Synthesis of Copolymers via Photocationic Polymerization (I)- Living Photocationic Polymerization of Tetrahydrofuran in the Presence of Diphenyliodonium Hexafluorophosphate -

광양이온 중합에 의한 공중합물의 합성 (I)디페닐요도늄 헥사플루오로포스페이트 존재하의 테트라히드로퓨란의 광양이온 리빙 중합-

  • 마석일 (인하대학교 공과대학 섬유공학과) ;
  • 유동권 (인하대학교 공과대학 섬유공학과)
  • Published : 1993.08.01

Abstract

Pholopolymerization of tetrahydrofuran(THF) was carried out in the presence of diphenyliodonium hexafluorophosphate(salt) and the mechanism of the polymerization was discussed on the basis of kinetic results. It has been cleared that the cationic polymerization is initiated by the addition of proton, a photolytic product of the salt, to THF forming an cyclic trialkyloxonium ion which is active species, responsible for the cationic propagation. The rate of the polymerization increases with temperature raising, however, decreases with the increasing conversion to polymer because equilibrium between propagation and depropagation is established as the polymer concentration increases. And the hither conversion to polymer and hither molecular weight of resulting polymer at lower temperature are attributable to the shift of equilibrium between propagation and depropagation to polymer side due to the negative enthalpy change of the polymerization. The living nature of the polymerization was confirmed by the monomer addition technique and explained in terms of the stability of the oxonium ion by the formation of ion pair with less nucleophilic hexafluorophospate anion.

Keywords

References

  1. J. Polym. Sci.: Chem. Ed. v.16 J.V.Crivello;J.H.W.Lam
  2. J. Polym. Sci.: Chem. Ed. v.17 J.V.Crivello;J.H.W.Lam
  3. J. Polym. Sci.: Chem. Ed. v.17 J.V.Crivello;J.H.W.Lam
  4. J. Polym. Sci.: Chem. Ed. v.18 J.V.Crivello;J.H.W.Lam
  5. J. Polym. Sci.: Chem. Ed. v.18 J.V.Crivello;J.H.W.Lam
  6. Macromol. v.10 J.V.Crivello;J.H.W.Lam
  7. J. Korean Fiber Soc. v.29 S.Mah;W.Park
  8. J. Polym. Sci.:Chem. Ed. v.20 S.Mah;Y.Yamamoto;K.Hayashi
  9. J.Polym. Sci.: Chem. Ed. v.20 S.Mah;Y.Yamamoto;K.Hayashi
  10. Macromol. v.16 S.Mah;Y.Yamamoto;K.Hayashi
  11. J. Polym. Sci. v.16 B.A.Rosenberg;E.B.Ludvig;A.R.Gantmakker;S.S.Medvedev
  12. Advances Chem. Ser. Am. Chem. Soc. v.91 P.Dreyfuss;M.P.Dreyfuss
  13. Polymer v.6 C.E.H.Bawn;R.M.Bell;L.Ledwith
  14. Polymer v.6 M.P.Dreyfuss;P.Dreyfuss
  15. Makromol. Chem. v.102 H.Imai;T.Saegusa;S.Matsumoto;T.Tadasa;J.Furukawa
  16. Macromol. v.1 T.Saegusa;S.Matsumoto
  17. J. Polym. Sci.: A-1 v.4 M.P.Dreyfuss;P.Dreyfuss