RU2845007C2 - Method of catalyzing carbonylation of olefins - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of catalysing carbonylation of olefins. Method includes following steps: using cyclic alkylcarbene-iridium as a catalyst and olefin as raw material for carbonylation reaction with formation of aldehydes, wherein structural formula of cyclic alkylcarbene-iridium is following:

;

where Dipp is 2,6-diisopropylbenzene; R₁ and R₂ are methyl or ethyl; X is Cl, Br, CH₃CO₂, NO₃, BF₄, PF₆ or SbF₆; where the olefin contains one or more of ethylene, propylene, butylene and high-carbon olefins.

EFFECT: according to the method of catalysing carbonylation of olefins according to the present invention, when using the iridium catalyst, catalytic activity is good and power consumption and reaction temperature are reduced.

7 cl, 2 dwg, 4 tbl, 16 ex

Description

AREA OF TECHNOLOGY

The present invention relates to the field of carbonylation reactions and, in particular, to a method for catalyzing the carbonylation of olefins.

LEVEL OF TECHNOLOGY

Butanol and octanol are very widely used bulk chemical raw materials. At present, the industrial synthesis of butyloctanol is mainly carried out by hydroformylation of propylene to produce n-butyraldehyde and isobutyraldehyde, and then they are used as feedstock for subsequent reactions. The reaction of propylene hydroformylation is a key step in the synthesis of butyloctanol.

At present, there are many patents registered on the hydroformylation of propylene for the synthesis of n-butyraldehyde and isobutyraldehyde. These patents, as well as modern industrial methods, usually use catalysts based on metallic rhodium. For example, in patents WO 0200583, EP 3712126 A1 and CN 102826967 A, triphenylphosphor-rhodium is used as a catalyst; in patent JP2002047294, cyclooctadiene acetate-rhodium is used as a catalyst; CN 110156580 uses 6,6'-((3,3'-di-tert-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,bis(oxy))biphenyl and [d,f][1,3,2]dioxaphospholene rhodium as a catalyst; CN 103896748 A uses acetylmorpholine rhodium as a catalyst; EP 3770144 A1 uses acetate rhodium as a catalyst; CN 111348995 A uses tris[2,4-di-tert-butylphenyl]phosphite rhodium as a catalyst; US9550179 uses long-chain carboxylic acid rhodium as a catalyst; CN 102826973 A uses acetylacetone carbonylrhodium as a catalyst; in patent EP 2 417 094 B1 triphenylphosphine carbonylrhodium hydride is used as a catalyst; and in patent EP 2 417 093 B1 rhodium dimer acetate and sodium triphenylphosphonium trisulfonate are used as a catalyst. Since metallic rhodium has high catalytic activity in the reaction of propylene hydroformylation, reaction conditions in reaction systems using it as a catalyst are generally mild. Typical reaction temperatures are in the range of 90-132°C, and typical reaction pressures are in the range of 1.6-5 MPa (see Table 1).

Although metallic rhodium can be recycled many times in the propylene hydroformylation reaction, slow losses and deactivation are inevitable. Due to the rapid increase in the world price of metallic rhodium, the cost of catalysts in the corresponding process has also increased rapidly.

In view of this, the present invention is proposed.

ESSENCE OF THE INVENTION

The first objective of the present invention is to provide a method for catalyzing the carbonylation of olefins. The method combines highly active carbene ligands with metallic iridium and uses coordination anions to further adjust the characteristics of the catalyst, which gives the catalyst good catalytic activity. This allows for a reduction in reaction temperature, reduced energy consumption and reduced 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 the carbonylation of olefins, comprising the following steps:

the use of cyclic alkylcarbene-iridium as a catalyst and olefin as a feedstock for carrying out the carbonylation reaction to form aldehydes, wherein the structural formula of cyclic alkylcarbene-iridium is as follows:

where 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 high carbon olefins.

The above catalyst can be preferably used in the olefin carbonylation reaction process, and compared with the previous rhodium catalysts, its cost is low, its activity is good, and the catalytic effect is good. Preferably, as a further embodiment, the reaction solvent includes a mixture of one or more of n-butyraldehyde, isobutyraldehyde, toluene, benzene and tetrahydrofuran.

Preferably, as a further embodiment, the dosage of the catalyst is 0.005-2 wt.% of the dosage of the reaction solvent, preferably 0.05-1 wt.%.

Preferably, as a further embodiment, the olefin is propylene, and the other raw materials include carbon monoxide and hydrogen, and the total reaction pressure is from 0.5 to 5.0 MPa, preferably from 1.0 to 3.0 MPa. The total reaction pressure may be 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, etc.

Preferably, as a further embodiment, the reaction temperature is from 60 to 180°C, preferably from 80 to 140°C. The reaction temperature may be 60°C, 70°C, 80°C or 90°C.

The scheme of the present invention is more suitable for the propylene hydroformylation reaction and can achieve a better reaction effect at a reaction temperature of 60~180°C and a reaction pressure of 0.5-5.0 MPa. At the same time, the price of metallic iridium is only about a third of that of metallic rhodium. Equivalently, the present invention provides an economical and gentle new method for synthesizing n-butyraldehyde and isobutyraldehyde through the propylene hydroformylation reaction.

Preferably, as a further embodiment, the partial pressure ratio of propylene to carbon monoxide is between 1:1-1:10, preferably between 1:2-1:5.

