(tert-ブチルアミドジメチルシリルフルオレニル)ジメチルチタン触媒系によるオレフィンリビング重合の成長反応機構  [in Japanese] Propagation Mechanism for Living Polymerization of Olefins Using [ η^1 : η^3-tert-Butyl( dimethylfluorenylsilyl)amido ] dimethyltitanium-Based Catalyst  [in Japanese]

Access this Article

Search this Article

Author(s)

Abstract

(η<SUP>1</SUP>: η<SUP>3</SUP>-<I>tert</I>-ブチルアミドジメチルシリルフルオレニル) ジメチルチタンとトリス (ペンタフルオロフエニル) ボラン (B (C<SUB>6</SUB>F<SUB>5</SUB>) <SUB>3</SUB>) を組み合わせトリオクチルアルミニウム存在下-50℃で1-オクテンの重合を行った・ポリマー収量は重合時間とともにほぼ直線的に増加し, 得られたポリマーの数平均分子量 (<I>M</I><SUB>n</SUB>) はポリマー収量に比例して増加するとともに分子量分布 (<I>M</I><SUB>w</SUB>/<I>M</I><SUB>n</SUB>) も約1.1と狭い値を示した. これより・本触媒系で1-オクテンのリビング重合が進行することを確認した. 転化率を抑え所定時間重合して得られたポリマーの<I>M</I><SUB>n</SUB>値は1-オクテン濃度に依存しないことから, 本系の成長反応速度はモノマー濃度に依存しないことがわかった. 1-ブテン, 1-ヘキセンのリビング重合においても同様に, 成長反応速度はモノマー濃度に依存しなかった. さらに, 1-オクテン重合において, 収量, <I>M</I><SUB>n</SUB>値はB (C<SUB>6</SUB>F<SUB>5</SUB>) <SUB>3</SUB>濃度に依存せず, また, <I>M</I><SUB>w</SUB>/<I>M</I><SUB>n</SUB>値は約1.1であった. これより本系では, B (C<SUB>6</SUB>F<SUB>5</SUB>) <SUB>3</SUB>濃度によらずリビング重合が進行し, 成長反応速度はB (C<SUB>6</SUB>F<SUB>5</SUB>) <SUB>3</SUB>濃度に依存しないことが明らかとなった.

1-Octene polymerization was conducted by [η<SUP>1</SUP>: η<SUP>3</SUP>-<I>tert</I>-butyl (dimethylfluorenylsilyl) amido] dimethyltitanium ([<I>t</I>-BuNSiMe<SUB>2</SUB>Flu] TiMe<SUB>2</SUB>) activated with tris (pentafluorophenyl) borane (B (C<SUB>6</SUB>F<SUB>5</SUB>) <SUB>3</SUB>) at-50°Cin the presence of trioctylaluminum (Oct<SUB>3</SUB>Al). The polymer yield linearly increased with increasing polymerization time. The poly (1-octene) obtained showed narrow molecular weight distributions (<I>M</I><SUB>w</SUB>/<I>M</I><SUB>n</SUB>) of about 1.1. In addition, the number average molecular weight (<I>M</I><SUB>n</SUB>) of the polymer was proportional to the polymer yield. These results indicated that living polymerization of 1-octene proceeded with this catalyst system. The dependence of propagation rate on 1-octene concentration was investigated under various 1-octene concentrations in the polymerization of low conversion (<10%). The <I>M</I><SUB>n</SUB> values at a certain polymerization time were independent of 1-octene concentrations, which indicated that the propagation rate was almost zeroth order in loctene. Polymerization of 1-butene and 1-hexene with this catalyst system also proceeded in a living manner, and their propagation rates were also independent of monomer concentration. 1-Octene polymerization was conducted by this catalyst system with various concentrations of B (C<SUB>6</SUB>F<SUB>5</SUB>) <SUB>3</SUB>. The polymer yield and Ain value did not depend on the [B (C<SUB>6</SUB>F<SUB>5</SUB>) <SUB>3</SUB>] / [Ti] ratio and the polymers with narrow <I>M</I><SUB>w</SUB>/<I>M</I><SUB>n</SUB> were obtained. The results indicated that the propagation rate was not affected by excess B (C<SUB>6</SUB>F<SUB>5</SUB>) <SUB>3</SUB>.

