A kind of preparation method of isomeric tridecanol

Abstract

The present invention relates to the technical field of C07F9 / 50, and more specifically to a method for preparing isotridecyl alcohol, comprising: isododecene is subjected to a hydroformylation reaction using a liquid-liquid two-phase catalytic system consisting of an ionic liquid phase and an organic solvent phase, and then subjected to extraction and hydrogenation to obtain the isododecyl alcohol. The present application uses a liquid-liquid two-phase reaction system, has a simple and efficient reaction process, has a good stability effect of catalyst recycling, is suitable for the preparation of higher alcohols such as isotridecyl alcohol, and has good industrialization prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of C07F9 / 50, and more specifically to a method for preparing isomeric tridecanol. Background Art

[0002] As a special type of isomeric alcohol, isomeric tridecanol is mainly used to react with ethylene oxide to synthesize isomeric alcohol polyoxyethylene ether as a special surfactant product. As a new generation of green surfactant, it is the most ideal product to replace alkylphenol ethers due to its extremely low pour point, no gelation at high concentration, excellent wettability and degreasing and oil removal ability. It has been widely used in the field of textile auxiliaries, and has very good application prospects in the field of daily chemicals, especially super-concentrated laundry detergents, as well as metal processing and industrial cleaning. At present, isomeric tridecanol products cannot be obtained from the hydrogenation process of natural oils and fats, and are prepared by high-pressure hydroformylation process in industry. However, the high-pressure method has large investment and high process risk. The low-pressure rhodium process developed by Johnson David has achieved great success in the field of short-chain olefin hydroformylation, especially butyl octanol, but it cannot solve the problem of homogeneous rhodium separation and deactivation in the field of long-chain olefin hydroformylation, making rhodium catalysts unable to be used on a large scale in the industrial field of high-chain olefin hydroformylation. Summary of the invention

[0003] In view of some problems existing in the prior art, the first aspect of the present invention provides a method for preparing isotridecyl alcohol, comprising: carrying out a hydroformylation reaction of isododecene using a liquid-liquid two-phase catalytic system consisting of an ionic liquid phase and an organic solvent phase, and then extracting and hydrogenating to obtain isotridecyl alcohol.

[0004] In one embodiment, the ionic liquid phase comprises an ionic liquid, an organic phosphine ligand containing an imidazolium salt, and a rhodium catalyst.

[0005] The ionic liquids described in the present application include but are not limited to ionic liquids such as imidazoles, pyridines, piperidines, guanidine salts, and quaternary ammonium salts. Specifically, 1-hexyl-3-methylimidazolium hexafluorophosphate, N-octylpyridinium bromide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-dodecyl-3-methylimidazolium bromide, N-hexylpyridinium hexafluorophosphate, etc. can be listed.

[0006] In one embodiment, the structure of the imidazolium salt-containing organic phosphine ligand is as follows: Where R1, R2, R3, and R4 are independently C 1-12 An alkane group or an alkoxy group.

[0007] In this application, C 1-12Examples of the alkyl group include methyl, ethyl, propyl, butyl, isopropyl, isobutyl and the like.

[0008] Examples of the alkoxy group in the present application include methoxy and ethoxy.

[0009] In one embodiment, the organic phosphine ligand containing imidazolium salt includes but is not limited to the following structure:

[0010] wait.

[0011] The organic phosphine ligand containing imidazolium salt in the present application can be purchased or prepared, and the preparation method thereof can be conventionally selected by those skilled in the art.

