Thiophene decorated block copolymers templated from poly(styrene-alt-maleic anhydride)-block-poly(styrene) one-shot block copolymer: effect of thiophene inclusion on morphology

  • Benoît H. Lessard
  • Milan Marić
Original Paper


Poly(styrene-alt-maleic anhydride) copolymer and poly(styrene-alt-maleic anhydride)-block-poly(styrene) block copolymer with narrow molecular weight distributions were synthesized by nitroxide mediated radical polymerization (NMP) and the anhydride units were selectively converted to thiophene units. The thiophene decorated poly(styrene-alt-maleic anhydride) copolymer was emulsified in water, resulting in rod-like or cylindrical morphologies with diameters ≈ 90 nm while the non-decorated copolymers and thiophene decorated block copolymer resulted in spheres.


Styrene and maleic anhydride Water dispersible Worm/rod-like morphology Thiophene Nitroxide mediated polymerization (NMP) 



We thank the Canada Foundation for Innovation (CFI) New Opportunities Fund and the NSERC Discovery Grant 288125–09 for funding this work. We would also like to thank Dr. Dmitrii Perepichka for the use of his laboratory and equipment to run the conductivity measurements along with Dr. Brandon Djukic for his help in performing the conductivity measurements. We would also like to thank the Centre for Self-Assembled Chemical Structures (CSACS) for the use of the FT-IR.

Supplementary material

10965_2016_931_MOESM1_ESM.doc (362 kb)
ESM 1 (DOC 361 kb)


