Textile Science and Engineering (한국섬유공학회지)

The Korean Fiber Society (한국섬유공학회)
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Synthesis of Poly(vinyl pivalate) and Its Block Copolymers by Cobalt-Mediated Radical Polymerization

코발트를 매개로 한 폴리비닐피발레이트 및 이의 블록 공중합체의 합성

  • Jeon, Hyun-Jeong (Department of Advanced Fiber Engineering, Division of Nano-Systems, Inha University) ;
  • Park, Mi-Seon (Department of Advanced Fiber Engineering, Division of Nano-Systems, Inha University) ;
  • Park, Dong-Min (Department of Advanced Fiber Engineering, Division of Nano-Systems, Inha University) ;
  • You, Young-Chang (Department of Advanced Fiber Engineering, Division of Nano-Systems, Inha University) ;
  • Youk, Ji-Ho (Department of Advanced Fiber Engineering, Division of Nano-Systems, Inha University)
  • 전현정 (인하대학교 나노시스템학부) ;
  • 박미선 (인하대학교 나노시스템학부) ;
  • 박동민 (인하대학교 나노시스템학부) ;
  • 유영창 (인하대학교 나노시스템학부) ;
  • 육지호 (인하대학교 나노시스템학부)
  • Published : 2008.12.31
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Abstract

Controlled radical polymerization of vinyl pivalate (VPi) was achieved by cobalt-mediated radical polymerization (CMRP) using cobalt(II) acetylacetonate (Co$(acac)_2$) and 2,2'-azo-bis(4-methoxy-2,4-dimethylvaleronitrile) (V-70). Poly(vinyl pivalate) (PVPi) chains having controlled molecular weights and low polydispersities ($M_w/M_n$=1.05-1.29) were successfully synthesized. PVPi macroinitiator ($M_n$=11,100 g/mol, $M_w/M_n$=1.13), which was end-capped by Co$(acac)_2$ was used to successive CMRP of well-defined PVPi-b-poly(vinyl acetate) (PVPi-b-PVAc) and PVPi-b-poly(acrylonitrile) (PVPi-b-PAN) block copolymers at 30 DC. The polymerization of PVPi-b-PV Ac was performed via a degenerative chain transfer (DT) mechanism using an excess of V-70. PVPi-b-PAN was synthesized via a reversible termination (RT) mechanism in DMF.

