Skip to main content
SpringerLink
Log in

Synthesis and self-assembly of a new amphiphilic thermosensitive poly(N-vinylcaprolactam)/poly(ε-caprolactone) block copolymer

  • Original Paper
  • Published:
Polymer Bulletin Aims and scope Submit manuscript

Abstract

New amphiphilic thermosensitive poly(N-vinylcaprolactam)/poly(ε-caprolactone) (PNVCL-b-PCL) block copolymers were synthesized by ring-opening polymerization of ε-caprolactone with hydroxy-terminated poly(N-vinylcaprolactam) (PNVCL-OH) as a macroinitiator. The structures of the polymers were confirmed by IR, 1H NMR and GPC. The critical micelle concentrations of copolymer in aqueous solution measured by the fluorescence probe technique reduced with the increasing of the proportion of hydrophobic parts, so did the diameter and distribution of the micelles determined by dynamic light scattering. The shape observed by transmission electron microscopy (TEM) demonstrated that the micelles are spherical. On the other hand, the UV–vis measurement showed that polymers exhibit a reproducible temperature-responsive behavior with a lower critical solution temperature (LCST). The LCST of PNVCL-OH can be adjusted by controlling the molecular weights, and that of copolymers can be adjusted by controlling the compositions and the concentration. Variable temperature TEM measurements demonstrated that LCST transition was the result of transition of individual micelles to larger aggregates.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Scheme 2

Similar content being viewed by others

Abbreviations

PNVCL-b-PCL:

Poly(N-vinylcaprolactam)/poly(ε-caprolactone)

ε-CL:

ε-Caprolactone

PNVCL-OH:

Hydroxy-terminated poly(N-vinylcaprolactam)

ROP:

Ring-opening polymerization

LCST:

Lower critical solution temperature

PNVCL:

Poly(N-vinylcaprolactam)

NVCL:

N-vinylcaprolactam

Sn(Oct)2 :

Stannous octoate

HSCH2CH2OH:

2-Mercaptoethanol

AIBN:

Azobisisobutyronitrile

THF:

Tetrahydrofuran

CH2Cl2 :

Dichloromethane

References

  1. Kuramochi H, Andoh Y, Yoshii N, Okazaki S (2009) All-atom molecular dynamics study of a spherical micelle composed of N-acetylated poly(ethylene glycol)-poly(γ-benzyl L-glutamate) block copolymers: a potential carrier of drug delivery systems for cancer. J Phys Chem B 113:15181–15188

    Article  CAS  Google Scholar 

  2. Zhang JX, Ellsworth K, Ma PX (2010) Hydrophobic pharmaceuticals mediated self-assembly of β-cyclodextrin containing hydrophilic copolymers: novel chemical responsive nano-vehicles for drug delivery. J Controlled Release 145:116–123

    Article  CAS  Google Scholar 

  3. Cai CH, Lin JP, Chen T, Tian XH (2010) Aggregation behavior of graft copolymer with rigid backbone. Langmuir 26:2791–2797

    Article  CAS  Google Scholar 

  4. Peng CL, Shieh MJ, Tsai MH, Chang CC, Lai PS (2008) Self-assembled star-shaped chlorin-core poly(ε-caprolactone)-poly(ethylene glycol) diblock copolymer micelles for dual chemo-photodynamic therapies. Biomaterials 29:3599–3608

    Article  CAS  Google Scholar 

  5. Zhang XW, Oddon M, Giani O, Monge S, Robin JJ (2010) Novel strategy for ROP of NCAs using thiols as initiators: synthesis of diblock copolymers based on polypeptides. Macromolecules 43:2654–2656

    Article  CAS  Google Scholar 

  6. Hu Y, Jiang ZP, Chen R, Wu W, Jiang XQ (2010) Degradation and degradation-induced re-assembly of PVP-PCL micelle. Biomacromolecules 11:481–488

    Article  CAS  Google Scholar 

  7. Yao J, Ruan YL, Zhai T, Guan J, Tang GP, Li HR, Dai S (2011) ABC block copolymer as “smart” pH-responsive carrier for intracellular delivery of hydrophobic drugs. Polymer 52:3396–3404

