화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of Industrial and Engineering Chemistry, Vol.12, No.1, 60-68, January, 2006
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Polymerization of Vinyl Acetate Catalyzed by a Cu(I) Complex having a Phosphorous Ligand
Sung Chul Hong, Hye Jin Kim1, Yong Rok Lee1, Seok Kyun Noh1, †, and Woo Seok Lyoo2
  • Department of Nano Science and Technology, Sejong University, Seoul 143-747, Korea
  • 1School of Chemical Engineering & Technology, Yeungnam University, Gyeongbuk 712-749, Korea
  • 2School of Textiles, Yeungnam University, 214-1 Gyeongbuk 712-749, Korea
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The polymerization of vinyl acetate (VAc) was performed successfully in the presence of triisobutylaluminum using CuBr/bidentate phosphorus ligand complexes, such as CuBr/phosphine-phos-phinidine ligand (PP) and CuBr/1,3-bis(diphenylphosphino)propane (BPP). The polymerization afforded high-molecular-weight poly(vinyl acetate) (Mn=15.3×103 g/mol for CuBr/PP and 16.1×103 g/mol for CuBr/BPP) in reasonably high yield (~50%). However, the molecular weights of the resulting polymers were independent of monomer conversion along with a broad molecular weight distribution of polymer (Mw/Mn~2.0). These results might be understood by the low deactivation rate constant (kdeact) of the catalyst systems and by considering the frequent chain transfer likely to occur to initiator, as evidenced by the determination of molecular weight (Mn) from the monomer-to-initiator concentration ratio ([VAc]o/[CCl4]o). The chain transfer to the initiator (e.g., CCl4) generated C-Cl terminal units at both ends of the resulting polymer, which actually allows the formation of a block copolymer by the subsequent addition of styrene. Overall, the polymerization of VAc using CuBr in conjunction with a bidentate phosphorus ligand is suggested to follow not a typical activation/deactivation process of ATRP but a redox-initiated radical telomerization mechanism, which generates poly(vinyl acetate) with high end group functionality in good yield.
Keywords:ATRP;vinyl acetate polymerization;Cu/phosphorous catalyst;redox-initiated polymerization
  1. Matyjaszewski K, ACS Symposium Series; Controlled Radical Polymerization, American Chemical Society, Washington, DC (1998)
  2. Matyjaszewski K, ACS symposium series; Controlled/Living Radical Polymerization: progress in ATRP NMP, and RAFT, American Chemical Society, Washington, DC (2000)
  3. Sawamoto M, Kamigaito M, Chem. Tech., 29, 30 (1999)
  4. Lee DW, J. Ind. Eng. Chem., 10(20), 592 (2004)
  5. Heo SU, Lee DW, J. Ind. Eng. Chem., 11(6), 911 (2005)
  6. Wang JS, Matyjaszewski K, J. Am. Chem. Soc., 117(20), 5614 (1995)
  7. Matyjaszewski K, Chem. Eur. J., 5, 3095 (1999) 
  8. Patten TE, Matyjaszewski K, Accounts Chem. Res., 32(9), 895 (1999)
  9. Patten TE, Matyjaszewski K, Adv. Mater., 10(25), 901 (1998)
  10. Matyjaszewski K, Xia JH, Chem. Rev., 101(9), 2921 (2001)
  11. Iovu MC, Matyjaszewski K, Macromolecules, 36(25), 9346 (2003)
  12. Ueda N, Kamigaito M, Sawamoto M, Polym. Prepr. Jpn., 47, 134 (1998)
  13. Ueda N, Kamigaito M, Sawamoto M, Polym. Prepr. Jpn., 46(2), 149 (1997)
  14. Ueda N, Kamigaito M, Sawamoto M, Polym. Prepr. Jpn., 45, 1267 (1996)
  15. Coote ML, Radom L, Macromolecules, 37(2), 590 (2004)
  16. Favier A, Barner-Kowollik C, Davis TP, Stenzel MH, Macromol. Chem. Phys., 205, 925 (2004)
  17. Stenzel MH, Cummins L, Roberts GE, Davis TR, Vana P, Barner-Kowollik C, Macromol. Chem. Phys., 204, 1160 (2003)
  18. Destarac M, Charmot D, Franck X, Zard SZ, Macromol. Rapid Commun., 21(3), 1035 (2000)
  19. Charmot D, Corpart P, Adam H, Zard SZ, Biadatti T, Bouhadir G, Macromol. Symp., 150(25), 23 (2000)
  20. Mardare D, Matyjaszewski K, Macromolecules, 27(3), 645 (1994)
  21. Xia JH, Paik HJ, Matyjaszewski K, Macromolecules, 32(25), 8310 (1999)
  22. Granel C, Jerome R, Teyssie P, Jasieczek CB, Shooter AJ, Haddleton DM, Hastings JJ, Gigmes D, Grimaldi S, Tordo P, Greszta D, Matyjaszewski K, Macromolecules, ACS symposium series; Vol. 704, American Chemical Society, Washington, DC, 31(21), 7133 (1998)
  23. Zaremski MY, Plutalova AV, Lachinov MB, Golubev VB, Macromolecules, 33(12), 4365 (2000)
  24. Matyjaszewski K, Coessens V, Nakagawa Y, Xia J, Qiu J, Gaynor S, Coca S, Jasieczek C, ACS symposium series; Vol. 704, American Chemical Society, Washington, DC (1998)
  25. Park ES, Yoon JS, J. Appl. Polym. Sci., 82(7), 1658 (2001)
  26. Paik HJ, Teodorescu M, Xia JH, Matyjaszewski K, Macromolecules, 32(21), 7023 (1999)
  27. Wakioka M, Baek KY, Ando T, Kamigaito M, Sawamoto M, Macromolecules, 35(2), 330 (2002)
  28. Kamigaito M, Ando T, Sawamoto M, Chem. Rev., 101(12), 3689 (2001)
  29. Uegaki H, Kotani Y, Kamigaito M, Sawamoto M, ACS symposium series; Vol. 760, American Chemical Society, Washington, DC (2000)
  30. Kotani Y, Kamigaito M, Sawamoto M, Macromolecules, 32(8), 2420 (1999)
  31. Kato M, Kamigaito M, Sawamoto M, Higashimura T, Macromolecules, 28(5), 1721 (1995)
  32. Simal F, Demonceau A, Noels AF, Angew. Chem.-Int. Edit., 38, 538 (1999)
  33. Matyjaszewski K, Wei ML, Xia JH, McDermott NE, Macromolecules, 30(26), 8161 (1997)
  34. Ando T, Kamigaito M, Sawamoto M, Macromolecules, 30(16), 4507 (1997)
  35. Moineau G, Dubois P, Jerome R, Senninger T, Teyssie P, Macromolecules, 31(2), 545 (1998)
  36. Percec V, Barboiu B, Neumann A, Ronda JC, Zhao MY, Macromolecules, 29(10), 3665 (1996)
  37. Moineau G, Granel C, Dubois P, Jerome R, Teyssie P, Macromolecules, 31(2), 542 (1998)
  38. Uegaki H, Kotani Y, Kamigaito M, Sawamoto M, Macromolecules, 30(8), 2249 (1997)
  39. Uegaki H, Kotani Y, Kamigaito M, Sawamoto M, Macromolecules, 31(20), 6756 (1998)
  40. Lecomte P, Drapier I, Dubois P, Teyssie P, Jerome R, Macromolecules, 30(24), 7631 (1997)
  41. Matyjaszewski K, Paik HJ, Zhou P, Diamanti SJ, Macromolecules, 34(15), 5125 (2001)