Journal

  • KOBUNSHI RONBUNSHU

    KOBUNSHI RONBUNSHU 59(6), 371-376, 2002-06-25

    The Society of Polymer Science, Japan

References:  27

  • <no title>

    DOI Y.

    Macromolecules 12, 814, 1979

    Cited by (14)

  • <no title>

    MORING V. M.

    Angew. Chem., Int. Ed. Engl. 24, 1001, 1985

    Cited by (1)

  • <no title>

    MASHIMA K.

    J. Am. Chem. Soc. 115, 10990, 1993

    Cited by (10)

  • <no title>

    BAUMANN R.

    J. Am. Chem. Soc. 119, 3830, 1997

    Cited by (14)

  • <no title>

    MURATA M.

    Macromol. Rapid Commun. 19, 267, 1998

    Cited by (3)

  • <no title>

    JEON Y.-M.

    Organometallics 17, 3161, 1998

    Cited by (6)

  • <no title>

    FUKUI Y.

    Macromol. Rapid Cammun. 20, 637, 1999

    Cited by (1)

  • <no title>

    JAYARATNE K. C.

    J. Am. Chem. Soc. 122, 958, 2000

    Cited by (11)

  • <no title>

    KEATON R. J.

    J. Am. Chem. Soc. 123, 6197, 2001

    Cited by (2)

  • <no title>

    GOTTFRIED A. C.

    Macromolecules 34, 1140, 2001

    Cited by (8)

  • <no title>

    MATSUGI T.

    Chem. Lett. 2001, 566

    Cited by (6)

  • <no title>

    TIAN J.

    J. Am. Chem. Soc. 123, 5134, 2001

    Cited by (11)

  • <no title>

    SAITO J.

    Chem. Lett. 2001, 576

    Cited by (6)

  • <no title>

    HAGIHARA H.

    Macromolecules 31, 3184, 1998

    Cited by (6)

  • <no title>

    HASAN T.

    Macromolecules 34, 3142, 2001

    Cited by (3)

  • <no title>

    HAGIHARA H.

    Macromol. Rapid Commun. 20, 200, 1999

    Cited by (1)

  • <no title>

    YSTENES M.

    J. Catal. 129, 383, 1991

    Cited by (2)

  • <no title>

    JUNGLING S.

    J. Polym. Sci., Part A: Polym. Chem. 33, 1305, 1995

    Cited by (1)

  • <no title>

    CHIEN J. C. W.

    J. Polym. Sci., Part A : Polym. Chem. 36, 319, 1998

    Cited by (2)

  • <no title>

    FAIT A.

    Macromolecules 32, 2104, 1999

    Cited by (1)

  • <no title>

    萩原英昭

    博士論文, 東京工業大学, 1997

    Cited by (1)

  • <no title>

    LECLERC M. K.

    Angew. Chem., Int. Ed. Engl. 37, 922, 1998

    Cited by (1)

  • <no title>

    SHIONO T.

    Metalorganic Catalysts for Synthesis and Polymerization 264, 1999

    Cited by (1)

  • <no title>

    SCOLLARD J. D.

    J. Am. Chem. Soc. 118, 10008, 1996

    DOI  Cited by (35)

  • <no title>

    KILLIAN K. M.

    Am. Chem. Soc. 118, 11664, 1996

    DOI  Cited by (34)

  • <no title>

    TSHUVA E. Y.

    J. Am. Chem. Soc. 122, 10706, 2000

    DOI  Cited by (11)

  • <no title>

    JAYARATNE K. C.

    J. Am. Chem. Soc. 122, 10490, 2000

    DOI  Cited by (1)

Codes

  • NII Article ID (NAID)
    10008834535
  • NII NACSIS-CAT ID (NCID)
    AN00085011
  • Text Lang
    JPN
  • Article Type
    ART
  • ISSN
    03862186
  • NDL Article ID
    6200467
  • 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