A process for the synthesis of olefin carbonyls

Abstract

The application belongs to the technical field of organic chemical industry, and particularly relates to an olefin carbonyl synthesis method, which comprises the following steps: dissolving a rhodium catalyst, an organic phosphine ligand, an olefin and a formaldehyde solution in a solvent to construct a homogeneous catalytic system, and preparing an aldehyde product under certain reaction conditions; wherein the rhodium catalyst comprises acetylacetone dicarbonyl rhodium and cyclooctadiene chlororhodium dimer, and the ligand comprises a bisphosphite ligand or a combination of the bisphosphite ligand and a monodentate / bidentate phosphine ligand. The application solves the problems of storage and transportation danger, high energy consumption and high-pressure reaction caused by the use of synthesis gas in the existing olefin hydroformylation, and achieves the technical effects of mild reaction conditions, wide reaction substrate range and suitability for various low and high carbon olefins.

Description

Technical Field

[0001] This invention relates to the technical field of organic chemical engineering, and in particular to a method for synthesizing olefin carbonyl groups. Background Technology

[0002] Hydroformylation is one of the most industrially valuable carbonyl synthesis reactions in the field of homogeneous catalysis, widely used to synthesize high-value-added oxygen-containing compounds such as aldehydes, alcohols, acids, and esters. Since its initial discovery, several commercial processes have been developed, such as the BASF-Oxo process, the Shell process, the LPOxo process, and the Ruhrchemie / Rhône-Poulenc (RCH / RP) process. These processes mainly employ cobalt or rhodium-based catalysts; the former requires operation under high temperature and pressure, while the latter can achieve high activity and high selectivity under milder conditions.

[0003] The hydroformylation of olefins is of great industrial significance, as its products can be used to synthesize plasticizers, surfactants, and other products. Traditional hydroformylation reactions rely on syngas (CO / H2) as the carbonyl source. Existing technology CN114436791B discloses a method for producing high-carbon aldehydes using a multi-ligand composite catalyst. This method uses syngas as the carbonyl source and requires pressures of 1 MPa or higher, but its optimization of the selectivity and N / I ratio of high-carbon olefin products is not significant. Furthermore, syngas is typically derived from natural gas reforming or coal gasification, posing storage and transportation risks and high energy consumption problems.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] One of the objectives of this invention is to provide a method for the hydroformylation of olefins that can solve the problems of storage and transportation hazards, high energy consumption, and high-pressure reactions caused by the use of syngas in existing hydroformylation methods for olefins.

[0006] The second objective of this invention is to provide a method for hydroformylation of olefins using syngas as a substitute.

[0007] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted: In a first aspect, a method for hydroformylation of an olefin includes the following steps: A homogeneous catalytic system was obtained by mixing a rhodium catalyst, a ligand, an olefin, and formaldehyde in a solvent. The rhodium catalyst includes rhodium acetylacetone dicarbonyl, rhodium chloride dimer of cyclooctadiene, or other rhodium catalysts; The ligands include bisphosphite ligands, or combinations of bisphosphite ligands and monodentate / bidate phosphine ligands; The homogeneous catalytic system was reacted to obtain an aldehyde.

[0008] Furthermore, the bisphosphite ligand comprises any one of the following structures: and ; R1, R2, R3 and R4 are each independently selected from hydrogen, tert-butyl and / or alkoxy.

[0009] Furthermore, the monodentate phosphine ligand or bidentate phosphine ligand comprises any one of the following structures: , , , , , .

[0010] Furthermore, the olefin has the following structure: ; R3 and R4 are both independently selected from hydrogen and / or alkyl groups.

[0011] Furthermore, the molar ratio of the olefin to formaldehyde is 1:(1-10), preferably 1:(4-6).

[0012] Furthermore, the molar ratio of the rhodium catalyst to the ligand is 1:(1-20), preferably 1:(5-15).

[0013] Furthermore, the concentration of rhodium in the homogeneous catalytic system is 50ppm-500ppm, preferably 200ppm-400ppm.

[0014] Furthermore, the solvent of the homogeneous catalytic system includes at least one of benzene, toluene, xylene, and aldehyde compounds.

[0015] Furthermore, the reaction temperature of the homogeneous catalytic system is 60℃-130℃, preferably 80℃-100℃; Preferably, the formaldehyde includes at least one of aqueous formaldehyde solution, anhydrous formaldehyde solution, paraformaldehyde, and formaldehyde solution obtained by depolymerization of trioxymethylene or paraformaldehyde or by other means. Preferably, the reaction time of the homogeneous catalytic system is 1h-20h.