[0012] The preparation method of the organic phosphine ligand L1 is as follows:

[0013] Under Ar gas protection, 2.8 g of 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM] PF6 was added to the three-necked flask. - and 60mL of redistilled anhydrous dichloromethane, after cooling to -78°C, 5.5mL of LDA in n-hexane solution (2M) was slowly added to the flask. After keeping warm for 1h, 4.2g of pre-prepared diphenylphosphonium chloride dichloromethane solution (50mL) was slowly added dropwise. After the addition was complete, the mixture was kept warm for 1h, and then the temperature was slowly raised to room temperature to continue the reaction for 6h. After the reaction was completed, 30mL of pure water was added to quench, and then the phases were separated. The upper aqueous phase was extracted twice with 30mL of anhydrous dichloromethane, and the organic phases were combined, dried, and concentrated to obtain a yellow oil. A small amount of n-hexane was added and stirred to precipitate a solid. After filtering, the solid was recrystallized again with a mixed solvent of ethyl acetate and n-hexane to obtain 3.5g of white imidazolium salt-containing phosphine ligand L1 with a yield of about 53%. The reactions involved are

[0014] The preparation method of the organic phosphine ligand L3 is as follows:

[0015] Under the protection of Ar gas, 3.6g of 1,1'-propyl-3,3'-ethylbisimidazole hexafluorophosphate and 60mL of redistilled anhydrous dichloromethane were added to a three-necked flask. After cooling to -78°C, 11mL of LDA in n-hexane (2M) was slowly added to the flask. After the reaction was kept warm for 1h, 8.4g of pre-prepared diphenylphosphonium chloride dichloromethane solution (70mL) was slowly added dropwise. After the addition was complete, the reaction was kept warm for 1h, and then the temperature was slowly raised to room temperature and the reaction was continued for 6h. After the reaction was completed, 50mL of pure water was added to quench, and then the phases were separated. The upper aqueous phase was extracted twice with 40mL of anhydrous dichloromethane, and the organic phases were combined, dried, and concentrated to obtain a yellow oil. After adding a small amount of n-hexane and stirring, a solid precipitated. After filtering, the solid was recrystallized again with a mixed solvent of ethyl acetate and n-hexane to obtain 4.9g of white imidazolium salt-containing phosphine ligand L3, with a yield of about 44%. The reactions involved are

[0016] In one embodiment, the rhodium catalyst includes but is not limited to rhodium chloride, rhodium acetate, acetylacetonato dicarbonyl rhodium, cyclooctadiene rhodium, rhodium octanoate dimer, and the like.

[0017] In one embodiment, the organic solvent is C 6-12 Alkane solvents.

[0018] In this application, C 6-12 Examples of the alkane solvent include hexane, cyclohexane, methylcyclohexane, heptane, octane, nonane, decane, and dodecane.

[0019] In one embodiment, the added amount of the ionic liquid and the organic solvent is (60-80) g:45 mL, preferably 70 g:45 mL.

[0020] In one embodiment, the volume ratio of the organic solvent to isododecene is (1-10):1, preferably 1.3:1.

[0021] In one embodiment, the isododecene and rhodium catalyst are in a ratio of (100-10000):1.

[0022] In one embodiment, the weight ratio of the organic phosphine ligand to the rhodium catalyst is (1-10) g: (30-200) mg.

[0023] In one embodiment, the preparation method of isomeric tridecanol comprises: in a liquid-liquid two-phase catalytic system consisting of an ionic liquid phase and an organic solvent phase, controlling the reaction synthesis gas pressure to 1-20 MPa, the synthesis gas H2 and CO volume ratio to 1: (0.1-10), the reaction temperature to 80-200°C, carrying out a hydroformylation reaction for 1-20 hours, and then separating the catalyst-containing ionic liquid phase and the hydroformylation product after phase separation and extraction, and obtaining the hydroformylation product by hydrogenation and distillation.

[0024] In the present application, the lower layer of ionic liquid containing the catalyst can be continuously circulated after being separated from the product.

[0025] In a preferred embodiment, the preparation method of isomeric tridecanol comprises: in a liquid-liquid two-phase catalytic system consisting of an ionic liquid phase and an organic solvent phase, controlling the reaction synthesis gas pressure to 4-5 MPa, the synthesis gas H2 and CO volume ratio to 1:1, the reaction temperature to 120°C, carrying out a hydroformylation reaction for 6 hours, and then separating the catalyst-containing ionic liquid phase and the hydroformylation product after phase separation and extraction, and hydrogenating the hydroformylation product and distilling it to obtain.

[0026] Preferably, the temperature of the hydrogenation reaction of the hydroformylation product is 80-200°C, more preferably 105°C.

