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    • 2. 发明公开
    • Hydroformylation of olefin feeds containing dienes
    • 加氢甲酰化von Dien enthaltenden ethyleneischenSpeiseströmen
    • EP0943597A2
    • 1999-09-22
    • EP99200792.2
    • 1999-03-15
    • SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
    • Drent, EitVan der Steen, Frederik HendrikMoene, Robert
    • C07C29/16
    • C07C29/16C07C31/125
    • A process for the hydroformylation of a feed comprising compounds having a single ethylenically unsaturated group by reaction thereof in the liquid phase with carbon monoxide and hydrogen in the presence of a catalyst system comprising

      a) a source of palladium cations;
      b) a source of anions;
      c) a source of at least one bidentate ligands of the formula

              R 1 R 2 M 1 RM 2 R 3 R 4      (I)

      wherein M 1 and M 2 independently represent a phosphorus, arsenic or antimony atom, R represents a bivalent bridging group containing from 1-4 atoms in the bridge, R 1 and R 2 independently represent a substituted or unsubstituted hydrocarbyl group, or together represent a bivalent substituted or unsubstituted cyclic group whereby the two free valencies are linked to M 1 , and R 3 and R 4 independently represent a substituted or unsubstituted hydrocarbyl group, or together represent a bivalent substituted or unsubstituted cyclic group whereby the two free valencies are linked to M 2 ; and
      d) a source of halide chosen from the group of chloride, iodide and bromide and mixtures thereof;
      characterized in that the ethylenically unsaturated feed comprises one or more dienes and/or further multiply unsaturated alkenes to an amount of 0.005 - 5 wt% based on the total amount of ethylenically unsaturated compounds in the feed, and in that component b) of the catalyst system is a source of anions of an acid having a pKa value, measured in aqueous solution at 18 °C, of between -1 and 4.
    • 在包含a)钯阳离子源的催化剂体系的存在下,通过其在液相中与一氧化碳和氢气反应的含有具有单个烯属不饱和基团的化合物的进料加氢甲酰化的方法, b)阴离子的来源; c)至少一种式R 1 R 2 M 2 R 3 R 4的二齿配位体的源,其中M 1和M 2独立地表示 磷,砷或锑原子,R表示在桥中含有1-4个原子的二价桥连基团,R 1和R 2独立地表示取代或未取代的烃基,或一起表示二价取代或未取代的环状 基团,其中两个自由价与M 1连接,R 3和R 4独立地表示取代或未取代的烃基,或一起表示二价取代或未取代的环状基团,由此两个自由价键连接 至M 2; 和d)选自氯化物,碘化物和溴化物的卤化物源及其混合物; 其特征在于烯属不饱和进料包含一种或多种二烯和/或多种不饱和烯烃,其量相对于进料中烯属不饱和化合物的总量为0.005-5重量%,催化剂的组分b) 系统是在18℃的水溶液中在-1和4之间具有pKa值的酸的阴离子源。