CN107952479B - Functionalized polyacid ionic liquid catalyst, preparation method and method for catalyzing direct esterification of cyclohexene by functionalized polyacid ionic liquid catalyst - Google Patents
Functionalized polyacid ionic liquid catalyst, preparation method and method for catalyzing direct esterification of cyclohexene by functionalized polyacid ionic liquid catalyst Download PDFInfo
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- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
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Abstract
The invention discloses a functionalized polyacid ionic liquid catalyst, a preparation method and a method for catalyzing direct esterification of cyclohexene by using the functionalized polyacid ionic liquid catalyst. The method for catalyzing the direct esterification of cyclohexene uses cyclohexene and acetic acid as raw materials, uses functionalized polyacid ionic liquid as a catalyst, and prepares the cyclohexyl acetate through an esterification reaction. The conversion rate of cyclohexene in the invention is up to 90%, the selectivity of cyclohexyl acetate is up to 99%, and the yield of cyclohexyl acetate is up to 89%. The method has the advantages of high catalyst activity, good selectivity, mild reaction conditions, high product yield, easy separation of the catalyst from the product and the like.
Description
Technical Field
The invention relates to a functionalized polyacid ionic liquid catalyst, a preparation method and a method for catalyzing direct esterification of cyclohexene by using the functionalized polyacid ionic liquid catalyst, and relates to the field of functionalized polyacid ionic liquids and the field of catalytic synthesis of esterification reaction cyclohexyl acetate.
Background
Cyclohexanol is an intermediate raw material for producing important chemical products such as adipic acid, caprolactam, cyclohexanone and the like, and is widely applied to the fields of organic chemical industry, textile, coating, dye and the like. Industrially, cyclohexanol is produced mainly by the air oxidation of cyclohexane, the hydrogenation of phenol and the direct hydration of cyclohexene. The direct cyclohexene hydration method has the advantages of safety, energy conservation, high atom utilization rate, no waste, no environmental pollution and the like, is an economic and safe green process, and shows good industrial application prospects. However, the process has the defects of low and unstable single-pass conversion rate of the catalyst, high operation difficulty of the production process and the like, and people expect to develop a cyclohexanol production method which is safer and more environment-friendly, has higher atom economy, lower cost and higher production efficiency. Therefore, a plurality of scholars at home and abroad research and develop a process for preparing cyclohexanol by a cyclohexene indirect method, namely, cyclohexene and acetic acid are esterified firstly and then hydrolyzed (ester exchange or hydrogenation) to prepare cyclohexanol. The process for producing cyclohexanol by the two-step method of esterification and hydrogenation of cyclohexene not only produces cyclohexanol, but also converts cheap carboxylic acid into corresponding alcohol with high price and huge market capacity, thereby greatly increasing the economical efficiency of the process and having huge industrial application value. Wherein, the hydrogenation process can adopt the existing copper ester hydrogenation catalyst in the market to obtain high conversion rate and selectivity. The process for synthesizing the cyclohexyl acetate by directly esterifying the cyclohexene and the acetic acid directly utilizes abundant cyclohexene resources, does not need alcohol as an intermediate, reduces the production cost of the cyclohexyl acetate, and has obvious economic benefit.
Some new catalytic systems are already applied to the direct esterification reaction process of cyclohexene and acetic acid, and acid cation exchange resin, mesoporous molecular sieve SBA-15,
When the acid-functionalized ionic liquid, copper trifluoromethanesulfonate and other catalysts are used for the direct esterification of olefin, a certain yield is obtained, but a better ideal reaction effect cannot be achieved. For example, an acidic cation exchange resin catalyst shows good catalytic activity, and is a commercial solid acid catalyst with excellent performance, but also has some defects, such as poor thermal stability, easy poisoning and inactivation, and mass transfer problems.
In conclusion, the cyclohexene and acetic acid can be efficiently and selectively converted into the cyclohexyl acetate, and difficulties and challenges exist, such as low esterification reaction rate, generation of a byproduct cyclohexene dimer in the reaction process, and low yield of the cyclohexyl acetate. Therefore, the development of a catalytic system with high activity, good selectivity and environmental friendliness is urgently needed to improve the cyclohexene esterification reaction rate and the yield of cyclohexyl acetate so as to solve the key problems.
