キレート配位子を有する5,6および8族遷移金属錯体を用いたオレフィン重合  [in Japanese] Olefin Polymerization by Using Group 5, 6, and 8 Transition Metal Complexes with Chelating Ligands  [in Japanese]

Access this Article

Search this Article

Author(s)

    • 緒方 敬治 OGATA Keiji
    • 広島大学大学院工学研究科 Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University
    • 馬場 勇志 BABA Yuji
    • 広島大学大学院工学研究科 Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University
    • 肥谷 幸司 HIYA Koji
    • 広島大学大学院工学研究科 Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University
    • 安田 源 YASUDA Hajime
    • 広島大学大学院工学研究科 Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University

Abstract

Cp-amine型配位子を有する種々めクロム錯体 (R'<SUB>2</SUB>NC<SUB>2</SUB>H<SUB>4</SUB>C<SUB>5</SUB>R<SUB>4</SUB>) CrX<SUB>2</SUB>を合成し. それらの錯体に助触媒を加えた触媒系によるエチレンやα-オレフィンの重合について検討した. エチレン重合においてCp部位をかさ高くするにつれて活性が向上した. この触媒系はエチレンとα-オレフィンやα-オレフィンどうしの共重合もスムーズに進行させた. 同様な配位子を有するモリブデン錯体 (Me<SUB>2</SUB>NC<SUB>2</SUB>H<SUB>4</SUB>C<SUB>5</SUB>Me<SUB>4</SUB>) MoCl<SUB>2</SUB>はモリブデン触媒としては比較的高いエチレン重合活性を示した. 対応する鉄錯体 [ (Me<SUB>2</SUB>NC<SUB>2</SUB>H<SUB>4</SUB>C<SUB>5</SUB>Me<SUB>4</SUB>) FeCl ] <SUB>2</SUB>はエチレン重合に対して不活性であった. また, さまざまな置換基を有するバナジウムトリス (アセチルアセトナート) (V (acac) <SUB>3</SUB>) /MMAO (modified methylaluminoxane) のエチレン重合触媒挙動について検討したところ, 電子吸引基の導入によって活性が向上し, かさ高い置換基の導入によって生成するポリマーの分子量が増大し分子量分布が狭くなる傾向がみられた.

A series of chromium complexes having Cp-amine type ligands, (R'<SUB>2</SUB>NC<SUB>2</SUB>H<SUB>4</SUB>C<SUB>5</SUB>R<SUB>4</SUB>) CrX<SUB>2</SUB>, were synthesized, whose catalytic behaviors for olefin polymerization were investigated upon activation with modified methylaluminoxane (MMAO). With increasing steric bulkiness of the complex, the catalytic activity increased for ethylene polymerization. These complexes showed high activity for copolymerizations of ethylene with a -olefins as well as for homopolymerizations. A indenyl type complex tended to produce polymers with higher molecular weights. The molybdenum analogues showed relatively high activities for ethylene polymerization among the reported molybdenum complexes, although their activities were much lower than those of the chromium catalysts and Group 4 metallocene catalysts. The corresponding iron complex, [ (Me<SUB>2</SUB>NC<SUB>2</SUB>H<SUB>4</SUB>C<SUB>5</SUB>Me<SUB>4</SUB>) FeCl] <SUB>2</SUB>, showed no catalytic activity for ethylene polymerization. Catalyses of variously substituted vanadium tris (acetylacetonate) (V (acac) <SUB>3</SUB>) /MMAO systems were also studied. Introduction of electron-withdrawing groups tended to enhance the catalytic activity, while catalysts having bulky substituents yielded polyethylenes with high molecular weight and narrow molecular weight distribution.

Journal

  • KOBUNSHI RONBUNSHU

    KOBUNSHI RONBUNSHU 59(4), 235-242, 2002-04-25

    The Society of Polymer Science, Japan

References:  34

  • <no title>

    HOGAN J. P.

    J. Polym. Sci., A-1 8, 2637, 1970

    Cited by (1)

  • <no title>

    MCDANIEL M. P.

    Adv. Catal. 33, 47, 1985

    Cited by (3)

  • <no title>

    MCDANIEL M. P.

