Advertisement

Colloid and Polymer Science

, Volume 296, Issue 9, pp 1545–1554 | Cite as

Synthesis and characterization of amphiphilic graft copolymers with poly(ethylene glycol) as the hydrophilic backbone and poly(butyl methacrylate) as the hydrophobic graft chain

  • Xin Liu
  • Xue Bai
  • Jian Li
  • Chenyi Wang
  • Qiang Ren
Original Contribution
  • 97 Downloads

Abstract

A series of amphiphilic graft copolymers with hydrophilic polyethylene glycol (PEG) backbone and different densities of hydrophobic poly(butyl methacrylate) (PBMA) side chains were synthesized via a strategy combining polycondensation and through activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) technology. The hydrophilic macro-ATRP initiators having different amounts of active side bromo atoms were first synthesized by reacting the small ATRP initiator which contains two hydroxyl groups with hexamethylene diisocyanate (HDI) and polyethylene glycol (PEG1000). By graft from technology, the amphiphilic graft copolymers were then synthesized via ARGET ATRP of butyl methacrylate (BMA) using the hydrophilic macro-ATRP initiators. The steric shield effects of the macro-initiator lowered the polymerization rate and final conversion of BMA. The amphiphilic graft copolymers in aqueous media had critical micelle concentration (CMC) in the range of 10−6 to 10−7 g/mL, which were determined by fluorescence method using pyrene as a probe. The aggregate sizes of the amphiphilic graft copolymers in different solvents changed greatly, which were due to different interactions between the amphiphilic graft copolymers and the solvents and the incompatibility between PEG and PBMA segments.

Keywords

Amphiphilic copolymers Graft copolymers Graft from ARGET ATRP Critical micelle concentration 