Disclosure of Invention
The invention aims to solve the defects of the background technology and provides a novel method for synthesizing cyclohexyl acetate by directly esterifying cyclohexene and acetic acid.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a functionalized polyacid ionic liquid catalyst is characterized in that the functionalized polyacid ionic liquid is bis-dimethylaminoethyl ether butyl sultone heteropoly acid metal salt, and the structural formula of the functionalized polyacid ionic liquid is as follows:
[Bis-Bs-BDMAEE](1/xM)x+R
in the formula, M is selected from Fe, Co, Al, Ni, Cu or Zn, and when M is Fe, Co and Al, x is 3; when M is Ni, Cu or Zn, x is 2; r is more than one of the following heteropoly acid radical ions: PW (pseudo wire)12O40 3-，PMo12O40 3-，HSiW12O40 3-，HPW11VO40 3-，HPMo11VO40 3-or H2SiW11VO40 3-。
The functionalized polyacid ionic liquid catalyst comprises:
[Bis-Bs-BDMAEE](1/2Cu)PW12O40、
[Bis-Bs-BDMAEE](1/2Cu)HPW11VO40、
[Bis-Bs-BDMAEE](1/3Fe)PMo12O40、
[Bis-Bs-BDMAEE](1/3Fe)PW12O40、
[Bis-Bs-BDMAEE](1/3Co)HSiW12O40、
[Bis-Bs-BDMAEE](1/3Co)HPMo11VO40、
[Bis-Bs-BDMAEE](1/3Al)HPW11VO40、
[Bis-Bs-BDMAEE](1/3Al)HSiW12O40、
[Bis-Bs-BDMAEE](1/2Ni)H2SiW11VO40、
[Bis-Bs-BDMAEE](1/2Zn)PMo12O40、
[Bis-Bs-BDMAEE](1/2Zn)HPMo11VO40。
a method for efficiently catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid comprises the following steps: putting a reaction mixture of cyclohexene and acetic acid and a functionalized polyacid ionic liquid catalyst in a certain molar ratio into a reaction kettle for esterification reaction, discharging, cooling and standing the obtained cyclohexyl acetate mixture after the reaction is finished, precipitating the functionalized polyacid ionic liquid catalyst from a feed liquid, simply filtering to realize the recycling of the functionalized polyacid ionic liquid catalyst, and further distilling the liquid phase mixture to obtain the product of cyclohexyl acetate.
The molar ratio of the cyclohexene raw material to the carboxylic acid is 0.5-6: 1; the mass of the functionalized polyacid ionic liquid catalyst accounts for 1-15% of the total mass of the raw materials; the ester exchange reaction temperature is 40-140 ℃; the reaction time is 1-12 h.
The functionalized polyacid ionic liquid catalyst is obtained by the following method: putting a certain molar amount of ylides in a water bath at 70-100 ℃, dissolving heteropoly acid in distilled water to form a solution, dropwise adding the solution into the ylides, stirring, condensing and refluxing for 10-20h, removing water by reduced pressure distillation after the reaction is finished, washing, and drying in vacuum to obtain a ylides heteropoly acid precursor; putting a certain molar amount of the ylide heteropoly acid precursor into a water bath at 70-100 ℃, adding a certain molar amount of metal oxide, stirring and condensing and refluxing for 10-20h, removing water by reduced pressure distillation after the reaction is finished, and drying for 12-36h at 70-90 ℃ in a vacuum drying oven to obtain a target product; wherein the molar ratio of the ylide to the heteropoly acid is 1: 1-1.5; the molar ratio of the precursor to the metal oxide is 2-4: 1.
The ylide is obtained by taking bis-dimethylamino ethyl ether and 1, 4-butyl sultone with certain molar weight, placing the mixture at 50-80 ℃ and stirring the mixture for rapid reaction to obtain white solid; washing the white solid with ethyl acetate for 3 times, filtering, and drying in vacuum at 70-90 ℃ for 10-15h to obtain the ylide; the molar ratio of the bis-dimethylamino ethyl ether to the 1, 4-butyl sultone is 1: 2-3.
The heteropoly acid is selected from phosphotungstic acid (H)3PW12O40) Phosphomolybdic acid (H)3PMo12O40) Silicotungstic acid (H)4SiW12O40) Phosphotungstic vanadic acid (H)4PW11VO40) Phosphomolybdic acid (H)4PMo11VO40) And silicotungstic vanadic acid (H)5SiW11VO40) More than one of (1).