[0027] Preferably, the pressure of the hydrogenation reaction of the hydroformylation product is 1-10 MPa, more preferably 3 MPa.

[0028] Preferably, the hydrogenation reaction time of the hydroformylation product is 1-24 h, more preferably 3 h.

[0029] During the hydrogenation reaction of the hydroformylation product, a commonly used hydrogenation catalyst can be conventionally selected in the art, such as a metal catalyst such as nickel, palladium, ruthenium, copper, etc., and the content thereof can be conventionally selected by those skilled in the art.

[0030] In the prior art, isomeric tridecanol is obtained by hydroformylation of isododecene followed by hydrogenation, according to the following structure of isododecene: As a long carbon chain olefin, the carbon chain structure contains not only terminal olefins but also some internal olefins. The catalytic hydroformylation reaction is difficult, and the industry has long been dominated by high-pressure methods. Due to the high boiling point of the hydroformylation product, deactivation is prone to occur when separating the rhodium catalyst, resulting in an industrial problem that it cannot be recycled for a long time. The present application adopts a liquid-liquid two-phase system, which greatly reduces the reaction pressure, can realize the reaction under medium and low pressure conditions, realizes the multiple recycling of the catalyst, and avoids the phenomenon of catalyst deactivation at high temperature. The catalytic system can effectively catalyze the hydroformylation reaction of isododecene and has good industrial prospects.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] (1) The present application uses a liquid-liquid two-phase reaction system, the reaction process is simple and efficient, the stability effect of the catalyst recycling is good, and it is suitable for the preparation of isomeric tridecanol and other high-carbon alcohols, and has good industrial prospects;

[0033] (2) The present application uses a liquid-liquid two-phase reaction system, which can react under low pressure conditions, solving the high-pressure reaction conditions in the prior art and avoiding the problems of catalyst deactivation and difficulty in circulation;

[0034] (3) The present application adopts a liquid-liquid two-phase reaction system and uses the organic phosphine ligands L3 and / or L4, and the intermediate product has a high content of isomeric tridecaldehyde, which is higher than 60%;

[0035] (4) In the present application, the system obtained by using the ionic liquid of 1-octyl-3-methylimidazolium hexafluorophosphate and / or 1-dodecyl-3-methylimidazolium bromide and the rhodium chloride catalyst has high catalytic efficiency and further improves the content of isomeric tridecaldehyde to above 65%;

[0036] (5) The ionic liquid phase composed of the ligand L3, 1-octyl-3-methylimidazolium hexafluorophosphate and rhodium trichloride in the present application has good recyclability and basically does not reduce the olefin conversion rate and product content. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a gas chromatogram of the product of Example 1 of the present application. DETAILED DESCRIPTION

[0038] The present invention is described below by specific implementation methods, but is not limited to the specific embodiments given below.

[0039] Example

[0040] Example 1

[0041] After adding 70g 1-butyl-3-methylimidazole hexafluorophosphate, 45mL n-heptane, 35mL isododecene, 2.1g phosphine ligand L1 and 40mg Rh(CO)2acac to a 250mL autoclave, the reactor was replaced with Ar for three times, and then evacuated, and synthetic gas (CO:H2=1:1, volume ratio) was introduced to 4MPa, stirring was started, and the temperature began to rise. The temperature in the autoclave rose to 120°C, the pressure was 5.5MPa, the reaction started, the reaction pressure was controlled to be maintained at 5MPa, and the reaction time was 6h. After the reaction was completed, it was cooled to room temperature, and the pressure was released to normal pressure before the autoclave was opened. The reaction liquid in the autoclave was phase-separated, and after the upper organic phase was separated, the lower ionic liquid phase was extracted twice with 50mL n-heptane. After combining the upper organic phases, a reaction liquid containing isomeric tridecanol was obtained. After removing the solvent, gas chromatography (see Figure 1 ) Analysis of isomeric tridecanal content was 47%.

