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ABA2-type triblock copolymer composed of PCL and PSt: synthesis and characterization

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Abstract

ABA2-type (Y-shaped) triblock copolymer made from poly(ε-caprolactone) (PCL) and polystyrene were synthesized by the combination of enzymatic ring-opening polymerization (eROP) and atom transfer radical polymerization (ATRP). First, CCl3-terminated PCL were synthesized by eROP of ε-caprolactone in the presence of initiator 2,2,2-trichloroethanol and biocatalyst Novozyme 435, followed by the esterification of the resulting PCL with 2,2-dichloro acetyl chloride to obtain trifunctional macroinitiator. The well-defined Y-shaped block copolymer was then synthesized by ATRP of styrene. The systems display characteristics of a living radical polymerization as indicated by linear first-order kinetics, linearly increasing molecular weight with conversion, and low polydispersities. The macromolecular structures and composition were characterized by HNMR, GPC, and FTIR. The thermal properties were characterized by differential scanning calorimetry.

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References

  1. McKee MG, Unal S, Wilkes GL, Long TE (2005) Branched polyesters: recent advances in synthesis and performance. Prog Polym Sci 30:507–539

    Article  CAS  Google Scholar 

  2. Tande BM, Wanger NJ, Mackay ME, Hawker CJ, Jeong MV (2001) Viscosimetric, hydrodynamic, and conformational properties of dendrimers and dendrons. Macromolecules 34:8580–8585

    Article  CAS  Google Scholar 

  3. Park SY, Han DK, Kim SC (2001) Synthesis and characterization of star-shaped PLLA-PEO block copolymers with temperature-sensitive sol–gel transition behavior. Macromolecules 34:8821–8824

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  5. Gungor E, Durmaz H, Hizal G, Tunca U (2008) H-shaped (ABCDE Type) quintopolymer via click reaction [3 + 2] strategy. J Polym Sci Part A Polym Chem 46:4459–4468

    Article  CAS  Google Scholar 

  6. Tunca U, Ozyurek Z, Erdogan T, Hizal G (2004) Novel miktofunctional initiator for the preparation of an ABC-type miktoarm star polymer via a combination of controlled polymerization techniques. J Polym Sci Part A Polym Chem 42:4228–4236

    Article  CAS  Google Scholar 

  7. Cai Y, Tang Y, Armes SP (2004) Direct synthesis and stimulus-responsive micellization of Y-shaped hydrophilic block copolymers. Macromolecules 37:9728–9737

    Article  CAS  Google Scholar 

  8. Cai Y, Armes S (2005) Synthesis of well-defined Y-shaped zwitterionic block copolymers via atom transfer radical polymerization. Macromolecules 38:271–279

    Article  CAS  Google Scholar 

  9. Lorenzo AJ, Müller AJ, Priftis D, Pitsikalis M, Hadjichristidis N (2007) Synthesis and morphological characterization of miktoarm star copolymers (PCL)2(PS)2 of poly(e-caprolactone) and polystyrene. J Polym Sci Part A Polym Chem 45:5387–5397

    Article  CAS  Google Scholar 

  10. Kobayashi S, Uyama H, Kimura S (2001) Enzymatic polymerization. Chem Rev 101:3793–3818

    Article  CAS  Google Scholar 

  11. Gross RA, Kumar A, Kalra B (2001) Polymer synthesis by in vitro enzyme catalysis. Chem Rev 101:2097–2124

    Article  CAS  Google Scholar 

  12. Cardova A, Hult A, Hult K, Ihre H, Iversen T, Malmstrom E (1998) Synthesis of a poly(ε-caprolactone) monosubstituted first generation dendrimer by lipase catalysis. J Am Chem Soc 120:13521–13522

    Article  Google Scholar 

  13. Meyer U, Palmans A, Loontjens T, Heise A (2002) Enzymatic ring-opening polymerization and atom transfer radical polymerization from a bifunctional initiator. Macromolecules 35:2873–2875

    Article  CAS  Google Scholar 

  14. Sha K, Li DS, Wang SW, Qin L, Wang JY (2005) Synthesis and characterization of diblock and triblock copolymer by enzymatic ring-opening polymerization of ε-caprolactone and ATRP of styrene. Polym Bull 54:1–7