The metal oxide is selected from CuO and Fe2O3、Co2O3、Al2O3One or more of NiO and ZnO.
Compared with the prior art, the method has the remarkable advantages that:
(1) the functionalized polyacid ionic liquid catalyst has high catalytic activity, good selectivity, mild reaction conditions and high product yield;
(2) the synthesis method of the functionalized polyacid ionic liquid catalyst provided by the invention is simple, good in stability and environment-friendly, and solves the problems that the inorganic liquid acid catalyst is easy to generate side reaction, equipment is seriously corroded, a large amount of waste acid water is generated, and the environment pollution is caused;
(3) the functionalized polyacid ionic liquid catalyst provided by the invention has the characteristic of easy separation from the product, can be recycled after simple filtration, washing and drying treatment, can still maintain high catalytic activity after repeated use, and has wide industrial application prospect.
Detailed Description
The present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited to these examples.
Example 1:
a preparation method of a functionalized polyacid ionic liquid catalyst comprises the following steps:
(1) a certain amount of dimethylamino ethyl ether (0.2mol) and 1, 4-butyl sultone (0.4mol) are taken to be put in a round-bottom flask, the temperature is slowly raised to 60 ℃ under stirring, and the white solid is obtained by fast reaction. The resulting solid was washed with ethyl acetate several times, filtered and dried under vacuum at 80 ℃ for 12 h. The white solid obtained was a ylide.
(2) An amount of the ylide (0.1mol) was taken in a round bottom flask and placed in a water bath at 80 ℃. Taking 0.1mol of phosphotungstic acid (H)3PW12O40) Dissolved in distilled water and added drop-wise to a round bottom flask, stirred and condensed under reflux for 18 h. Removing water by vacuum distillation after reaction to obtain light yellow solid, washing the obtained solid with diethyl ether and toluene for multiple times, and vacuum drying at 80 deg.C for 12 hr to obtain [ Bis-Bs-BDMAEE ]]HPW12O40。
Mixing phosphotungstic acid (H)3PW12O40) Replacement by phosphomolybdic acid (H)3PMo12O40) Silicotungstic acid (H)4SiW12O40) Phosphotungstic vanadic acid (H)4PW11VO40) Phosphomolybdic acid (H)4PMo11VO40) Silicotungstic vanadic acid (H)5SiW11VO40) In the same manner, [ Bis-Bs-BDMAEE ] can be prepared]HPMo12O40、[Bis-Bs-BDMAEE]H2SiW12O40、[Bis-Bs-BDMAEE]H2PW11VO40、[Bis-Bs-BDMAEE]H2PMo11VO40、[Bis-Bs-BDMAEE]H3SiW11VO40And the like.
(3) Taking a certain amount of [ Bis-Bs-BDMAEE]HPW12O40(0.05mol) was placed in a round bottom flask and placed in a water bath at 80 ℃ to dissolve it in distilled water, and an appropriate amount of CuO (0.025mol) was added, stirred and condensed under reflux for 18 h. Reaction ofRemoving water by vacuum distillation, and vacuum drying at 80 deg.C for 24 hr to obtain grey green solid [ Bis-Bs-BDMAEE ]](1/2Cu)PW12O40。
Replacement of CuO by Fe2O3、Co2O3、Al2O3NiO, ZnO, can be prepared by the same method
[Bis-Bs-BDMAEE](1/2Cu)HPW11VO40、
[Bis-Bs-BDMAEE](1/3Fe)PMo12O40、
[Bis-Bs-BDMAEE](1/3Fe)PW12O40、
[Bis-Bs-BDMAEE](1/3Co)HSiW12O40、
[Bis-Bs-BDMAEE](1/3Co)HPMo11VO40、
[Bis-Bs-BDMAEE](1/3Al)HPW11VO40、
[Bis-Bs-BDMAEE](1/3Al)HSiW12O40、
[Bis-Bs-BDMAEE](1/2Ni)H2SiW11VO40、
[Bis-Bs-BDMAEE](1/2Zn)PMo12O40、
[Bis-Bs-BDMAEE](1/2Zn)HPMo11VO40And the like.