[0042] Example 2

[0043] After adding 70g 1-hexyl-3-methylimidazole hexafluorophosphate, 45mL methylcyclohexane, 35mL isododecene, 4.4g phosphine ligand L2 and 125mg rhodium octanoate to a 250mL autoclave, the reactor was replaced with Ar air three times, and then vacuumed, and synthetic gas (CO:H2=1:1, volume ratio) was introduced to 4MPa, stirring was started, and the temperature began to rise. The temperature in the autoclave rose to 120°C, the pressure was 5.5MPa, the reaction started, the reaction pressure was controlled to be maintained at 5MPa, and the reaction time was 6h. After the reaction was completed, it was cooled to room temperature, and the pressure was released to normal pressure before the autoclave was opened. The reaction liquid in the autoclave was phase-separated, and after separating the upper organic phase, the lower ionic liquid phase was extracted twice with 50mL methylcyclohexane. After combining the upper organic phase, a reaction solution containing isomeric tridecanol was obtained. After removing the solvent, the content of isomeric tridecanal was 52% by gas chromatography analysis.

[0044] Example 3

[0045] After adding 70g 1-hexyl-3-methylimidazole hexafluorophosphate, 45mL dodecane, 35mL isododecene, 5.6g phosphine ligand L3 and 40mg acetylacetone dicarbonyl rhodium to a 250mL autoclave, the reactor was replaced with Ar air three times, and then vacuumed, and synthetic gas (CO:H2=1:1, volume ratio) was introduced to 4MPa, stirring was started, and the temperature began to rise. The temperature in the autoclave rose to 120°C, the pressure was 5.5MPa, the reaction started, the reaction pressure was controlled to be maintained at 5MPa, and the reaction time was 6h. After the reaction was completed, it was cooled to room temperature, and the pressure was released to normal pressure before the autoclave was opened. The reaction liquid in the autoclave was phase-separated, and after separating the upper organic phase, the lower ionic liquid phase was extracted twice with 50mL of dodecane. After combining the upper organic phase, a reaction solution containing isomeric tridecanol was obtained. After removing the solvent, gas chromatography analysis showed that the content of isomeric tridecanal was 67%.

[0046] Example 4

[0047] After adding 70g N-octylpyridinium bromide, 45mL dodecane, 35mL isododecene, 9.1g phosphine ligand L4 and 35mg rhodium trichloride to a 250mL autoclave, the reactor was replaced with Ar air three times, and then vacuumed, and synthetic gas (CO:H2=1:1, volume ratio) was introduced to 4MPa, stirring was started, and the temperature began to rise. The temperature in the autoclave rose to 120°C, the pressure was 5.5MPa, the reaction started, the reaction pressure was controlled to be maintained at 5MPa, and the reaction time was 6h. After the reaction was completed, it was cooled to room temperature, and the pressure was released to normal pressure before the autoclave was opened. The reaction liquid in the autoclave was phase-separated, and after separating the upper organic phase, the lower ionic liquid phase was extracted twice with 50mL of dodecane. After combining the upper organic phase, a reaction solution containing isomeric tridecanol was obtained. After removing the solvent, the content of isomeric tridecanal was 61% by gas chromatography.

[0048] Example 5

[0049] 6 g of Raney nickel catalyst was added to the combined upper organic phase of the hydroformylation reaction of Example 3 magnified 8 times, the reactor was replaced with hydrogen, the reaction temperature was 105° C., the reaction pressure was controlled at 3 MPa, the reaction was completed after 3 h, and after cooling to room temperature, the pressure was released from the reactor. After the reaction liquid was freed from the solvent, 162 g of the product isomeric tridecanol was obtained by distillation, and the yield was 64% and the purity was 99% by gas chromatography.

[0050] Example 6

[0051] The preparation method steps are the same as those of Example 3, except that 1-hexyl-3-methylimidazole hexafluorophosphate is replaced by 1-ethyl-3-methylimidazole hexafluorophosphate, acetylacetonato dicarbonyl rhodium is replaced by rhodium trichloride, and the molar ratio of the organic phosphine ligand and the rhodium catalyst remains unchanged.

