CN109433270B - Catalyst for preparing isooctanoic acid by oxidizing isooctaldehyde, preparation method thereof and method for preparing isooctanoic acid - Google Patents
Catalyst for preparing isooctanoic acid by oxidizing isooctaldehyde, preparation method thereof and method for preparing isooctanoic acid Download PDFInfo
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- CN109433270B CN109433270B CN201811176355.0A CN201811176355A CN109433270B CN 109433270 B CN109433270 B CN 109433270B CN 201811176355 A CN201811176355 A CN 201811176355A CN 109433270 B CN109433270 B CN 109433270B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
Abstract
The invention discloses a catalyst for preparing isooctanoic acid by oxidizing isooctaldehyde, a preparation method thereof and a method for preparing isooctanoic acid. The adopted catalyst is a porphyrin bionic catalyst with a simulated enzyme catalysis function, so that the preparation process is clean and effective; meanwhile, the catalyst is loaded on the magnetic nano structure, and the high specific surface area of the catalyst is favorable for improving the mass transfer process of the substrate. The catalyst has the characteristics of green catalytic performance of simulating biological enzyme and easy separation, recovery and cyclic utilization of magnetic materials. When the method is used for preparing the isooctanoic acid by oxidizing the isooctyl aldehyde, the conversion rate of raw materials and the selectivity of products are obviously improved.
Description
Technical Field
The invention relates to a catalyst for preparing isooctanoic acid by oxidizing isooctylaldehyde, a preparation method thereof and a method for preparing isooctanoic acid by oxidizing isooctylaldehyde.
Technical Field
2-Ethylhexanoic Acid (2-Ethylhexanoic Acid,2-EHA), also known as isooctanoic Acid, is an oily liquid that is slightly soluble in cold water and ethanol, and soluble in hot water and ether. It features high purity and light lustre. Can react with various metal compounds to generate metal salts of isooctanoic acid, and has the following main applications: the paint drying agent, lubricating oil assistant, plastic plasticizer, PVC stabilizer, medical salt forming agent and reaction catalyst assistant.
At present, China is the second largest world paint producing country second to the United states, particularly, high-grade paints are developed rapidly, in addition, the synthetic resin and unsaturated polyester industries of China are developed rapidly, high-grade ink is developed rapidly, isooctanoic acid and salt substances thereof are used more widely in the industries, and the market prospect of isooctanoic acid and isooctanoic acid salt is expected to be very good in the coming years.
The isooctanoic acid industrial synthesis mainly has two routes, one is isooctanol oxidation method, although the method has high selectivity, reliable raw material source and simple operation, the process flow is long, the large-scale production is difficult, and at present, several companies in China adopt the route for production; secondly, n-butyraldehyde is used as a raw material, 2-ethyl hexenal is generated through condensation and dehydration, isooctyl aldehyde (2-ethyl hexanal) is obtained through hydrogenation, and isooctanoic acid is obtained through oxidation. The aldehyde oxidation process has reliable raw material sources, is a continuous and totally-enclosed process, is easy for large-scale production, and is mostly adopted by some major companies in Europe and America.
Patent CN1357527A discloses a method for producing 2-ethyl hexanoic acid, which discloses an optimal reaction temperature of 0-15 ℃ and a maximum selectivity of 94.9%, but the engineering temperature control energy consumption is high, and the industrialization is not ideal. Patent CN1410407A discloses a method for producing 2-ethyl hexanoic acid, which overcomes the disadvantages of the above patent and improves the optimum reaction temperature to 30-50 ℃, and the reaction equipment is changed from a bubble column to a falling film reactor, but the investment cost of industrial production equipment is high, and the selectivity is not obviously improved. Patent CN1422840A discloses a method for producing 2-ethylhexanoic acid, which uses a reaction column, greatly shortens the reaction time, and has a maximum selectivity of 96.8%, but the post-treatment of the catalyst is troublesome. The above 3 patents are all published by the company Qilu petrochemical company, and the catalyst used is Mn (OAc)2Or KOAc or Cu (OAc)2Or NaOAc or a mixture of these four substances in any ratio, the selectivity is not very satisfactory and no work-up of the catalyst is reported.
Patent CN102701944A discloses a method for preparing 2-ethylhexanoic acid by catalyzing and oxidizing 2-ethylhexanal with phosphomolybdovanadate heteropoly acid, wherein the selectivity of 2-ethylhexanoic acid can reach more than 98%, but the preparation of the catalyst needs molybdate, phosphate, metavanadate, concentrated sulfuric acid, hydrochloric acid and the like, the preparation process is complex, the regeneration is difficult, and the method has a long distance from industrial application.
