Advertisement

Journal of Polymer Research

, 25:254 | Cite as

Diblock and triblock copolymers catalyzed by benzo-12-crown-4 bridged N-heterocyclic carbene: synthesis, characterization and degradation behavior

  • Yan Wang
  • Ni Wu
  • Junhua Bai
  • Qianru Li
  • Lifang ZhangEmail author
ORIGINAL PAPER

Abstract

The sequential ring-opening polymerizations (ROP) of ε-caprolactone (ε-CL) and L-lactide (LLA) with benzo-12-crown-4-imidazole carbene (B-12-C-4imY) as the catalyst have been performed. Using either benzyl alcohol or ethylene glycol as an initiator, the corresponding poly(ε-caprolactone)-poly(L-lactide) (PCL-b-PLLA) diblock or poly(L-lactide)-poly(ε-caprolactone)-poly(L-lactide) (PLLA-PCL-PLLA) triblock copolymers were easily prepared. The results indicated that B-12-C-4imY was quite effective for the copolymerization. The diblock copolymerization of ε-CL with LLA could only be achieved when ε-CL was first polymerized followed by LLA. Feeding the two monomers simultaneously, however, only resulted in the formation of LLA homopolymers. Thermogravimetric analysis (TGA) measurements demonstrated that block copolymers exhibited the decomposition temperature lower than the PCL homopolymer. The copolymers were characterized by 1H NMR and 13C NMR, FT-IR, GPC, and DSC analyses. 20 × 10 mm2 rectangular specimens made of the triblock copolymer were allowed to degrade in a pH = 7.4 phosphate buffer at 37 °C. Degradation was monitored by various analytical techniques such as GPC, IR, and ESEM.

Keywords

Block copolymers Ring-opening polymerization Copolymerization L-Lactide ε-Caprolactone 

Notes

Acknowledgements

This work was supported by Basic Research Project of Shanxi Province of China (No.2015011029), Undergraduate Innovative Experiment Program of Shanxi Normal University (No.SD2014CXXM-36) and Shanxi Province Education Innovation Project for Postgraduate (No.2015BY38).

