화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.24, No.8, 710-715, August, 2016
DOI10.1007/s13233-016-4096-3  Export Citation
Poly(styrene-alt-maleic anhydride)-block-poly(methacrylate-ran-styrene) block copolymers with tunable mechanical properties by nitroxide mediated controlled radical polymerization
Benoît H. Lessard1, 2, †, Sarah Mackay2, Adrien Métafiot2, and Milan Marić2, †
  • 1Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis Pasteur, K1N 6N5, Ottawa, Ontario, Canada
  • 2Department of Chemical Engineering, McGill University, 3610 University Street, H3A 2B2, Montreal, Quebec, Canada
E-mail:,
Poly(styrene-alt-maleic anhydride)-block-poly(methacrylate-ran-styrene) block copolymers were synthesized from low dispersity (Mw/Mn=1.24) and perfectly alternating poly(styrene-alt-maleic anhydride) macroinitiators, by nitroxide mediated controlled radical polymerization (NMP), using various methacrylate-rich mixtures: methyl methacrylate/styrene (MMA/S), ethyl methacrylate/styrene (EMMA/S), n-butyl methacrylate/styrene (BMA/S) and benzyl methacrylate/styrene (BzMA/S). Some irreversible termination was present during the chain extension from the macroinitiator, resulting in some bimodality in the molecular weight distribution of the final block copolymer (≈2% to ≈25% dead chains) which is common for methacrylate/styrene copolymerizations by NMP. The resulting final block copolymers were determined to be methacrylate-rich (molar ratio XMA/S ≈3.3 to 5.5) by 1H NMR and the resulting glass transition temperature (Tg) of the chain-extended segments were found to be similar to the coresponding pure poly(methacrylate)s. NMP allows the controlled placement of functional maleic anhydride containing segments within a block copolymer with tunable mechanical properties by simple substitution of methacrylate monomer used in synthesis.
Keywords:nitroxide mediated controlled radical polymerization (NMP);maleic anhydride (MA);methacrylate;alternating copolymer;block copolymer
  1. Szwarc M, Nature, 178, 1168 (1956)
  2. Szwarc M, Levy M, Milkovich R, J. Am. Chem. Soc., 78, 2656 (1956)
  3. Siegwart DJ, Oh JK, Matyjaszewski K, Prog. Polym. Sci, 37, 18 (2012)
  4. Min K, Matyjaszewski K, Central Eur. J. Chem., 7, 657 (2009)
  5. Grubbs R, Polym. Rev., 51, 104 (2011)
  6. Nicolas J, Guillaneuf Y, Lefay C, Bertin D, Gigmes D, Charleux B, Prog. Polym. Sci, 38, 63 (2013)
  7. Lessard BH, in Nitroxide Mediated Polymerization: From Fundamentals to Applications in Materials Science, Gigmes D, Ed., The Royal Society of Chemistry, Cambridge, 2016, pp 441-493.
  8. Chiefari J, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad G, Rizzardo E, Thang SH, Macromolecules, 31(16), 5559 (1998)
  9. Quinn JF, Barner L, Barner-Kowollik C, Rizzardo E, Davis TP, Macromolecules, 35(20), 7620 (2002)
  10. Georges M, Veregin R, Kazmaier P, Macromolecules, 26, 2987 (1993)
  11. Veregin P, Georges M, Kazmaier M, Hamer K, Macromolecules, 26, 5316 (1993)
  12. Lessard BH, Tervo C, Maric M, Macromol. React. Eng., 3, 245 (2009)
  13. Lessard BHB, Maric M, Maric M, Polym. Int., 54, 1141 (2008)