Preferably, as a further embodiment, the partial pressure ratio of propylene to hydrogen is between 1:1-1:10, preferably between 1:2-1:5.

By adjusting each working parameter in the above reaction process within the appropriate proportion range, the reaction effect can be significantly improved.

Compared with the prior art, the advantageous effects of the present invention are:

(1) The carbonylation reaction method of the present invention uses highly active carbene ligands to coordinate metallic iridium and uses coordination anions to further adjust the characteristics of the catalyst, which imparts good catalytic activity to the catalyst.

(2) The temperature of the catalytic reaction of the present invention is low, the energy consumption is low, and the cost of the catalyst used is also low.

BRIEF DESCRIPTION OF DRAWINGS

Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of preferred embodiments. The drawings are intended to illustrate preferred embodiments only and should not be construed as limiting the present invention. Furthermore, the same reference symbols are used throughout the drawings to refer to the same components. In the drawings:

FIG. 1 is a diagram of a carbon nuclear magnetic resonance spectrum of the (C2c2)-IrCl CAAC catalyst provided in Embodiment 1 of the present invention.

FIG. 2 is a diagram of a hydrogen nuclear magnetic resonance spectrum of the (C2c2)-IrCl CAAC catalyst provided in Embodiment 1 of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED IMPLEMENTATION OPTION

The present invention will be described in detail below with reference to embodiments, however, those skilled in the art will understand that the following embodiments are used only to illustrate the present invention and should not be construed as limiting the scope of the present invention.

If specific conditions are not specified in the embodiments, the conditions should be carried out in accordance with the usual conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, all of them are common products that can be purchased commercially.

Implementation option 1

In a 50 ml high-pressure reaction kettle, 10 ml of a toluene solution containing 0.25 wt % CAAC (C2C2)-IrCl are added. After replacing hydrogen three times, 3 bar of propylene, 8 bar of carbon monoxide and 8 bar of hydrogen are successively added and the temperature is increased to 90°C with stirring. The reaction is stirred at this temperature for 8 hours and the reaction solution is cooled to 0°C. After slowly releasing the pressure, samples are taken for gas chromatographic analysis. The results show that the conversion of propylene is 92.1%, and the selectivity for n-butyraldehyde and isobutyraldehyde is 99.9% (n-butyraldehyde: isobutyraldehyde=3.3:1). The confirmed hydrogen nuclear magnetic resonance spectrum diagram and the carbon nuclear magnetic resonance spectrum diagram of the catalyst used in a specific embodiment are shown in Fig. 1 to Fig. 2.

Implementation options 2-7

The method of the propylene hydroformylation reaction according to embodiment 1 is used by changing the coordination anion of the ions CAAC(C2C2)-Ir-X, and the results are shown in Table 2.

Implementation options 8-12

The propylene hydroformylation reaction method of Embodiment 1 is used by changing different temperatures to carry out the reaction, and the results are shown in Table 3.

Implementation options 13-16

The propylene hydroformylation reaction method of Embodiment 1 is used by changing the gas pressure, and the results are shown in Table 4.

As can be seen from the above tables, when using the iridium catalyst for the catalytic reaction, even under the conditions of low temperature and low pressure, it still has good reaction selectivity and good reaction conversion rate. Therefore, the present invention uses a new catalyst to carry out the catalytic reaction and investigates the reaction conditions, thereby realizing the reaction under the conditions of low energy consumption and high reaction efficiency.

Finally, it should be noted that the above embodiments are used only to illustrate the technical schemes of the present invention, and not to limit the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical schemes recorded in the above embodiments or make equivalent substitutions of some or all of the technical features. However, these modifications or substitutions do not cause the essence of the corresponding technical scheme to go beyond the technical scheme of each embodiment of the present invention.

Claims (11)

1. A method for catalyzing the carbonylation of olefins, comprising the following stages: the use of cyclic alkylcarbene-iridium as a catalyst and olefin as a feedstock for the carbonylation reaction to form aldehydes, as well as a reaction solvent, wherein the structural formula of cyclic alkylcarbene-iridium is as follows: ; where 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 high carbon olefins. 2. The method of catalyzing the carbonylation of olefins according to claim 1, wherein the reaction solvent comprises a mixture of one or more of n-butyraldehyde, isobutyraldehyde, toluene, benzene and tetrahydrofuran. 3. The method for catalyzing the carbonylation of olefins according to claim 2, wherein the catalyst dosage is 0.005-2 wt.% of the reaction solvent dosage, preferably 0.05-1 wt.%. 4. The method for catalyzing the carbonylation of olefins according to claim 1, wherein the olefin is propylene and the other feedstocks include carbon monoxide and hydrogen, and the total reaction pressure is from 0.5 to 5.0 MPa, preferably from 1.0 to 3.0 MPa. 5. The method for catalyzing the carbonylation of olefins according to claim 4, wherein the ratio of the partial pressure of propylene to carbon monoxide is between 1:1-1:10, preferably between 1:2-1:5. 6. The method for catalyzing the carbonylation of olefins according to claim 4, wherein the ratio of the partial pressure of propylene to hydrogen is between 1:1-1:10, preferably between 1:2-1:5. 7. The method for catalyzing the carbonylation of olefins according to claim 4, wherein the reaction temperature is from 60 to 180°C, preferably from 80 to 140°C.