    Article  CAS  Google Scholar 

  8. Li YY, Zhang XZ, Cheng H, Zhu JL, Cheng SX, Zhuo RX (2006) Self-assembled, thermosensitive PCL-g-P(NIPAAm-co-HEMA) micelles for drug delivery. Macromol Rapid Commun 27:1913–1919

    Article  CAS  Google Scholar 

  9. Virtanen J, Tenhu H (2001) Studies on copolymerization of n-isopropylacrylamide and glycidyl methacrylate. J Polym Sci Part A Polym Chem 39:3716–3725

    Article  CAS  Google Scholar 

  10. Wang YC, Tang LY, Li Y, Wang J (2009) Thermoresponsive block copolymers of poly(ethylene glycol) and polyphosphoester: thermo-induced self-assembly, biocompatibility, and hydrolytic degradation. Biomacromolecules 10:66–73

    Article  CAS  Google Scholar 

  11. Bigot J, Charleux B, Cooke G, Delattre F, Fournier D, Lyskawa J, Sambe L, Stoffelbach F, Woisel P (2010) Tetrathiafulvalene end-functionalized poly(N-isopropylacrylamide): a new class of amphiphilic polymer for the creation of multistimuli responsive micelles. J Am Chem Soc 132:10796–10801

    Article  CAS  Google Scholar 

  12. Kumar A, Srivastava A, Galaev IY, Mattiasson B (2007) Smart polymers: physical forms and bioengineering applications. Prog Polym Sci 32:1205–1237

    Article  CAS  Google Scholar 

  13. Qu TH, Wang AR, Yuan JF, Shi JH, Gao QY (2009) Preparation and characterization of thermo-responsive amphiphilic triblock copolymer and its self-assembled micelle for controlled drug release. Colloids Surf B Biointerfaces 72:94–100

    Article  CAS  Google Scholar 

  14. Iwasaki Y, Wachiralarpphaithoon C, Akiyoshi K (2007) Novel thermoresponsive polymers having biodegradable phosphoester backboness. Macromolecules 40:8136–8138

    Article  CAS  Google Scholar 

  15. Liu X, Ni PH, He JL, Zhang MZ (2010) Synthesis and micellization of pH/temperature-responsive double-hydrophilic diblock copolymers polyphosphoester-block-poly[2-(dimethylamino)ethyl methacrylate] prepared via ROP and ATRP. Macromolecules 43:4771–4781

    Article  CAS  Google Scholar 

  16. Vihola H, Laukkanen A, Tenhu H, Hirvonen J (2008) Drug release characteristics of physically cross-linked thermosensitive poly(N-vinylcaprolactam) hydrogel particles. J Pharm Sci 97:4783–4793

    Article  CAS  Google Scholar 

  17. Prabaharan SM, Grailer JJ, Steeber DA, Gong SQ (2008) Stimuli-responsive chitosan-graft-poly(N-vinylcaprolactam) as a promising material for controlled hydrophobic drug delivery. Macromol Biosci 8:843–851

    Article  CAS  Google Scholar 

  18. Shah S, Pal A, Gude R, Devi S (2010) Synthesis and characterization of thermo-responsive copolymeric nanoparticles of poly(methyl methacrylate-co-N-vinylcaprolactam). Eur Polym J 46:958–967

    Article  CAS  Google Scholar 

  19. Viholal H, Laukkanen A, Valtola L, Tenhu H, Hirvonen J (2005) Cytotoxicity of thermosensitive polymers poly(N-isopropylacrylamide), poly(N-vinylcaprolactam) and amphiphilically modified poly(N-vinylcaprolactam). Biomaterials 26:3055–3064

    Article  Google Scholar 

  20. Loos W, Verbrugghe S, Goethals EJ, Prez FED, Bakeeva IV, Zubov VP (2003) Thermo-responsive organic/inorganic hybrid hydrogels based on poly(N-vinylcaprolactam). Macromol Chem Phys 204:98–103

    Article  CAS  Google Scholar 

  21. Verbrugghe S, Bernaerts K, Prez FED (2003) Thermo-responsive and emulsifying properties of poly(N-vinylcaprolactam) based graft copolymers. Macromol Chem Phys 204:1217–1225

    Article  CAS  Google Scholar 

  22. Hurtgen M, Liu J, Debuigne A, Jerome C, Detrembleur C (2012) Synthesis of thermo-responsive poly(N-vinylcaprolactam)-containing block copolymers by cobalt-mediated radical polymerization. J Polym Sci Part A Polym Chem 50:400–408

