CN107952479A - A kind of functionalization more acids ionic-liquid catalyst, preparation method and the methods with its catalysis cyclohexene direct esterification - Google Patents
A kind of functionalization more acids ionic-liquid catalyst, preparation method and the methods with its catalysis cyclohexene direct esterification Download PDFInfo
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Abstract
The method of cyclohexene direct esterification is catalyzed the invention discloses a kind of more acids ionic-liquid catalysts of functionalization, preparation method and with it.The method of the catalysis cyclohexene direct esterification, using the more acidic ionic liquids of functionalization as catalyst, cyclohexyl acetate is prepared by esterification using cyclohexene and acetic acid as raw material.The Transformation efficiency is up to 90 % of cyclohexene of the present invention, for the high selectivity of cyclohexyl acetate up to 99%, the yield of cyclohexyl acetate has reached 89%.Method of the present invention has the advantages that catalyst activity is high, and selectivity is good, and reaction condition is gentle, product yield high, catalyst is easily separated with product.
Description
Technical field
It is direct that cyclohexene is catalyzed the present invention relates to a kind of more acids ionic-liquid catalysts of functionalization, preparation method and with it
The method of esterification, is related to the more acids field of ionic liquid of functionalization, catalyzes and synthesizes the synthesis field of esterification cyclohexyl acetate.
Background technology
Cyclohexanol is the intermediate raw material for producing the important chemical products such as adipic acid, caprolactam, cyclohexanone, goes back extensive use
In fields such as organic chemical industry, weaving, coating, dyestuffs.Industrially, the production method of cyclohexanol mainly has air oxidation of cyclohexane
Method, phenol hydrogenation method and cyclohexene direct hydration method.Wherein, cyclohexene direct hydration method has safe, energy saving, atom utilization
It is high, without discarded object and the advantages that environmental pollution, be a kind of friendly process of economic security, before showing good commercial Application
Scape.But the shortcomings of technique is low and unstable there is also catalyst conversion per pass in itself, and production technology operation difficulty is big, people
Be desirable to develop safer environmental protection, Atom economy is stronger, cost is lower, the cyclohexanol production side of production efficiency higher
Method.For this reason, lot of domestic and foreign scholar, which has researched and developed cyclohexene indirect method, prepares cyclohexanol technique, i.e. cyclohexene and acetic acid elder generation ester
Change, then hydrolyze (ester exchange or hydrogenation) again and prepare cyclohexanol.Wherein cyclohexene is first esterified repeated hydrogenation two-step method production cyclohexanol
Technique, in addition to cyclohexanol is produced, also changes into the corresponding alcohol that price is high and market capacity is huge by cheap carboxylic acid, increases
The economy of process is added, there is huge industrial application value.Wherein hydrogenation technique can be added using the existing copper system ester in market
Hydrogen catalyst is achieved with very high conversion ratio and selectivity.And cyclohexene and acetic acid direct esterification Synthesis of Cyclohexyl Acetate technique
It is that directly make use of abundant cyclohexene resource, makees intermediate without alcohol, reduce cyclohexyl acetate production cost have obvious
Economic benefit.
Some new catalyst system and catalyzings are applied to during cyclohexene and acetic acid direct esterification reaction, using acid sun
Ion exchange resin, mesoporous molecular sieve SBA-15,Acidic functionalized ionic liquid, copper triflate salt etc. are catalyzed
Agent is used for the direct esterification reaction of alkene, obtains certain yield, but still do not reach preferable ideal response effect.Example
Such as, acid cation exchange resin catalyst shows good catalytic activity, is a kind of commercial solid acid of excellent performance
Catalyst, but at the same time there is also some defects, as heat endurance is poor, be easily poisoned and inactivate, there are the problems such as mass transfer.
In conclusion how by cyclohexene and acetic acid are efficient, being converted into cyclohexyl acetate with high selectivity, also there is one
It is a little difficult with challenging, as esterification reaction rate is low, generation and ethyl cyclohexyl of the reaction process with by-product cyclic hexene dimer
The problems such as ester yield is relatively low.Therefore, there is an urgent need to develop active high, selectively good and environmental-friendly catalyst system and catalyzing to improve ring
The yield of hexene esterification reaction rate and cyclohexyl acetate is so as to solve above-mentioned key issue.
