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EP-4424661-B1 - METHOD FOR CATALYZING OLEFIN CARBONYLATION

EP4424661B1EP 4424661 B1EP4424661 B1EP 4424661B1EP-4424661-B1

Inventors

  • HU, Xingbang
  • ZHANG, ZHIBING
  • YAO, Chenfei
  • LI, LEI
  • ZHOU, ZHENG

Dates

Publication Date
20260506
Application Date
20211116

Claims (7)

  1. A method for catalyzing olefin carbonylation, comprising the following steps: using cyclic alkylcarbene iridium as a catalyst and olefin as a raw material to carry out carbonylation reaction to generate aldehydes, wherein a structural formula of the cyclic alkylcarbene iridium is as follows: wherein Dipp is 2,6-diisopropylbenzene; R 1 and R 2 are methyl or ethyl; X is Cl, Br, CH 3 CO 2 , NO 3 , BF 4 , PF 6 or SbF 6 ; wherein the olefin comprises one or more of ethylene, propylene, butylene and higher carbon olefins.
  2. The method for catalyzing olefin carbonylation according to claim 1, wherein a reaction solvent includes a mixture of one or more of n-butyraldehyde, isobutyraldehyde, toluene, benzene and tetrahydrofuran.
  3. The method for catalyzing olefin carbonylation according to claim 2, wherein a dosage of the catalyst is 0.005-2wt% of a dosage of the reaction solvent, preferably 0.05-1wt%.
  4. The method for catalyzing olefin carbonylation according to claim 1, wherein the olefin is propylene, and the other raw materials comprise carbon monoxide and hydrogen, and a total reaction pressure is between 0.5-5.0MPa, preferably between 1.0-3.0MPa.
  5. The method for catalyzing olefin carbonylation according to claim 4, wherein a partial pressure ratio of propylene to carbon monoxide is between 1:1-1:10, preferably between 1:2-1:5.
  6. The method for catalyzing olefin carbonylation according to claim 4, wherein a partial pressure ratio of propylene to hydrogen is between 1:1-1:10, preferably between 1:2-1:5.
  7. The method for catalyzing olefin carbonylation according to claim 4, wherein a reaction temperature is between 60~180°C, preferably between 80°C~140°C.

Description

FIELD OF THE INVENTION The present invention relates to the field of carbonylation reactions, and specifically to a method for catalyzing olefin carbonylation. BACKGROUND OF THE INVENTION Butanol and octanol are very widely used bulk chemical raw materials. At present, the industrial synthesis of butyl octanol is mainly through the hydroformylation of propylene to produce n-butyraldehyde and isobutyraldehyde, and then they are used as raw materials for subsequent reactions. The hydroformylation reaction of propylene is a key step in the synthesis of butyl octanol. So far, there have been many patents reported on the hydroformylation of propylene to synthesize n-butyraldehyde and isobutyraldehyde. These patents, as well as current industrial methods, commonly use catalysts based on metal rhodium. For example, patents WO0200583, EP3712126A1, and CN102826967A use triphenylphosphorus-rhodium as catalyst; a patent JP2002047294 uses cyclooctadiene acetate-rhodium as catalyst; a patent CN110156580 uses 6,6'-((3,3'-di-tert-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2, bis(oxy))diphenyl and [d,f] [1,3,2] dioxaphospholene-rhodium as catalyst; a patent CN103896748A uses acetylmorpholine-rhodium as catalyst; a patent EP3770144A1 uses acetate-rhodium as catalyst; a patent CN111348995A uses tris [2,4-di-tert-butylphenyl] phosphite-rhodium as catalyst; a patent US9550179 uses long-chain carboxylic acid-rhodium as the catalyst; a patent CN102826973A uses acetylacetone carbonyl-rhodium as catalyst; a patent EP2417094B1 uses triphenylphosphine carbonyl rhodium hydride as catalyst; and a patent EP2417093B 1 uses rhodium dimer acetate and triphenyl phosphonium tri sulfonate sodium salt as catalyst. Zhang Heng et al., Journal of molecular catalysis a chemical, vol. 411, pages 337-343, discloses hydroformylation (olefin carbonylation) processes using Iridium with diphosphinoimidazolium ligands as catalysts. Because metal rhodium has high catalytic activity in the hydroformylation reaction of propylene, the reaction conditions of reaction systems using this as a catalyst are generally mild. Typical reaction temperatures are between 90-132°C, and typical reaction pressures are between 1.6-5MPa (see Table 1). Although rhodium metal can be recycled many times in the propylene hydroformylation reaction, the slow loss and deactivation are inevitable. Due to the rapid increase in international rhodium metal prices, the cost of catalysts in the corresponding process has also increased rapidly. Table 1. Reaction pressures of existing technologies.Patent NumberTypical reaction temperature (°C)Typical reaction pressure (MPa)CN110156580901.6CN103896748A80-1302-6EP3770144A11265CN111348995A90-1304-6EP 3712126A11105US 9550179951.8CN102826967A901.8CN 102826973 A901.9EP2417094B11325EP2417093B 11225 In view of this, the present invention is proposed. SUMMARY OF THE INVENTION A first objective of the present invention is to provide a method for catalyzing olefin carbonylation. The method combines highly active carbene ligands with metal iridium and uses coordination anions to further adjust the catalyst performance, which gives the catalyst a good catalytic activity. It can lower the reaction temperature, reduce energy consumption and reduce costs. In order to achieve the above objectives of the present invention, the following technical schemes are adopted. The method provides a method for catalyzing olefin carbonylation, including the following steps: using cyclic alkylcarbene iridium as a catalyst and olefin as a raw material to carry out carbonylation reaction to generate aldehydes, wherein a structural formula of the cyclic alkylcarbene iridium is as follows: wherein Dipp is 2,6-diisopropylbenzene; R1 and R2 are methyl or ethyl; X is Cl, Br, CH3CO2, NO3, BF4, PF6 or SbF6;wherein the olefin includes one or more of ethylene, propylene, butylene and higher carbon olefins. The above-mentioned catalyst can be preferably used in the process of the olefin carbonylation reaction, and compared with previous rhodium catalysts, its cost is low, its activity is good, and its catalytic effect is good. Preferably, as a further embodiment, a reaction solvent includes a mixture of one or more of n-butyraldehyde, isobutyraldehyde, toluene, benzene and tetrahydrofuran. Preferably, as a further embodiment, a dosage of the catalyst is 0.005-2wt% of a dosage of the reaction solvent, preferably 0.05-1wt%. Preferably, as a further embodiment, the olefin is propylene, and the other raw materials include carbon monoxide and hydrogen, and a total reaction pressure is between 0.5-5.0MPa, preferably between 1.0-3.0MPa. A total reaction pressure can be 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, etc. Preferably, as a further embodiment, a reaction temperature is between 60~180°C, preferably between 80°C~140°C. The reaction temperature can be 60°C, 70°C, 80°C or 90°C. The scheme of the present invention is more suitable for propylene hydroformylation reaction, and can obtain better