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EP-4393589-B1 - IRIDIUM-BASED CATALYST AND PREPARATION METHOD THEREFOR, AND HYDROFORMYLATION METHOD

EP4393589B1EP 4393589 B1EP4393589 B1EP 4393589B1EP-4393589-B1

Inventors

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

Dates

Publication Date
20260506
Application Date
20211116

Claims (7)

  1. A method for olefin hydroformylation using an iridium-based catalyst, comprising the following steps: under a condition that the iridium-based catalyst is existed, olefins, carbon monoxide, and hydrogen are used as raw materials to perform a catalytic reaction; before the catalytic reaction, the iridium-based catalyst is dissolved in a solvent; the solvent is one of n-butyraldehyde, iso-butyraldehyde, toluene or tetrahydrofuran; wherein a chemical structural formula of the iridium-based catalyst is: wherein Ph is a phenyl, R is a methyl or an ethyl, and X is one of CH 3 CO 2 , NO 3 , BF 4 , PF 6 and SbF 6 ; the method further comprising prior to the catalytic reaction, preparing the iridium-based catalyst by the steps of: mixing and stirring 4,5-bis(diphenylphosphoryl)-9,9-dimethylxanthene, solvent and iridium compound, and then heating and stirring to obtain the iridium-based catalyst; wherein a time for mixing and stirring 4,5-bis(diphenylphosphoryl)-9,9-dimethylxanthene, solvent and iridium compound is 2h; wherein during the heating and stirring process, a temperature is raised to 50°C, and then stirring for 2h; when X in the iridium-based catalyst is CH 3 CO 2 , NO 3 , BF 4 , PF 4 or SbF 6 , the temperature is first raised and stirred to obtain a substance to be substituted, and then a compound containing an X-based group is added to replace the substance to be substituted, wherein the catalytic reaction is performed at a reaction temperature between 80°C and 110°C and at a reaction pressure between 1.0Mpa and 2.0Mpa.
  2. The method for olefin hydroformylation according to claim 1, wherein a partial pressure ratio of the olefin to the carbon monoxide is 10:1-1:10.
  3. The method for olefin hydroformylation according to claim 1, wherein a partial pressure ratio of the olefin to the carbon monoxide is 5:1-1:5.
  4. The method for olefin hydroformylation according to claim 1, wherein a partial pressure ratio of the olefin to the hydrogen is 10:1-1:10.
  5. The method for olefin hydroformylation according to claim 1, wherein a partial pressure ratio of the olefin to the hydrogen is 5:1-1:5.
  6. The method for olefin hydroformylation according to claim 1, where a mass of the iridium-based catalyst is 0.005wt%-2.0wt% of a mass of the solvent.
  7. The method for olefin hydroformylation according to claim 1, where a mass of the iridium-based catalyst is 0.05wt%-1.0wt% of a mass of the solvent.