The content of the invention
Present invention aim to address the deficiency of above-mentioned background technology, proposes that a kind of cyclohexene is synthesized with acetic acid direct esterification
The new method of cyclohexyl acetate, its main feature is that use the more acidic ionic liquids of functionalization as catalyst, using cyclohexene and acetic acid as
Raw material, cyclohexyl acetate is generated through direct esterification reaction.
For achieving the above object, technical scheme is as follows:
A kind of more acids ionic-liquid catalysts of functionalization, it is characterised in that the more acidic ionic liquids of functionalization are
Double dimethylaminoethyl ether butyl sulfonic acid lactone heteropolyacid metal salts, its structural formula are:
[Bis-Bs-BDMAEE](1/xM)x+R
In above-mentioned formula, M is selected from Fe, Co, Al, Ni, Cu or Zn, and when M is Fe, when Co, Al, x=3;When M is Ni, Cu, Zn
When, x=2;Below R heteropoly acid radical ions more than one:PW12O40 3-, PMo12O40 3-, HSiW12O40 3-, HPW11VO40 3-,
HPMo11VO40 3- or H2SiW11VO40 3-。
The above-mentioned more acids ionic-liquid catalysts of functionalization include:
[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 kind of method of the more acidic ionic liquids efficient catalytic cyclohexene direct esterifications of functionalization, comprises the following steps:Will
Acids ionic-liquid catalyst input reaction more than the reaction mixture and functionalization of the certain mole of cyclohexene for measuring ratio and acetic acid
Kettle carries out esterification, after completion of the reaction, obtained ethyl cyclohexyl ester admixture discharging cooling and standings, the more acidic ionics of functionalization
Liquid catalyst is precipitated out from feed liquid, is that the recycling of the more acids ionic-liquid catalysts of functionalization can be achieved through simple filtration
Recycle, liquid phase mixture obtains product cyclohexyl acetate through further distillation.
Above-mentioned raw material cyclohexene and the molar ratio of carboxylic acid are 0.5~6: 1;The more acids ionic-liquid catalysts of functionalization
Quality accounts for the 1~15% of raw material gross mass;Transesterification reaction temperature is 40~140 DEG C;Reaction time is 1~12h.
The above-mentioned more acids ionic-liquid catalysts of functionalization obtain in accordance with the following methods:The inner salt of certain molar weight is taken to put
In 70-100 DEG C of water-bath, heteropoly acid is dissolved in distilled water and forms solution, the solution is added drop-wise in the inner salt,
Stir and condensing reflux 10-20h, after reaction vacuum distillation remove water, washing, obtains inner salt heteropoly acid after vacuum drying
Precursor;Take the inner salt heteropoly acid precursor of certain molar weight to be placed in 70-100 DEG C of water-bath, add the gold of certain molar weight
Belong to oxide, stir and condensing reflux 10-20h, after reaction vacuum distillation remove water, and the 70-90 in vacuum drying chamber
DEG C dry 12-36h, obtains target product;Wherein, the molar ratio of the inner salt and the heteropoly acid is 1: 1~1.5;It is described
The molar ratio of precursor and the metal oxide is 2~4: 1.
Above-mentioned inner salt is prepared by the following, and takes the double dimethylaminoethyl ethers and Isosorbide-5-Nitrae-butyl sulphur of certain molar weight
Acid lactone, is placed at 50-80 DEG C and stirs fast reaction, obtain white solid;The white solid is washed 3 times with ethyl acetate
After filtering, 10-15h is dried in vacuo at 70-90 DEG C, obtains the inner salt;Double dimethylaminoethyl ethers and described 1,
The molar ratio of 4- butyl sulfonic acid lactones is 1: 2~3.
