CN109433270A - A kind of different octanal oxidation prepares catalyst of isooctyl acid and preparation method thereof, and the method for preparing isooctyl acid - Google Patents
A kind of different octanal oxidation prepares catalyst of isooctyl acid and preparation method thereof, and the method for preparing isooctyl acid Download PDFInfo
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- CN109433270A CN109433270A CN201811176355.0A CN201811176355A CN109433270A CN 109433270 A CN109433270 A CN 109433270A CN 201811176355 A CN201811176355 A CN 201811176355A CN 109433270 A CN109433270 A CN 109433270A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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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Abstract
The present invention discloses a kind of different octanal oxidation and prepares catalyst of isooctyl acid and preparation method thereof, and the method for preparing isooctyl acid.Used catalyst is a kind of porphyrin bionic catalyst with mimetic enzyme catalysis function, keeps preparation process cleaning effective；This catalyst is carried on magnetic Nano structure simultaneously, high-specific surface area is conducive to improve substrate mass transport process.This catalyst has both the green catalysis performance and the easily separated recycling of magnetic material of simulation biological enzyme, the characteristics of recycling.It is used for different octanal oxidation and prepares isooctyl acid, feed stock conversion and selectivity of product are improved significantly.
Description
Technical field
The present invention relates to a kind of different octanal oxidations to prepare catalyst of isooctyl acid and preparation method thereof and the oxidation of different octanal
The method for preparing isooctyl acid.
Technical background
2 ethyl hexanoic acid (2-Ethylhexanoic Acid, 2-EHA), Chinese nickname isooctyl acid, it is cold to be that one kind is slightly soluble in
Water and ethyl alcohol are dissolved in the oily liquids of hot water and ether.Feature is high-purity, lighter color.It can be with various metals compound effects
Generate isooctyl acid metal salt, main application is as follows: the drier of coating, lubricating oil adjuvant, plastic plasticizer, PVC stabilizer,
Medical salt forming agent, catalytic reaction agent aid.
China has become the second-biggest-in-the-world coating material production state for being only second to the U.S. at present, and the development of especially high-grade paint is fast
Suddenly, in addition China's synthetic resin and unsaturated polyester (UP) industrial development are rapid, and high-grade ink is also in faster development trend, and different pungent
Acid and its salts substances will more be widely used in these industries, it is contemplated that in the coming years, isooctyl acid and isooctyl acid
The market prospects of salt are very good.
Isooctyl acid industry is combined to mainly have two lines, first is that isooctanol oxidizing process, although method selectivity is high, raw material
It is from the horse's mouth easy to operate, but process flow is long, is not easy large-scale production, and domestic several companies are raw using the route at present
It produces；Second is that being dehydrated by condensation using n-butanal as raw material and generating 2- ethyl hexenal, repeated hydrogenation obtains different octanal (2- ethyl hexyl
Aldehyde), then oxidation obtains isooctyl acid.Oxidation of aldehydes method raw materials technology is from the horse's mouth, and is serialization, totally-enclosed technique, is easy to advise
Modelling production, American-European some big companies mostly use the route to produce.
Patent CN1357527A discloses the manufacturing method for reporting a kind of 2 ethyl hexanoic acid, the optimum response of the patent disclosure
Temperature is 0-15 DEG C, and highest is selectively 94.9%, but engineering temperature control energy consumption is high, is industrialized unsatisfactory.Patent
The shortcomings that CN1410407A discloses the manufacturing method for reporting a kind of 2 ethyl hexanoic acid, which overcomes a patent, most
Good reaction temperature is improved to 30-50 DEG C, and consersion unit is changed to falling film reactor by bubble tower, but industrial investment of production equipment at
This height is selectively not obvious improvement.Patent CN1422840A discloses a kind of manufacturing method of 2 ethyl hexanoic acid, which makes
With reaction tower, the reaction time is substantially reduced, highest is selectively 96.8%, but catalyst post-processing trouble.Above 3 patents
Report is all disclosed by Qilu Petrochemical Company, catalyst used is Mn (OAc)2Or KOAc or Cu (OAc)2NaOAc or these four
Substance is selectively not very ideal with a mixture of arbitrary proportions, does not also report the aftertreatment technology of catalyst.
Patent CN102701944A, which is disclosed, reports a kind of phosphorus molybdenum vanadium heteropolyacid catalysis oxidation 2- ethyl hexanal preparation 2-
The method of thylhexoic acid, the selectivity of 2 ethyl hexanoic acid can reach 98% or more, but the catalyst preparation needs molybdate, phosphoric acid
Salt, metavanadate, the concentrated sulfuric acid, hydrochloric acid etc., preparation process is complicated and regeneration is relatively difficult, and apart from industrial applications, there are also very long
Distance.