    Article  CAS  Google Scholar 

  15. Sha K, Li D, Li Y, Liu X, Guan J, Wang S, Wang J (2007) Synthesis, characterization, and micellization of an epoxy-based amphiphilic diblock copolymer of ε-caprolactone and glycidyl methacrylate by enzymatic ring-opening polymerization and atom transfer radical polymerization. J Polym Sci Part A Polym Chem 45:5037–5049

    Article  CAS  Google Scholar 

  16. Sha K, Li DS, Li YP, Zhang B, Wang JY (2008) The chemoenzymatic synthesis of a novel CBABC-type pentablock copolymer and its self-assembled “Crew-Cut” aggregation. Macromolecules 41:361–371

    Article  CAS  Google Scholar 

  17. Zhang B, Li Y, Xu Y, Wang S, Ma L, Wang J (2008) Chemozymatic synthesis and characterization of H-shaped triblock copolymer. Polym Bull 60:733–740

    Article  CAS  Google Scholar 

  18. Zhang B, Li Y, Wang W, Chen L, Sun J, Wang J (2009) Chemoenzymatic synthesis of Y-shaped block copolymers. Polym Bull 62:643–655

    Article  CAS  Google Scholar 

  19. Zhang B, Li Y, Ai P, Wang S, Li M, Wang J (2009) Y-shaped block copolymer with a functional monomer glycidyl methacrylate: synthesis, characterization and its micellization behavior. J Polym Sci Part A Polym Chem 47:5509–5526

    Article  CAS  Google Scholar 

  20. Sha K, Li D, Li Y, Zhang B, Wang J (2006) The chemoenzymatic synthesis of ab-type diblock copolymers from a novel bifunctional initiator. Polymer 47:4292–4299

    Article  CAS  Google Scholar 

  21. Hawker CJ, Hedrick JL, Malmstrom EE, Trollsas M, Mecerreyes D, Moineau G, Dubois P, Jerome R (1998) Dual living free radical and ring opening polymerizations from a double-headed initiator. Macromolecules 31(2):213–219

    Article  CAS  Google Scholar 

  22. Karanam S, Goossens H, Klumperman B, Lemstra P (2003) “Controlled” synthesis and characterization of high molecular weight methyl methacrylate/tert-butyl methacrylate diblock copolymers via ATRP. Macromolecules 36(22):8304–8311

    Article  CAS  Google Scholar 

  23. Destarac M, Matyjaszewski K, Silverman E (2000) Atom transfer radical polymerization initiated with vinylidene fluoride telomers. Macromolecules 33(13):4613–4615

    Article  CAS  Google Scholar 

  24. Mayo FR (1968) The dimerization of styrene. J Am Chem Soc 90:1289–1295

    Article  CAS  Google Scholar 

  25. Pascual S, Coutin B, Tardi M, Polton A, Vairon JP (2001) Kinetic and mechanistic study of copper chloride-mediated atom transfer polymerization of styrene in the presence of N,N-dimethylformamide. Macromolecules 34:5752–5758

    Article  CAS  Google Scholar 

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Acknowledgments

This study was supported by the Natural Science Foundation of China (no. 20574028) and Natural Science Foundation for Youth.

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Authors and Affiliations

  1. Alan G. MacDiarmid Institute, Jilin University, Changchun, 130023, People’s Republic of China

    Bao Zhang, Yapeng Li & Jingyuan Wang

  2. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, People’s Republic of China

    Bao Zhang, Yapeng Li, Wei Wang & Xuesi Chen

Authors
  1. Bao Zhang
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  2. Yapeng Li
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  3. Wei Wang
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  4. Jingyuan Wang
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  5. Xuesi Chen
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Correspondence to Yapeng Li or Xuesi Chen.

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Zhang, B., Li, Y., Wang, W. et al. ABA2-type triblock copolymer composed of PCL and PSt: synthesis and characterization. Polym. Bull. 67, 1507–1518 (2011). https://doi.org/10.1007/s00289-011-0469-0

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  • DOI: https://doi.org/10.1007/s00289-011-0469-0

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