  14. Bian K, Cunningham MF, Macromolecules, 38(3), 695 (2005)
  15. Farcet C, Nicolas J, Charleux B, J. Polym. Sci. A: Polym. Chem., 40(24), 4410 (2002)
  16. Wang ZJ, Lessard BH, Maric M, eXPRESS Polym. Lett., 7, 1020 (2013)
  17. Gibbons O, Carroll W, Aldabbagh F, Zetterlund P, Yamada B, Macromol. Chem. Phys., 209, 2434 (2008)
  18. Schierholz K, Givehchi M, Fabre P, Nallet F, Papon E, Guerret O, Gnanou Y, Macromolecules, 36(16), 5995 (2003)
  19. Lessard B, Tervo C, De Wahl S, Clerveaux FJ, Tang KK, Yasmine S, Andjelic S, D'Alessandro A, Maric M, Macromolecules, 43(2), 868 (2010)
  20. Lessard BH, Savelyeva X, Maric M, Polymer, 53(25), 5649 (2012)
  21. Nicolas J, Brusseau S, Charleux B, J. Polym. Sci. A: Polym. Chem., 48(1), 34 (2010)
  22. Belleney J, Magnet S, Couvreur L, Charleux B, J. Polym. Sci. A: Polym. Chem., 1, 720 (2010)
  23. Lessard B, Maric M, J. Polym. Sci. A: Polym. Chem., 49(24), 5270 (2011)
  24. Lang JL, Pavelich WA, Clarey HD, J. Polym. Sci. A: Polym. Chem., 1, 1123 (1963)
  25. Ratzsch M, Prog. Polym. Sci, 13, 277 (1988)
  26. Lessard B, Maric M, Macromolecules, 43(2), 879 (2010)
  27. Benoit D, Hawker CJ, Huang EE, Lin ZQ, Russell TP, Macromolecules, 33(5), 1505 (2000)
  28. Park ES, Kim MN, Lee IM, Lee HS, Yoon JS, J. Polym. Sci. A: Polym. Chem., 38(12), 2239 (2000)
  29. Saldivar G, Gonzalez M, US Patent 7,323, 528 B2 (2008).
  30. Chiang CR, Chang FC, Polymer, 38(19), 4807 (1997)
  31. Filippi S, Minkova L, Dintcheva N, Narducci P, Magagnini P, Polymer, 46(19), 8054 (2005)
  32. Lessard B, Aumand-Bourque C, Chaudury R, Gomez D, Haroon A, Ibrahimian N, Mackay S, Noel MC, Patel R, Sitaram S, Valla S, White B, Maric M, Int. Polym. Process., 26(2), 197 (2011)
  33. Wang MT, Zhu XG, Wang SX, Zhang LD, Polymer, 40(26), 7387 (1999)
  34. Al-Sabagh AM, El-Din MRN, Morsi RE, Elsabee MZ, J. Pet. Sci. Eng., 65, 139 (2009)
  35. Henry SM, El-Sayed MEH, Pirie CM, Hoffman AS, Stayton PS, Biomacromolecules, 7(8), 2407 (2006)
  36. Lin JJ, Hsu YC, J. Colloid Interface Sci., 336(1), 82 (2009)
  37. Pompe T, Zschoche S, Herold N, Salchert K, Gouzy MF, Sperling C, Werner C, Biomacromolecules, 4(4), 1072 (2003)
  38. Lessard BH, Maric M, J. Polym. Res., 23, 40 (2016)
  39. Lessard B, Maric M, Macromolecules, 41(21), 7881 (2008)
  40. Zetterlund PB, Saka Y, McHale R, Nakamura T, Aldabbagh F, Okubo M, Polymer, 47(23), 7900 (2006)
  41. Nicolas J, Dire C, Mueller L, Belleney J, Charleux B, Marque SRA, Bertin D, Magnet S, Couvreur L, Macromolecules, 39(24), 8274 (2006)
  42. Charleux B, Nicolas J, Guerret O, Macromolecules, 38(13), 5485 (2005)
  43. Guillaneuf Y, Gigmes D, Marque S, Tordo P, Bertin D, Macromol. Chem. Phys., 207, 1278 (2006)
  44. Lessard B, Maric M, J. Polym. Sci. A: Polym. Chem., 47(10), 2574 (2009)
  45. Meyer VE, J. Polym. Sci. A: Polym. Chem., 5, 1289 (1967)
  46. Otsu T, Ito T, Imoto M, J. Polym. Sci. B: Polym. Lett., 3, 113 (1965)
  47. Mayo FR, Lewis FM, J. Am. Chem. Soc., 66, 1594 (1944)
  48. Brandrup J, Immergut EH, Grulke EA, Polymer Handbook, 4th ed., John Wiley & Sons, New York, 2003.