[0016] Secondly, the application of any of the methods described above in aldehyde production.

[0017] Compared with the prior art, the present invention has at least the following beneficial effects: The olefin hydroformylation method provided by this invention uses formaldehyde as the carbonyl source to replace syngas (CO / H2), with mild reaction conditions and a wide range of reaction substrates, applicable to a variety of low and high carbon olefins. It avoids the risks of high-pressure CO processes, as well as CO leakage and transportation issues. It solves the problems of storage and transportation hazards, high energy consumption, and high-pressure reactions associated with the use of syngas in existing olefin hydroformylation methods. It also provides opportunities for companies that do not have syngas resources but have olefin resources, and has good industrial promotion value. Detailed Implementation

[0018] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] According to a first aspect of the present invention, a method for hydroformylation of an olefin is provided, comprising the following steps: A homogeneous catalytic system was obtained by mixing a rhodium catalyst, a ligand, an olefin, and formaldehyde in a solvent. The rhodium catalyst includes rhodium acetylacetone dicarbonyl, rhodium chloride dimer of cyclooctadiene, or other rhodium catalysts; The ligands include bisphosphite ligands, or combinations of bisphosphite ligands and monodentate / bidate phosphine ligands; The homogeneous catalytic system was reacted to obtain aldehydes.

[0020] This invention uses formaldehyde as the carbonyl source to replace syngas (CO / H2), resulting in mild reaction conditions and a wide range of reaction substrates, applicable to a variety of low and high carbon olefins. It avoids the risks of high-pressure CO processes, as well as CO leakage and transportation issues, and solves the problems of storage and transportation hazards, high energy consumption, and high-pressure reactions associated with the use of syngas in existing olefin hydroformylation processes.

[0021] In this invention, a homogeneous catalytic system is obtained by dissolving a rhodium catalyst, ligands, olefins, and formaldehyde in a degassed solvent. By adjusting the type of rhodium catalyst, the ratio of monodentate and bidentate phosphine ligands to diphosphite ligands, the ratio of catalyst to ligands, the reaction temperature, and the reaction time, a suitable homogeneous catalytic system is obtained, thereby producing the corresponding aldehyde product.

[0022] The bisphosphite ligand can be selected from any of the following structures: and ; R1, R2, R3 and R4 can each be independently selected from hydrogen, tert-butyl and / or alkoxy.

[0023] Monodentate or bidentate phosphine ligands can be selected from any of the following structures: , , , , , .

[0024] In a preferred embodiment, the molar ratio of rhodium catalyst to ligand can be 1:(1-20), and more preferably 1:(5-15), wherein the molar amount of rhodium catalyst is expressed in terms of the amount of metal atoms.

[0025] In a preferred embodiment, the concentration of rhodium in the homogeneous catalytic system can be 50ppm-500ppm, and more preferably 200ppm-400ppm.

[0026] The method of this invention, with the combination of a specific rhodium catalyst, a bisphosphite ligand, a monodentate phosphine ligand, and a bidentate phosphine ligand in a specific ratio, can effectively activate formaldehyde to participate in the hydroformylation reaction of olefins, which is beneficial to achieving efficient hydroformylation of olefins under mild reaction conditions.

[0027] In a preferred embodiment, the reaction temperature of the homogeneous catalytic system can be 60℃-130℃, and more preferably 80℃-100℃.

[0028] In a preferred embodiment, the solvent used in the homogeneous catalytic system includes, but is not limited to, at least one of benzene, toluene, xylene, and aldehyde compounds.

[0029] In this invention, the high carbon olefin does not require additional pressure; the molar ratio of olefin to formaldehyde can be 1:(1-10), and is more preferably 1:(4-6).

[0030] Formaldehyde can be obtained in the formaldehyde aqueous solution, anhydrous formaldehyde solution, paraformaldehyde, or formaldehyde solution obtained by depolymerization of triformaldehyde or paraformaldehyde, or by other means.

[0031] In this invention, olefins can have the following structures: ; R3 and R4 can each be independently selected from hydrogen and / or alkyl groups.

[0032] In a preferred embodiment, the reaction time of the homogeneous catalytic system can be 1h-20h. When high carbon olefins are used as substrates, the reaction time of the catalytic system can be further preferably 10h-15h. When low carbon olefins are used as substrates, the reaction time of the catalytic system can be further preferably 4h-8h.

