酸化的カルボニル化反応に基づく一酸化炭素とビスフェノールAからのポリカーボネートへの一段重合  [in Japanese] One-Step Synthesis of Polycarbonate from Carbon Monoxide and Bisphenol A Based on Oxidative Carbonylation  [in Japanese]

Access this Article

Search this Article

Author(s)

Abstract

代表的なエンジニアリング・プラスチックであるポリカーボネート (PC) は衝撃強度, 耐熱性などに優れた透明材料として広く利用されている有用な材料であり, 主にビスフェノールA (bis-A) とホスゲンとの重縮合により工業的に生産されている. さらなる生産コストの低減とホスゲン使用による潜在的危険性の回避を目的として, Pd触媒存在下一酸化炭素を用いる酸化的カルボニル化反応に基づくビスフェノールAからのポリカーボネート一段合成法の開発を行った. 最初にフェノールから炭酸ジフェニルへの酸化的カルボニル化反応をモデル反応として, 新たにPd錯体触媒系をデザインした結果, 従来の触媒系で大量に必要であったアンモニウムハライドが不要になるPd-Sn錯体触媒系を見いだした. また, アンモニウムハライドは必要ではあるが極めて高活性な触媒としてPd複核錯体, Pd-ジイミン錯体, Pd-ビピリジル錯体触媒系を見いだし, さらにPd錯体触媒系の固定化についても検討した. これらのPd錯体触媒系を目的のビスフェノールAからのポリカーボネート一段合成法に適用したところ, 6, 6'位に置換基を有する2, 2'-ビピリジルを配位子とするPd錯体を用いることにより, 従来の触媒系を用いた場合を大きく上回る数平均分子量5600, 重量平均分子量12900のポリカーボネートを, 高収率で得ることが可能となった.

Polycarbonate (PC) is one of the most important engineering plastics, which is produced by polycondensation reaction of bisphenol A (bis-A) with phosgene. To achieve a more economical and safe process, a direct one-step synthesis of PC from bis-A and carbon monoxide was developed on the basis of Pd catalyzed oxidative carbonylation. New catalyst systems for the one-step synthesis of diphenyl carbonate (DPC) from carbon monoxide and phenol were investigated in the model reaction to develop efficient catalyst systems. The Pd-Sn complex including [Pd-Pd-Sn] or [Sn-Pd-Pd-Sn] structure with a Mn redox catalyst was found to produce DPC effectively without addition of any ammonium halide. In the presence of an ammonium halide, Pd catalyst systems, such as the Pd dinuclear complex possessing a 2-pyridylphosphine ligand, Pd-diimine complex derived from 2, 6-di-<I>iso</I>-propylaniline with a 1, 2-diketone or 1, 2-dialdehyde, and Pd-bipyridyl complex consisting of a 6, 6′-disubstituted-2, 2′-bipyridyl ligand, promoted the oxidative carbonylation of phenol more effectively. The immobilization of Pd complex catalyst systems was also investigated. These novel Pd complex catalyst systems were applied to the one-step synthesis of PC from bis-A and carbon monoxide. PC with the number- and weight-average molecular weights of 5600 and 12900 respectively, was successfully obtained using Pd-6, 6′-disubstituted-2, 2′-bipyridyl complexes. These molecular weights were much higher than the one-step synthesis of PC by oxidative carbonylation using conventional Pd catalyst systems such as PdBr<SUB>2</SUB>.

Journal

  • KOBUNSHI RONBUNSHU

    KOBUNSHI RONBUNSHU 59(4), 137-149, 2002-04-25

    The Society of Polymer Science, Japan

References:  47

  • <no title>

    FREITAG D.

    Encyclopedia of Polymer Science and Engineering 11, 648, 1988

    Cited by (3)

  • <no title>

    FREITAG D.

    Angew. Chem. Int. Ed. Engl. 30, 1598, 1991

    Cited by (2)

  • <no title>

    高田聡明

    プラスチックス 51(1), 53, 2000

    Cited by (1)

  • <no title>

    プラスチックス 52(6), 49, 2001

    Cited by (1)

  • <no title>

    布施正孝

    プラスチックス 52(1), 52, 2001

    Cited by (1)

  • <no title>

    マーケットシェア マンスリー 2001(1), 37

    Cited by (1)

  • <no title>

    下田智明

    ファインケミカル 29(8), 21, 2000

    Cited by (2)

  • <no title>

    伊藤光則

    出光技報 37, 215, 1994

    Cited by (2)

  • <no title>

    HERSH S. N.

    J. Appl. Polym. Sci. 41, 1033, 1990

    Cited by (2)

  • <no title>

    KIM Y.

