Living free-radical polymerization by reversible addition - Fragmentation chain transfer: The RAFT process

Macromolecules

Volumn 31, Issue 16, 1998, Pages 5559-5562

  Chiefari, John ^a   Chong, Y K ^a   Ercole, Frances ^a   Krstina, Julia ^a   Jeffery, Justine ^a   Le, Tam P T ^a   Mayadunne, Roshan T A ^a   Meijs, Gordon F ^a   Moad, Catherine L ^a   Moad, Graeme ^a   Rizzardo, Ezio ^a   Thang, San H ^a  

^a CSIRO   (Australia)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; AGENTS; AROMATIC POLYMERS; MOLECULAR STRUCTURE; MOLECULAR WEIGHT DISTRIBUTION; MONOMERS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POLYACRYLATES; POLYACRYLONITRILES; POLYSTYRENES; REACTION KINETICS;

LIVING POLYMERIZATION; REVERSIBLE ADDITION FRAGMENTATION CHAIN TRANSFER (RAFT) PROCESS;

FREE RADICAL POLYMERIZATION;

EID: 0032135925     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma9804951     Document Type: Article

References (36)

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28. o is the molecular weight of the monomer. The agreement between found and calculated molecular weight is within experimental error (±10%).
29. The polymers made in the presence of reagents 1 are colored due to the presence of the thiocarbonylthio chromophore. Colors range from pale yellow through pink depending on the substituents Z and R. This chromophore is an aid in characterization. The chromophore can be readily removed, and the polymer decolorised, by reacting the thiocarbonylthio group with various reagents including amines [to produce a thioamide and a thiol-terminated polymer (Haraoubia, R.; Bonnans, C.; Gressier, J.-C.; Levesque, G. Makromol. Chem. 1982, 183, 2383)] or sodium hypochlorite or hydroperoxide solution [to provide a sulfine (Carreta, F.; Le Nocher, A.-M.; Leriverend, C.; Metzner, P.; Pham, T. N. Bull. Soc. Chim. Fr. 1995, 132, 67)]. For leading references on the reactions of dithio compounds, see: Kato, S.; Ishida, M. Sulfur Rep. 1988, 8, 155. Mayer, R.; Scheithauer, S. In Houben - Weyl Methods of Organic Chemistry; Buechel, K. H., Falbe, J., Hagemann, H., Hanack, M., Eds.; Thieme: Stuttgart, Germany, 1985; Vol. E, p 891.
30. The polymers made in the presence of reagents 1 are colored due to the presence of the thiocarbonylthio chromophore. Colors range from pale yellow through pink depending on the substituents Z and R. This chromophore is an aid in characterization. The chromophore can be readily removed, and the polymer decolorised, by reacting the thiocarbonylthio group with various reagents including amines [to produce a thioamide and a thiol-terminated polymer (Haraoubia, R.; Bonnans, C.; Gressier, J.-C.; Levesque, G. Makromol. Chem. 1982, 183, 2383)] or sodium hypochlorite or hydroperoxide solution [to provide a sulfine (Carreta, F.; Le Nocher, A.-M.; Leriverend, C.; Metzner, P.; Pham, T. N. Bull. Soc. Chim. Fr. 1995, 132, 67)]. For leading references on the reactions of dithio compounds, see: Kato, S.; Ishida, M. Sulfur Rep. 1988, 8, 155. Mayer, R.; Scheithauer, S. In Houben - Weyl Methods of Organic Chemistry; Buechel, K. H., Falbe, J., Hagemann, H., Hanack, M., Eds.; Thieme: Stuttgart, Germany, 1985; Vol. E, p 891.
31. The polymers made in the presence of reagents 1 are colored due to the presence of the thiocarbonylthio chromophore. Colors range from pale yellow through pink depending on the substituents Z and R. This chromophore is an aid in characterization. The chromophore can be readily removed, and the polymer decolorised, by reacting the thiocarbonylthio group with various reagents including amines [to produce a thioamide and a thiol-terminated polymer (Haraoubia, R.; Bonnans, C.; Gressier, J.-C.; Levesque, G. Makromol. Chem. 1982, 183, 2383)] or sodium hypochlorite or hydroperoxide solution [to provide a sulfine (Carreta, F.; Le Nocher, A.-M.; Leriverend, C.; Metzner, P.; Pham, T. N. Bull. Soc. Chim. Fr. 1995, 132, 67)]. For leading references on the reactions of dithio compounds, see: Kato, S.; Ishida, M. Sulfur Rep. 1988, 8, 155. Mayer, R.; Scheithauer, S. In Houben - Weyl Methods of Organic Chemistry; Buechel, K. H., Falbe, J., Hagemann, H., Hanack, M., Eds.; Thieme: Stuttgart, Germany, 1985; Vol. E, p 891.
32. The polymers made in the presence of reagents 1 are colored due to the presence of the thiocarbonylthio chromophore. Colors range from pale yellow through pink depending on the substituents Z and R. This chromophore is an aid in characterization. The chromophore can be readily removed, and the polymer decolorised, by reacting the thiocarbonylthio group with various reagents including amines [to produce a thioamide and a thiol-terminated polymer (Haraoubia, R.; Bonnans, C.; Gressier, J.-C.; Levesque, G. Makromol. Chem. 1982, 183, 2383)] or sodium hypochlorite or hydroperoxide solution [to provide a sulfine (Carreta, F.; Le Nocher, A.-M.; Leriverend, C.; Metzner, P.; Pham, T. N. Bull. Soc. Chim. Fr. 1995, 132, 67)]. For leading references on the reactions of dithio compounds, see: Kato, S.; Ishida, M. Sulfur Rep. 1988, 8, 155. Mayer, R.; Scheithauer, S. In Houben - Weyl Methods of Organic Chemistry; Buechel, K. H., Falbe, J., Hagemann, H., Hanack, M., Eds.; Thieme: Stuttgart, Germany, 1985; Vol. E, p 891.
33. β); see Scheme 2 for definition of terms.
34. These compounds have very low transfer constants, typically <0.1. For example, the transfer constant of S-benzyl N,N-diethyldithiocarbamate in styrene polymerization has been measured as 0.009 at 80°C while that of S-(2-cyanoprop-2-yl) O-ethylxanthate in MMA polymerization at 60°C is 0.08 (Krstina, J.; Le, N.; Moad, C. Unpublished results).
35. Otsu, T.; Yoshida, M.; Kuriyama, A. Polym. Bull. (Berlin) 1982, 7, 45.
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