Patent US5739352 discloses a kind of method for preparing carboxylic acid, and this method is with peracid in amine or amine-n-oxides
Under conditions of making catalyst, oxidation aldehyde prepares carboxylic acid.Used catalyst includes substituted or unsubstituted alkylamine, alkyl amine-n-
Oxide or aromatic amine, fragrant amine-n-oxides or their mixture.But defect be the catalyst boiling point containing N element very
Height, and post-processing is more complicated, requires consersion unit relatively high.
In conclusion it is existing disclose different octanal prepare in the technology of isooctyl acid or its homogeneous catalyst difficulty separating treatment (such as
Mn(OAc)2Or KOAc or Cu (OAc)2Deng) or catalyst preparation process is cumbersome and corrosivity is high or complex process, mass transfer effect
Difference, the defects of selectivity of product is undesirable.
Need to provide a kind of catalyst, easily separated for the different octanal isooctyl acid of catalysis oxidation, product selectivity is high, and
The difficulty that catalyst difficulty separates in homogeneous catalysis in current technology can be overcome, realization can recycle.
Summary of the invention
The object of the invention is that the catalyst for providing the new different octanal isooctyl acid of catalysis oxidation of one kind and its preparation side
Method is catalyzed easily recycling and reuses, and selectivity of product is high.
The present invention also provides a kind of method that different octanal oxidation prepares isooctyl acid, process conditions cleaning is mild, can be managed
The selectivity and yield thought reuse convenient for separation and recovery of catalyst, are suitble to industrialization.Compared with prior art, of the invention
Technique clean and effective is catalyzed easily recycling and reuses, and selectivity of product is high.
In order to achieve the above objectives, The technical solution adopted by the invention is as follows:
A kind of different octanal catalysis oxidation prepares the catalyst of isooctyl acid, general structure are as follows:
Wherein C represents γ-AlOOH or Al2O3,R1=-OH or-H, R2=-NH- or-CH2-,R3=-COOMe ,-COOH ,-
NO2Or-CONHNH2。
It include ferriporphyrin and magnetic ferroferric oxide nanometer structure in catalyst structure of the present invention.
The activated centre of catalyst of the present invention is heme group, and there is big pi-electron to be conjugated cyclic structure, will replace
Base is introduced on porphyrin ring, and central metal ion current potential will change, and then regulates and controls its catalytic activity.Work as porphin
There is electron-withdrawing group (such as ester group, carboxyl, nitro, formohydrazide group) on phenyl ring in quinoline ring, electron attraction makes central metal
Cloud density reduce, i.e., so that metal-oxygen key weakened, it is easy to occur redox reaction, namely activity is intermediate
The activity of body increases, therefore the catalytic effect of metalloporphyrin will enhance.
With metal Fe coordination ligand be imidazoles, can play the role of following: (1) it is also a pi-electron system, it with
Pi bond is with metallic ion coordination；(2) c h bond on imidazole ring forms a kind of weak hydrogen bond with the N on porphyrin ring, both effects make
It obtains metal and imidazoles coordination is stronger, structure is more stable.
Preferably, when containing-OH and-NH- simultaneously on the bridge chain for connecting imidazoles and magnetic material, with electron conjugated
Effect and hydrogen bond effect.With the imidazole ring pi-electron system on chain electron conjugated effect can occur for the lone pair electrons on oxygen and nitrogen, this
Sample makes the bond energy being coordinated with metal bigger, keeps structure more stable, catalytic performance is higher.Secondly the hydrogen on-OH and-NH- can be with
Weak hydrogen bond action occurs with the N on porphyrin ring, this equally makes magnetic nano particle minor structure and porphyrin ring pass through bridge chain link more
Add close and firm, both effects cooperate with so that monolith design is more stable, and the activity of catalyst is also more excellent.-OH
Presence with-NH- is obvious to the catalytic effect of reaction.
It is SiO that magnetic Nano material, which wraps up common used material,2, but catalyst of the present invention be γ-AlOOH or
Al2O3.By γ-AlOOH@Fe3O4Al can be formed through high-temperature roasting2O3@Fe3O4.The coated effect of γ-AlOOH is better than
Al2O3, it may be possible to because high-temperature roasting destroys γ-AlOOH@Fe3O4Meso-hole structure in carrier shell.