[0033] According to a second aspect of the present invention, there is provided an application of the method described in any of the above-mentioned methods in aldehyde production.

[0034] The present invention will be further illustrated by the following examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or purchased directly from the market.

[0035] Example 1 A method for hydroformylation of an olefin includes the following steps: 10 mmol of 1-decene was dissolved in 60 mL of toluene, degassed by sonication for 10 minutes, and then transferred to a Schlenk flask. Weigh 0.2 mol% of rhodium dicarbonyl acetylacetone and 2 mol% of bisphosphite ligand (structural formula shown in L1, where R1 and R2 are both tert-butyl) and dissolve them in the above solution. Then add 4 mL of 37% formalin solution. Use nitrogen to purge and purge the Schlenk flask three times to replace the air. Then stir the reaction at 90 °C for 12 hours. (L1); After the reaction was completed, samples were taken and analyzed by gas chromatography (GC): the conversion rate of 1-decene was 100%, the total yield of undecaldehyde was 61.57%, of which the yield of n-undecaldehyde was 56.47%, the yield of 2-methyldecaldehyde was 5.1%, the ratio of n-to-iso-decaldehyde was 11.07, and the yield of iso-olefins was 38.34%.

[0036] Example 2 A method for hydroformylation of an olefin includes the following steps: 10 mmol of 1-decene was dissolved in 60 mL of toluene, degassed by sonication for 10 minutes, and then transferred to a Schlenk flask. Weigh 0.2 mol% of rhodium dicarbonyl acetylacetone, 2 mol% of bisphosphite ligand (structural formula shown in L1, where R1 and R2 are both tert-butyl) and 2 mol% of Biphep (structural formula shown below) and dissolve them in the above solution. Then add 4 mL of 37% formalin solution. Use nitrogen to purge and purge the Schlenk flask three times to replace the air. Then stir the reaction at 90 °C for 12 hours. (L1); (Biphep); After the reaction was completed, samples were taken and analyzed by gas chromatography (GC): the conversion rate of 1-decene was 100%, the total yield of undecaldehyde was 83.46%, of which the yield of n-undecaldehyde was 78.5%, the yield of 2-methyldecaldehyde was 4.96%, the ratio of n-to-iso-decaldehyde was 15.8, and the yield of iso-olefins was 16.54%.

[0037] Example 3 A method for hydroformylation of an olefin includes the following steps: 10 mmol of 1-decene was dissolved in 60 mL of toluene, degassed by sonication for 10 minutes, and then transferred to a Schlenk flask. Weigh out 0.2 mol% of rhodium dicarbonyl acetylacetone, 2 mol% of bisphosphite ligand (structural formula shown in L1, where R1 and R2 are both tert-butyl) and 2 mol% of Xantphos (structural formula shown below) and dissolve them in the above solution. Then add 4 mL of 37% formalin solution. Use nitrogen to purge and purge the Schlenk flask three times to replace the air. Then stir the reaction at 90 °C for 12 hours. (L1); (Xantphos); After the reaction was completed, samples were taken and analyzed by gas chromatography (GC): the conversion rate of 1-decene was 100%, the total yield of undecaldehyde was 72.46%, of which the yield of n-undecaldehyde was 66.57%, the yield of 2-methyldecaldehyde was 5.89%, the ratio of n-to-iso-decaldehyde was 11.3, and the yield of iso-olefins was 28.54%.

[0038] Example 4 A method for hydroformylation of an olefin includes the following steps: 10 mmol of 1-decene was dissolved in 60 mL of toluene, degassed by sonication for 10 minutes, and then transferred to a Schlenk flask. Weigh 0.1 mol% of cyclooctadiene rhodium chloride dimer, 2 mol% of Biphep (structural formula below) and 2 mol% of Xantphos (structural formula below) and dissolve them in the above solution. Then add 4 mL of 37% formalin solution. Use nitrogen to purge and purge the Schlenk flask three times to replace the air. Then stir the reaction at 90 °C for 12 hours. (Biphep); (Xantphos); After the reaction was completed, samples were taken and analyzed by gas chromatography (GC): the conversion rate of 1-decene was 100%, the total yield of undecane was 46.29%, of which the yield of n-undecane was 43.32%, the yield of 2-methyldecane was 2.97%, the ratio of n-to-iso was 14.59, and the yield of isomeric olefins was 53.71%.