Keywords

References

  1. W. A. Braunecker and K. Matyjaszewski, "Controlled/ Living Radical Polymerization: Features, Developments, and Perspectives", Prog Polym Sci, 2007, 32, 93-146 https://doi.org/10.1016/j.progpolymsci.2006.11.002
  2. M. C. Iovu and K. Matyjaszewski, "Controlled/Living Radical Polymerization of Vinyl Acetate by Degenerative Transfer with Alkyl Iodides", Macromolecules, 2003, 36, 9346-9354 https://doi.org/10.1021/ma034892+
  3. M. L. Coote and L. Radom, "Substituent Effects in Xanthate-Mediated Polymerization of Vinyl Acetate: Ab Initio Evidence for an Alternative Fragmentation Pathway", Macromolecules, 2004, 37, 590-596 https://doi.org/10.1021/ma035477k
  4. M. H. Stenzel, L. Cummins, G. E. Roberts, T. P. Davis, P. Vana, and C. Barner-Kowollik, "Xanthate Mediated Living Polymerization of Vinyl Acetate: A Systematic Variation in MADIX/RAFT Agent Structure", Macromol Chem Phys, 2003, 204, 1160-1168 https://doi.org/10.1002/macp.200390089
  5. R. W. Simms, T. P. Davis, and M. F. Cunningham, "Xanthate-Mediated Living Radical Polymerization of Vinyl Acetate in Miniemulsion", Macromol Rapid Comm, 2005, 26, 592-596 https://doi.org/10.1002/marc.200400652
  6. M. Destarac, D. Charmot, X. Franck, and S. Z. Zard, "Dithiocarbamates as Universal Reversible Addition- Fragmentation Chain Transfer Agents", Macromol Rapid Comm, 2000, 21, 1035-1039 https://doi.org/10.1002/1521-3927(20001001)21:15<1035::AID-MARC1035>3.0.CO;2-5
  7. M. Wakioka, K. Baek, T. Ando, M. Kamigaito, and M. Sawamoto, "Possibility of Living Radical Polymerization of Vinyl Acetate Catalyzed by Iron(I) Complex", Macromolecules, 2002, 35, 330-333 https://doi.org/10.1021/ma0115444
  8. A. Debuigne, J. Caille, and R. Jerome, "Highly Efficient Cobalt-Mediated Radical Polymerization of Vinyl Acetate", Angew Chem Int Ed, 2005, 44, 1101-1104 https://doi.org/10.1002/anie.200461333
  9. H. Kaneyoshi and K. Matyjaszewski, "Effect of Ligand and n-Butyl Acrylate on Cobalt-Mediated Radical Polymerization of Vinyl Acetate", Macromolecules, 2005, 38, 8163-8169 https://doi.org/10.1021/ma051433v
  10. R. Bryaskova, C. Detrembleur, A. Debuigne, and R. Jerome, "Cobalt-Mediated Radical Polymerization (CMRP) of Vinyl Acetate Initiated by Redox Systems: Toward the Scale-Up of CMRP", Macromolecules, 2006, 39, 8263-8268 https://doi.org/10.1021/ma060339r
  11. A. Debuigne, J. Caille, and R. Jerome, "Synthesis of End- Functional Poly(vinyl acetate) by Cobalt-Mediated Radical Polymerization", Macromolecules, 2005, 38, 5452-5458 https://doi.org/10.1021/ma047726q
  12. H. Kaneyoshi and K. Matyjaszewski, "Synthesis of Poly(vinyl acetate)-graft-polystyrene by a Combination of Cobalt-Mediated Radical Polymerization and Atom Transfer Radical Polymerization", J Polym Sci: Polym Chem, 2007, 45, 447-459 https://doi.org/10.1002/pola.21840
  13. C. Detrembleur, O. Stoilova, R. Bryaskova, A. Debuigne, A. Mouithys-Mickalad, and R. Jerome, "Preparation of Well- Defined PVOH/C60 Nanohybrids by Cobalt-Mediated Radical Polymerization of Vinyl Acetate", Macromol Rapid Comm, 2006, 27, 498-504 https://doi.org/10.1002/marc.200500871
  14. C. Detrembleur, A. Debuigne, R. Bryaskova, B. Charleux, and R. Jerome, "Cobalt-Mediated Radical Polymerization of Vinyl Acetate in Miniemulsion: Very Fast Formation of Stable Poly(vinyl acetate) Latexes at Low Temperature", Macromol Rapid Comm, 2006, 27, 37-41 https://doi.org/10.1002/marc.200500645
  15. A. Debuigne, J. Caille, C. Detrembleur, and R. Jerome, "Effective Cobalt Mediation of the Radical Polymerization of Vinyl Acetate in Suspension", Angew Chem Int Ed, 2005, 44, 3439-3442 https://doi.org/10.1002/anie.200500112