In the present invention by porphyrin in conjunction with insoluble magnetic Nano material, it is unstable, easy to overcome porphyrin homogeneous catalysis
The problems such as inactivation and difficulty recycle, while specific surface area is further increased, promote mass transfer effect.After reaction, magnet is used
Magnetic nano-catalyst is sucked out, it is easy to accomplish from the separation in solution, be re-used in next reaction.The synthesis of this catalyst
Conventional chemical processes synthesis can be used.
A method of preparing catalyst of the present invention, comprising the following steps:
(1) by γ-AlOOH@Fe3O4Or Al2O3@Fe3O4With compound IIt reacts and ferriferrous oxide nano compound II is madeWherein C represents γ-AlOOH or Al2O3, R1=-OH or-H,
R2=-NH- or-CH2-；
(2) compound IIIIt is reacted with frerrous chloride and prepares iron porphin
Quinoline compound IVWherein R3=-COOMe ,-COOH ,-NO2Or-
CONHNH2；
(3) ferriporphyrin compound IV and ferriferrous oxide nano compound IIMixing, washing, is dried in vacuo to obtain catalyst
In step (1) of the present invention, as the R of compound I1=-OH, R2When=- NH-, preparation method includes following step
Rapid: N- (3- aminopropyl) imidazoles and γ-glycidoxypropyl trimethoxy silane reaction are madeN- (3- aminopropyl) imidazoles and γ-glycidoxypropyl trimethoxy
The molar ratio of base silane is 1:1.05~1.2, preferably 1:1.05~1.1.
In step (1) of the present invention, as the R of compound I1=-OH, R2=-CH2When, preparation method includes following
Step: N- (3- chloropropyl) imidazoles and γ-glycidoxypropyl trimethoxy silane reaction are madeN- (3- chloropropyl) imidazoles and γ-glycidoxypropyl trimethoxy
The molar ratio of silane is 1:1.05~1.2.
In step (1) of the present invention, as the R of compound I1=-H, R2When=- NH-, preparation method includes following step
Rapid: 3- chloropropyl trimethyl silane is reacted with 3- chloropropyl alcohol, then is reacted and be made with N- (3- aminopropyl) imidazoles
In step (1) of the present invention, as the R of compound I1=-H, R2=-CH2When, preparation method includes following step
Rapid: N- (1- carboxyhexyl) imidazoles restores preparation N- (1- Hydroxyheptyl) imidazoles through boron trifluoride, with 3- chloropropyl trimethyl silicane
Alkane reaction is made
In step (2) of the present invention, substituent R3=-CONHNH2Compound IV preparation method, including following step
It is rapid: substituent R3The compound III and hydration hydrazine reaction of=- COOMe, then reacted with frerrous chloride.
In step (2) of the present invention, substituent group R3The preparation method of the compound III of=- COOH, including following step
It is rapid: substituent group R3Reaction is hydrolyzed in the compound III of=- COOMe.
In step (2) of the present invention, compound IIIWith chlorination
Ferrous molar ratio is 1:5~7.
In step (3) of the present invention the dosage of ferriporphyrin compound IV and ferriferrous oxide nano compound II according to
Lower ratio calculates: 0.15mmol ferriporphyrin compound IV is mixed with 1~1.5g ferriferrous oxide nano compound II.
γ-AlOOH@Fe of the present invention3O4Preparation method, comprising the following steps: use Fe3O4Nanoparticle with it is different
Propyl alcohol reactive aluminum is made.
Al of the present invention2O3@Fe3O4Preparation method, comprising the following steps: by γ-AlOOH@Fe3O4High-temperature roasting
Obtain Al2O3@Fe3O4。
A kind of method that different octanal oxidation prepares isooctyl acid comprising the steps of: using different octanal solution as raw material, in this hair
Under bright catalyst, in the presence of oxygen-containing gas, oxidation prepares isooctyl acid.
In different octanal solution of the present invention, the concentration of different octanal is 25-50wt%, preferably 35-50wt%.It is described molten
The solvent of liquid is caprylic acid and/or 2 ethyl hexanoic acid, preferably 2 ethyl hexanoic acid, can save the step of solvent separates in this way.
In the preparation method of isooctyl acid of the present invention, the oxygen-containing gas can be (excellent for pure oxygen, air or inert gas
Select nitrogen) oxygen rich gas with oxygen composition, from the aspect of the requirement of process safety tail oxygen concentration, preferred air.