[0039] Example 5 A method for hydroformylation of an olefin includes the following steps: 10 mmol of 1-octene was dissolved in 60 mL of toluene, degassed by sonication for 10 minutes, and then transferred to a Schlenk flask. Weigh 0.2 mol% of rhodium dicarbonyl acetylacetone, 2 mol% of bisphosphite ligand (structural formula shown in L1, where R1 and R2 are both tert-butyl) and 2 mol% of Biphep (structural formula shown below) and dissolve them in the above solution. Then add 4 mL of 37% formalin solution. Use nitrogen to purge and purge the Schlenk flask three times to replace the air. Then stir the reaction at 90 °C for 12 hours. (L1); (Biphep); After the reaction was completed, samples were taken and analyzed by gas chromatography (GC): the conversion rate of 1-octene was 100%, the total yield of nonanal was 51.04%, of which the yield of n-nonanal was 45.97%, the yield of 2-methyloctaldehyde was 5.07%, the n-to-iso ratio was 9.07, the yield of 2-octene (including cis and trans) was 14.14%, and the yield of 3-octene (including cis and trans) was 34.92%.

[0040] Example 6 A method for hydroformylation of an olefin includes the following steps: 10 mmol of 1-octene was dissolved in 60 mL of toluene, degassed by sonication for 10 minutes, and then transferred to a Schlenk flask. Weigh out 0.2 mol% of rhodium dicarbonyl acetylacetone, 2 mol% of bisphosphite ligand (structural formula shown in L1, where R1 and R2 are both tert-butyl) and 2 mol% of BINAP (structural formula shown below) and dissolve them in the above solution. Then add 4 mL of 37% formalin solution. Use nitrogen to purge and purge the Schlenk flask three times to replace the air. Then stir the reaction at 90 °C for 12 hours. (L1); (BINAP); After the reaction was completed, samples were taken and analyzed by gas chromatography (GC): the conversion rate of 1-octene was 100%, the total yield of nonanal was 14.28%, of which the yield of n-nonanal was 12.32%, the yield of 2-methyloctaldehyde was 1.96%, the n-to-iso ratio was 9.07, the yield of 2-octene (including cis and trans) was 32.59%, and the yield of 3-octene (including cis and trans) was 53.13%.

[0041] Example 7 A method for hydroformylation of an olefin includes the following steps: 0.2 mol% of rhodium dicarbonyl acetylacetone, 2 mol% of bisphosphite ligand (structural formula shown in L1, where R1 and R2 are both tert-butyl) and 2 mol% of Biphep (structural formula shown below) were dissolved in toluene solution, and then 4 mL of 37% formalin solution was added. After purging with nitrogen three times to ensure that the reaction vessel was under a nitrogen atmosphere, 10 mmol (560 mg) of 1-butene was added to the reaction vessel, and the reaction was stirred at 90 °C for 6 hours. (L1); (Biphep); After the reaction was completed, samples were taken and analyzed by gas chromatography (GC): the conversion rate of 1-butene was 100%, the total yield of pentanal was 90.2%, of which the yield of n-pentanal was 85.1%, the yield of isovaleral was 5.1%, and the ratio of n-pentanal to isovaleral was 16.8.

[0042] Example 8 The only difference between this embodiment and Example 1 is that cyclooctadiene rhodium chloride dimer is used instead of acetylacetone dicarbonyl rhodium. Everything else is the same as in Example 1; After the reaction was completed, samples were taken and analyzed by gas chromatography (GC): the conversion rate of 1-decene was 100%, the total yield of undecaldehyde was 56.48%, of which the yield of n-undecaldehyde was 51.96%, the yield of 2-methyldecaldehyde was 4.52%, the ratio of n-to-iso was 11.5, and the yield of isoolefins was 43.52%.

[0043] Example 9 The only difference between this embodiment and Example 1 is that R1 and R2 in the structural formula L1 of the bisphosphite ligand used are both methoxy groups; Everything else is the same as in Example 1; After the reaction was completed, samples were taken and analyzed by gas chromatography (GC): the conversion rate of 1-decene was 100%, the total yield of undecaldehyde was 72.45%, of which the yield of n-undecaldehyde was 65.8%, the yield of 2-methyldecaldehyde was 6.65%, the ratio of n-to-iso-decaldehyde was 9.89, and the yield of iso-olefins was 27.55%.

