High-efficiency synthesis of dendrimer-like poly(ethylene oxide) via “arm-first” approach

Abstract

In this study, a dendrimer-like polymer based on poly(ethylene oxide) (PEO) was synthesized through a combination of anionic ring-opening polymerization (AROP) and click reaction via arm-first method. Firstly, the polymeric arm, a linear PEO with one alkynyl group and two bromo groups, was synthesized by AROP of ethylene oxide followed by functionalization with propargyl bromide and esterified with 2-bromopropionic bromide. Second, a star PEO carrying three azide groups was synthesized though AROP of ethylene oxide used 1,1,1-tris(hydrosymethyl) ethane as initiator followed esterificated with 2-bromopropionic acid and azidation. By azide–alkyne click reactions between the azide-terminated PEO star polymer and linear PEO with functionalization alkynyl group, a three generation dendrimer-like PEO, G3-PEO-24Br, was successfully synthesized. The resulting polymers were observed to have precisely controlled molecular weights and compositions with narrow molecular weight distributions.

This is a preview of subscription content, access via your institution.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Scheme 2
Scheme 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

References

  1. 1.

    Kolate A, Baradia D, Patil S, et al (2014) PEG—a versatile conjugating ligand for drugs and drug delivery systems. J Control Release 192:67–81

    CAS  Article  Google Scholar 

  2. 2.

    Senevirathne SA, Washington KE, Biewer MC, et al (2016) PEG based anti-cancer drug conjugated prodrug micelles for the delivery of anti-cancer agents. J Mater Chem B 4:360–370

    CAS  Article  Google Scholar 

  3. 3.

    Parmar AV, Bahadur A, Kuperkar K, et al (2013) PEO-PPO based star-block copolymer T904 as pH responsive nanocarriers for quercetin: Solubilization and release study. Eur Polym J 49:12–21

    CAS  Article  Google Scholar 

  4. 4.

    Zhao H, Ding X, Yang P, et al (2015) A novel multi-armed and star-like poly(ethylene oxide) membrane for CO2 separation. J Membrane Sci 489:258–263

    CAS  Article  Google Scholar 

  5. 5.

    Lapienis G, Penczek S (2005) One-pot synthesis of star-shaped macromolecules containing polyglycidol and poly(ethylene oxide) arms. Biomacromolecules 6:752–762

    CAS  Article  Google Scholar 

  6. 6.

    Pfister A, Fraser CL (2006) Synthesis and unexpected reactivity of iron tris (bipyridine) complexes with poly(ethylene glycol) macroligands. Biomacromolecules 7:459–468

    CAS  Article  Google Scholar 

  7. 7.

    Feng X, Taton D, Ibarboure EEL, et al (2008) Janus-type dendrimer-like poly(ethylene oxide)s. J Am Chem Soc 130:11662–11676

    CAS  Article  Google Scholar 

  8. 8.

    Feng X, Taton D, Chaikof EL, et al (2009) 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 42:7292–7298

    CAS  Article  Google Scholar 

  9. 9.

    Feng X, Pinaud J, Chaikof EL, et al (2011) Sequential functionalization of Janus-type dendrimer-like poly(ethylene oxide)s with camptothecin and folic acid. J Poly Sci Poly Chem 49:2839–2849

    CAS  Article  Google Scholar 

  10. 10.

    Cao WQ, Zhou J, Mann A, et al (2011) Folate-functionalized unimolecular micelles based on a degradable amphiphilic dendrimer-like star polymer for cancer cell-targeted drug delivery. Biomacromolecules 12:2697–2707

    CAS  Article  Google Scholar 

  11. 11.

    Rele SM, Cui WX, Wang LC, et al (2005) Dendrimer-like PEO glycopolymers exhibit anti-inflammatory properties. J Am Chem Soc 127:10132–10133

    CAS  Article  Google Scholar 

  12. 12.

    Zhang H, He J, Zhang C, et al (2012) Continuous process for the synthesis of dendrimer-like star polymers by anionic polymerization. Macromolecules 45:828–841

    Article  Google Scholar 

  13. 13.

    Hirao A, Matsuo A, Watanabe T (2005) 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 38:8701–8711

    CAS  Article  Google Scholar 

  14. 14.

    Hirao A, Sugiyama K, Tsunoda Y, et al (2006) Precise synthesis of well-defined dendrimer-like star-branched polymers by iterative methodology based on living anionic polymerization. J Poly Sci Poly Chem 44:6659–6687

    CAS  Article  Google Scholar 

  15. 15.

    Hirao A, Watanabe T, Ishizu K, et al (2009a) 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 42:682–693

    CAS  Article  Google Scholar 

  16. 16.

    Hirao A, Watanabe T, Yoo HS (2009b) Precise synthesis of dendrimer-like hyperbranched polymers. J Syn Org Chem Jpn 67:1033–1043

    CAS  Article  Google Scholar 

  17. 17.

    Yoo HS, Watanabe T, Hirao A (2009) Precise synthesis of dendrimer-like star-branched polystyrenes and block copolymers composed of polystyrene and poly(methyl methacrylate) segments by an iterative methodology using living anionic polymerization. Macromolecules 42:4558–4570

    CAS  Article  Google Scholar 

  18. 18.

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

    CAS  Article  Google Scholar 

  19. 19.

    Lallana E, Fernandez-Trillo F, Sousa-Herves A, et al (2012) Click chemistry with polymers, dendrimers, and hydrogels for drug delivery. Pharm Res 29:902–921

    CAS  Article  Google Scholar 

  20. 20.

    Tunca U (2014) Orthogonal multiple click reactions in synthetic polymer chemistry. J Poly Sci Poly Chem 52:3147–3165

    CAS  Article  Google Scholar 

  21. 21.

    Wan XJ, Xu J, Liu SY (2010) Facile synthesis of dendrimer-like star-branched poly(isopropylacrylamide) via combination of click chemistry and atom transfer radical polymerization. Sci China Chem 53:2520–2527

    CAS  Article  Google Scholar 

  22. 22.

    Liu QC, Zhao P, Chen YM (2007) Divergent synthesis of dendrimer-like macromolecules through a combination of atom transfer radical polymerization and click reaction. J Poly Sci Poly Chem 45:3330–3341

    CAS  Article  Google Scholar 

  23. 23.

    Feng XS, Taton D, Borsali RA, et al (2006) pH responsiveness of dendrimer-like poly(ethylene oxide)s. J Am Chem Soc 128:11551–11562

    CAS  Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 21174001 and No. 51403001), the “211 Project” of the Anhui University (No. J01001319), and the Research Foundation of the College of Chemistry and Chemical Engineering of Anhui University. The authors acknowledge the support from the “Institute of High Performance Rubber Materials & Products” (Hefei) and "Collaborative Innovation Center for Petrochemical New Materials (Anqing)."

Author information

Affiliations

Authors

Corresponding authors

Correspondence to Ru Xia or Ming Cao.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Zhu, S., Xia, R., Chen, P. et al. High-efficiency synthesis of dendrimer-like poly(ethylene oxide) via “arm-first” approach. J Polym Res 24, 73 (2017). https://doi.org/10.1007/s10965-017-1213-8

Download citation

Keywords

  • Dendrimer-like poly(ethylene oxide)
  • Arm-first
  • Anionic ring-opening polymerization
  • Click chemistry