References

  1. 1.
    Wang F, Bronich TK, Kabanov AV, Rauh RD, Roovers J (2005) Synthesis and evaluation of a star amphiphilic block copolymer from poly(ε-caprolactone) and poly(ethylene glycol) as a potential drug delivery carrier. Bioconjug Chem 16:397–405CrossRefPubMedGoogle Scholar
  2. 2.
    Ho MH, Hou LT, Tu CY, Hsieh HJ, Lai JY, Chen WJ, Wang DM (2006) Promotion of cell affinity of porous PLLA scaffolds by immobilization of RGD peptides via plasma treatment. Macromol Biosci 6:90–98CrossRefPubMedGoogle Scholar
  3. 3.
    Meng FL, Zheng SX, Zhang WA, Li HQ, Liang Q (2006) Nanostructured thermosetting blends of epoxy resin and amphiphilic poly(ε-caprolactone)-block-polybutadiene-block-poly(ε-caprolactone) triblock copolymer. Macromolecules 39:711–719CrossRefGoogle Scholar
  4. 4.
    Wang CH, Hsiue GH (2005) Polymer-DNA hybrid nanoparticles based on folate-polyethylenimine-block-poly(L-lactide). Bioconjug Chem 16:391–396CrossRefPubMedGoogle Scholar
  5. 5.
    Albertsson AC, Varma IK (2003) Recent developments in ring opening polymerization of lactones for biomedical applications. Biomacromolecules 4:1466–1486CrossRefPubMedGoogle Scholar
  6. 6.
    Arbaoui A, Redshaw C (2010) Metal catalysts for ε-caprolactone polymerization. Polym Chem 1:801–826CrossRefGoogle Scholar
  7. 7.
    Dijkstra PJ, Du HZ, Feijen J (2011) Single site catalysts for stereoselective ring-opening polymerization of lactides. Polym Chem 2:520–527CrossRefGoogle Scholar
  8. 8.
    Pitt CG, Marks TA, Schindler A (1980) Biodegradable drug delivery systems based on aliphatic polyesters: application to contraceptives and narcotic antagonists. In: Baker R (ed) Controlled release of bioactive materials. Academic Press, New YorkGoogle Scholar
  9. 9.
    Riess C, Hurtrez C, Bahadur P (1985) Block copolymers. Encyclopedia of polymer science and engineering 2nd edn. Wiley, New YorkGoogle Scholar
  10. 10.
    Wilson JA, Hopkins SA, Wright PM, Dove AP (2015) Synthesis of ω-pentadecalactone copolymers with independently tunable thermal and degradation behavior. Macromolecules 48:950–958CrossRefGoogle Scholar
  11. 11.
    Dechy-Cabaret O, Martin-Vaca B, Bourissou D (2004) Controlled ring-opening polymerization of lactide and glycolide. Chem Rev 104:6147–6176CrossRefPubMedGoogle Scholar
  12. 12.
    Bouyahyi M, Duchateau R (2014) Metal-based catalysts for controlled ring-opening polymerization of macrolactones: high molecular weight and well-defined copolymer architectures. Macromolecules 47:517–524CrossRefGoogle Scholar
  13. 13.
    Pérez Y, del Hierro I, Zazo L, Fernández-Galán R, Fajardo M (2015) The catalytic performance of metal complexes immobilized on SBA-15 in the ring opening polymerization of ε-caprolactone with different metals (Ti, Al, Zn and mg) and immobilization procedures. Dalton Trans 44:4088–4101CrossRefPubMedGoogle Scholar
  14. 14.
    Gilmour DJ, Webster RL, Perry MR, Schafer LL (2015) Titanium pyridonates for the homo- and copolymerization of rac-lactide and ε-caprolactone. Dalton Trans 44:12411–12419CrossRefPubMedGoogle Scholar
  15. 15.
    Platel RH, Hodgson LM, Williams CK (2008) Biocompatible initiators for lactide polymerization. Polym Rev 48:11–63CrossRefGoogle Scholar
  16. 16.
    Penczek S, Cypryk M, Duda A, Kubisa P, Slomkowski S (2007) Living ring-opening polymerizations of heterocyclic monomers. Prog Polym Sci 32:247–282CrossRefGoogle Scholar
  17. 17.
    Gupta AP, Kumar V (2007) New emerging trends in synthetic biodegradable polymers-polylactide: a critique. Eur Polym J 43:4053–4074CrossRefGoogle Scholar
  18. 18.
    Kamber NE, Jeong W, Waymouth RM, Pratt RC, Lohmeijer BGG, Hedrick JL (2007) Organocatalytic ring-opening polymerization. Chem Rev 107:5813–5840CrossRefPubMedGoogle Scholar
  19. 19.
    Ottou WN, Sardon H, Mecerreyes D, Vignolle J, Taton D (2016) Update and challenges in organo-mediated polymerization reactions. Prog Polym Sci 56:64–115CrossRefGoogle Scholar
  20. 20.
    Guillerm B, Lemaur V, Ernould B, Cornil J, Lazzaroni R, Gohy J-F, Dubois P, Coulembier O (2014) A one-pot two-step efficient metal-free process for the generation of PEO-b-PCL-b-PLA amphiphilic triblock copolymers. RSC Adv 4:10028–10038CrossRefGoogle Scholar
  21. 21.
    Makiguchi K, Kikuchi S, Yanai K, Ogasawara Y, Sato S, Satoh T, Kakuchi T (2014) Diphenyl phosphate/4-dimethylaminopyridine as an efficient binary organocatalyst system for controlled/living ring-opening polymerization of L-lacitde leading to diblock and end-functionalized poly(L-lactide)s. J Polym Sci, Part A: Polym Chem 52:1047–1054CrossRefGoogle Scholar
  22. 22.
    Wang X, Liu JQ, Xu SQ, Xu JX, Pan XF, Liu JJ, Cui SD, Li ZJ, Guo K (2016) Tranceless switch organocatalysis enables multiblock ring-opening copolymerizations of lactones, carbonates, and lactides: by a one plus one approach in one pot. Polym Chem 7:6297–6308CrossRefGoogle Scholar
  23. 23.
    Dove AP, Pratt RC, Lohmeijer BGG, Culkin DA, Hagberg EC, Nyce GW, Waymouth RM, Hedrick JL (2006) N-heterocyclic carbenes: effective organic catalysts for living polymerization. Polymer 47:4018–4025CrossRefGoogle Scholar
  24. 24.
    Xiao XD, Bai YL, Liu JQ, Wang JW (2016) Synthesis of novel pillar[5]arene-based N-heterocyclic carbene ligands for Pd-catalysed heck reactions. Tetrahedron Lett 57:3385–3388CrossRefGoogle Scholar
  25. 25.
    Coulembier O, Mespouille L, Hedrick JL, Waymouth RM, Dubois P (2006) Metal-free catalyzed ring-opening polymerization of β-lactones: synthesis of amphiphilic triblock copolymers based on poly(dimethylmalic acid). Macromolecules 39:4001–4008CrossRefGoogle Scholar
  26. 26.
    Raynaud J, Absalon C, Gnanou Y, Taton D (2009) N-heterocyclic carbene-induced zwitterionic ring-opening polymerization of ethylene oxide and direct synthesis of α, ω-difunctionalized poly(ethylene oxide)s and poly(ethylene oxide)-b-poly(ε-caprolactone) block copolymers. J Am Soc 131:3201–3209Google Scholar
  27. 27.
    Nyce GW, Glauser T, Connor EF, Mock A, Waymouth RM, Hedrick JL (2003) In situ generation of carbenes: a general and versatile platform for organocatalytic living polymerization. J Am Chem Soc 125:3046–3056CrossRefPubMedGoogle Scholar
  28. 28.
    Zhang LF, Li N, Wang Y, Guo JZ, Li JF (2014) Ring-opening block copolymerization of ε-caprolactone with L-lactide catalyzed by N-heterocyclic carbenes: synthesis, characteristics, mechanism. Macromol Res 22:600–605CrossRefGoogle Scholar
  29. 29.
    Kamber NE, Jeong W, Gonzalez S, Hedrick JL, Waymouth RM (2009) N-heterocyclic carbene for the organocatalytic ring-opening polymerization of ε-caprolactone. Macromolecules 42:1634–1639CrossRefGoogle Scholar
  30. 30.
    Bai JH, Wu N, Wang Y, Li QR, Wang XQ, Zhang LF (2016) Triblock and pentablock copolymerizations of ε-caprolactone with L-lactide catalyzed by N-heterocyclic carbene. RSC Adv 6:108045–108050CrossRefGoogle Scholar
  31. 31.
    Coulembier O, Lohmeijer BGG, Dove AP, Pratt RC, Mespouille L, Culkin DA, Benight SJ, Dubois P, Waymouth RM, Hedrick JL (2006) Alcohol adducts of N-heterocyclic carbenes: latent catalysts for the thermally-controlled living polymerization of cyclic esters. Macromolecules 39:5617–5628CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  • Yan Wang
    • 1
  • Ni Wu
    • 1
  • Junhua Bai
    • 1
  • Qianru Li
    • 1
  • Lifang Zhang
    • 1
    Email author
  1. 1.Institute of Material ChemistryShanxi Normal UniversityLinfenPeople’s Republic of China

Personalised recommendations