[0052] Example 7

[0053] The preparation method steps are the same as those of Example 3, except that 1-hexyl-3-methylimidazole hexafluorophosphate is replaced by 1-butyl-3-methylimidazole hexafluorophosphate, acetylacetonato dicarbonyl rhodium is replaced by rhodium trichloride, and the molar ratio of the organic phosphine ligand and the rhodium catalyst remains unchanged.

[0054] Example 8

[0055] The preparation method and steps are the same as those of Example 3, except that acetylacetonato dicarbonyl rhodium is replaced by rhodium trichloride, and the molar ratio of the organic phosphine ligand and the rhodium catalyst remains unchanged.

[0056] Example 9

[0057] The preparation method steps are the same as those of Example 3, except that 1-hexyl-3-methylimidazole hexafluorophosphate is replaced by 1-octyl-3-methylimidazole hexafluorophosphate, acetylacetonato dicarbonyl rhodium is replaced by rhodium trichloride, and the molar ratio of the organic phosphine ligand and the rhodium catalyst remains unchanged.

[0058] Example 10

[0059] The preparation method steps are the same as those of Example 3, except that 1-hexyl-3-methylimidazolium hexafluorophosphate is replaced by 1-dodecyl-3-methylimidazolium bromide, acetylacetonato dicarbonyl rhodium is replaced by rhodium trichloride, and the molar ratio of the organic phosphine ligand and the rhodium catalyst remains unchanged.

[0060] Embodiment 11

[0061] The preparation method steps are the same as those of Example 3, except that 1-hexyl-3-methylimidazole hexafluorophosphate is replaced by N-hexylpyridinium hexafluorophosphate, acetylacetonato dicarbonyl rhodium is replaced by rhodium trichloride, and the molar ratio of the organic phosphine ligand and the rhodium catalyst remains unchanged.

[0062] After gas chromatography analysis, the proportions of various substances in the reaction products of Examples 6-11 are shown in Table 1.

[0063] Table 1

[0064]

[0065]

[0066] The lower ionic liquid phase of Example 9 was extracted with dodecane and reused, and the content of each substance in the product was recorded by gas chromatography after each reuse, and the conversion rate of isododecene and the content of isomeric tridecaldehyde were calculated. The results are shown in Table 2.

[0067] Table 2

[0068]

[0069] It can be seen from the results in Table 2 that after multiple cycles of use, the conversion rate of isododecene and the yield of isomeric tridecaldehyde are relatively stable and have not decreased significantly.

Claims

1. A method for preparing isomeric tridecanol, characterized in that: include: The preparation method of isomeric tridecanol comprises: in a liquid-liquid two-phase catalytic system consisting of an ionic liquid phase and an organic solvent phase, controlling the reaction synthesis gas pressure to be 4-5 MPa, the synthesis gas H2 and CO volume ratio to be 1:1, the reaction temperature to be 120°C, performing a hydroformylation reaction for 6 hours, and then separating the catalyst-containing ionic liquid phase and the hydroformylation product through phase separation and extraction, and performing a hydrogenation reaction on the hydroformylation product and then distilling to obtain; The ionic liquid phase comprises an ionic liquid, an organic phosphine ligand containing an imidazolium salt, and a catalyst. The organic phosphine ligand containing imidazolium salt is selected from: and / or ; The catalyst is rhodium dicarbonyl acetylacetonate; The ionic liquid is 1-hexyl-3-methylimidazolium hexafluorophosphate; The temperature of the hydrogenation reaction of the hydroformylation product is 80-200°C; The pressure of the hydrogenation reaction of the hydroformylation product is 1-10MPa; The hydrogenation reaction time of the hydroformylation product is 1-24h; The organic solvent is selected from the group consisting of hexane, cyclohexane, methylcyclohexane, heptane, octane, nonane, decane and dodecane.

2. The method for preparing isomeric tridecanol according to claim 1, characterized in that: The added amounts of the ionic liquid and the organic solvent are (60-80) g:45 mL.

3. The method for preparing isomeric tridecanol according to claim 2, characterized in that: The weight ratio of the organic phosphine ligand to the catalyst is (1-10) g: (30-200) mg.

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