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    Carbonylation process employing a catalyst stabilised in soluble form
    1.
    发明公开
    Carbonylation process employing a catalyst stabilised in soluble form 失效
    Verfahren zur Carbonylierung unter Verwendung eines inflüssigerForm stableiserten Katalysators。

    公开(公告)号：EP0055618A1

    公开(公告)日：1982-07-07

    申请号：EP81306130.6

    申请日：1981-12-24

    申请人： MONSANTO COMPANY

    发明人： Singleton, Thomas Clark ,  Urry, Wilbert Herbert ,  Paulik, Frank Edward

    IPC分类号： C07C51/12 ,  C07C51/10 ,  C07C53/08 ,  C07C67/36 ,  C07C67/37 ,  B01J27/08 ,  B01J31/30

    CPC分类号： C07C51/14 ,  C07C51/12 ,  C07C53/08

    摘要： The present invention provides for an improved process wherein an olefin, an alcohol, or an ester, halide or ether derivative of said alcohol is reacted with carbon monoxide in a liquid phase in the presence of a catalyst system that contains (a) a rhodium component, and (b) an iodine or bromine component. By passing at least a portion of the liquid reaction mass from the reaction zone to a separation zone of substantially lower CO partial pressure, at least a portion of the carbonylation products, as well as unreacted carbon monoxide, inert gases, and unreacted olefin, alcohol, or alcohol derivatives are vaporized and can be withdrawn from the separation zone. Precipitation of the rhodium catalyst under carbon monoxide deficient conditions is prevented or retarded by addition to the system of a stabilizer component selected from

    (1) N,N,N',N' - tetramethyl-o-phenylenediamine and 2,3' dipyridyl,
    (2) a substituted diphosphine having the formula
    wherein R 1 , R 2 , R 4 and R s are alkyl or aryl substituted alkyl having 1 to 20 carbon atoms or in which R 1 , R 2 , R 4 and R 5 are aryl or alkyl substituted aryl radicals having 6 to 20 carbon atoms; and R 3 is a polymethylene group having 1-3 atoms,
    (3) a dibasic or polybasic carboxylic acid having the formula

    摘要翻译： 本发明提供了一种改进的方法，其中所述醇的烯烃，醇或酯，卤化物或醚衍生物在液相中与一氧化碳在催化剂体系存在下反应，所述催化剂体系含有（a）铑组分 ，和（b）碘或溴成分。 通过将至少一部分液体反应物质从反应区通过至基本上较低CO分压的分离区，至少部分羰基化产物，以及未反应的一氧化碳，惰性气体和未反应的烯烃，醇 ，或醇衍生物蒸发，并可从分离区取出。 在一氧化碳缺乏条件下铑催化剂的沉淀通过加入到选自（1）N，N，Nmin，Nmin-四甲基邻苯二胺和2,3min二吡啶基的稳定剂组分的体系来防止或延迟， （2）具有式CHEM的取代二膦，其中R 1，R 2，R 4和R 5是具有1至20个碳原子的烷基或芳基取代的烷基，或其中R 1，R 2，R 4和R 5是具有芳基或烷基取代的芳基， 6至20个碳原子; R3为具有1-3个原子的多亚甲基，（3）具有式CHEM> r的二元或多元羧酸

    Preparation of alkylidene diesters
    2.
    发明公开
    Preparation of alkylidene diesters 失效
    亚烷基二酯的制备

    公开(公告)号：EP0077116A1

    公开(公告)日：1983-04-20

    申请号：EP82303506.8

    申请日：1982-07-05

    申请人： MONSANTO COMPANY

    发明人： Paulik, Frank Edward ,  Schultz, Robert George

    IPC分类号： C07C69/16 ,  C07C67/37 ,  C07C67/36

    CPC分类号： C07C67/36 ,  C07C67/37 ,  C07C69/16

    摘要： Alkylidene diesters such as ethylidene diacetate are selectively produced in high yields by reacting an ether and/or an ester under substantially anhydrous conditions with carbon monoxide and hydrogen in contact with a catalyst system comprising a rhodium compound, a halogen component, a palladium cocatalyst and a promoter component which is an agent for liberation of carboxylic acid anions. The process is carried out in the liquid phase in a solvent comprising a carboxylic acid at a temperature in the range of 150 to 190°C. and at a carbon monoxide partial pressure in the range from about 1.0 to 1100 kg/ cm 2 and a carbon monoxide/hydrogen mole ratio of 6:1 to 1:2 for the ester reaction and 10:1 to 1:2 for the ether reaction. When ethylidene diacetate is the product, it can then be decomposed to produce vinyl acetate and acetic acid by well-known techniques. Since one mole of acetic acid is also produced in the synthesis of the diacetate, the invention makes possible an overall process for the production of vinyl acetate which produces acetic acid rather than consumes it.

    摘要翻译： 通过在基本上无水的条件下使醚和/或酯与一氧化碳和氢气反应，与包含铑化合物，卤素组分，钯助催化剂和催化剂的催化剂体系接触，高选择性地产生亚烷基二酯如亚乙基二乙酸酯 促进剂组分，其是用于释放羧酸阴离子的试剂。 该方法在液相中在150-190℃范围内的温度下，在包含羧酸的溶剂中进行。 并且在一氧化碳分压为约1.0-1100kg / cm2和酯化反应的一氧化碳/氢摩尔比为6:1-1:2和醚反应为10:1-1:2的情况下 。 当二乙酸亚乙酯是产物时，它可以通过熟知的技术分解生成乙酸乙烯酯和乙酸。 由于在二乙酸酯的合成中也生成1摩尔的乙酸，因此本发明使得生产乙酸而不是消耗乙酸的乙酸乙烯酯的总生产成为可能。