Patent US5739352 discloses a process for preparing carboxylic acids by oxidizing aldehydes with peracids in the presence of amines or amine-N-oxides as catalysts. The catalyst used comprises substituted or unsubstituted alkylamines, alkylamine-N-oxides, or aromatic amines, aromatic amine-N-oxides or mixtures thereof. But has the defects that the boiling point of the catalyst containing the N element is very high, the post-treatment is relatively complex, and the requirement on reaction equipment is relatively high.
In summary, the prior art discloses that the homogeneous catalyst or the technology for preparing isooctanoic acid from isooctylaldehyde is difficult to separate (such as Mn (OAc))2Or KOAc or Cu (OAc)2And the like), or the catalyst preparation process is complicated and has high corrosivity, or the process is complex, the mass transfer effect is poor, the product selectivity is not ideal, and the like.
The catalyst is used for preparing isooctanoic acid by catalytic oxidation of isooctaldehyde, is easy to separate, has high product selectivity, can overcome the difficulty that the catalyst is difficult to separate in homogeneous catalysis in the prior art, and can be recycled.
Disclosure of Invention
The invention aims to provide a novel catalyst for preparing isooctanoic acid by catalytic oxidation of isooctaldehyde and a preparation method thereof, the catalyst is easy to recycle and reuse, and the product selectivity is high.
The invention also provides a method for preparing isooctanoic acid by oxidizing isooctaldehyde, which has clean and mild process conditions, can obtain ideal selectivity and yield, is convenient for separating, recovering and recycling the catalyst and is suitable for industrialization. Compared with the prior art, the method has the advantages of clean and efficient process, easy recovery and reuse of catalysis, and high product selectivity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a catalyst for preparing isooctanoic acid by catalytic oxidation of isooctylaldehyde has a structural general formula as follows:
wherein C represents gamma-AlOOH or Al2O3,R1or-H, R2is-NH-or-CH2-,R3＝-COOMe、-COOH、-NO2or-CONHNH2。
The catalyst structure comprises ferriporphyrin and a magnetic ferroferric oxide nano structure.
The active center of the catalyst is an iron porphyrin ring, the iron porphyrin ring has a large pi electron conjugated ring structure, and when a substituent is introduced onto the porphyrin ring, the potential of central metal ions will change, so that the catalytic activity of the catalyst is regulated. When the benzene ring in the porphyrin ring is provided with an electron-withdrawing group (such as an ester group, a carboxyl group, a nitro group and a formyl hydrazine group), the electron-withdrawing action reduces the electron cloud density of the central metal, namely the strength of the metal-oxygen bond is weakened, so that the oxidation-reduction reaction is easy to occur, namely the activity of the active intermediate is increased, and the catalytic effect of the metalloporphyrin is enhanced.
The ligand coordinated with the metal Fe is imidazole, and can play the following roles: (1) it is also a pi-electron system, which coordinates to the metal ion by a pi bond; (2) the C-H bond on the imidazole ring and the N on the porphyrin ring form a weak hydrogen bond, and the two effects enable the coordination of metal and imidazole to be firmer and the structure to be more stable.
Preferably, when the bridge chain connecting the imidazole and the magnetic material contains both-OH and-NH-, it has an electron conjugation effect and a hydrogen bonding effect. The lone pair electrons on oxygen and nitrogen can generate electron conjugation effect with an imidazole ring pi electron system on a chain, so that the bond energy of coordination with metal is larger, the structure is more stable, and the catalytic performance is higher. Secondly, hydrogen on-OH and-NH-can generate weak hydrogen bond interaction with N on the porphyrin ring, so that the connection between the magnetic nanoparticle structure and the porphyrin ring through a bridge chain is more compact and firm, the two effects cooperate to ensure that the whole structure of the catalyst is more stable, and the activity of the catalyst is better. The presence of-OH and-NH-has a significant catalytic effect on the reaction.
The common material for wrapping the magnetic nano material is SiO2However, the catalyst of the invention uses gamma-AlOOH or Al2O3. Reacting gamma-AlOOH @ Fe3O4Al is formed by high-temperature roasting2O3@Fe3O4. The coating effect of the gamma-AlOOH is better than that of Al2O3Probably because the high-temperature roasting destroys the gamma-AlOOH @ Fe3O4A mesoporous structure in the carrier shell.
In the invention, porphyrin and insoluble magnetic nano material are combined, so that the problems of unstable homogeneous catalysis, easy inactivation, difficult cyclic utilization and the like of porphyrin are solved, the specific surface area is further increased, and the mass transfer effect is promoted. After the reaction is finished, the magnetic nano catalyst is sucked out by a magnet, so that the separation from the solution is easy to realize, and the magnetic nano catalyst is repeatedly used for the next reaction. The catalyst can be synthesized by a conventional chemical method.
