화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.23, No.2, 139-144, February, 2015
DOI10.1007/s13233-015-3031-3  Export Citation
Co(acac)2 mediated controlled radical copolymerization of vinyl acetate and methyl acrylate initiated by benzoyl peroxide
Mohammad Ali Semsarzadeh†, and Parisa Alamdari
  • Polymer Engineering Department, Faculty of Chemical Engineering, Modares University, P.O. Box: 14155/143, Tehran, Iran
E-mail:
Cobalt mediated radical copolymerization of vinyl acetate (VAc) and methyl acrylate (MA) was successfully performed in the presence of cobalt(II) acetylacetonate (Co(acac)2), dimethylformamide (DMF) and benzoyl peroxide (BPO) as catalyst, cobalt coordinating agent and initiator, respectively, at 45°C. The individual monomer conversion and comonomer composition of copolymers were determined by 1H NMR spectroscopy. Molecular weight (M n ) and its distribution (M w /M n ) were analyzed by GPC technique. The time dependence of ln[M]0/[M], the variation of molecular weight with respect to the conversion, and molecular weight distribution of copolymers were studied to evaluate controlled characteristics of copolymerization. It was found that Co(acac)2 successfully mediated the radical copolymerization of VAc and MA. Moreover, copolymer molecular weight and copolymerization rate increased with increasing initial MA ratio. The spectroscopy analysis revealed VAc content in the copolymer increased with conversion regardless of VAc initial ratio, indicating a gradient sequence distribution of the copolymer.
Keywords:cobalt(II) acetylacetonate;vinyl acetate;methyl acrylate;benzoyl peroxide;controlled radical copolymerization
  1. Debuigne A, Poli R, Jerame C, Jerome R, Detrembleur C, Prog. Polym. Sci., 34, 3 (2009)
  2. Hurtgen M, Detrembleur C, Jerome C, Debuigne A, Polym. Rev., 51, 2 (2011)
  3. Allan LEN, Perry MR, Shaver MP, Prog. Polym. Sci., 37, 1 (2012)
  4. Debuigne A, Jerome R, Jerome C, Detrembleur C, Synthesis of Polymers: New Structures and Methods, 1, 67 (2012)
  5. Wayland BB, Poszmik G, Mukerjee SL, Debuigne A, Jerome R, Jerome C, Fryd M, J. Am. Chem. Soc., 116, 17 (1994)
  6. Arvanitopoulos L, Greuel M, Harwood H, Living Free-radical Polymerization Using Alkyl Cobaloximes as Photoinitiators. American Chemical Society, Washington, DC (1994)
  7. Debuigne A, Caille JR, Jerome R, Angew. Chem. Int. Ed. Engl., 117, 7 (2005)
  8. Kaneyoshi H, Matyjaszewski K, Macromolecules, 38, 20 (2005)
  9. Barner-Kowollik C, Vana P, Davis T P, Handbook of Radical Polymerization. Wiley-Interscience, New York (2002)
  10. Debuigne A, Detrembleur C, Bryaskova R, Caille JR, Jerome R, Controlled/Living Radical Polymerization, 944, 372 (2006)
  11. Antoine D, Rinaldo P, Robert J, Christine J, Christophe D, Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP, 1024, 131 (2009)
  12. Peng CH, Li S, Wayland BB, J. Chinese Chem. Soc., 56, 2 (2009)
  13. Wayland BB, Basickes L, Mukerjee S, Wei M, Fryd M, Macromolecules, 30, 26 (1997)
  14. Sherwood RK, Kent CL, Patrick BO, McNeil WS, Chem. Commun., 46, 14 (2010)
  15. Bryaskova R, Detrembleur C, Debuigne A, Jerome R, Macromolecules, 39, 24 (2006)
  16. Repollet-Pedrosa MH, Weber RL, Schmitt AL, Mahanthappa MK, Macromolecules, 43, 19 (2010)
  17. Piette Y, Debuigne A, Jerome C, Bodart V, Poli R, Detrembleur C, Polym. Chem., 3, 10 (2012)
  18. Piette Y, Debuigne A, Bodart V, Willet N, Duwez AS, Jerome C, Detrembleur C, Polym. Chem., 4, 5 (2013)
  19. Debuigne A, Schoumacher M, Willet N, Riva R, Zhu X, Rutten S, Jerome C, Detrembleur C, Chem. Commun., 47, 47 (2011)
  20. Debuigne A, Willet N, Jerome R, Detrembleur C, Macromolecules, 40, 20 (2007)
  21. Jeon HJ, You Y, Yoon MJ, Youk JH, Polymer, 52, 18 (2011)
  22. Debuigne A, Warnant J, Jerome R, Voets I, Keizer A, Cohen Stuart MA, Detrembleur C, Macromolecules, 41, 7 (2008)
  23. Kalyanam N, Gandhi VG, Sivaram S, Polym. Bull., 11, 2 (1984)
  24. Buchmeiser MR, Marino MG, Macromol. Mater. Eng., 297, 9 (2012)
  25. Debuigne A, Michaux C, Jerome C, Jerome R, Poli R, Detrembleur C, Chemistry, 14, 25 (2008)
  26. Roberts GE, Barner-Kowollik C, Davis TP, Heuts JPA, Macromolecules, 36, 4 (2003)
  27. Destarac M, Macromol. React. Eng., 4, 3 (2010)
  28. Morin AN, Detrembleur C, Jerome C, Tullio P, Poli R, Debuigne A, Macromolecules, 46, 11 (2013)
  29. Piette Y, Debuigne A, Jerome C, Bodart V, Poli R, Detrembleur C, Polym. Chem., 3, 10 (2012)
  30. Debuigne A, Warnant J, Jerome R, Voets I, Keizer A, Cohen MA, Detrembleur SC, Macromolecules, 41, 7 (2008)
  31. Metrangolo P, Resnati G, Pilati T, Liantonio R, Meyer F, J. Polym. Sci. A: Polym. Chem., 45(1), 1 (2007)
  32. Jeon HJ, Youk JH, Macromolecules, 43, 5 (2010)
  33. Kaneyoshi H, Matyjaszewski K, J. Polym. Sci. Part A: Polym. Chem., 45, 3 (2007)
  34. Semsarzadeh MA, Amiri S, J. Polym. Res., 19, 6 (2012)
  35. Semsarzadeh MA, Amiri S, J. Inorg. Organomet. Polym. Mater., 23, 432 (2013)
  36. Semsarzadeh M, Amiri S, J. Polym. Res., 20, 5 (2013)
  37. Semsarzadeh MA, Amiri S, Silicon, 6, 27 (2013)
  38. Hurtgen M, Debuigne A, Jerome C, Detrembleur C, Macromolecules, 43, 2 (2010)
  39. Detrembleur C, Versace DL, Piette Y, Hurtgen M, Jerome C, Lalevee J, Debuigne A, Polym. Chem., 3, 7 (2012)
  40. Abdollahi M, Mahdavian AR, Nouri A, J. Macromol. Sci. Part A, 44, 8 (2007)
  41. Semsarzadeh M, Alamdari P, J. Polym. Res., 20, 10 (2013)
  42. Brandrup J, Immergut EH, Grulke EA, Abe A, Bloch DR, Polymer Handbook. Wiley, New York (1999)
  43. Semsarzadeh MA, Daronkola MRR, Abdollahi M, J. Macromol. Sci. Part A, 44, 9 (2007)