    Article  CAS  Google Scholar 

  23. Lequieu W, Shtanko NI, Prez FED (2005) Track etched membranes with thermo-adjustable porosity and separation properties by surface immobilization of poly(N-vinylcaprolactam). J Membr Sci 256:64–71

    CAS  Google Scholar 

  24. Dimitrov I, Trzebicka B, Müller AHH, Dworak A, Tsvetanov CB (2007) Thermosensitive water-soluble copolymers with doubly responsive reversibly interacting entities. Prog Polym Sci 32:1275–1343

    Article  CAS  Google Scholar 

  25. Castillo RV, Müller AJ, Raquez JM, Dubois P (2010) Crystallization kinetics and morphology of biodegradable double crystalline PLLA-b-PCL diblock copolymers. Macromolecules 43:4149–4160

    Article  CAS  Google Scholar 

  26. Loh XJ, Sng KBC, Li J (2008) Synthesis and water-swelling of thermo-responsive poly(ester urethane)s containing poly(ε-caprolactone), poly(ethylene glycol) and poly(propylene glycol). Biomaterials 29:3185–3194

    Article  CAS  Google Scholar 

  27. Li JB, Ren J, Cao Y, Yuan WZ (2010) Synthesis of biodegradable pentaarmed star-block copolymers via an asymmetric BIS-TRIS core by combination of ROP and RAFT: from star architectures to double responsive micelles. Polymer 51:1301–1310

    Article  CAS  Google Scholar 

  28. Rong GZ, Deng MX, Deng C, Tang ZH, Piao LH, Chen XS, JingX B (2003) Synthesis of poly(ε-caprolactone)-b-poly(γ-benzyl-l-glutamic acid) block copolymer using amino organic calcium catalyst. Biomacromolecules 4:1800–1804

    Article  CAS  Google Scholar 

  29. Sahoo S, Sasmal A, Nanda R, Phani AR, Nayak PL (2010) Synthesis of chitosan-polycaprolactone blend for control delivery of ofloxacin drug. Carbohydr Polym 79:106–113

    Article  CAS  Google Scholar 

  30. Sarazin P, Li G, Orts WJ, Favis BD (2008) Binary and ternary blends of polylactide, polycaprolactone and thermoplastic starch. Polymer 49:599–609

    Article  CAS  Google Scholar 

  31. Loontjens CAM, Vermonden T, Leemhuis M, Van Steenbergen MJ, Van Nostrum CF, Hennink WE (2007) Synthesis and characterization of random and triblock copolymers of ε-caprolactone and (benzylated) hydroxymethyl glycolide. Macromolecules 40:7208–7216

    Article  CAS  Google Scholar 

  32. Miguel VS, Limer AJ, Haddleton DM, Catalina F, Peinado C (2008) Biodegradable and thermoresponsive micelles of triblock copolymers based on 2-(N,N-dimethylamino)ethyl methacrylate and ε-caprolactone for controlled drug delivery. Eur Polym J 44:3853–3863

    Article  Google Scholar 

  33. Zhang GL, Liang F, Song XM, Liu DL, Li MJ, Wu QH (2010) New amphiphilic biodegradable β-cyclodextrin/poly(l-leucine) copolymers: synthesis, characterization, and micellization. Carbohydr Polym 80:885–890

    Article  CAS  Google Scholar 

  34. Xiao CS, Wang YC, Du JZ, Chen XS, Wang J (2006) Kinetics and mechanism of 2-ethoxy-2-oxo-1,3,2-dioxaphospholane polymerization initiated by stannous octoate. Macromolecules 39:6825–6831

    Article  CAS  Google Scholar 

  35. Kowalski A, Duda A, Penczek S (2000) Kinetics and mechanism of cyclic esters polymerization initiated with tin(II) octoate. 3. Polymerization of l,l,-dilactide. Macromolecules 33:7359–7370

    Article  CAS  Google Scholar 

  36. Kowalski A, Libiszowski J, Biela T, Cypryk M, Duda A, Penczek S (2005) Kinetics and mechanism of cyclic esters polymerization initiated with tin(II) octoate. polymerization of ε-caprolactone and l,l,-lactide co-initiated with primary amines. Macromolecules 38:8170–8176