Description

FIELD OF THE INVENTION The present invention relates to a method for olefin hydroformylation using an iridium-based catalyst. BACKGROUND OF THE INVENTION Butyraldehyde and octanol are very widely used bulk chemical raw materials. At present, the industrial synthesis of butyl-octanol is mainly through the olefin hydroformylation reaction to produce n-butyraldehyde and iso-butyraldehyde, which are then used as raw materials for subsequent reactions. The olefin hydroformylation reaction is a key step in the synthesis of butyl-octanol. So far, there have been many patents on the olefin hydroformylation to synthesize n-butyraldehyde and iso-butyraldehyde. These patents and current industrial methods generally use rhodium-based catalysts. For example, patents WO0200583, EP3712126A1, and CN102826967A use triphenylphosphorus-rhodium as the catalyst; the patent JP2002047294 uses cyclooctadiene acetate-rhodium as the catalyst; the patent CN110156580 uses 6,6'-((3,3'-di-tert-butyl-5 ,5'-dimethoxy-[1,1'-biphenyl]-2, bis(oxy))dibenzo[d,f] [1,3,2] dioxaphosphocyclopentane Alkene-rhodium as the catalyst; the patent CN103896748Auses acetylmorpholine-rhodium as the catalyst; the patent EP3770144A1 uses acetate-rhodium as the catalyst; the patent CN111348995A uses tris[2,4-di-tert-butylphenyl] phosphite-rhodium as the catalyst; the patent US9550179 uses long Chain carboxylic acid-rhodium as the catalyst; the patent CN102826973A uses acetylacetone carbonyl-rhodium as the catalyst; the patent EP2417094B1 uses triphenylphosphine carbonyl rhodium hydride as the catalyst; the patent EP2417093B1 uses dipolyrhodium acetate + triphenylphosphine trisulfonate sodium salt as the catalyst. In addition to the above patents, rhodium-based catalysts are also commonly used in published papers. For example, Angew. Chem. Int. Ed. 2019, 58, 2120 -2124 used heterocyclic phosphorus ligand-rhodium as the catalyst, and the obtained highest n-butyraldehyde/iso-butyraldehyde ratio is 2.6; ACS Catal. 2018, 8, 5799-5809 used N-Triphos ligand-rhodium as the catalyst, the obtained highest n-butyraldehyde/iso-butyraldehyde ratio is 2.3; Journal of Molecular Catalysis A: Chemical, 2009, 300, 116-120 used triphenylphosphorus carbonyl rhodium hydride as the catalyst, and the obtained highest n-butyraldehyde/iso-butyraldehyde ratio is 12.7; Chem. Eur. J. 2017, 23, 14769-14777 used porphyrin-modified triphenylphosphorus ligand-rhodium as the catalyst, the obtained highest n-butyraldehyde/iso-butyraldehyde ratio is 2.3. The article ASHLEY J PONTIGGIA ET AL: "Cationic iridium complexes of the Xantphos ligand. Flexible coordination modes and the isolation of the hydride insertion product with an alkene" (Journal of Organometallic Chemistry, 696 (2011) 2870-2876) discloses the synthesis and structural characterization of a cationic iridium complex containing a Xantphos ligand. The publication studies the coordination chemistry and reactivity of this complex, including its reaction with hydrogen to form hydrido complexes and the subsequent insertion of a hydride into an alkene. The introduction mentions that Xantphos-type ligands have found application in catalytic hydroformylation reactions. The document WO 2012/062558 A1 discloses a method for the hydroformylation of unsaturated compounds using an iridium catalyst and a phosphorus-containing ligand. The disclosed method is characterized by a specific reaction procedure to suppress hydrogenation, wherein either the synthesis gas is introduced only after the reaction mixture has been heated to the reaction temperature, or a pre-forming step with pure carbon monoxide is employed before heating and introducing the synthesis gas. The working examples demonstrate the method using an iridium catalyst in combination with triphenylphosphine as the ligand, achieving an n/iso selectivity ratio of approximately 76:24. Although rhodium metal can be recycled many times in olefin hydroformylation reactions. Slow loss and deactivation during the reaction process are inevitable. Due to the rapid increase in international rhodium metal prices, the cost of catalysts in the corresponding process has also increased rapidly. Secondly, the low n-butyraldehyde/iso-butyraldehyde ratio causes the production process to produce a large amount of low-value iso-butyraldehyde. In view of this, the present invention as defined by the claims is proposed. SUMMARY OF THE INVENTION A first objective of the present invention is to provide an iridium-based catalyst. Compared with the existing rhodium-based catalyst, the iridium-based catalyst used in the present invention is cheaper and greatly reduces the production cost. A second objective of the present invention is to provide a preparation method of an iridium-based catalyst, which has mild reaction conditions, can significantly reduce energy consumption, and the obtained iridium-based catalyst has better catalytic effects than previous catalysts. A third objective of the present invention is to