    Ind. Eng. Chem Res. 31, 2118, 1992

    Cited by (3)

  • <no title>

    KOMIYA K.

    ACS Symp. Ser. 626, 20, 1996

    Cited by (1)

  • <no title>

    八谷広志

    高分子論文集 57, 15, 2000

    Cited by (3)

  • <no title>

    GROSS S. M.

    Macromolecules 32, 3167, 1999

    Cited by (2)

  • <no title>

    GROSS S. M.

    Macromolecules 33, 40, 2000

    Cited by (2)

  • <no title>

    高木雅敏

    触媒 42, 272, 2000

    Cited by (3)

  • <no title>

    HALLGREN J. E.

    J.Organomet.Chem. 175, 135, 1979

    Cited by (3)

  • <no title>

    HALLGREN J. E.

    J.Organomet.Chem. 204, 135, 1981

    Cited by (3)

  • <no title>

    HALLGREN J. E.

    J.Organomet.Chem. 212, 135, 1981

    Cited by (3)

  • <no title>

    MOISEEV I. I.

    J. Mol. Catal. A : Chem. 108, 77, 1996

    Cited by (2)

  • <no title>

    TAKAGI M.

    J.Mol.Catal.A:Chem. 129, L1, 1998

    Cited by (3)

  • <no title>

    GOYAL M.

    Catal. Lett. 54, 29, 1998

    Cited by (2)

  • <no title>

    GOYAL M.

    J. Mol. Catal. A : Chem. 137, 147, 1999

    Cited by (2)

  • <no title>

    VAVASORI A.

    J.Mol.Catal.A:Chem. 139, 109, 1999

    Cited by (3)

  • <no title>

    SONG H. Y.

    J. Mol. Catal. A : Chem. 154, 243, 2000

    Cited by (2)

  • <no title>

    YIN G.

    J. Organomet. Chem. 630, 11, 2001

    Cited by (1)

  • <no title>

    GOYAL M.

    Polymer 40, 3237, 1999

    Cited by (3)

  • <no title>

    GOYAL M.

    Polymer 41, 2289, 2000

    Cited by (4)

  • <no title>

    石井宏寿

    有機合成化学協会誌 59, 790, 2001

    Cited by (2)

  • <no title>

    石井宏寿

    化学と工業 54, 1045, 2001

    Cited by (1)

  • <no title>

    ISHII H.

    J.Mol.Catal.A:Chem. 138, 311, 1999

    Cited by (3)

  • <no title>

    ISHII H.

    J.Mol.Catal.A:Chem. 144, 369, 1999

    Cited by (3)

  • <no title>

    東島通夫

    触媒 38, 336, 1996

    Cited by (1)

  • <no title>

    RIVETTI F.

    J. Organomet. Chem. 174, 221, 1979

    Cited by (3)

  • <no title>

    ROMANO U.

    Ind. Eng. Chem. Prod. Res. Dev. 19, 396, 1980

    Cited by (6)

  • <no title>

    DELLEDONNE D.

    J. Organomet. Chem. 488, C15, 1995

    Cited by (1)

  • <no title>

    SHAIKH A.-A. G.

    Ind. Eng. Chem. Res. 31, 1167, 1992

    Cited by (2)

  • <no title>

    ISHII H.

    J.Mol.Catal.A:Chem. 144, 477, 1999

    Cited by (3)

  • <no title>

    ISHII H.

    J. Mol. Catal. A : Chem. 148, 289, 1999

    Cited by (2)

  • <no title>

    ISHII H.

    Catal. Lett. 65, 57, 2000

    Cited by (2)

  • <no title>

    JOHNSON L. K.

    J. Am. Chem. Soc. 117, 6414, 1995

    Cited by (46)

  • <no title>

    SMALL B. L.

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

    Cited by (29)

  • <no title>

    BRITOVSEK G. J. P.

    J. Chem. Soc., Chem. Commun. 1998, 849

    Cited by (2)

  • <no title>

    ISHII H.

    Appl. Catal., A 201, 101, 2000

    Cited by (1)

  • <no title>

    ISHII H.

    Catal. Commun. 2, 17, 2001

    Cited by (3)

  • <no title>

    ISHII H.

    Catal. Commun. 2, 145, 2001

    Cited by (3)

  • <no title>

    ISHII H.

    Macromol. Rapid Commun. 22, 376, 2001

    Cited by (3)

  • <no title>

    VAVASORI A.

    Chem. 151, 37, 2000

    DOI  Cited by (2)

Codes

  • NII Article ID (NAID)
    10008223715
  • NII NACSIS-CAT ID (NCID)
    AN00085011
  • Text Lang
    JPN
  • Article Type
    REV
  • ISSN
    03862186
  • NDL Article ID
    6154144
  • 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