    Article  CAS  Google Scholar 

  37. Deng C, Chen XS, Yu HJ, Sun J, Lu TC, Jing XB (2007) A biodegradable triblock copolymer poly(ethylene glycol)-b-poly(l,-lactide co-initiated with primary amines-lactide)-b-poly(l-lysine): synthesis, self-assembly, and RGD peptide modification. Polymer 48:139–149

    Article  CAS  Google Scholar 

  38. Wu QH, Wang C, Zhang D, Song XM, Wang LP, Zhang GL (2012) Synthesis and micellization of a new amphiphilic star-shaped poly(d, l,-lactide co-initiated with primary amines-lactide)/polyphosphoester block copolymer. React Funct Polym 72:372–377

    Article  CAS  Google Scholar 

  39. Hain J, Schrinner M, Lu Y, Pich A (2008) Design of multicomponent microgels by selective deposition of nanomaterials. Small 4:2016–2024

    Article  CAS  Google Scholar 

  40. Meeussen F, Nies E, Berghmans H, Verbrugghe S, Goethals E, Du Prez F (2000) Phase behaviour of poly(N-vinyl caprolactam) in water. Polymer 41:8597–8602

    Article  CAS  Google Scholar 

  41. Laukkanen A, Valtola L, Winnik FM, Tenhu H (2004) Formation of colloidally stable phase separated poly(N-vinylcaprolactam) in water: a study by dynamic light scattering, microcalorimetry, and pressure perturbation calorimetry. Macromolecules 37:2268–2274

    Article  CAS  Google Scholar 

  42. Shtanko NI, Lequieu W, Goethals EJ, Du Prez FE (2003) pH- and thermo-responsive properties of poly(N-vinylcaprolactam-co-acrylic acid) copolymers. Polym Int 52:1605–1610

    Article  CAS  Google Scholar 

  43. Medeiros SF, Barboza JCS, Ré MI, Giudici R, Santos AM (2010) Solution polymerization of N-vinylcaprolactam in 1,4-dioxane. Kinetic dependence on temperature, monomer, and initiator concentrations. J Appl Polym Sci 118:229–240

    Article  CAS  Google Scholar 

  44. Kohori F, Sakai K, Aoyagi T, Yokoyama M, Sakurai Y, Okano T (1998) Preparation and characterization of thermally responsive block copolymer micelles comprising poly(N-isopropylacrylamide-b-dl-lactide). J Controlled Release 55:87–98

    Article  CAS  Google Scholar 

  45. Maeda Y, Tsubota M, Ikeda I (2003) Temperature-responsive graft copolymers with poly(propylene glycol) side chains. Macromol Rapid Commun 24:242–245

    Article  CAS  Google Scholar 

  46. Kim YS, Gil ES, Lowe TL (2006) Synthesis and characterization of thermoresponsive-co-biodegradable linear-dendritic copolymers. Macromolecules 39:7805–7811

    Article  CAS  Google Scholar 

  47. Shao LD, Hu MQ, Chen L, Xu L, Bi YM (2012) RAFT polymerization of N-vinylcaprolactam and effects of the end group on the thermal response of poly(N-vinylcaprolactam). React Funct Polym 72:407–413

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors are grateful to the financial supports from the Natural Science Foundation for Education Department of Liaoning Province of China (No. L2012007), Program for Liaoning Innovative Research Team in University (No. LT2011001) and Foundation of 211 Project for Innovative Talents Training, Liaoning University.

Author information

Authors and Affiliations

  1. Liaoning Province Key Laboratory for Green Synthesis and Preparative Chemistry of Advanced Materials, College of Chemistry, Liaoning University, Shenyang, 110036, People’s Republic of China

    Qiuhua Wu, Liping Wang, Xiaofei Fu, Ximing Song, Qi Yang & Guolin Zhang

Authors
  1. Qiuhua Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Liping Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiaofei Fu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ximing Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Qi Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Guolin Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Guolin Zhang.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Wu, Q., Wang, L., Fu, X. et al. Synthesis and self-assembly of a new amphiphilic thermosensitive poly(N-vinylcaprolactam)/poly(ε-caprolactone) block copolymer. Polym. Bull. 71, 1–18 (2014). https://doi.org/10.1007/s00289-013-1041-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00289-013-1041-x

Keywords

Search

Navigation