Re(V)-mediated living radical polymerization of styrene:: ReO2I(PPh3)2/R-I initiating systems

被引:134
作者
Kotani, Y [1 ]
Kamigaito, M [1 ]
Sawamoto, M [1 ]
机构
[1] Kyoto Univ, Grad Sch Engn, Dept Polymer Chem, Kyoto 6068501, Japan
关键词
D O I
10.1021/ma981614f
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Rhenium(V) iododioxobis(triphenyl phosphine) [Re O2I(PPh3)(2)] proved an effective metal catalyst for living radical polymerization of styrene in conjunction with alkyl iodide as an initiator [R-I: CH3CH(Ph)I, (CH3)(2)C(CO2Et)I, and CH3CH(CO2Et)I] in the presence of Al(Oi-Pr)(3). Compared to RuCl2-(PPh3)(3), the group 7 complex was highly effective for styrene, so as to induce the living polymerization even at 30 degrees C to yield well-controlled polystyrene, with (M) over bar(n), up to similar to 4 x 10(4) and very narrow molecular weight distributions (MWDs) ((M) over bar(w)/(M) over bar(n) = 1.19). The polystyrene thus obtained possessed one initiator moiety (R) at the alpha-end and one iodine atom at the omega-end, both from the initiator R-I, which indicates that the polymerization proceeds via activation of the C-I terminal, derived from R-I, by the Re(V) complex. Addition of methanol or water did not inhibit these polymerizations, while a stable nitroxide radical (TEMPO) immediately and completely quenched them. The quenching experiments thereby supported intervention of radical species in the Re(V)-mediated living polymerization.
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页码:2420 / 2424
页数:5
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共 40 条
  • [1] Living radical polymerization of methyl methacrylate with ruthenium complex: Formation of polymers with controlled molecular weights and very narrow distributions
    Ando, T
    Kato, M
    Kamigaito, M
    Sawamoto, M
    [J]. MACROMOLECULES, 1996, 29 (03) : 1070 - 1072
  • [2] Design of initiators for living radical polymerization of methyl methacrylate mediated by ruthenium(II) complex
    Ando, T
    Kamigaito, M
    Sawamoto, M
    [J]. TETRAHEDRON, 1997, 53 (45) : 15445 - 15457
  • [3] Iron(II) chloride complex for living radical polymerization of methyl methacrylate
    Ando, T
    Kamigaito, M
    Sawamoto, M
    [J]. MACROMOLECULES, 1997, 30 (16) : 4507 - 4510
  • [4] ANDO T, 1998, POLYM PREPR JPN, V47, P1586
  • [5] Curran D. P., 1991, COMPREHENSIVE ORGANI, V4, P715
  • [6] RATE CONSTANTS FOR HALOGEN ATOM TRANSFER FROM REPRESENTATIVE ALPHA-HALOCARBONYL COMPOUNDS TO PRIMARY ALKYL RADICALS
    CURRAN, DP
    BOSCH, E
    KAPLAN, J
    NEWCOMB, M
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (08) : 1826 - 1831
  • [7] GEORGES MK, 1994, TRENDS POLYM SCI, V2, P66
  • [8] Controlled radical polymerization of methacrylic monomers in the presence of a bis(ortho-chelated) arylnickel(II) complex and different activated alkyl halides
    Granel, C
    Dubois, P
    Jerome, R
    Teyssie, P
    [J]. MACROMOLECULES, 1996, 29 (27) : 8576 - 8582
  • [9] Grigg R., 1987, J CHEM SOC P1, V1, P1515
  • [10] Halogen exchange during atom transfer polymerisation of methyl methacrylate mediated by copper(I) N-alkyl-2-pyridylmethanimine complexes
    Haddleton, DM
    Heming, AM
    Kukulj, D
    Jackson, SG
    [J]. CHEMICAL COMMUNICATIONS, 1998, (16) : 1719 - 1720