Above-mentioned heteropoly acid is selected from phosphotungstic acid (H3PW12O40), phosphomolybdic acid (H3PMo12O40), silico-tungstic acid (H4SiW12O40), phosphorus tungsten
Vanadic acid (H4PW11VO40), molybdovanaphosphoric acid (H4PMo11VO40) and silicon tungsten vanadic acid (H5SiW11VO40) more than one.
Above-mentioned metal oxide is selected from CuO, Fe2O3、Co2O3、Al2O3, one or more of NiO, ZnO.
Compared with the conventional method, remarkable advantage of the invention is:
(1) the more acids ionic-liquid catalyst catalytic activity of functionalization are high, and selectivity is good, and reaction condition is gentle, and product is received
Rate is high;
(2) the more acids ionic-liquid catalyst synthetic methods of functionalization provided by the invention are simple, and stability is good, and green is right
It is environmental-friendly, solve inorganic liquid acid catalyst and side reaction easily occurs, serious corrosion of equipment, produces a large amount of waste acid waters, cause
The problems such as environmental pollution;
(3) the more acids ionic-liquid catalysts of functionalization provided by the invention have the characteristics that easily to separate with product, through letter
The recycling of catalyst can be achieved after single-filtering, washing, drying and processing, can still keep higher after being used for multiple times and urge
Change activity, there is wide industrial applications prospect.
Embodiment
Below by way of specific embodiment, the present invention is described further, but protection scope of the present invention is not limited to
These embodiments.
Embodiment 1:
A kind of preparation method of the more acids ionic-liquid catalysts of functionalization, the described method comprises the following steps:
(1) a certain amount of double dimethylaminoethyl ethers (0.2mol) are taken to be burnt with Isosorbide-5-Nitrae-butyl sulfonic acid lactone (0.4mol) in round bottom
In bottle, 60 DEG C are to slowly warm up under agitation, fast reaction obtains white solid.Obtained solid is washed repeatedly with ethyl acetate
After filtering, 12h is dried in vacuo at 80 DEG C.Obtained white solid is inner salt.
(2) take a certain amount of inner salt (0.1mol) to be placed in round-bottomed flask, be placed in 80 DEG C of water-baths.Take 0.1mol's
Phosphotungstic acid (H3PW12O40) be dissolved in distilled water and be added dropwise in round-bottomed flask, stir simultaneously condensing reflux 18h.After reaction
Vacuum distillation removes water, obtains faint yellow solid, true at 80 DEG C after the solid of gained is washed repeatedly using ether and toluene
The dry 12h of sky can obtain [Bis-Bs-BDMAEE] HPW12O40。
By phosphotungstic acid (H3PW12O40) replace with phosphomolybdic acid (H3PMo12O40), silico-tungstic acid (H4SiW12O40), tungstovanadophosphoric acid
(H4PW11VO40), molybdovanaphosphoric acid (H4PMo11VO40), silicon tungsten vanadic acid (H5SiW11VO40), it can prepare [Bis- with same method
Bs-BDMAEE]HPMo12O40、[Bis-Bs-BDMAEE]H2SiW12O40、[Bis-Bs-BDMAEE]H2PW11VO40、[Bis-Bs-
BDMAEE]H2PMo11VO40、[Bis-Bs-BDMAEE]H3SiW11VO40Deng.
(3) a certain amount of [Bis-Bs-BDMAEE] HPW is taken12O40(0.05mol) is placed in round-bottomed flask, is placed in 80 DEG C
It is dissolved in distilled water in water-bath, and add appropriate CuO (0.025mol), stir simultaneously condensing reflux 18h.Reaction terminates
Vacuum distillation removes water afterwards, and is dried in vacuo 24h at 80 DEG C and can obtain celadon solid [Bis-Bs-BDMAEE] (1/2Cu)
PW12O40。
CuO is replaced with into Fe2O3、Co2O3、Al2O3, NiO, ZnO, can be prepared with 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)HPMo11VO40Deng.