In the preparation method of isooctyl acid of the present invention, the molar ratio of different octanal and oxygen is 1:0.5-1.0, dense from tail oxygen
Degree and reaction selectivity consider, preferred 1:0.5-0.8.
In the preparation method of isooctyl acid of the present invention, the mass fraction that catalyst accounts for the different octanal of reaction raw materials is 10-
60ppm, preferably 10-50ppm, more preferable 15-25ppm.
The reaction that different octanal in the present invention aoxidizes isooctyl acid processed is exothermic reaction, and temperature is unable to accurately control, but in order to
Environmental condition needed for reducing reaction, reduces cost, and reaction is reacted in room temperature or so, and reaction temperature can be controlled in 10-50 DEG C, excellent
20-35 DEG C, most preferably 30-35 DEG C are selected, heat can be taken away by the cooling water in the coil pipe outside device.
In the preparation method of isooctyl acid of the present invention, reaction time 3-9h, preferably 6-8h.
Catalyst after reaction, is sucked out with magnet and is recycled by isooctyl acid of the present invention preparation, and catalyst crude product can be with
It is cleaned 2-3 times with ethyl alcohol, it is i.e. reusable after dry to remove remaining reaction solution.
Technical solution of the present invention has the advantages that porphyrin is supported on insoluble magnetic Nano material by (1)
On, the chemical stability of porphyrin structure can be increased, preferably play its good catalytic effect；(2) catalyst has very
Big specific surface area, the mass transfer effect for largely improving material, increase reaction rate；(3) porphyrin can be overcome homogeneously to urge
Change the defect for being not readily separated simultaneously regeneration.
The liquid phase oxidation of different octanal is radical reaction, and rate determining step is the dissolution mass transfer effect of oxygen, i.e., in reaction solution
Oxyty is higher, and mass transfer effect is better, and reaction effect is better.The catalyst has high oxygen carrying capability and greatly compares table
Area mixes oxygen with reactant, to improve mass transfer effect.This technique can inherently improve the effect of reaction, catalysis
It is high-efficient, increase the selectivity of product, high conversion rate also can achieve 99% or more；Selectivity is high, can achieve 99% with
On.The cleaning of technological reaction condition is mild, and the three wastes are seldom.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and the scope of the present invention includes but is not limited to institute
The embodiment enumerated.
Fe3O4Nanoparticle is purchased from Beijing Deco Dao Jin Science and Technology Ltd. (average grain diameter 20nm)；
γ-glycidoxypropyl trimethoxy silane (GTMS) is purchased from Shin-Etsu Chemial Co., Ltd, trade mark KBM-
403, chemistry is pure；
5,10,15,20- (tetracarboxylic methyl esters phenyl) porphyrin, 5,10,15,20- (tetranitro phenyl) porphyrin are purchased from lark prestige
Reagent, chemistry are pure；
5,10,15,20- (tetramethoxy phenyl) porphyrins are purchased from Aladdin reagent, and chemistry is pure.
Gas chromatograph: Agilent7890, chromatographic column SH-RTX-WAX, method: temperature programming, tail flow: 30mL/
Min, hydrogen flowing quantity: 40mL/min, air mass flow: 400mL/min, split ratio 30:1；Temperature program: by 60 DEG C with 20 DEG C/min
Rate rise to 80 DEG C, then rise to 250 DEG C through 8min, total procedure time: 23.3min, detector temperature: 260 DEG C.
Embodiment 1
By 5,10,15,20- (tetracarboxylic methyl esters phenyl) porphyrins (2g, 2.4mmol) and Iron dichloride tetrahydrate (2.38g,
It 12mmol) is dissolved in 60mL DMF solution, flows back after 12h, DMF is distilled off in vacuum decompression.After being cooled to room temperature, round-bottomed flask
In pour into 60mL deionized water, stir 40min under room temperature, then filter, then washed repeatedly with water three times, obtained after dry
R3The ferriporphyrin compound IV of=- COOMe.
Embodiment 2
Referring to the method for embodiment 1, by 5,10,15,20- (tetranitro phenyl) porphyrins (1.59g, 2mmol) and four hydrations
Frerrous chloride (1.99g, 10mmol) reaction preparation R3=-NO2Ferriporphyrin compound IV.