A method of preparing the catalyst of the present invention, comprising the steps of:
(1) reacting gamma-AlOOH @ Fe3O4Or Al2O3@Fe3O4With compounds I
The ferroferric oxide nano compound II is prepared by reaction
Wherein C represents gamma-AlOOH or Al2O3，R1or-H, R2is-NH-or-CH2-；
(2) Compound III
Reaction with ferrous chloride to prepare iron porphyrin compound IV
Wherein R is3＝-COOMe、-COOH、-NO2or-CONHNH2；
(3) Ferriporphyrin compound IV and ferriferrous oxideRice compound II
Mixing, washing and vacuum drying to obtain the catalyst
In step (1) of the present invention, when R of compound I1＝-OH、R2When the compound is-NH-, the preparation method comprises the following steps: n- (3-aminopropyl) imidazole and gamma-glycidoxypropyltrimethoxysilane
The molar ratio of the N- (3-aminopropyl) imidazole to the gamma-glycidoxypropyltrimethoxysilane is 1:1.05 to 1.2, preferably 1:1.05 to 1.1.
In step (1) of the present invention, when R of compound I1＝-OH、R2＝-CH2-when the preparation method comprises the following steps: n- (3-chloropropyl) imidazole and gamma-glycidoxypropyltrimethoxysilane
The molar ratio of the N- (3-chloropropyl) imidazole to the gamma-glycidoxypropyltrimethoxysilane is 1: 1.05-1.2.
In step (1) of the present invention, when R of compound I1＝-H、R2When the compound is-NH-, the preparation method comprises the following steps: 3-chloropropyltrimethylsilane reacts with 3-chloropropanol and then reacts with N- (3-aminopropyl) imidazole to prepare the compound
In step (1) of the present invention, when R of compound I1＝-H、R2＝-CH2-when the preparation method comprises the following steps: the N- (1-carboxyl hexyl) imidazole is reduced by boron trifluoride to prepare N- (1-hydroxyl heptyl) imidazole, and the N- (1-hydroxyl heptyl) imidazole reacts with 3-chloropropyltrimethylsilane to prepare the compound
In the step (2) of the present invention, the substituent R3＝-CONHNH2The process for the preparation of compound IV of (a), comprising the steps of: substituent R3Compound III of ═ -COOMe is reacted with hydrazine hydrate and then with ferrous chloride.
In the step (2) of the present invention, the substituent is R3A process for the preparation of compound III ═ COOH, comprising the steps of: the substituent is R3Compound III of-COOMe undergoes a hydrolysis reaction.
In the step (2) of the present invention, the compound III
The molar ratio of the ferrous chloride to the ferrous chloride is 1: 5-7.
In the step (3), the dosage of the ferriporphyrin compound IV and the ferroferric oxide nano compound II is calculated according to the following proportion: 0.15mmol of ferriporphyrin compound IV is mixed with 1-1.5 g of ferroferric oxide nano compound II.
The invention relates to gamma-AlOOH @ Fe3O4The preparation method comprises the following steps: with Fe3O4The nano particles are reacted with aluminum isopropoxide to obtain the nano-particles.
Al according to the invention2O3@Fe3O4The preparation method comprises the following steps: reacting gamma-AlOOH @ Fe3O4Roasting at high temperature to obtain Al2O3@Fe3O4。
A method for preparing isooctanoic acid by oxidizing isooctanal comprises the following steps: isooctyl aldehyde solution is used as raw material, and is oxidized in the presence of oxygen-containing gas under the catalysis of the catalyst to prepare isooctanoic acid.
In the isooctylaldehyde solution of the invention, the concentration of isooctylaldehyde is 25-50 wt%, preferably 35-50 wt%. The solvent of the solution is n-octanoic acid and/or 2-ethylhexanoic acid, preferably 2-ethylhexanoic acid, so that the step of solvent separation can be omitted.
In the method for preparing isooctanoic acid of the present invention, the oxygen-containing gas can be pure oxygen, air, or oxygen-enriched gas composed of inert gas (preferably nitrogen) and oxygen, and air is preferred in view of the requirement of safe tail oxygen concentration of the process.
In the method for producing isooctanoic acid of the present invention, the molar ratio of isooctylaldehyde to oxygen is 1:0.5-1.0, and preferably 1:0.5-0.8 from the viewpoint of tail oxygen concentration and reaction selectivity.