Embodiment 2:
A kind of method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, comprises the following steps:Anti-
Answer in kettle, sequentially add acetic acid 18.02g (0.3mol), obtained [Bis- in cyclohexene 8.21g (0.1mol) and embodiment 1
Bs-BDMAEE](1/2Cu)PW12O40Catalyst 1.84g (7wt% for accounting for raw material gross mass), agitating and heating are warming up to reaction temperature
90 DEG C, isothermal reaction 7h of degree, the conversion ratio of cyclohexene is 90%, and the selectivity of cyclohexyl acetate is 99%, cyclohexyl acetate
Yield is 89%.
Embodiment 3:
A kind of method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, comprises the following steps:Anti-
Answer in kettle, sequentially add acetic acid 6.01g (0.1mol), obtained [Bis- in cyclohexene 16.43g (0.2mol) and embodiment 1
Bs-BDMAEE](1/3Fe)PMo2O40Catalyst 1.12g (5wt% for accounting for raw material gross mass), agitating and heating are warming up to reaction temperature
120 DEG C, isothermal reaction 3h of degree, the conversion ratio of cyclohexene is 37%, and the selectivity of cyclohexyl acetate is 89%, cyclohexyl acetate
Yield is 33%.
Embodiment 4:
A kind of method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, comprises the following steps:Anti-
Answer in kettle, sequentially add acetic acid 36.03g (0.6mol), obtained [Bis- in cyclohexene 8.21g (0.1mol) and embodiment 1
Bs-BDMAEE](1/3Co)HSiW12O40Catalyst 6.64g (15wt% for accounting for raw material gross mass), agitating and heating is warming up to reaction
Temperature 70 C, isothermal reaction 12h, the conversion ratio of cyclohexene is 43%, and the selectivity of cyclohexyl acetate is 90%, cyclohexyl acetate
Yield be 39%.
Embodiment 5:
A kind of method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, comprises the following steps:Anti-
Answer in kettle, sequentially add acetic acid 12.01g (0.2mol), obtained [Bis- in cyclohexene 8.21g (0.1mol) and embodiment 1
Bs-BDMAEE](1/3A1)HPW11VO40Catalyst 1.82g (9wt% for accounting for raw material gross mass), agitating and heating is warming up to reaction
110 DEG C, isothermal reaction 8h of temperature, the conversion ratio of cyclohexene is 85%, and the selectivity of cyclohexyl acetate is 95%, cyclohexyl acetate
Yield be 81%.
Embodiment 6:
A kind of method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, comprises the following steps:Anti-
Answer in kettle, sequentially add acetic acid 24.02g (0.4mol), obtained [Bis- in cyclohexene 8.21g (0.1mol) and embodiment 1
Bs-BDMAEE](1/2Ni)H2SiW11VO40Catalyst 0.32g (1wt% for accounting for raw material gross mass), agitating and heating is warming up to reaction
100 DEG C, isothermal reaction 10h of temperature, the conversion ratio of cyclohexene is 20%, and the selectivity of cyclohexyl acetate is 91%, ethyl cyclohexyl
The yield of ester is 18%.
Embodiment 7:
A kind of method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, comprises the following steps:Anti-
Answer in kettle, sequentially add acetic acid 6.01g (0.1mol), obtained [Bis-Bs- in cyclohexene 8.21g (0.1mol) and embodiment 1
BDMAEE](1/2Zn)HPMo11VO40Catalyst 1.85g (13wt% for accounting for raw material gross mass), agitating and heating are warming up to reaction temperature
50 DEG C, isothermal reaction 7h of degree, the conversion ratio of cyclohexene is 27%, and the selectivity of cyclohexyl acetate is 85%, cyclohexyl acetate
Yield is 23%.
Embodiment 8:
A kind of method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, comprises the following steps:Anti-
Answer in kettle, sequentially add acetic acid 18.02g (0.3mol), obtained [Bis- in cyclohexene 8.21g (0.1mol) and embodiment 1
Bs-BDMAEE](1/3Fe)PW12O40Catalyst 1.84g (7wt% for accounting for raw material gross mass), agitating and heating are warming up to reaction temperature
80 DEG C, isothermal reaction 5h of degree, the conversion ratio of cyclohexene is 68%, and the selectivity of cyclohexyl acetate is 94%, cyclohexyl acetate
Yield is 64%.
