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化学学报
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化学学报 ›› 1990, Vol. 48 ›› Issue (2): 121-126. 上一篇    下一篇

研究论文

甲醇羰基化为乙酸的新型高聚物铑催化剂的合成, 结构与性能

陈予英;袁国卿;陈荣耀   

  1. 中国科学院化学研究所
  • 发布日期:1990-02-15

Synthesis , structure and catalytic activity of a series of heterogenized rhodium complex for the carbonylation of methanol

CHEN YUYING;YUAN GUOQING;CHEN RONGYAO   

  • Published:1990-02-15

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489

被引次数

38 | 16

以交联或非交联的丁烯酮2-乙烯吡啶共聚物为配体的新型铑配合物催化剂能在较温和的条件下直接催化甲醇羰基化为乙酸, 实验结果表明, 这类新型高聚物铑配合物具有螯合型顺-二羰基铑(I)的结构特征, 并且有良好的热稳定性及高的催化活性和选择性, 其周转率可达10^4摩尔甲醇转化(摩尔铑)^-^1(时)^-^1, 产物除乙酸甲酯和乙酸外, 无其它副产物, 选择性近100%。

关键词: 吡啶 P, 催化, 催化剂, 甲醇, 共聚物, 结构与性能关系, 乙酸, 羰基化作用, 交联, 铑络合物

A series of heterogenized Rh complex catalysts for the carbonylation of MeOH were synthesized by the reaction of Rh2(CO)4Cl2 with linear and cross-linked copolymers of 2-vinylpyridine and Me vinyl ketone. The active centers of these catalysts consist of (1) a cis-Rh(CO)2 moiety coordinated with the borderline base pyridine N and the adjacent hard base keto O to form N甊h and O甊h coordination bond, resp., and (2) the said moiety coordinated with 2 adjacent pyridine N's to form 2 N甊h bonds. The former plays a more active role than the latter in catalysis. These catalysts are thermally stable. With MeI as promoter, MeOH in AcOH could be carbonylated to AcOH and Ac2O simultaneously as final products with a turnover rate at 104 mol of MeOH converted/mol Rh/h.

Key words: PYRIDINE P, CATALYSIS, CATALYST, METHANOL, COPOLYMERS, STRUCTURE AND PROPERTY CORRELATION, ACETIC ACID, CARBONYLATION, CROSSLINKING, RHODIUM COMPLEX

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