In the preparation method of isooctanoic acid, the mass fraction of the catalyst in the reaction raw material isooctaldehyde is 10-60ppm, preferably 10-50ppm, more preferably 15-25 ppm.
The reaction for preparing the isooctanoic acid by oxidizing the isooctyl aldehyde is exothermic reaction, the temperature cannot be accurately controlled, but in order to reduce the environmental conditions required by the reaction and reduce the cost, the reaction is carried out at normal temperature, the reaction temperature can be controlled to be 10-50 ℃, preferably 20-35 ℃, most preferably 30-35 ℃, and the heat can be taken away by cooling water in a coil outside the device.
In the preparation method of the isooctanoic acid, the reaction time is 3-9h, preferably 6-8 h.
After the reaction for preparing the isooctanoic acid is finished, the catalyst is sucked out and recovered by a magnet, the crude catalyst can be cleaned for 2-3 times by ethanol to remove residual reaction liquid, and the crude catalyst can be reused after being dried.
The technical scheme of the invention has the following beneficial effects: (1) the porphyrin is loaded on the insoluble magnetic nano material, so that the chemical stability of the porphyrin structure can be improved, and the good catalytic effect of the porphyrin structure can be better exerted; (2) the catalyst has a very large specific surface area, the mass transfer effect of materials is improved to a great extent, and the reaction rate is increased; (3) can overcome the defect that porphyrin is not easy to separate and regenerate for homogeneous catalysis.
The liquid-phase oxidation of isooctyl aldehyde is free radical reaction, and the speed-determining step is the dissolution and mass transfer effect of oxygen, namely the higher the concentration of dissolved oxygen in the reaction liquid is, the better the mass transfer effect is, and the better the reaction effect is. The catalyst has extremely high oxygen carrying capacity and extremely large specific surface area, and oxygen is mixed with reactants, so that the mass transfer effect is improved. The process can essentially improve the reaction effect, has high catalytic efficiency, increases the selectivity of the product, has high conversion rate, and can also reach more than 99 percent; the selectivity is high and can reach more than 99 percent. The process reaction conditions are clean and mild, and the three wastes are few.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the scope of the invention.
Fe3O4Nanoparticles were purchased from Beijing Deke island gold technologies, Inc. (average particle size 20 nm);
Gamma-Glycidoxypropyltrimethoxysilane (GTMS) was purchased from shin-Etsu chemical Co., Ltd, under the designation KBM-403, chemically pure;
5,10,15,20- (tetracarboxymethylphenyl) porphyrin, 5,10,15,20- (tetranitrophenyl) porphyrin purchased from carbofuran reagent, chemically pure;
5,10,15,20- (tetramethoxyphenyl) porphyrin was purchased from the Aladdin reagent and was chemically pure.
Gas chromatograph: agilent7890, chromatographic column SH-RTX-WAX, method: temperature programming, tail-blow flow: 30mL/min, hydrogen flow: 40mL/min, air flow: 400mL/min, the split ratio is 30: 1; temperature rising procedure: from 60 ℃ to 80 ℃ at a rate of 20 ℃/min, and then to 250 ℃ over 8min, the total program time: 23.3min, detector temperature: at 260 ℃.
Example 1
5,10,15,20- (Tetracarboxymethylmethylphenyl) porphyrin (2g,2.4mmol) and ferrous chloride tetrahydrate (2.38g, 12mmol) were dissolved in 60mL of DMF solution, refluxed for 12h, and then the DMF was distilled off under reduced pressure. Cooling to room temperature, pouring 60mL of deionized water into the round-bottom flask, stirring for 40min at room temperature, performing suction filtration, repeatedly washing with water for three times, and drying to obtain R3Ferriporphyrin compound IV of-COOMe.
Example 2
Referring to the procedure of example 1, 5,10,15,20- (tetranitrophenyl) porphyrin (1.59g,2mmol) was reacted with ferrous chloride tetrahydrate (1.99g,10mmol) to prepare R3＝-NO2Ferriporphyrin compound IV.
Example 3
5,10,15,20- (Tetracarboxymethylmethylphenyl) porphyrin (2g,2.4mmol) and hydrazine hydrate N2H4·H2O150mL was dissolved in 200mL of DMF, heated to reflux for 10h, cooled to room temperature, and then 300mL of deionized water was added. Stirring at room temperature for 1h, vacuum filtering, repeatedly washing with water for three times, and drying to obtain mauve solid powder R3＝-CONHNH2Compound III of (1). R is to be3＝-CONHNH2The compound III (1.7g,2mmol) and ferrous chloride tetrahydrate (2.78g,14mmol) were dissolved in 50mL DMF, refluxed for 12h, after the reaction was completed, DMF was distilled off under reduced pressure, washed with water three times, the organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain R3＝-CONHNH2Ferriporphyrin compound IV.