    Ind. Eng. Chem. Res. 27, 1559, 1988

    Cited by (1)

  • <no title>

    KAROL F. J.

    J. Polym. Sci., A-1 10, 2621, 1972

    Cited by (1)

  • <no title>

    KAROL K. F. J.

    J. Polym. Sci., Polym. Chem. Ed. 11, 413, 1973

    Cited by (1)

  • <no title>

    KAROL F. J.

    J. Polym. Sci., Polym. Chem. Ed. 12, 1549, 1974

    Cited by (1)

  • <no title>

    KAROL F. J.

    J. Catal. 60, 68, 1979

    Cited by (2)

  • <no title>

    ZHANG G.

    Jpn. J. Appl. Phys. 32, 511, 1993

    Cited by (1)

  • <no title>

    ELLIS P. J.

    J. Mol. Catal. A : Chem. 111, 297, 1996

    Cited by (1)

  • <no title>

    BLOM R.

    J. Mol. Catal. A : Chem. 138, 97, 1999

    Cited by (1)

  • <no title>

    BLOM R.

    J. Catal. 194, 352, 2000

    Cited by (1)

  • <no title>

    THEOPOLD K. H.

    Eur. J. Inorg. Chem. 1998, 15

    Cited by (1)

  • <no title>

    JENSEN V. R.

    Organometallics 19, 403, 2000

    Cited by (2)

  • <no title>

    ANKER B. W.

    J. Chem. Soc., Dalton Trans. 1975, 2639

    Cited by (1)

  • <no title>

    ZHU F.

    Macromolecules 33, 5006, 2002

    Cited by (1)

  • <no title>

    ZAMBELLI A.

    Macromolecules 13, 267, 1980

    Cited by (2)

  • <no title>

    ASAKURA T.

    Macromolecules 24, 2334, 1991

    Cited by (3)

  • <no title>

    HSIEH E. T.

    Macromolecules 15, 1402, 1982

    Cited by (1)

  • <no title>

    SOGA K.

    Makromol. Chem. 191, 2853, 1990

    Cited by (1)

  • <no title>

    DRAGUTAN V.

    Olefin Metathesis and Ring-Opening Polymerization of Cyclo-Olefins, 1985

    Cited by (3)

  • <no title>

    IVIN K. J.

    "Olefin Metathesis and Metathesis Polymerization", 1997

    Cited by (11)

  • <no title>

    増田俊夫

    高分子 46, 64, 1997

    Cited by (2)

  • <no title>

    中山祐正

    高分子加工 47, 448, 1998

    Cited by (1)

  • <no title>

    COLES M. P.

    J. Organomet. Chem. 591, 78, 1999

    Cited by (2)

  • <no title>

    SMALL B. L.

    J. Am. Chem. Soc. 120, 4049, 1998

    Cited by (29)

  • <no title>

    BRITOVSEK G. J. P.

    Chem.Commun. 1998, 849

    Cited by (12)

  • <no title>

    松田勇

    有機金属化学 1996, 174

    Cited by (1)

  • <no title>

    NOMURA K.

    Chem. Lett. 2001, 36

    Cited by (3)

  • <no title>

    WITTE P. T.

    Organometallics 18, 2944, 1999

    Cited by (4)

  • <no title>

    KIM W. K.

    Organometallics 17, 4541, 1998

    Cited by (2)

  • <no title>

    MA Y.

    Organometallics 18, 2773, 1999

    Cited by (1)

  • <no title>

    DOHRING A.

    Organometallics 19, 388, 2000

    DOI  Cited by (2)

  • <no title>

    SCHILLING F. C.

    Macromolecules 13, 1980

    Cited by (1)

  • <no title>

    GAUSING V. W.

    Angew. Chem. 93, 201, 1981

    DOI  Cited by (1)

Codes

  • NII Article ID (NAID)
    10008224107
  • NII NACSIS-CAT ID (NCID)
    AN00085011
  • Text Lang
    JPN
  • Article Type
    ART
  • ISSN
    03862186
  • NDL Article ID
    6154434
  • NDL Source Classification
    ZP16(科学技術--化学・化学工業--高分子化学・高分子化学工業)
  • NDL Call No.
    Z17-92
  • Data Source
    CJP  NDL  J-STAGE 
Page Top