Notes

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

References

  1. 1.
    Grubbs RB, Grubbs RH (2017) 50th Anniversary perspective: living polymerization emphasizing the molecule in macromolecules. Macromolecules 50:6979–6997CrossRefGoogle Scholar
  2. 2.
    Ouchi M, Sawamoto M (2017) 50th Anniversary perspective: metal-catalyzed living radical polymerization: discovery and perspective. Macromolecules 50:2603–2614CrossRefGoogle Scholar
  3. 3.
    Polymeropoulos G, Zapsas G, Ntetsikas K, Bilalis P, Gnanou Y, Hadjichristidis N (2017) 50th Anniversary perspective: polymers with complex architectures. Macromolecules 50:1253–1290CrossRefGoogle Scholar
  4. 4.
    Anastasaki A, Nikolaou V, Nurumbetov G, Wilson P, Kempe K, Quinn JF, Davis TP, Whittaker MR, Haddleton DM (2016) Cu(0)-mediated living radical polymerization: a versatile tool for materials synthesis. Chem Rev 116:835–877CrossRefPubMedGoogle Scholar
  5. 5.
    Matyjaszewski K (2012) Atom transfer radical polymerization (ATRP): current status and future perspectives. Macromolecules 45:4015–4039CrossRefGoogle Scholar
  6. 6.
    Ilgach DM, Meleshko TK, Yakimansky AV (2015) Methods of controlled radical polymerization for the synthesis of polymer brushes. Polym Sci Ser C 57:3–19CrossRefGoogle Scholar
  7. 7.
    Verduzco R, Li XY, Peseka SL, Steinc GE (2015) Structure, function, self-assembly, and applications of bottlebrush copolymers. Chem Soc Rev 14:2405–2420CrossRefGoogle Scholar
  8. 8.
    Thakur VK, Thakur MK (2014) Recent advances in graft copolymerization and applications of chitosan: a review. ACS Sustain Chem Eng 2:2637–2652CrossRefGoogle Scholar
  9. 9.
    Ito S, Goseki R, Ishizone T, Hirao A (2014) Synthesis of well-controlled graft polymers by living anionic polymerization towards exact graft polymers. Polym Chem 5:5523–5534CrossRefGoogle Scholar
  10. 10.
    Wang HD, Roeder RD, Whitney RA, Champagne P, Cunningham MF (2015) Graft modification of crystalline nanocellulose by Cu(0)-mediated SET living radical polymerization. J Polym Sci, Part A: Polym Chem 53:2800–2808CrossRefGoogle Scholar
  11. 11.
    Wu DD, Huang YJ, Xu FG, Mai YY, Yan DY (2017) Recent advances in the solution self-assembly of amphiphilic “rod-coil” copolymers. J Polym Sci Part A Polym Chem 55:1459–1477CrossRefGoogle Scholar
  12. 12.
    Bollhorst T, Rezwan K, Maas M (2017) Colloidal capsules: nano- and microcapsules with colloidal particle shells. Chem Soc Rev 46:2091–2126CrossRefPubMedGoogle Scholar
  13. 13.
    Galli G, Martinelli E (2017) Amphiphilic polymer platforms: surface engineering of films for marine antibiofouling. Macromol Rapid Commun 38:1600704CrossRefGoogle Scholar
  14. 14.
    Wei J, Sun ZK, Luo W, Li YH, Elzatahry AA, Al-Enizi AM, Deng YH, Zhao DY (2017) New insight into the synthesis of large-pore ordered mesoporous materials. J Am Chem Soc 139:1706–1713CrossRefPubMedGoogle Scholar
  15. 15.
    Bertrand O, Gohy J-F (2017) Photo-responsive polymers: synthesis and applications. Polym Chem 8:52–73CrossRefGoogle Scholar
  16. 16.
    Patil Y, Almahdali S, Vu KB, Zapsas G, Hadjichristidis N, Rodionov VO (2017) pH-sensitive amphiphilic block-copolymers for transport and controlled release of oxygen. Polym Chem 8:4322–4326CrossRefGoogle Scholar
  17. 17.
    Breitenbach BB, Schmid I, Wich PR (2017) Amphiphilic polysaccharide block copolymers for pH-responsive micellar nanoparticles. Biomacromolecules 18:2839–2848CrossRefPubMedGoogle Scholar
  18. 18.
    Pal A, Pal S (2017) Synthesis of poly(ethylene glycol)-block-poly(acrylamide)-block-poly(lactide) amphiphilic copolymer through ATRP, ROP and click chemistry: characterization, micellization and pH-triggered sustained release behaviour. Polymer 127:150–158CrossRefGoogle Scholar
  19. 19.
    Obata M, Otobuchi R, Kuroyanagi T, Takahashi M, Hirohara S (2017) Synthesis of amphiphilic block copolymer consisting of glycopolymer and poly(L-lactide) and preparation of sugar-coated polymer aggregates. J Polym Sci A Polym Chem 55:395–403CrossRefGoogle Scholar
  20. 20.
    Guerre M, Schmidt J, Talmon Y, Ameduri B, Ladmiral V (2017) An amphiphilic poly(vinylidene fluoride)-b-poly(vinyl alcohol) block copolymer: synthesis and self-assembly in water. Polym Chem 8:1125–1128CrossRefGoogle Scholar
  21. 21.
    Rayeroux D, Travelet C, Lapinte V, Borsali R, Robin JJ, Bouilhac C (2017) Tunable amphiphilic graft copolymers bearing fatty chains and polyoxazoline: synthesis and self-assembly behavior in solution. Polym Chem 8:4246–4263CrossRefGoogle Scholar
  22. 22.