Example 4
LiCl (1.3g,31mmol) and R were mixed3Ferriporphyrin compound IV (1.8g, 2mmol) of ═ COOMe was dissolved in 75mL DMSO and 7.5mL H2O, then placing the reaction solution at 160 ℃ for reaction for 24h, after the reaction is finished, extracting the reaction solution by using ethyl acetate and water, then drying the reaction solution by using anhydrous sodium sulfate, decompressing and concentrating the reaction solution, and then carrying out column chromatography to obtain R3-COOH iron porphyrin compound IV.
Example 5
N- (3-aminopropyl) imidazole (1.8g,14.4mmol), NaH (0.36g,15mmol) and 30mL of dry tetrahydrofuran were added sequentially to a 100mL round bottom flask, stirred at room temperature for 2h, gamma-glycidoxypropyltrimethoxysilane (3.6g,15.1mmol) was added dropwise slowly under nitrogen, and the reaction was stirred at 90 ℃ for 20 h. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered, concentrated, and subjected to silica gel column chromatography (petroleum ether/ethyl acetate 3:1) to obtain compound 1.
Example 6
Referring to the procedure of example 5, compound 2 was prepared by reacting the starting compounds N- (3-chloropropyl) imidazole (2.2g,15mmol), NaH (0.36g,15mmol) and gamma-glycidoxypropyltrimethoxysilane (3.7g,15.8mmol)
Example 7
3-chloropropyltrimethylsilane (2g,10mmol) and 3-chloropropanol (1.5g,15.9mmol) are added in sequence to a 100mL round-bottomed flask, 20mg of sodium methoxide is slowly added dropwise to the flask under a nitrogen atmosphere, dried 40mL of tetrahydrofuran is added dropwise to the flask to react for 4 hours at room temperature, after the reaction is finished, the solvent is removed by rotary evaporation under reduced pressure, and silica gel column chromatography (petroleum ether/ethyl acetate: 5:1) is carried out to obtain the compound 3-1.
In a 100mL round bottom flask were added N- (3-aminopropyl) imidazole (1.0g,8mmol), NaH (0.36g,15mmol) and 30mL dry tetrahydrofuran in this order, stirred at room temperature for 2h, slowly added dropwise compound 3-1(2.16g,8.4mmol) under nitrogen, and then stirred at 90 ℃ for 20 h. After completion of the reaction, it was cooled to room temperature, filtered, concentrated, and subjected to silica gel column chromatography (petroleum ether/ethyl acetate 3:1) to obtain compound 3.
Example 8
After the reaction was completed, 3-chloropropyltrimethylsilane (2.3g,11.6mmol) and N- (1-hydroxyheptyl) imidazole (2.0g,11mmol) were added in this order to a 100mL round-bottomed flask, 20mg of sodium methoxide was added, dried 50mL of tetrahydrofuran was slowly dropped in a nitrogen atmosphere, and the mixture was reacted at room temperature for 4 hours, followed by reduced pressure rotary evaporation to remove the solvent, and silica gel column chromatography (petroleum ether/ethyl acetate ═ 5:1) was performed to obtain compound 4.
Example 9
γ-AlOOH@Fe3O4Preparation of
Weighing 5.8g of aluminum isopropoxide, dissolving in absolute ethyl alcohol, stirring at 60 ℃ until the aluminum isopropoxide is completely dissolved, adding 1.0g of Fe3O4Carrying out ultrasonic treatment on nano particles for 30min, then violently stirring for 13h in a constant-temperature water bath at 45 ℃, adding absolute ethyl alcohol-deionized water (5/1, v/v, 50mL) in the stirring process, after uniformly stirring, transferring the suspension in a reaction bottle into a sealed tube, placing the sealed tube into a forced air drying oven, crystallizing for 21h at 80 ℃, after the reaction is finished, transferring the product suspension into a beaker, washing for three times with water and ethanol respectively after magnetic separation, and finally, carrying out vacuum drying on the product for 12h at 50 ℃ to obtain the product gamma-AlOOH @ Fe3O4。
Example 10
Al2O3@Fe3O4Preparation of
The gamma-AlOOH @ Fe is obtained by the preparation method3O4Placing in a high-temperature reaction furnace, roasting and dehydrating for 3h at 600 ℃ in the nitrogen atmosphere, and then naturally cooling to room temperature to obtain Al2O3@Fe3O4。
Example 11
2.0g of gamma-AlOOH @ Fe was added to a 250ml round bottom flask3O4And 100mL of anhydrous toluene, ultrasonically dispersing for 1h, then adding a mixed solution of the compound 1(1.0g,2.8mmol) and 0.5mL of pyridine, refluxing and reacting for 24h under a nitrogen atmosphere, cooling to room temperature after the reaction is finished, separating suspended black powder by using a magnet, washing with toluene and acetone for multiple times, and drying in vacuum at 80 ℃ to obtain a compound 5.
