Mixture of two structural isomer bisphosphites

Abstract

To provide a mixture with which an increased yield can be achieved in the hydroformylation of olefins, and a method of hydroformylation.SOLUTION: There is provided a method for hydroformylating an olefin to an aldehyde, which comprises using a catalyst obtained from a mixture of the following formula compound (1a) and its structural isomer bisphosphite compound as well as Rh compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a mixture of two structural isomer bisphosphites and its use in hydroformylation.

Background Art

[0002] EP 2906572 describes a mixture (2a + 2b) of structural isomer bisphosphites.

[0003]

Chemical formula

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The technical object of the present invention is to provide a mixture capable of achieving an increase in yield in the hydroformylation of olefins.

Means for Solving the Problems

[0006] This object is achieved by the mixture according to claim 1.

[0007] A mixture comprising compound (1a) and compound (1b).

[0008]

Chemical formula

[0009] In addition to the mixture itself, a method of using the mixture is also claimed.

[0010] (a) A step of first adding an olefin; (b) A step of adding the above mixture; (c) A step of adding a Rh compound; (d) A step of supplying H2 and CO; (e) A step of heating the reaction mixture from steps (a) to (d) to convert the olefin to an aldehyde. A method comprising:

[0011] In one variation of this method, the olefin in step (a) is selected from ethene, propene, 1-butene, cis- and / or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and / or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, or a mixture thereof.

[0012] In one variation of this method, the Rh compound is selected from Rh(acac)(CO)2, [(acac)Rh(COD)] (Umicore, acac = acetylacetonate anion, COD = 1,5-cyclooctadiene), Rh4CO 12 and the like.

[0013] In one variation of this method, the Rh compound is Rh(acac)(CO)2.

[0014] In one variation of this method, the H2 and CO in step (d) are supplied at a pressure in the range of 1 to 6 MPa (10 to 60 bar).

[0015] In one variation of this method, the heating of the reaction mixture in step (e) is carried out at a temperature in the range of 80°C to 160°C.

[0016] Hereinafter, the present invention will be described in more detail with reference to examples.

Examples

[0017] Catalyst experiment Hydroformylation was carried out in a 16 mL autoclave manufactured by HEL Group (Hertfordshire, UK) equipped with a constant pressure device, a gas flow meter and a sparging stirrer. The substrate (1-octene) was heated on sodium under reflux for several hours and distilled under argon.

[0018] The reaction solution for the experiment was prepared in advance under an argon atmosphere. For this purpose, 100 ppm of Rh(acac)(CO)2 and the corresponding amount of phosphite compound (L:Rh = 50:1) were weighed and prepared with 8.0 ml of toluene. The mass of toluene introduced in each case was measured by GC analysis. Then, 1.80 g of 1-octene (16 mmol) was added. Then, the prepared solution was introduced into the autoclave, and the autoclave was purged three times with argon and three times with synthesis gas (Linde, H2(99.999%):CO(99.997%) = 1:1). Then, the autoclave was heated to the desired temperature at a total pressure of 10 bar while stirring (900 rpm). When the reaction temperature was reached, the synthesis gas pressure was increased to 17 bar, and the reaction was carried out at a constant pressure for 1 hour. After the reaction time had elapsed, the autoclave was cooled to room temperature, depressurized while stirring, and purged with argon. After the reaction was completed, 0.5 mL of each reaction mixture was taken out, diluted with 4 mL of pentane, and analyzed by gas chromatography (HP5890 series II plus, PONA method, 50 m × 0.2 mm × 0.5 μm). Residual olefins and aldehydes were quantitatively measured using solvent toluene as an internal standard.

[0019] Experiments were carried out using the mixture (1a + 1b) and the mixture (2a + 2b). The mixture (2a + 2b) functions as a comparative example.

[0020] Results of the catalyst experiment Humidity [Rh]: 100 ppm, Pressure (p): 17 bar, Temperature (T): 120 °C, Time (t): 1 hour Table: Hydroformylation of 1-octene

[0021]

Table 1

[0022] The experiments conducted demonstrate that the given objective is achieved by the mixture of the present invention.

Claims

1. Compound (1a): 【Chemical 1】 and compound (1b): [Chemical Formula 2] A mixture containing the same.

2. (a) A step of first adding an olefin; (b) A step of adding the mixture according to Claim 1; (c) A step of adding a Rh compound; (d) H 2 and a step of supplying CO (e) A step of heating the reaction mixture from the above step (a) to the above step (d) to convert the olefin into an aldehyde. A method comprising the same.

3. The olefin in the above step (a) is selected from ethene, propene, 1-butene, cis- and / or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and / or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, or a mixture thereof. The method according to Claim 2.

4. The Rh compound is Rh(acac)(CO) 2 , [(acac)Rh(COD)] (acac = acetylacetonate anion; COD = 1,5-cyclooctadiene), Rh 4 CO 12 The method according to claim 2, selected from

5. The Rh compound is Rh(acac)(CO) 2 The method according to claim 2, wherein it is such.

6. The H of the step (d) 2 and CO are supplied at a pressure in the range of 1 to 6 MPa (10 to 60 bar), the method according to claim 2.

7. The heating of the reaction mixture in the above step (e) is carried out at a temperature in the range of 80°C to 160°C. The method according to Claim 2.

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