Example 2:
a method for catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid comprises the following steps: in the reaction vessel, 18.02g (0.3mol) of acetic acid, 8.21g (0.1mol) of cyclohexene and [ Bis-Bs-BDMAEE ] obtained in example 1 were charged in this order](1/2Cu)PW12O401.84g of catalyst (accounting for 7 wt% of the total mass of the raw materials), stirring, heating to the reaction temperature of 90 ℃, reacting at constant temperature for 7 hours, wherein the conversion rate of cyclohexene is 90%, the selectivity of cyclohexyl acetate is 99%, and the yield of the cyclohexyl acetate is 89%.
Example 3:
a method for catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid comprises the following steps: in the reaction kettle, 6.01g (0.1mol) of acetic acid and 16 g of cyclohexene are added in sequence43g (0.2mol) and [ Bis-Bs-BDMAEE obtained in example 1](1/3Fe)PMo2O401.12g of catalyst (accounting for 5 wt% of the total mass of the raw materials), stirring, heating to 120 ℃, reacting at constant temperature for 3 hours, wherein the conversion rate of cyclohexene is 37%, the selectivity of cyclohexyl acetate is 89%, and the yield of the cyclohexyl acetate is 33%.
Example 4:
a method for catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid comprises the following steps: 36.03g (0.6mol) of acetic acid, 8.21g (0.1mol) of cyclohexene and [ Bis-Bs-BDMAEE ] obtained in example 1 were charged in this order into the reactor](1/3Co)HSiW12O406.64g of catalyst (accounting for 15 wt% of the total mass of the raw materials), stirring, heating to the reaction temperature of 70 ℃, reacting at constant temperature for 12 hours, wherein the conversion rate of cyclohexene is 43%, the selectivity of cyclohexyl acetate is 90%, and the yield of cyclohexyl acetate is 39%.
Example 5:
a method for catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid comprises the following steps: in the reaction vessel, 12.01g (0.2mol) of acetic acid, 8.21g (0.1mol) of cyclohexene and [ Bis-Bs-BDMAEE ] obtained in example 1 were charged in this order](1/3A1)HPW11VO401.82g of catalyst (accounting for 9 wt% of the total mass of the raw materials), stirring, heating to the reaction temperature of 110 ℃, reacting at constant temperature for 8 hours, wherein the conversion rate of cyclohexene is 85%, the selectivity of cyclohexyl acetate is 95%, and the yield of the cyclohexyl acetate is 81%.
Example 6:
a method for catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid comprises the following steps: in the reaction vessel, 24.02g (0.4mol) of acetic acid, 8.21g (0.1mol) of cyclohexene and [ Bis-Bs-BDMAEE ] obtained in example 1 were charged in this order](1/2Ni)H2SiW11VO400.32g of catalyst (accounting for 1 wt% of the total mass of the raw materials), stirring, heating to the reaction temperature of 100 ℃, reacting at constant temperature for 10 hours, wherein the conversion rate of the cyclohexene is 20%, the selectivity of the cyclohexyl acetate is 91%, and the yield of the cyclohexyl acetate is 18%.
Example 7:
a kind ofThe method for catalyzing direct esterification of cyclohexene by using the functionalized polyacid ionic liquid comprises the following steps: in the reaction vessel, 6.01g (0.1mol) of acetic acid, 8.21g (0.1mol) of cyclohexene and [ Bis-Bs-BDMAEE ] obtained in example 1 were charged in this order](1/2Zn)HPMo11VO401.85g of catalyst (accounting for 13 wt% of the total mass of the raw materials), stirring, heating to the reaction temperature of 50 ℃, reacting at constant temperature for 7 hours, wherein the conversion rate of cyclohexene is 27%, the selectivity of cyclohexyl acetate is 85%, and the yield of cyclohexyl acetate is 23%.
Example 8:
a method for catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid comprises the following steps: in the reaction vessel, 18.02g (0.3mol) of acetic acid, 8.21g (0.1mol) of cyclohexene and [ Bis-Bs-BDMAEE ] obtained in example 1 were charged in this order](1/3Fe)PW12O401.84g of catalyst (accounting for 7 wt% of the total mass of the raw materials), stirring, heating to the reaction temperature of 80 ℃, reacting at constant temperature for 5 hours, wherein the conversion rate of cyclohexene is 68%, the selectivity of cyclohexyl acetate is 94%, and the yield of the cyclohexyl acetate is 64%.