Example 12
With reference to the procedure of example 11, compound 6 was prepared starting from compound 2(970mg, 2.8mmol)
The remaining parameters were the same as in example 11.
Example 13
With reference to the procedure of example 11, compound 7 was prepared starting from compound 3(967mg, 2.8mmol)
The remaining parameters were the same as in example 11.
Example 14
With reference to the procedure of example 11, compound 8 was prepared starting from compound 4(964mg, 2.8mmol)
The remaining parameters were the same as in example 11.
Example 15
With reference to the method of example 11, with Al2O3@Fe3O4Preparation of Compound 9 as starting Material
The remaining parameters were the same as in example 11.
Example 16
Under nitrogen atmosphere, add R to a 100mL round bottom flask3Ferriporphyrin compound IV of-COOMe (270mmg,0.3mmol) and 60mL of deionized water were stirred rapidly at room temperature for 40min, followed by the addition of 2.0g of compound 5 and stirring continued at 30 ℃ for 24 h. After the reaction is finished, the black powder is subjected to magnetic separation, washed by acetone for multiple times and then dried in vacuum to obtain the catalyst 1.
Example 17
With reference to the procedure of example 16, with R3＝-NO2Ferriporphyrin compound IV (255mg, 0.3mmol) was used as a starting material to prepare catalyst 2.
Example 18
With reference to the procedure of example 16, with R3＝-CONHNH2Ferriporphyrin compound IV (270mg, 0.3mmol) was used as a starting material to prepare catalyst 3.
Example 19
With reference to the procedure of example 16, with R3Catalyst 4 was prepared starting from ferriporphyrin compound IV (253mg, 0.3mmol) at-COOH and 2.0g of compound 5.
Example 20
Catalyst 5 was prepared starting from compound 6 by the method of example 16.
Example 21
Catalyst 6 was prepared starting from compound 7 by the method of example 16.
Example 22
Catalyst 7 was prepared starting from compound 8 by the method of example 16.
Example 23
With reference to the procedure of example 16, with compounds 9 and R3＝-NO2Ferriporphyrin compound IV (255mg, 0.3mmol) was used as a starting material to prepare catalyst 8.
The structures of catalysts 1-8 prepared in examples 16-23 are as follows:
example 24
Adding isooctylaldehyde (160g, 1.25mol), solvent 2-ethylhexanoic acid (160g, 1.11mol) and 4mg of catalyst 2 into a dry 1L three-necked bottle, placing in a water bath, mechanically stirring under nitrogen atmosphere, starting to introduce air when the temperature is raised to 30 ℃, keeping the reaction temperature at 30-35 ℃ by adding cooling water into the water bath, reacting for 8 hours, sucking out the catalyst by using a magnet, washing 3 times by using ethanol, drying and recycling for later use. The conversion rate of isooctyl aldehyde is 99.6%, the selectivity of 2-ethyl hexanoic acid is 99.5%, and the yield is 99.1%.
Example 25
Referring to the method of example 24, only the kind of the catalyst was changed and the reaction results are detailed in table 1.
TABLE 1 results of example 25
| Kind of catalyst | Selectivity% | Conversion rate% | Yield% |
| Catalyst 1 | 98.1 | 99.0 | 97.12 |
| Catalyst 3 | 98.2 | 99.1 | 97.31 |
| Catalyst 4 | 98.3 | 99.2 | 97.51 |
| Catalyst 5 | 97.8 | 98.5 | 96.33 |
| Catalyst 6 | 97.6 | 98.9 | 96.52 |
| Catalyst 7 | 97.3 | 98.7 | 96.03 |
| Catalyst 8 | 98.3 | 99.0 | 97.31 |
Example 26
Adding isooctyl aldehyde (80g, 0.62mol) and solvent 2-ethylhexanoic acid 240g and catalyst 2 (12.8 mg) into a dry 1L three-necked bottle, placing the bottle in a water bath, mechanically stirring the bottle under nitrogen atmosphere, starting to introduce air when the temperature is raised to 20 ℃, keeping the reaction temperature at 20-25 ℃ by adding cooling water into the water bath, after 8 hours of reaction, sucking the catalyst out by a magnet, washing the catalyst for 3 times by ethanol, drying and recycling the catalyst for later use, and sampling GC analysis shows that the conversion rate of the isooctyl aldehyde is 99.6%, the selectivity of the 2-ethylhexanoic acid is 98.5%, and the yield is 98.10%.