  16. C. Peng, J. Scricco, S. Li, M. Fryd, and B. B. Wayland, "Organo-Cobalt Mediated Living Radical Polymerization of Vinyl Acetate", Macromolecules, 2008, 41, 2368-2373 https://doi.org/10.1021/ma702500b
  17. A. Debuigne, Y. Champouret, R. Jerome, R. Poli, and C. Detrembleur, "Mechanistic Insights into the Cobalt-Mediated Radical Polymerization (CMRP) of Vinyl Acetate with Cobalt(III) Adducts as Initiators", Chem Eur J, 2008, 14, 4046-4059 https://doi.org/10.1002/chem.200701867
  18. S. Maria, H. Kaneyoshi, K. Matyjaszewski, and R. Poli, "Effect of Electron Donors on the Radical Polymerization of Vinyl Acetate Mediated by [$Co(acac)_2$]: Degenerative Transfer versus Reversible Homolytic Cleavage of an Organocobalt(III) Complex", Chem Eur J, 2007, 13, 2480- 2492 https://doi.org/10.1002/chem.200601457
  19. R. Bryaskova, N. Willet, P. Degee, P. Dubois, R. Jerome, and C. Detrembleur, "Copolymerization of Vinyl Acetate with 1-Octene and Ethylene by Cobalt-Mediated Radical Polymerization", J Polym Sci: Polym Chem, 2007, 45, 2532- 2542 https://doi.org/10.1002/pola.21963
  20. A. Debuigne, J. Caille, N. Willet, and R. Jerome, "Synthesis of Poly(vinyl acetate) and Poly(vinyl alcohol) Containing Block Copolymers by Combination of Cobalt-Mediated Radical Polymerization and ATRP", Macromolecules, 2005, 38, 9488-9496 https://doi.org/10.1021/ma051246x
  21. A. Debuigne, N. Willet, R. Jerome, and C. Detrembleur, "Amphiphilic Poly(vinyl acetate)-b-poly(N-vinylpyrrolidone) and Novel Double Hydrophilic Poly(vinyl alcohol)-bpoly( N-vinylpyrrolidone) Block Copolymers Prepared by Cobalt-Mediated Radical Polymerization", Macromolecules, 2007, 40, 7111-7118 https://doi.org/10.1021/ma0712908
  22. R. Bryaskova, N. Willet, A. Debuigne, R. Jerome, and C. Detrembleur, "Synthesis of Poly(vinyl acetate)-b-polystyrene and Poly(vinyl alcohol)-b-polystyrene Copolymers by Cobalt-Mediated Radical Polymerization", J Polym Sci: Polym Chem, 2007, 45, 81-89 https://doi.org/10.1002/pola.21806
  23. A. Debuigne, J. Warnant, R. Jerome, I. Voets, A. de Keizer, M. A. Cohen Stuart, and C. Detrembleur, "Synthesis of Novel Well-Defined Poly(vinyl acetate)-b-poly(acrylonitrile) and Derivatized Water-Soluble Poly(vinyl alcohol)-bpoly( acrylic acid) Block Copolymers by Cobalt-Mediated Radical Polymerization", Macromolecules, 2008, 41, 2353- 2360 https://doi.org/10.1021/ma702341v
  24. D. H. Song and W. S. Lyoo, "Preparation of High Molecular Weight Poly(vinyl pivalate) with High Yield and High Molecular Weight Poly(vinyl alcohol) by Emulsion Polymerization of Vinyl Pivalate and Saponification", J Appl Polym Sci, 2007, 104, 410-414 https://doi.org/10.1002/app.25166
  25. R. Fukae and T. Yanmamoto, "Melting Behavior of Syndiotacticity-Rich Poly(vinyl alcohol) Hydrogel Derived from Poly(vinyl pivalate)", Sen'i Gakkaishi, 2003, 59, 448- 452 https://doi.org/10.2115/fiber.59.448
  26. T. L. Uyen Nguyen, B. Farrugia, T. P. Davis, C. Barner- Kowollik, and M. H. Stenzel, "Core-Shell Microspheres with Surface Grafted Poly(vinyl alcohol) as Drug Carriers for the Treatment of Hepatocellular Carcinoma", J Polym Sci: Polym Chem, 2007, 45, 3256-3272 https://doi.org/10.1002/pola.22074
  27. J. Bernard, A. Favier, L. Zhang, A. Nilasaroya, T. P. Davis, C. Barner-Kowollik, and M. H. Stenzel, "Poly(vinyl ester) Star Polymers via Xanthate-Mediated Living Radical Polymerization: From Poly(vinyl alcohol) to Glycopolymer Stars", Macromolecules, 2005, 38, 5475-5484 https://doi.org/10.1021/ma050050u
  28. B. B. Wayland, G. Poszmik, S. L. Mukerjee, and M. Fryd, "Living Radical Polymerization of Acrylates by Organocobalt Porphyrin Complexes", J Am Chem Soc, 1994, 116, 7943-7944 https://doi.org/10.1021/ja00096a080