화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.25, No.9, 931-935, September, 2017
DOI10.1007/s13233-017-5099-4  Export Citation
Dependence of Cross-Termination Rate on RAFT Agent Concentration in RAFT Polymerization
Yanggang Gao, Ling Lv, Gang Zou, and Qijin Zhang†
  • CAS Key Laboratory of Soft Matter Chemistry, Key Laboratory of Optoelectronic Science and Technology, Innovation Centre of Chemistry for Energy Materials, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China
E-mail:
Rate retardation is an intrinsic property of reversible addition-fragmentation chain transfer (RAFT) radical polymerization. One of reasons for this phenomenon is cross-termination reaction between intermediate radicals and other active radicals. With the help of Stationary State Model and experimentally controlling on kt,cross, the kinetics of styrene RAFT polymerization were performed at different concentrations of RAFT agent. Results show that there is a difference in two effects of cross-termination rate coefficient and concentration of intermediate radicals on cross-termination at different RAFT agent concentrations: at the low concentration range, the cross-termination reaction is mainly affected by its rate coefficient, and at the high concentration range, the cross-termination reaction is mainly affected by the concentration of the intermediate radicals. It shows that there is an optimal concentrations of RAFT agent for a RAFT polymerization with the least rate retardation by considering the balance between these two effects.
Keywords:reversible addition-fragmentation chain transfer (RAFT) radical polymerization;rate retardation;cross-termination;RAFT agent concentrations;intermediate radicals
  1. 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)
  2. Moad G, Rizzardo E, Thang SH, Aust. J. Chem., 58, 379 (2005)
  3. Perrier S, Takolpuckdee P, J. Polym. Sci. A: Polym. Chem., 43(22), 5347 (2005)
  4. Gregory A, Stenzel MH, Prog. Polym. Sci, 37, 38 (2012)
  5. Monteiro MJ, de Brouwer H, Macromolecules, 34(3), 349 (2001)
  6. Feldermann A, Coote ML, Stenzel MH, Davis TP, Barner-Kowollik C, J. Am. Chem. Soc., 126(48), 15915 (2004)
  7. Moad G, Chiefari J, Krstina J, Mayadunne RTA, Postma A, Rizzardo E, Thang SH, Polym. Int., 49, 993 (2000)
  8. Barner-Kowollik C, Quinn JF, Nguyen TLU, Heuts JPA, Davis TP, Macromolecules, 34(22), 7849 (2001)
  9. Konkolewicz D, Hawkett BS, Gray-Weale A, Perrier S, Macromolecules, 41(17), 6400 (2008)
  10. Konkolewicz D, Hawkett BS, Gray-Weale A, Perrier S, J. Polym. Sci. A: Polym. Chem., 47(14), 3455 (2009)
  11. Ting SRS, Davis TP, Zetterlund PB, Macromolecules, 44(11), 4187 (2011)
  12. Barner-Kowollik C, Quinn JF, Morsley DR, Davis TP, J. Polym. Sci. A: Polym. Chem., 39(9), 1353 (2001)
  13. Barner-Kowollik C, Buback M, Charleux B, Coote ML, Drache M, Fukuda T, Goto A, Klumperman B, Lowe AB, Mcleary JB, Moad G, Monteiro MJ, Sanderson RD, Tonge MP, Vana P, J. Polym. Sci. A: Polym. Chem., 44(20), 5809 (2006)
  14. Goto A, Sato K, Tsujii Y, Fukuda T, Moad G, Rizzardo E, Thang SH, Macromolecules, 34(3), 402 (2001)
  15. Coote ML, Krenske EH, Izgorodina EI, Macromol. Rapid Commun., 27(7), 473 (2006)
  16. Kwak Y, Goto A, Tsujii Y, Murata Y, Komatsu K, Fukuda T, Macromolecules, 35(8), 3026 (2002)
  17. Calitz FM, Tonge MP, Sanderson RD, Macromolecules, 36(1), 5 (2003)
  18. Calitz F, Tonge M, Sanderson R, Macromol. Symp., 193, 277 (2003)
  19. Meiser W, Barth J, Buback M, Kattner H, Vana P, Macromolecules, 44(8), 2474 (2011)
  20. Chernikova E, Golubev V, Filippov A, Lin CY, Coote ML, Polym. Chem., 1, 1437 (2010)
  21. Meiser W, Buback M, Macromol. Rapid Commun., 32(18), 1490 (2011)
  22. Meiser W, Buback M, Ries O, Ducho C, Sidoruk A, Macromol. Chem. Phys., 214, 924 (2013)
  23. Golubev V, Filippov A, Chernikova E, Coote M, Lin CY, Gryn’ova G, Polym. Sci. Ser. C,, 53, 14 (2011)
  24. Ranieri K, Delaittre G, Barner-Kowollik C, Junkers T, Macromol. Rapid Commun., 35(23), 2023 (2014)
  25. McLeary J, McKenzie J, Tonge M, Sanderson R, Klumperman B, Chem. Commun., 10, 1950 (2004)
  26. McLeary JB, Tonge MP, Klumperman B, Macromol. Rapid Commun., 27(15), 1233 (2006)
  27. van den Dungen ETA, Matahwa H, McLeary JB, Sanderson RD, Klumperman B, J. Polym. Sci. A: Polym. Chem., 46(7), 2500 (2008)
  28. Sivtsov E, Gostev A, Parilova E, Dobrodumov A, Chernikova E, Polym. Sci. Ser. C, 57, 110 (2015)
  29. Moad G, Macromol. Chem. Phys., 215, 9 (2014)
  30. Lv L, Wu W, Zou G, Zhang Q, Polym. Chem, 4, 908 (2013)
  31. Lv L, Zhou J, Zou G, Zhang Q, Macromol. Chem. Phys., 216, 614 (2015)
  32. Lai JT, Filla D, Shea R, Macromolecules, 35(18), 6754 (2002)
  33. Kwak Y, Goto A, Fukuda T, Macromolecules, 37(4), 1219 (2004)
  34. Chernikova E, Terpugova P, Garina E, Golubev V, Polym. Sci. Ser. A, 49, 108 (2007)
  35. Turro NJ, Kraeutler B, Acc. Chem. Res., 13, 369 (1980)
  36. Khudyakov IV, Serebrennikov YA, Turro NJ, Chem. Rev., 93, 537 (1993)
  37. Olaj OF, Vana P, Zoder M, Kornherr A, Zifferer G, Macromol. Rapid Commun., 21(13), 913 (2000)
  38. Han XQ, Fan J, He JP, Xu JT, Fan DQ, Yang YL, Macromolecules, 40(15), 5618 (2007)