Example 27
Adding isooctyl aldehyde (80g, 0.62mol) and 240g of 2-ethylhexanoic acid and 19.2mg of catalyst 2 into a dry 1L three-necked bottle, placing the bottle in a water bath, mechanically stirring the bottle under the nitrogen atmosphere, starting to introduce air when the temperature is raised to 20 ℃, keeping the reaction temperature at 20-25 ℃ by adding cooling water into the water bath, reacting for 8 hours, sucking out the catalyst by using a magnet, washing the catalyst for 3 times by using ethanol, drying and recycling the catalyst for later use, and sampling GC analysis shows that the conversion rate of the isooctyl aldehyde is 99.0 percent, the selectivity of the 2-ethylhexanoic acid is 98.6 percent, and the yield is 97.6 percent.
Example 28
Adding isooctyl aldehyde (112g, 0.87mol) and a solvent of 208g of n-octanoic acid and 25.6mg of catalyst 2 into a dry 1L three-mouth bottle, placing the bottle in a water bath, mechanically stirring the bottle under the nitrogen atmosphere, starting to introduce air when the temperature is raised to 20 ℃, keeping the reaction temperature at 20-25 ℃ by adding cooling water into the water bath, after reacting for 8 hours, sucking the catalyst out by a magnet, washing the catalyst for 3 times by ethanol, drying and recovering the catalyst for later use, and sampling GC analysis shows that the conversion rate of the isooctyl aldehyde is 99.9 percent, the selectivity of the 2-ethylhexanoic acid is 98.8 percent, and the yield is 98.70 percent.
Example 29
Adding isooctyl aldehyde (112g, 0.87mol) and a solvent 2-ethylhexanoic acid 208g and a catalyst 2 of 25.6mg into a dry 1L three-necked bottle, placing the bottle in a water bath, mechanically stirring the bottle under a nitrogen atmosphere, starting to introduce air when the temperature is raised to 25 ℃, keeping the reaction temperature at 25-30 ℃ by adding cooling water into the water bath, reacting for 8 hours, sucking out the catalyst by using a magnet, washing the catalyst for 3 times by using ethanol, drying and recycling the catalyst for later use, and sampling GC analysis shows that the conversion rate of the isooctyl aldehyde is 99.8%, the selectivity of the 2-ethylhexanoic acid is 99.1%, and the yield is 98.9%.
Example 30
Adding isooctyl aldehyde (112g, 0.87mol) and a solvent of 208g of 2-ethylhexanoic acid and 19.2mg of catalyst 2 into a dry 1L three-necked bottle, placing the bottle in a water bath, mechanically stirring the bottle under the nitrogen atmosphere, starting to introduce air when the temperature is raised to 25 ℃, keeping the reaction temperature at 25-30 ℃ by adding cooling water into the water bath, reacting for 8 hours, sucking out the catalyst by using a magnet, washing the catalyst for 3 times by using ethanol, drying and recycling the catalyst for later use, and sampling GC analysis shows that the conversion rate of the isooctyl aldehyde is 99.1 percent, the selectivity of the 2-ethylhexanoic acid is 99.0 percent, and the yield is 98.1 percent.
Example 31
Adding isooctyl aldehyde (160g, 1.25mol) and solvent n-octanoic acid (160g, 19.2 mg) catalyst 2 into a dry 1L three-mouth bottle, placing the bottle in a water bath, mechanically stirring the bottle under the nitrogen atmosphere, starting to introduce oxygen when the temperature is raised to 30 ℃, keeping the reaction temperature at 30-35 ℃ by adding cooling water into the water bath, reacting for 6 hours, sucking out the catalyst by using a magnet, washing the catalyst for 3 times by using ethanol, drying and recycling the catalyst for later use, and sampling GC analysis shows that the conversion rate of the isooctyl aldehyde is 98.8 percent, the selectivity of the 2-ethylhexanoic acid is 98.9 percent, and the yield is 97.7 percent.
Example 32
Adding isooctyl aldehyde (160g, 1.25mol) and solvent 2-ethyl hexanoic acid 160g and catalyst 2 (19.2 mg) into a dry 1L three-mouth bottle, placing the bottle in a water bath, mechanically stirring the bottle under the nitrogen atmosphere, starting to introduce air when the temperature is raised to 30 ℃, keeping the reaction temperature at 30-35 ℃ by adding cooling water into the water bath, reacting for 6 hours, sucking the catalyst out by a magnet, washing the catalyst for 3 times by ethanol, drying and recycling the catalyst for later use, and sampling GC analysis shows that the conversion rate of the isooctyl aldehyde is 98.9%, the selectivity of the 2-ethyl hexanoic acid is 99.6%, and the yield is 98.5%.