Embodiment 9:
A kind of method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, comprises the following steps:Anti-
Answer in kettle, sequentially add acetic acid 30.03g (0.5mol), obtained [Bis- in cyclohexene 8.21g (0.1mol) and embodiment 1
Bs-BDMAEE](1/3Al)HSiW12O40Catalyst 1.15g (3wt% for accounting for raw material gross mass), agitating and heating is warming up to reaction
140 DEG C, isothermal reaction 1h of temperature, the conversion ratio of cyclohexene is 47%, and the selectivity of cyclohexyl acetate is 90%, cyclohexyl acetate
Yield be 42%.
Embodiment 10:
A kind of method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, comprises the following steps:Anti-
Answer in kettle, sequentially add acetic acid 36.03g (0.6mol), obtained [Bis- in cyclohexene 8.21g (0.1mol) and embodiment 1
Bs-BDMAEE](1/2Zn)PMo12O40Catalyst 3.98g (9wt% for accounting for raw material gross mass), agitating and heating are warming up to reaction temperature
60 DEG C, isothermal reaction 10h of degree, the conversion ratio of cyclohexene is 42%, and the selectivity of cyclohexyl acetate is 87%, cyclohexyl acetate
Yield is 37%.
Embodiment 11:
A kind of method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, comprises the following steps:Anti-
Answer in kettle, sequentially add acetic acid 24.02g (0.4mol), obtained [Bis- in cyclohexene 8.21g (0.1mol) and embodiment 1
Bs-BDMAEE](1/2Cu)HPW11VO40Catalyst 3.55g (11wt% for accounting for raw material gross mass), agitating and heating is warming up to reaction
130 DEG C, isothermal reaction 7h of temperature, the conversion ratio of cyclohexene is 81%, and the selectivity of cyclohexyl acetate is 93%, cyclohexyl acetate
Yield be 75%.
Embodiment 12:
A kind of method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, comprises the following steps:Anti-
Answer in kettle, sequentially add acetic acid 36.03g (0.6mol), obtained [Bis- in cyclohexene 8.21g (0.1mol) and embodiment 1
Bs-BDMAEE](1/2Ni)H2SiW11VO40Catalyst 3.98g (9wt% for accounting for raw material gross mass), agitating and heating is warming up to reaction
40 DEG C, isothermal reaction 12h of temperature, the conversion ratio of cyclohexene is 33%, and the selectivity of cyclohexyl acetate is 91%, cyclohexyl acetate
Yield be 30%.
Embodiment 13:
A kind of method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, comprises the following steps:Anti-
Answer in kettle, sequentially add acetic acid 30.03g (0.5mol), obtained [Bis- in cyclohexene 8.21g (0.1mol) and embodiment 1
Bs-BDMAEE](1/3Co)HPMo11VO40Catalyst 1.91g (5wt% for accounting for raw material gross mass), agitating and heating is warming up to reaction
120 DEG C, isothermal reaction 4h of temperature, the conversion ratio of cyclohexene is 52%, and the selectivity of cyclohexyl acetate is 88%, cyclohexyl acetate
Yield be 46%.
The foregoing is only a preferred embodiment of the present invention, therefore the scope that the present invention is implemented cannot be limited with this, and
The equivalent changes and modifications made according to the scope of the claims and description of the present patent application, all should still belong to patent of the present invention and cover
In the range of.