Example 9:
a method for catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid comprises the following steps: in the reaction vessel, 30.03g (0.5mol) of acetic acid, 8.21g (0.1mol) of cyclohexene and [ Bis-Bs-BDMAEE ] obtained in example 1 were charged in this order](1/3Al)HSiW12O401.15g of catalyst (accounting for 3 wt% of the total mass of the raw materials), stirring, heating to the reaction temperature of 140 ℃, reacting at constant temperature for 1h, wherein the conversion rate of cyclohexene is 47%, the selectivity of cyclohexyl acetate is 90%, and the yield of the cyclohexyl acetate is 42%.
Example 10:
a method for catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid comprises the following steps: 36.03g (0.6mol) of acetic acid, 8.21g (0.1mol) of cyclohexene and [ Bis-Bs-BDMAEE ] obtained in example 1 were charged in this order into the reactor](1/2Zn)PMo12O403.98g of catalyst (accounting for 9wt percent of the total mass of the raw materials), stirring, heating to the reaction temperature of 60 ℃, reacting for 10 hours at constant temperature, wherein the conversion rate of the cyclohexene is 42 percent, and the selectivity of the cyclohexyl acetate is87% and the yield of cyclohexyl acetate was 37%.
Example 11:
a method for catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid comprises the following steps: in the reaction vessel, 24.02g (0.4mol) of acetic acid, 8.21g (0.1mol) of cyclohexene and [ Bis-Bs-BDMAEE ] obtained in example 1 were charged in this order](1/2Cu)HPW11VO403.55g of catalyst (11 wt% of the total mass of the raw materials), stirring, heating to the reaction temperature of 130 ℃, reacting at constant temperature for 7 hours, wherein the conversion rate of the cyclohexene is 81%, the selectivity of the cyclohexyl acetate is 93%, and the yield of the cyclohexyl acetate is 75%.
Example 12:
a method for catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid comprises the following steps: 36.03g (0.6mol) of acetic acid, 8.21g (0.1mol) of cyclohexene and [ Bis-Bs-BDMAEE ] obtained in example 1 were charged in this order into the reactor](1/2Ni)H2SiW11VO403.98g of catalyst (accounting for 9 wt% of the total mass of the raw materials), stirring, heating to the reaction temperature of 40 ℃, reacting at constant temperature for 12 hours, wherein the conversion rate of cyclohexene is 33%, the selectivity of cyclohexyl acetate is 91%, and the yield of the cyclohexyl acetate is 30%.
Example 13:
a method for catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid comprises the following steps: in the reaction vessel, 30.03g (0.5mol) of acetic acid, 8.21g (0.1mol) of cyclohexene and [ Bis-Bs-BDMAEE ] obtained in example 1 were charged in this order](1/3Co)HPMo11VO401.91g of catalyst (accounting for 5 wt% of the total mass of the raw materials), stirring, heating to 120 ℃, reacting at constant temperature for 4 hours, wherein the conversion rate of cyclohexene is 52%, the selectivity of cyclohexyl acetate is 88%, and the yield of the cyclohexyl acetate is 46%.
The above description is only a preferred embodiment of the present invention, and therefore, the scope of the present invention should not be limited by the above description, and all equivalent changes and modifications made in the claims and the contents of the specification should be included in the scope of the present invention.