Comparative example
Referring to the procedure of example 1, 5,10,15,20- (tetramethoxyphenyl) porphyrin (1.47g,2mmol) was reacted with ferrous chloride tetrahydrate (2.39g,12mmol) to prepare R3＝-OCH3Ferriporphyrin compound IV.
With reference to the procedure of example 17, with R3＝-OCH3Ferriporphyrin compound IV (236mg, 0.3mmol) was used as a starting material to prepare catalyst 9.
Referring to the procedure of example 24, using catalyst 9, the reaction selectivity was 97%, conversion 98.1%, and yield 95.16%.
Claims (13)
1. A catalyst for preparing isooctanoic acid by catalytic oxidation of isooctylaldehyde has a structural general formula as follows:
wherein C represents gamma-AlOOH or Al2O3，R1or-H, R2is-NH-or-CH2-，R3＝-COOMe、-COOH、-NO2or-CONHNH2。
2. A process for preparing the catalyst of claim 1, comprising the steps of:
(1) reacting gamma-AlOOH @ Fe3O4Or Al2O3@Fe3O4With compounds I
The ferroferric oxide nano compound II is prepared by reaction
Wherein C represents gamma-AlOOH or Al2O3，R1or-H, R2is-NH-or-CH2-；
(2) Compound III
Reaction with ferrous chloride to prepare iron porphyrin compound IV
Wherein R is3＝-COOMe、-COOH、-NO2or-CONHNH2；
(3) Ferriporphyrin compound IV and ferroferric oxide nano compound II
Mixing, washing and vacuum drying to obtain the catalyst
3. The method of claim 2, wherein R is prepared1＝-OH、R2A process for compound I which is-NH-, comprising the steps of: n- (3-aminopropyl) imidazole and gamma-glycidoxypropyltrimethoxysilane
The molar ratio of the N- (3-aminopropyl) imidazole to the gamma-glycidoxypropyltrimethoxysilane is 1: 1.05-1.2.
4. The method according to claim 3, wherein the molar ratio of N- (3-aminopropyl) imidazole to gamma-glycidoxypropyltrimethoxysilane is 1:1.05 to 1.1.
5. The method of claim 2, wherein R is prepared1＝-OH、R2＝-CH2-a method of compound I comprising the steps of: n- (3-chloropropyl) imidazole and gamma-glycidoxypropyltrimethoxysilane
The molar ratio of the N- (3-chloropropyl) imidazole to the gamma-glycidoxypropyltrimethoxysilane is 1: 1.05-1.2.
6. The method of claim 2, wherein R is prepared1＝-H、R2A process for compound I which is-NH-, comprising the steps of: 3-chloropropyltrimethylsilane reacts with 3-chloropropanol and then reacts with N- (3-aminopropyl) imidazole to prepare the compound
7. The method of claim 2, wherein R is prepared1＝-H、R2＝-CH2-a method of compound I comprising the steps of: the N- (1-carboxyl hexyl) imidazole is reduced by boron trifluoride to prepare N- (1-hydroxyl heptyl) imidazole, and the N- (1-hydroxyl heptyl) imidazole reacts with 3-chloropropyltrimethylsilane to prepare the compound
8. A method for preparing isooctanoic acid by oxidizing isooctanal comprises the following steps: using isooctylaldehyde solution as raw material, and making isooctanoic acid by oxidation in the presence of oxygen-containing gas under the catalysis of catalyst described in claim 1 or catalyst prepared by any one of claims 2-7.
9. The method according to claim 8, wherein the concentration of isooctanal in said isooctanal solution is 25-50 wt%; the solvent of the solution is n-octanoic acid and/or 2-ethylhexanoic acid.
10. The method according to claim 8, wherein the concentration of isooctanal in said isooctanal solution is 35-50 wt%; the solvent of the solution is 2-ethyl hexanoic acid.
11. The method according to claim 8, wherein the mass fraction of the catalyst in the reaction raw material isooctaldehyde is 10-60 ppm.
12. The method according to claim 8, wherein the mass fraction of the catalyst in the reaction raw material isooctaldehyde is 10-50 ppm.
13. The method according to claim 8, wherein the mass fraction of the catalyst in the reaction raw material isooctaldehyde is 15-25 ppm.
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