Embodiment 3
By 5,10,15,20- (tetracarboxylic methyl esters phenyl) porphyrin (2g, 2.4mmol) and hydrazine hydrate N2H4·H2O150mL is molten
It in 200mLDMF, after being heated to reflux 10h, is cooled to room temperature, 300mL deionized water is then added.It is filtered after 1h is stirred at room temperature,
It is washed repeatedly with water three times, obtains aubergine solid powder after dry, be R3=-CONHNH2Compound III.By R3=-
CONHNH2Compound III (1.7g, 2mmol) He Sishui frerrous chloride (2.78g, 14mmol) be dissolved in 50mLDMF, flow back
12h, after reaction, vacuum distillation remove DMF, after washing three times, are evaporated under reduced pressure to after organic phase anhydrous magnesium sulfate drying
To R3=-CONHNH2Ferriporphyrin compound IV.
Embodiment 4
By LiCl (1.3g, 31mmol) and R3The ferriporphyrin compound IV (1.8g, 2mmol) of=- COOMe is dissolved in 75mL
DMSO and 7.5mL H2Then O is placed reaction liquid at 160 DEG C and is reacted for 24 hours, after reaction, extracted with ethyl acetate and water
Reaction solution, then anhydrous sodium sulfate is dry, is concentrated under reduced pressure, then chromatograph to obtain R through column3The ferriporphyrin compound IV of=- COOH.
Embodiment 5
Sequentially added in 100mL round-bottomed flask N- (3- aminopropyl) imidazoles (1.8g, 14.4mmol), NaH (0.36g,
15mmol) and the dry tetrahydrofuran of 30mL, 2h is stirred at room temperature, γ-glycidoxypropyl is slowly dropped under nitrogen protection
Trimethoxy silane (3.6g, 15.1mmol) is then stirred to react 20h for 90 DEG C.After reaction, it is cooled to room temperature, filters, it is dense
Contracting, through silica gel column chromatography (petrol ether/ethyl acetate=3:1), obtains compound 1.
Embodiment 6
Referring to the method for embodiment 5, by raw material compound N- (3- chloropropyl) imidazoles (2.2g, 15mmol), NaH
(0.36g, 15mmol) and γ-glycidoxypropyl trimethoxy silane (3.7g, 15.8mmol) reaction can prepare compounds 2
Embodiment 7
3- chloropropyl trimethyl silane (2g, 10mmol) and 3- chloropropyl alcohol are sequentially added in 100mL round-bottomed flask
The tetrahydrofuran of dry 40mL is slowly added dropwise in (1.5g, 15.9mmol), the sodium methoxide of 20mg under nitrogen atmosphere, and room temperature is anti-
4h is answered, vacuum rotary steam removes solvent after reaction, and silica gel column chromatography (petrol ether/ethyl acetate=5:1) obtains compound 3-1.
Sequentially added in 100mL round-bottomed flask N- (3- aminopropyl) imidazoles (1.0g, 8mmol), NaH (0.36g,
15mmol) and the dry tetrahydrofuran of 30mL, 2h is stirred at room temperature, be slowly dropped under nitrogen protection compound 3-1 (2.16g,
8.4mmol), then 90 DEG C be stirred to react 20h.After reaction, it is cooled to room temperature, filters, concentration, through silica gel column chromatography (stone
Oily ether/ethyl acetate=3:1), obtain compound 3.
Embodiment 8
In the three-necked flask of 100mL, N- (1- carboxyhexyl) imidazoles (2.0g, 10mmol) is dissolved in the dry tetrahydro furan of 30mL
It mutters, sodium borohydride NaBH is slowly added at 0 DEG C4(5.67g, 15mmol) after adding, is to slowly warm up to room temperature, continues to stir
3h is reacted, after reaction, is concentrated under reduced pressure, silica gel column chromatography obtains product N- (1- Hydroxyheptyl) imidazoles.
3- chloropropyl trimethyl silane (2.3g, 11.6mmol) and N- (1- hydroxyl are sequentially added in 100mL round-bottomed flask
Heptyl) imidazoles (2.0g, 11mmol), the tetrahydrofuran of dry 50mL is slowly added dropwise in the sodium methoxide of 20mg under nitrogen atmosphere,
4h is reacted at room temperature, vacuum rotary steam removes solvent after reaction, and silica gel column chromatography (petrol ether/ethyl acetate=5:1) obtains chemical combination
Object 4.