Claims (10)
1. A functionalized polyacid ionic liquid catalyst is characterized in that the functionalized polyacid ionic liquid is bis-dimethylaminoethyl ether butyl sultone heteropoly acid metal salt, and the structural formula of the functionalized polyacid ionic liquid is as follows:
[Bis-Bs-BDMAEE](1/xM)x+R
wherein M is selected from Fe, Co, Al, Ni, Cu or Zn, and when M is Fe, Co, a1, x is 3; when M is Ni, Cu or Zn, x is 2; r is selected from more than one of the following heteropoly acid radical ions: PW (pseudo wire)12O40 3-，PMol2O40 3-，HSiWl2040 3-，HPWl1VO40 3-，HPMol1VO40 3-Or H2SiWl1VO40 3-。
2. The functionalized polyacid-based ionic liquid catalyst of claim 1, wherein the catalyst comprises:
[Bis-Bs-BDMAEE](1/2Cu)PW12O40、
[Bis-Bs-BDMAEE](1/2Cu)HPWl1VO40、
[Bis-Bs～BDMAEE](1/3Fe)PMol2O40、
[Bis-Bs-BDMAEE](1/3Fe)PW12O40、
[Bis-Bs-BDMAEE](1/3Co)HSiWl2O40、
[Bis-Bs-BDMAEE](1/3Co)HPMol1VO40、
[Bis-Bs-BDMAEE](1/3A1)HPWl1VO40、
[Bis-Bs-BDMAEE](1/3Al)HSiWl2O40、
[Bis-Bs-BDMAEE](1/2Ni)H2SiWl1VO40、
[Bis-Bs-BDMAEE](1/2Zn)PMol2O40、
[Bis-Bs-BDMAEE](1/2Zn)HPMol1VO40。
3. the method for preparing the functionalized polyacid-based ionic liquid catalyst of claim 1, comprising the steps of: putting a certain molar amount of ylide Bis-Bs-BDMAEE into a water bath at 70-100 ℃, dissolving heteropoly acid in distilled water to form a solution, dropwise adding the solution into the ylide Bis-Bs-BDMAEE, stirring and condensing and refluxing for 10-20h, removing water by reduced pressure distillation after the reaction is finished, washing, and drying in vacuum to obtain a ylide heteropoly acid precursor; putting a certain molar amount of the ylide heteropoly acid precursor into a water bath at 70-100 ℃, adding a certain molar amount of metal oxide, stirring and condensing and refluxing for 10-20h, removing water by reduced pressure distillation after the reaction is finished, and drying for 12-36h at 70-90 ℃ in a vacuum drying oven to obtain a target product; wherein the molar ratio of the ylide Bis-Bs-BDMAEE to the heteropoly acid is 1: 1-1.5; the molar ratio of the precursor to the metal oxide is 2-4: 1.
4. The preparation method of the functionalized polyacid ionic liquid catalyst of claim 3, wherein the ylium salt Bis-Bs-BDMAEE is obtained by taking Bis-dimethylamino ethyl ether and 1, 4-butyl sultone in certain molar amounts, placing at 50-80 ℃ and stirring for rapid reaction to obtain a white solid; washing the white solid with ethyl acetate for 3 times, filtering, and drying in vacuum at 70-90 ℃ for 10-15h to obtain the ylide Bis-Bs-BDMAEE; the molar ratio of the bis-dimethylamino ethyl ether to the 1, 4-butyl sultone is 1: 2-3.
5. The method for preparing the functionalized polyacid-based ionic liquid catalyst according to claim 3, wherein: the heteropoly acid is selected from phosphotungstic acid H3PWl2O40Phosphomolybdic acid H3PMol2O40Silicotungstic acid H4SiWl2O40Phosphotungstic vanadic acid H4PWl1VO40Phosphomolybdic acid H4PMol1VO40And silicotungstic vanadic acid H5SiW11VO40More than one of (1).
6. The method for preparing the functionalized polyacid-based ionic liquid catalyst according to claim 3, wherein: the metal oxide is selected from CuO and Fe2O3、Co2O3、Al2O3One or more of NiO and ZnO.
7. A method for catalyzing direct esterification of cyclohexene by using functionalized polyacid ionic liquid is characterized in that: cyclohexene and acetic acid are used as raw materials, the functionalized polyacid ionic liquid as claimed in claim 1 or 2 is used as a catalyst, and the cyclohexyl acetate is prepared through direct esterification reaction.
8. The process for direct esterification of cyclohexene according to claim 7 wherein: the mass of the polyacid ionic liquid catalyst accounts for 1-15% of the total mass of the raw materials; the mol ratio of the cyclohexene to the acetic acid is 0.5-6: 1.
9. A process for direct esterification of cyclohexene as claimed in claim 7 or 8 wherein: the esterification reaction temperature is 40-140 ℃; the reaction time is 1-12 h.
10. The process for direct esterification of cyclohexene according to claim 7 wherein: the functionalized polyacid ionic liquid catalyst is filtered, washed and dried to realize the recycling of the catalyst.
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