Claims (10)
1. a kind of more acids ionic-liquid catalysts of functionalization, it is characterised in that the more acidic ionic liquids of functionalization are double
Dimethylaminoethyl ether butyl sulfonic acid lactone heteropolyacid metal salt, its structural formula are:
[Bis-Bs-BDMAEE](1/xM)x+R
In above-mentioned formula, M is selected from Fe, Co, Al, Ni, Cu or Zn, and when M is Fe, when Co, Al, x=3;When M is Ni, when Cu, Zn, x
=2;Below R heteropoly acid radical ions more than one:PW12O40 3-, PMo12O40 3-, HSiW12O40 3-, HPW11VO40 3-,
HPMo11VO40 3-Or H2SiW11VO40 3-。
2. the more acids ionic-liquid catalysts of functionalization according to claim 1, it is characterised in that the catalyst bag
Include:
[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。
3. the preparation method of the more acids ionic-liquid catalysts of functionalization according to claim 1, it is characterised in that described
Method comprises the following steps:Take the inner salt of certain molar weight to be placed in 70-100 DEG C of water-bath, heteropoly acid is dissolved in distilled water
Solution is formed, the solution is added drop-wise in the inner salt, stir and condensing reflux 10-20h, after reaction decompression are steamed
Water is removed in distillation, and washing, obtains inner salt heteropoly acid precursor after vacuum drying;Before taking the inner salt heteropoly acid of certain molar weight
Body is placed in 70-100 DEG C of water-bath, adds the metal oxide of certain molar weight, stirs and condensing reflux 10-20h, reaction terminate
Vacuum distillation removes water, and the 70-90 DEG C of dry 12-36h in vacuum drying chamber afterwards, obtains target product;Wherein, in described
The molar ratio of salt and the heteropoly acid is 1: 1~1.5;The molar ratio of the precursor and the metal oxide is 2~4: 1.
4. the preparation method of the more acids ionic-liquid catalysts of functionalization according to claim 3, it is characterised in that described
Inner salt is prepared by the following, and is taken the double dimethylaminoethyl ethers and Isosorbide-5-Nitrae-butyl sulfonic acid lactone of certain molar weight, is placed in
Fast reaction is stirred at 50-80 DEG C, obtains white solid;After the white solid is washed 3 filterings with ethyl acetate,
10-15h is dried in vacuo at 70-90 DEG C, obtains the inner salt;Double dimethylaminoethyl ethers and the Isosorbide-5-Nitrae-butyl sulfonic acid
The molar ratio of lactone is 1: 2~3.
5. the preparation method of the more acids ionic-liquid catalysts of functionalization according to claim 3, it is characterised in that:It is described
Heteropoly acid is selected from phosphotungstic acid (H3PW12O40), phosphomolybdic acid (H3PMo12O40), silico-tungstic acid (H4SiW12O40), tungstovanadophosphoric acid
(H4PW11VO40), molybdovanaphosphoric acid (H4PMo11VO40) and silicon tungsten vanadic acid (H5SiW11VO40) more than one.
6. the preparation method of the more acids ionic-liquid catalysts of functionalization according to claim 3, it is characterised in that:It is described
Metal oxide is selected from CuO, Fe2O3、Co2O3、Al2O3, one or more of NiO, ZnO.
A kind of 7. method with the ionic liquid-catalyzed cyclohexene direct esterification of the more acids of functionalization, it is characterised in that:With cyclohexene
It is raw material with acetic acid, using the more acidic ionic liquids of the functionalization any one of claim 1-6 as catalyst, by direct
Esterification prepares cyclohexyl acetate.
8. the method for cyclohexene direct esterification according to claim 7, it is characterised in that:More acidic ionic liquids are urged
The quality of agent accounts for the 1~15% of raw material gross mass;The molar ratio of the amphene and acetic acid is 0.5~6: 1.
9. the method for the cyclohexene direct esterification according to claim 7 or 8, it is characterised in that:The esterification reaction temperature
For 40~140 DEG C;Reaction time is 1~12h.
10. the method for cyclohexene direct esterification according to claim 7, it is characterised in that:The more acids of functionalization from
The recycling that sub- liquid catalyst is filtered, washs, catalyst is realized after drying and processing.
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CN106748908A (en) * | 2017-01-17 | 2017-05-31 | 闽江学院 | Many heteropolyacid anions heteropoly acid ion hybrids of multi-sulfonic functionalization and its preparation method and application |
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CN106748908A (en) * | 2017-01-17 | 2017-05-31 | 闽江学院 | Many heteropolyacid anions heteropoly acid ion hybrids of multi-sulfonic functionalization and its preparation method and application |
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