Embodiment 9
γ-AlOOH@Fe3O4Preparation
5.8g aluminium isopropoxide is weighed to be dissolved in dehydrated alcohol, at 60 DEG C stirring until aluminium isopropoxide be completely dissolved, be added
1.0gFe3O4Then nanoparticle, ultrasonic 30min are vigorously stirred 13h in 45 DEG C of waters bath with thermostatic control, are added in whipping process anhydrous
Suspension in reaction flask is transferred in tube sealing, is placed in after mixing evenly by EtOH-DI water (5/1, v/v, 50mL)
In air dry oven, crystallization 21h at 80 DEG C, after reaction, product suspension is transferred in beaker, after Magnetic Isolation with water and
Ethyl alcohol washs three times respectively, and product is finally dried in vacuo 12h at 50 DEG C, can obtain product γ-AlOOH@Fe3O4。
Embodiment 10
Al2O3@Fe3O4Preparation
γ-AlOOH@Fe is produced to obtain by above-mentioned3O4It is placed in high temperature reaction stove, under nitrogen atmosphere, 600 DEG C of roasting dehydrations
3h, then cooled to room temperature, can be prepared by Al2O3@Fe3O4。
Embodiment 11
2.0g γ-AlOOH@Fe is added in 250ml round-bottomed flask3O4With 100mL dry toluene, ultrasonic disperse 1h, then
Be added above compound 1 (1.0g, 2.8mmol) and 0.5mL pyridine mixed solution, under nitrogen atmosphere back flow reaction for 24 hours, instead
It after answering, is cooled to room temperature, the black powder to be suspended with magnet separation, 80 DEG C at vacuum multiple with toluene and acetone washing
Dry compound 5.
Embodiment 12
Referring to the method for embodiment 11, with compound 2 (970mg, 2.8mmol) for raw material prepare compound 6Remaining parameter is the same as embodiment 11.
Embodiment 13
Referring to the method for embodiment 11, with compound 3 (967mg, 2.8mmol) for raw material prepare compound 7Remaining parameter is the same as embodiment 11.
Embodiment 14
Referring to the method for embodiment 11, with compound 4 (964mg, 2.8mmol) for raw material prepare compound 8Remaining parameter is the same as embodiment 11.
Embodiment 15
Referring to the method for embodiment 11, with Al2O3@Fe3O4For raw material prepare compound 9Remaining parameter is the same as embodiment 11.
Embodiment 16
Under nitrogen atmosphere, R is added into 100mL round-bottomed flask3=-COOMe ferriporphyrin compound IV (270mmg,
0.3mmol) and 60mL deionized water, room temperature quickly stir 40min, and 2.0g compound 5 is then added, and continue to stir at 30 DEG C
24h.After reaction, vacuum drying obtains catalyst 1 after black powder is repeatedly washed through Magneto separate, acetone.
Embodiment 17
Referring to the method for embodiment 16, with R3=-NO2Ferriporphyrin compound IV (255mg, 0.3mmol) be raw material preparation
Catalyst 2.
Embodiment 18
Referring to the method for embodiment 16, with R3=-CONHNH2Ferriporphyrin compound IV (270mg, 0.3mmol) be raw material
Prepare catalyst 3.
Embodiment 19
Referring to the method for embodiment 16, with R3The ferriporphyrin compound IV (253mg, 0.3mmol) of=- COOH be raw material with
2.0g compound 5 prepares catalyst 4.
Embodiment 20
It is that raw material prepares catalyst 5 with compound 6 referring to the method for embodiment 16.
Embodiment 21
It is that raw material prepares catalyst 6 with compound 7 referring to the method for embodiment 16.
Embodiment 22
It is that raw material prepares catalyst 7 with compound 8 referring to the method for embodiment 16.
Embodiment 23
Referring to the method for embodiment 16, with compound 9 and R3=-NO2Ferriporphyrin compound IV (255mg, 0.3mmol)
Catalyst 8 is prepared for raw material.
The structure of the catalyst 1-8 prepared in embodiment 16-23 such as following formula:
Embodiment 24
In the there-necked flask of a dry 1L, be added different octanal (160g, 1.25mol) and solvent 2 ethyl hexanoic acid (160g,
1.11mol), 4mg catalyst 2, is placed in water-bath, under nitrogen atmosphere mechanical stirring, after temperature rises to 30 DEG C, starts to be passed through
Air, flow 11.9g/h after reacting 8h, use magnet by adding cooling water to keep reaction temperature at 30-35 DEG C into water-bath
Catalyst is sucked out, with ethanol washing 3 times, drying recycling is spare.It is computed, the conversion ratio 99.6% of different octanal, 2- ethyl hexyl
The selectivity 99.5% of acid, yield 99.1%.
Embodiment 25
Referring to the method for embodiment 24, only change the type of catalyst, see Table 1 for details for reaction result.