  1. 1.
    Hillmyer M (2005) Nanoporous Materials from Block Copolymer Precursors. 137–181Google Scholar
  2. 2.
    Allen C, Maysinger D, Eisenberg A (1999) Nano-engineering block copolymer aggregates for drug delivery. Colloids Surf B: Biointerfaces 16:3–27CrossRefGoogle Scholar
  3. 3.
    Moughton AO, Patterson YJP, OReilly RK (2011) Reversible morphological switching of nanostructures in solution. Chem Commun 47:355–357CrossRefGoogle Scholar
  4. 4.
    Lazzara TD, Whitehead MA, van de Ven T (2009) Linear nano-templates of styrene and maleic anhydride alternating copolymers. Eur Polym J 45:1883–1890CrossRefGoogle Scholar
  5. 5.
    Matyjaszewski K, Tsarevsky N (2009) Nanostructured functional materials prepared by atom transfer radical polymerization. Nat Chem 1:276–288CrossRefGoogle Scholar
  6. 6.
    Hawker CJ, Bosman A, Harth E (2001) New polymer synthesis by nitroxide mediated living radical polymerizations. Chem Rev 101:3661–3688CrossRefGoogle Scholar
  7. 7.
    Wang R, Wang W, Lu S, Liu T (2009) Controlled radical synthesis of fluorene-based blue-light-emitting copolymer nanospheres with core − shell structure via self-assembly. Macromolecules 42:4993–5000CrossRefGoogle Scholar
  8. 8.
    Yin X, Stöver H (2002) Thermosensitive and pH-sensitive polymers based on maleic anhydride copolymers. Macromolecules 35:10178–10181CrossRefGoogle Scholar
  9. 9.
    Henry S, El-Sayed M, Pirie C (2006) pH-responsive poly (styrene-alt-maleic anhydride) alkylamide copolymers for intracellular drug delivery. Biomacromolecules 7:2407–2414CrossRefGoogle Scholar
  10. 10.
    Salahuddin N, Akelah A (2002) Synthesis and characterization of poly (styrene-maleic anhydride)-montmorillonite nanocomposite. Polym Adv Technol 13:339–345CrossRefGoogle Scholar
  11. 11.
    Oshinski A, Keskkula H (1992) Rubber toughening of polyamides with functionalized block copolymers: 1. Nylon-6. Polymer 33:268–283CrossRefGoogle Scholar
  12. 12.
    Lazzara TD, Bourret GR, Lennox RB, de Ven TGMV (2009) Polymer templated synthesis of AgCN and Ag nanowires. Chem Mater 21:2020–2026CrossRefGoogle Scholar
  13. 13.
    Pompe T, Zschoche S, Herold N, Salchert K (2003) Maleic anhydride CopolymersA versatile platform for molecular biosurface engineering. Biomacromolecules 4:1072–1079CrossRefGoogle Scholar
  14. 14.
    Ratzsch M (1988) Alternating maleic anhydride copolymers. Prog Polym Sci 13:277–337CrossRefGoogle Scholar
  15. 15.
    Benoit D, Harth E, Fox P et al (2000) Accurate structural control and block formation in the living polymerization of 1,3-dienes by nitroxide-mediated procedures. Macromolecules 33:363–370CrossRefGoogle Scholar
  16. 16.
    Zhu M-Q, Wei L-H, Li M et al (2001) A unique synthesis of a well-defined block copolymer having alternating segments constituted by maleic anhydride and styrene and the self-assembly aggregating behavior thereof. Chem Commun 4:365–366CrossRefGoogle Scholar
  17. 17.
    Zhang Z, Hong L, Gao Y, Zhang W (2014) One-pot synthesis of POSS-containing alternating copolymers by RAFT polymerization and their microphase-separated nanostructures. Polym Chem 5:4534CrossRefGoogle Scholar
  18. 18.
    Lessard BH, Maric M (2010) One-step poly(styrene-alt-maleic anhydride)-block-poly(styrene) copolymers with highly alternating styrene/maleic anhydride sequences Are possible by nitroxide-mediated polymerization. Macromolecules 43:879–885CrossRefGoogle Scholar
  19. 19.
    Zhang Q, Cirpan A, Russell TP, Emrick T (2009) Donor-acceptor poly(thiophene-block-perylene diimide) copolymers: synthesis and solar cell fabrication. Macromolecules 42:1079–1082CrossRefGoogle Scholar
  20. 20.
    Wu P, Xin H, Kim F et al (2009) Regioregular poly (3-pentylthiophene): synthesis, self-assembly of nanowires, high-mobility field-effect transistors, and efficient photovoltaic cells. Macromolecules 42:8817–8826CrossRefGoogle Scholar
  21. 21.
    Yilmaz F, Cianga L, Guner Y et al (2004) Synthesis and characterization of alternating copolymers of thiophene-containing N-phenyl maleimide and styrene by photoinduced radical polymerization and their use in electropolymerization. Polymer 45:5765–5774CrossRefGoogle Scholar
  22. 22.
    Cianga L, Yagci Y (2002) Synthesis and characterization of thiophene-substituted N-phenyl maleimide polymers by photoinduced radical polymerization. J Polym Sci Pol Chem 995–1004.Google Scholar
  23. 23.
    Lin J-J, Hsu Y-C (2009) Temperature and pH-responsive properties of poly(styrene-co-maleic anhydride)-grafting poly(oxypropylene)-amines. J Colloid Interface Sci 336:82–89CrossRefGoogle Scholar
  24. 24.
    Aldea G, Vyprachticky D, Cimrova V (2004) Modification of poly(styrene-alt-maleic anhydride) with 1,3,4-oxadiazole units for electroluminescent devices. Macromol Symp 212:523–528CrossRefGoogle Scholar
  25. 25.
    Dharmarajan N, Datta S (1992) Toughening styrene maleic anhydride copolymers with functionalized ethylene propylene rubbers. Polymer 33:3848–3857CrossRefGoogle Scholar
  26. 26.
    Kim B, Park S (1991) Reactive melt blends of nylon with poly (styrene-co-maleic anhydride). J Appl Polym Sci 43:357–363CrossRefGoogle Scholar
  27. 27.
    McCullough R, Tristram-Nagle S (1993) Self-orienting head-to-tail poly (3-alkylthiophenes): new insights on structure–property relationships in conducting polymers. J Chem Soc 115:4910–4911CrossRefGoogle Scholar
  28. 28.
    Kale TS, Klaikherd A, Popere B, Thayumanavan S (2009) Supramolecular assemblies of amphiphilic homopolymers. Langmuir 25:9660–9670CrossRefGoogle Scholar
  29. 29.
    Strauss U, Gershfel NL (1954) The transition from typical polyelectrolyte to polysoap. I. Viscosity and solubilization studies on copolymers of 4-vinyl-N-ethylpyridinium bromide and 4-vinyl-N-n-dodecylpyridinium bromide. J Phys Chem 58:747–753CrossRefGoogle Scholar
  30. 30.
    Hu Y, Armentrout R, McCormick C (1997) Water soluble polymers. 75. Responsive microdomains in labeled N-octylamide-substituted poly (sodium maleate-alt-ethyl vinyl ether): transient fluorescence and time-resolved fluorescence anisotropy studies. Macromolecules 30:3538–3546CrossRefGoogle Scholar
  31. 31.
    Ueda M, Hashidzume A, Sato T (2011) Unicore multicore transition of the micelle formed by an amphiphilic alternating copolymer in aqueous media by changing molecular weight. Macromolecules 44:2970–2977CrossRefGoogle Scholar
  32. 32.
    Matsuno R, Yamamoto K, Otsuka H (2004) Polystyrene-and poly (3-vinylpyridine)-grafted magnetite nanoparticles prepared through surface-initiated nitroxide-mediated radical polymerization. Macromolecules 37:1089–1094CrossRefGoogle Scholar
  33. 33.
    Rong Y, Chen H-Z, Wei D-C et al (2004) Microcapsules with compact membrane structure from gelatin and styrene–maleic anhydride copolymer by complex coacervation. Colloids Surf A Physicochem Eng Asp 242:17–20CrossRefGoogle Scholar
  34. 34.
    Endō R, Hinokuma T, Takeda M (1968) Studies of solution properties of copolymers II. Copolymer of maleic anhydride and styrene. J Polym Sci A A-2(6):665–673CrossRefGoogle Scholar
  35. 35.
    Bhargava P, Tu Y, Zheng J et al (2007) Temperature-induced reversible morphological changes of polystyrene-block-poly (ethylene oxide) micelles in solution. J Am Chem Soc 129:1113–1121CrossRefGoogle Scholar
  36. 36.
    Malardier-Jugroot C, de Ven TGMV, Whitehead MA (2005) Linear conformation of poly (styrene-a lt-maleic anhydride) capable of self-assembly: a result of chain stiffening by internal hydrogen bonds. J Phys Chem B 109:7022–7032CrossRefGoogle Scholar
  37. 37.
    Chan ASW, Groves M, Malardier-Jugroot C (2010) Self-assembly of alternating copolymers and the role of hydrophobic interactions: characterisation by molecular modelling. Molecular Simulation 1–9.Google Scholar
  38. 38.
    Dang TD, Bai SJ, Heberer DP et al (1993) Ionic conductivity of conjugated water-soluble rigid-rod polymers. J Polym Sci B Polym Phys 31:1941–1950CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2016

Authors and Affiliations

  1. 1.Department of Chemical and Biological EngineeringUniversity of OttawaOttawaCanada
  2. 2.Department of Chemical EngineeringMcGill UniversityMontrealCanada

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