert-butyl methacrylate)s and their block copolymers by a methodology combining α-terminal-functionalized living anionic polymers with a specially designed linking reaction in an iterative fashion. Macromolecules 2012, 45, 100–112.

    Article  CAS  Google Scholar 

  36. Deffieux, A.; Schappacher, M.; Hirao, A.; Watanabe, T. Synthesis and AFM structural imaging of dendrimer-like star-branched polystyrenes. J. Am. Chem. Soc. 2008, 130, 5670–5672.

    Article  CAS  PubMed  Google Scholar 

  37. Zhang, H.; He, J.; Zhang, C.; Ju, Z.; Li, J.; Yang, Y. Continuous process for the synthesis of dendrimer-like star polymers by anionic polymerization. Macromolecules 2012, 45, 828–841.

    Article  CAS  Google Scholar 

  38. Zhang, H.; Zhu, J.; He, J.; Qiu, F.; Zhang, H.; Yang, Y.; Lee, H.; Chang, T. Easy synthesis of dendrimer-like polymers through a divergent iterative “end-grafting” method. Polym. Chem. 2013, 4, 830–839.

    Article  CAS  Google Scholar 

  39. Wang, Y.; Qi, G.; He, J. Unimolecular micelles from layered amphiphilic dendrimer-like block copolymers. ACS Macro Lett. 2016, 5, 547–551.

    Article  CAS  Google Scholar 

  40. Natalello, A.; Tonhauser, C.; Berger-Nicoletti, E.; Frey, H. A combined DPE/epoxide termination strategy for hydroxyl end-functional poly(2-vinylpyridine) and amphiphilic AB2-miktoarm stars. Macromolecules 2011, 44, 9887–9890.

    Article  CAS  Google Scholar 

  41. Zheng, K.; He, J. Thermally “switchable” nanoreactor from amphiphilic dendrimer-like copolymer with dense hydrophilic shell. Manuscript in preparation.

  42. Ruckenstein, E.; Zhang, H. Well-defined graft copolymers based on the selective living anionic polymerization of the bi-functional monomer 4-(vinylphenyl)-1-butene. Macromolecules 1999, 32, 6082–6087.

    Article  CAS  Google Scholar 

  43. Wang, X.; He, J.; Yang, Y. Synthesis of ABCD-type miktoarm star copolymers and transformation into zwitterionic star co-polymers. J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 4818–4828.

    Article  CAS  Google Scholar 

  44. Gauthier, M.; Li, J.; Dockendorff, J. Arborescent polystyrenegraft-poly(2-vinylpyridine) copolymers as unimolecular micelles synthesis from acetylated substrates. Macromolecules 2003, 36, 2642–2648.

    Article  CAS  Google Scholar 

  45. Kee, R. A.; Gauthier, M. Arborescent polystyrene-graft-poly(2-vinylpyridine) copolymers: Synthesis and enhanced polyelectrolyte effect in solution. Macromolecules 2002, 35, 6526–6532.

    Article  CAS  Google Scholar 

  46. Kee, R. A.; Gauthier, M. Arborescent polystyrene-graft-poly(tert-butyl methacrylate) copolymers: Synthesis and enhanced polyelectrolyte effect in solution. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 2335–2346.

    Article  CAS  Google Scholar 

  47. Chu, B.; Liu, T. Characterization of nanoparticles by scattering techniques. J. Nanopart. Res. 2000, 2, 29–41.

    Article  CAS  Google Scholar 

  48. Li, L.; He, C.; He, W.; Wu, C. Formation kinetics and scaling of “defect-free” hyperbranched polystyrene chains with uniform subchains prepared from seesaw-type macromonomers. Macromolecules 2011, 44, 8195–8206.

    Article  CAS  Google Scholar 

  49. Trollsȧs, M.; Atthof, B.; Würsch, A.; Hedrick, J. L. Constitutional isomers of dendrimer-like star polymers: Design, synthesis, and conformational and structural properties. Macromolecules 2000, 33, 6423–6438.

    Article  CAS  Google Scholar 

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 21474016) and Senior Visiting Scholar Foundation of Key Laboratory in Fudan University (Nos. 16FHJ08 & 18FGJ01). We are grateful to Professor Akira Hirao and Professor Redouane Borsali for many helpful discussions.

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  1. State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, 200438, China

    Ke Zheng & Jun-Po He

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  1. Ke Zheng
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Correspondence to Jun-Po He.

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Invited article for special issue of “Ionic Polymerization”

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Zheng, K., He, JP. Amphiphilic Dendrimer-like Copolymers with High Chain Density by Living Anionic Polymerization. Chin J Polym Sci 37, 875–883 (2019). https://doi.org/10.1007/s10118-019-2247-7

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