1 embodiment of table, 25 result
| Catalyst type | Selective % | Conversion ratio % | 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 |
Embodiment 26
In the there-necked flask of a dry 1L, be added different octanal (80g, 0.62mol) and solvent 2 ethyl hexanoic acid 240g,
12.8mg catalyst 2, is subsequently placed in water-bath, under nitrogen atmosphere mechanical stirring, after temperature is raised to 20 DEG C, starts to be passed through sky
Gas, flow 11.9g/h, will with magnet after reacting 8h by adding cooling water to keep reaction temperature at 20-25 DEG C into water-bath
Catalyst is sucked out, and with ethanol washing 3 times, drying recycling is spare, sampling GC analysis, the conversion ratio 99.6% of different octanal, 2- ethyl
The selectivity 98.5% of caproic acid, yield 98.10%.
Embodiment 27
In the there-necked flask of a dry 1L, different octanal (80g, 0.62mol) and 2 ethyl hexanoic acid 240g, 19.2mg is added
Catalyst 2, is placed in water-bath, under nitrogen atmosphere mechanical stirring, after temperature is raised to 20 DEG C, starts to be passed through air, flow is
After reaction 8h, catalyst is sucked out with magnet by adding cooling water to keep reaction temperature at 20-25 DEG C into water-bath by 5.9g/h,
With ethanol washing 3 times, drying recycling is spare, sampling GC analysis, the conversion ratio 99.0% of different octanal, the selectivity of 2 ethyl hexanoic acid
98.6%, yield 97.6%.
Embodiment 28
In the there-necked flask of a dry 1L, be added different octanal (112g, 0.87mol) and solvent caprylic acid 208g,
25.6mg catalyst 2, is placed in water-bath, under nitrogen atmosphere mechanical stirring, after temperature rises to 20 DEG C, starts to be passed through air,
Flow is 8.3g/h, by adding cooling water to keep reaction temperature at 20-25 DEG C into water-bath, after reacting 8h, will be catalyzed with magnet
Agent is sucked out, and with ethanol washing 3 times, drying recycling is spare, sampling GC analysis, the conversion ratio 99.9% of different octanal, 2 ethyl hexanoic acid
Selectivity 98.8%, yield 98.70%.
Embodiment 29
In the there-necked flask of a dry 1L, be added different octanal (112g, 0.87mol) and solvent 2 ethyl hexanoic acid 208g,
25.6mg catalyst 2, is placed in water-bath, under nitrogen atmosphere mechanical stirring, after temperature rises to 25 DEG C, starts to be passed through air,
Flow is 13.2g/h, by adding cooling water to keep reaction temperature at 25-30 DEG C into water-bath, after reacting 8h, will be catalyzed with magnet
Agent is sucked out, and with ethanol washing 3 times, drying recycling is spare, sampling GC analysis, the conversion ratio 99.8% of different octanal, 2 ethyl hexanoic acid
Selectivity 99.1%, yield 98.9%.
Embodiment 30
In the there-necked flask of a dry 1L, be added different octanal (112g, 0.87mol) and solvent 2 ethyl hexanoic acid 208g,
19.2mg catalyst 2, is placed in water-bath, under nitrogen atmosphere mechanical stirring, after temperature rises to 25 DEG C, starts to be passed through air,
Flow is 9.9g/h, by adding cooling water to keep reaction temperature at 25-30 DEG C into water-bath, after reacting 8h, will be catalyzed with magnet
Agent is sucked out, and with ethanol washing 3 times, drying recycling is spare, sampling GC analysis, the conversion ratio 99.1% of different octanal, 2 ethyl hexanoic acid
Selectivity 99.0%, yield 98.1%.
Embodiment 31
In the there-necked flask of a dry 1L, be added different octanal (160g, 1.25mol) and solvent caprylic acid 160g,
19.2mg catalyst 2, is placed in water-bath, under nitrogen atmosphere mechanical stirring, after temperature rises to 30 DEG C, starts to be passed through oxygen,
Flow is 25.4g/h, by adding cooling water to keep reaction temperature at 30-35 DEG C into water-bath, after reacting 6h, will be catalyzed with magnet
Agent is sucked out, and with ethanol washing 3 times, drying recycling is spare, sampling GC analysis, the conversion ratio 98.8% of different octanal, 2 ethyl hexanoic acid
Selectivity 98.9%, yield 97.7%.