    Qian WH, Song T, Ye M, Xu PC, Lu GL, Huang XY (2017) PAA-g-PLA amphiphilic graft copolymer: synthesis, self-assembly, and drug loading ability. Polym Chem 8:4098–4107CrossRefGoogle Scholar
  23. 23.
    Lim JY, Kim JK, Lee JM, Ryu DY, Kim JH (2016) An amphiphilic block-graft copolymer electrolyte: synthesis, nanostructure, and use in solid-state flexible supercapacitors. J Mater Chem A 4:7848–7858CrossRefGoogle Scholar
  24. 24.
    Lu GL, Jiang XJ, Li YJ, Lv XL, Huang XY (2015) Synthesis and self-assembly of PMBTFVB-g-PNIPAM fluorine-containing amphiphilic graft copolymer. RSC Adv 5:74947–74952CrossRefGoogle Scholar
  25. 25.
    Fan XS, Wang XY, Cao MY, Wang CG, Hu ZG, Wu YL, Li ZB, Loh XJ (2017) “Y”-shape armed amphiphilic star-like copolymers: design, synthesis and dual-responsive unimolecular micelle formation for controlled drug delivery. Polym Chem 8:5611–5620CrossRefGoogle Scholar
  26. 26.
    Cui SD, Pan XF, Gebru H, Wang X, Liu JQ, Liu JJ, Li ZJ, Guo K (2017) Amphiphilic star-shaped poly(sarcosine)-block-poly(ε-caprolactone) diblock copolymers: one-pot synthesis, characterization, and solution properties. J Mater Chem B 5:679–690CrossRefGoogle Scholar
  27. 27.
    Yuan H, Chi H, Yuan WZ (2016) A star-shaped amphiphilic block copolymer with dual responses: synthesis, crystallization, self-assembly, redox and LCST-UCST thermoresponsive transition. Polym Chem 7:4901–4911CrossRefGoogle Scholar
  28. 28.
    Guo QQ, Liu CY, Tang TT, Huang J, Zhang XG, Wang GW (2013) Synthesis of amphiphilic A4B4 star-shaped copolymers by mechanisms transformation combining with thiol-ene reaction. J Polym Sci A Polym Chem 51:4572–4583CrossRefGoogle Scholar
  29. 29.
    Gao F, Xing YH, Yao Y, Sun LY, Sun Y, He XH, Lin SL (2017) Self-assembly and multi-stimuli responsive behavior of PAA-b-PAzoMA-b-PNIPAM triblock copolymers. Polym Chem 8:7529–7536CrossRefGoogle Scholar
  30. 30.
    Hattori G, Hirai Y, Sawamoto M, Terashima T (2017) Self-assembly of PEG/dodecyl-graft amphiphilic copolymers in water: consequences of the monomer sequence and chain flexibility on uniform micelles. Polym Chem 8:7248–7259CrossRefGoogle Scholar
  31. 31.
    Shi XX, Hou ML, Bai S, Ma XQ, Gao YE, Xiao B, Xue P, Kang YJ, Xu ZG, Li CM (2017) Acid-activatable theranostic unimolecular micelles composed of amphiphilic star-like polymeric prodrug with high drug loading for enhanced cancer therapy. Mol Pharm 14:4032–4041CrossRefPubMedGoogle Scholar
  32. 32.
    Tan HN, Yu CY, Lu ZY, Zhou YF, Yan DY (2017) A dissipative particle dynamics simulation study on phase diagrams for the self-assembly of amphiphilic hyperbranched multiarm copolymers in various solvents. Soft Matter 13:6178–6188CrossRefPubMedGoogle Scholar
  33. 33.
    Peng D, Zhang XH, Huang XY (2006) Synthesis of amphiphilic graft copolymer with hydrophilic poly(acrylic acid) backbone and hydrophobic polystyrene side chains. Polymer 47:6072–6080CrossRefGoogle Scholar
  34. 34.
    Peng D, Zhang XH, Feng C, Lu GL, Zhang S, Huang XY (2006) Synthesis and characterization of amphiphilic graft copolymers with hydrophilic poly(acrylic acid) backbone and hydrophobic poly(methyl methacrylate) side chains. Polymer 48:5250–5258CrossRefGoogle Scholar
  35. 35.
    Wang W, Zhou X, Wei M, Liu ZD, Lu GL, Huang XY (2017) Synthesis of an amphiphilic graft copolymer bearing a hydrophilic poly(acrylate acid) backbone for drug delivery of methotrexate. RSC Adv 7:54562–54569CrossRefGoogle Scholar
  36. 36.
    Manfred W, Zhao CL, Wang YC (1991) Poly(styrene-ethylene oxide) block copolymer micelle formation in water: a fluorescence probe study. Macromolecules 24:1033–1040CrossRefGoogle Scholar
  37. 37.
    Irinaa A, Zhong XF, Adi E (1993) Critical micellization phenomena in block polyelectrolyte solutions. Macromolecules 26:7339–7352CrossRefGoogle Scholar
  38. 38.
    Reuther JF, Siriwardane DA, Campos R, Novak BM (2015) Solvent tunable self-assembly of amphiphilic rod-coil block copolymers with chiral, helical polycarbodiimide segments: polymeric nanostructures with variable shapes and sizes. Macromolecules 48:6890–6899CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Xin Liu
    • 1
    • 2
  • Xue Bai
    • 1
    • 2
  • Jian Li
    • 1
    • 2
  • Chenyi Wang
    • 1
    • 2
  • Qiang Ren
    • 1
    • 2
  1. 1.Jiangsu Collaborative Innovation Center of Photovolatic Science and EngineeringChangzhou UniversityChangzhouChina
  2. 2.Department of Materials Chemistry, Faculty of Materials Science and EngineeringChangzhou UniversityChangzhouChina

Personalised recommendations