[0044] Example 10 The only difference between this embodiment and Example 1 is that the structural formula of the bisphosphite ligand used is shown in L2, where R3 and R4 are both tert-butyl groups; (L2); Everything else is the same as in Example 1; After the reaction was completed, samples were taken and analyzed by gas chromatography (GC): the conversion rate of 1-decene was 100%, the total yield of undecaldehyde was 59.8%, of which the yield of n-undecaldehyde was 55.87%, the yield of 2-methyldecaldehyde was 3.93%, the ratio of n-to-iso-decaldehyde was 14.22, and the yield of iso-olefins was 40.2%.

[0045] Example 11 The only difference between this embodiment and Example 2 is that the structural formula of the bisphosphite ligand used is shown in L2, where R3 and R4 are both tert-butyl groups; (L2); Everything else is the same as in Example 1; After the reaction was completed, samples were taken and analyzed by gas chromatography (GC): the conversion rate of 1-decene was 100%, the total yield of undecaldehyde was 78.49%, of which the yield of n-undecaldehyde was 73.6%, the yield of 2-methyldecaldehyde was 4.89%, the ratio of n-to-iso-decaldehyde was 15.05, and the yield of iso-olefins was 21.51%.

[0046] Comparative Example 1 The only difference between this comparative example and Example 1 is that no bisphosphite ligand was added; otherwise, they are the same as in Example 1, and no aldehyde product was obtained from the reaction.

[0047] In summary, this invention uses formaldehyde as the carbonyl source to replace syngas (CO / H2). With the specific combination of a rhodium catalyst, bisphosphite ligands, monodentate phosphine ligands, and bidentate phosphine ligands in specific proportions, the reaction conditions are mild, the reaction substrate range is broad, and it is applicable to a variety of low and high carbon olefins. It avoids the risks of high-pressure CO processes, as well as CO leakage and transportation issues. It solves the problems of storage and transportation hazards, high energy consumption, and high-pressure reactions associated with the use of syngas in the hydroformylation of olefins. It also provides opportunities for companies that do not have syngas resources but have olefin resources, and has good industrial promotion value.

[0048] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for hydroformylation of olefins, characterized in that, Includes the following steps: A homogeneous catalytic system was obtained by mixing a rhodium catalyst, a ligand, an olefin, and formaldehyde in a solvent. The rhodium catalyst includes rhodium acetylacetone dicarbonyl, rhodium chloride dimer of cyclooctadiene, or other rhodium catalysts; The ligands include bisphosphite ligands, or combinations of bisphosphite ligands and monodentate / bidate phosphine ligands; The homogeneous catalytic system was reacted to obtain an aldehyde.

2. The method according to claim 1, characterized in that, The bisphosphite ligand comprises any one of the following structures: and ; R1, R2, R3 and R4 are each independently selected from hydrogen, tert-butyl and / or alkoxy.

3. The method according to claim 1, characterized in that, The monodentate phosphine ligand or bidentate phosphine ligand comprises any one of the following structures: 、 、 、 、 、 。 4. The method according to claim 1, characterized in that, The olefin has the following structure: ； R3 and R4 are both independently selected from hydrogen and / or alkyl groups.

5. The method according to any one of claims 1-4, characterized in that, The molar ratio of the olefin to formaldehyde is 1:(1-10), preferably 1:(4-6).

6. The method according to any one of claims 1-4, characterized in that, The molar ratio of the rhodium catalyst to the ligand is 1:(1-20), preferably 1:(5-15).

7. The method according to any one of claims 1-4, characterized in that, The concentration of rhodium in the homogeneous catalytic system is 50ppm-500ppm, preferably 200ppm-400ppm.

8. The method according to claim 7, characterized in that, The solvent of the homogeneous catalytic system includes at least one of benzene, toluene, xylene, and aldehyde compounds.

9. The method according to claim 8, characterized in that, The reaction temperature of the homogeneous catalytic system is 60℃-130℃, preferably 80℃-100℃; Preferably, the formaldehyde includes at least one of aqueous formaldehyde solution, anhydrous formaldehyde solution, paraformaldehyde, and formaldehyde solution obtained by depolymerization of trioxymethylene or paraformaldehyde or by other means. Preferably, the reaction time of the homogeneous catalytic system is 1h-20h.

10. The application of the method according to any one of claims 1-9 in aldehyde production.

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