Embodiment 32
In the there-necked flask of a dry 1L, be added different octanal (160g, 1.25mol) and solvent 2 ethyl hexanoic acid 160g,
19.2mg catalyst 2, is placed in water-bath, under nitrogen atmosphere mechanical stirring, after temperature rises to 30 DEG C, starts to be passed through air,
Flow is 25.4g/h, by adding cooling water to keep reaction temperature at 30-35 DEG C into water-bath, after reacting 6h, will be catalyzed with magnet
Agent is sucked out, and with ethanol washing 3 times, drying recycling is spare, sampling GC analysis, the conversion ratio 98.9% of different octanal, 2 ethyl hexanoic acid
Selectivity 99.6%, yield 98.5%.
Comparative example
Referring to the method for embodiment 1, by 5,10,15,20- (tetramethoxy phenyl) porphyrins (1.47g, 2mmol) and four water
Close frerrous chloride (2.39g, 12mmol) reaction preparation R3=-OCH3Ferriporphyrin compound IV.
Referring to the method for embodiment 17, with R3=-OCH3Ferriporphyrin compound IV (236mg, 0.3mmol) be raw material system
Standby catalyst 9.
Referring to the method for embodiment 24, catalyst 9, reaction selectivity 97%, conversion ratio 98.1%, yield are used
95.16%.
Claims (9)
1. a kind of different octanal catalysis oxidation prepares the catalyst of isooctyl acid, general structure are as follows:
Wherein C represents γ-AlOOH or Al2O3, R1=-OH or-H, R2=-NH- or-CH2, R3=-COOMe ,-COOH ,-NO2
Or-CONHNH2。
2. a kind of method for preparing catalyst described in claim 1, comprising the following steps:
(1) by γ-AlOOH@Fe3O4Or Al2O3@Fe3O4With compound I
It reacts and ferriferrous oxide nano compound II is madeWherein C
Represent γ-AlOOH or Al2O3, R1=-OH or-H, R2=-NH- or-CH2-；
(2) compound IIIIt is reacted with frerrous chloride and prepares ferriporphyrin
Close object IVWherein R3=-COOMe ,-COOH ,-NO2Or-CONHNH2；
(3) ferriporphyrin compound IV and ferriferrous oxide nano compound IIMixing, washing, is dried in vacuo to obtain catalyst
3. according to the method described in claim 2, it is characterized in that, preparation R1=-OH, R2The method of the compound I of=- NH-,
The following steps are included: N- (3- aminopropyl) imidazoles and γ-glycidoxypropyl trimethoxy silane reaction are madeN- (3- aminopropyl) imidazoles and γ-glycidoxypropyl trimethoxy
The molar ratio of base silane is 1:1.05~1.2, preferably 1:1.05~1.1.
4. according to the method described in claim 2, it is characterized in that, preparation R1=-OH, R2=-CH2Compound I method,
The following steps are included: N- (3- chloropropyl) imidazoles and γ-glycidoxypropyl trimethoxy silane reaction are madeN- (3- chloropropyl) imidazoles and γ-glycidoxypropyl trimethoxy
The molar ratio of silane is 1:1.05~1.2.
5. according to the method described in claim 2, it is characterized in that, preparation R1=-H, R2The method of the compound I of=- NH-, packet
Include following steps: 3- chloropropyl trimethyl silane is reacted with 3- chloropropyl alcohol, then is reacted and be made with N- (3- aminopropyl) imidazoles
6. according to the method described in claim 2, it is characterized in that, preparation R1=-H, R2=-CH2Compound I method,
The following steps are included: N- (1- carboxyhexyl) imidazoles restores preparation N- (1- Hydroxyheptyl) imidazoles through boron trifluoride, with 3- chlorine third
The reaction of base trimethyl silane is made
7. a kind of method that different octanal oxidation prepares isooctyl acid comprising the steps of: using different octanal solution as raw material, wanted in right
Under the catalysis for the catalyst for asking any one of 1 catalyst or claim 2-6 the method to prepare, exist in oxygen-containing gas
Under, oxidation prepares isooctyl acid.
8. the method according to the description of claim 7 is characterized in that the concentration of different octanal is 25- in the different octanal solution
50wt%, preferably 35-50wt%；The solvent of the solution is caprylic acid and/or 2 ethyl hexanoic acid, preferably 2 ethyl hexanoic acid.
9. method according to claim 7 or 8, which is characterized in that the catalyst accounts for the quality of the different octanal of reaction raw materials
Score is 10-60ppm, preferably 10-50ppm, more preferable 15-25ppm.
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