CN108558598A - A kind of method that acid swelling poly ion liquid catalysis hexamethylene esters compound hydrolysis reaction prepares cyclohexanol - Google Patents
A kind of method that acid swelling poly ion liquid catalysis hexamethylene esters compound hydrolysis reaction prepares cyclohexanol Download PDFInfo
- Publication number
- CN108558598A CN108558598A CN201810384848.7A CN201810384848A CN108558598A CN 108558598 A CN108558598 A CN 108558598A CN 201810384848 A CN201810384848 A CN 201810384848A CN 108558598 A CN108558598 A CN 108558598A
- Authority
- CN
- China
- Prior art keywords
- acid
- ion liquid
- poly ion
- reaction
- hexamethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—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
- B01J31/0278—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 containing nitrogen as cationic centre
- B01J31/0281—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 containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—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 containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—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
- 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
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of methods that acid swelling poly ion liquid catalysis hexamethylene esters compound hydrolysis reaction prepares cyclohexanol, the acid swelling poly ion liquid is using ionic liquid and sodium p styrene sulfonate as polymerized monomer, it is acidified through free radical polymerization and sulfuric acid, the acid poly ion liquid being swollen in the organic solvents such as water, ethylene glycol is obtained, with structure shown in formula I.The hexamethylene esters compound hydrolysis reaction is that the reaction of cyclohexanol is prepared using acid swelling poly ion liquid as catalyst hexamethylene esters compound hydrolysis compared under temperate condition.The present invention has the following advantages：(1) acid swelling poly ion liquid is swollen in reaction substrate water, the exposure level of catalytic active center and reaction substrate is considerably increased, to greatly improve reactivity；(2) acid swelling poly ion liquid stable structure, it is easily separated, can be recycled for multiple times.
Description
Technical field
The invention belongs to poly ion liquid catalysis technical fields, and in particular to a kind of acid swelling poly ion liquid catalysis ring
The method that own ester type compound hydrolysis prepares cyclohexanol.
Background technology
Cyclohexanol is a kind of important Elementary Chemical Industry raw material, mainly for the production of adipic acid, hexamethylene diamine and caprolactam etc.
Compound has been widely used in the fields such as organic synthesis, coating and textile industry.Currently, industrial mainly use hexamethylene
Oxidizing process and cyclohexene direct hydration method produce cyclohexanol.Wherein, cyclohexane oxidation process is using air as oxidant, and there are selectivity
The shortcomings of difference, high energy consumption, poor safety, which greatly limits its development.And cyclohexene direct hydration method, although high selectivity,
But since the intersolubility of cyclohexene and water is poor, cause its reaction rate slower.The shortcomings that in order to overcome the above method, scientific research
Worker by cyclohexene and carboxylic acid (such as：Formic acid, acetic acid etc.) the corresponding hexamethylene ester type compound of reaction generation, then through hydrolysis
Prepare cyclohexanol.This method is referred to as the indirect hydration method of cyclohexene, has many advantages, such as that low energy consumption, high selectivity
(Reaction Kinetics Mechanisms and Catalysis 117(2016)329-339)。
Hexamethylene esters compound hydrolysis reaction prepares the second step reaction that cyclohexanol is cyclohexene indirect hydration method.So far,
Have some catalyst system and catalyzings to be reported, two classes can be divided into：(1) homogeneous catalyst：Sulfuric acid, ionic liquid are (such as：1- butyl -3- first
Base imidazole bisulfate) etc.；(2) heterogeneous catalyst：Molecular sieve is (such as：H-ZSM-5), heteropoly acid is (such as：H3PW12O40), charcoal base
Solid acid (43 (2004) 2955-2958 of Angewandte Chemie International Edition), acid cesium salt
(Applied Catalysis A:General 165 (1997) 227-240) etc..Wherein, although homogeneous catalyst catalytic activity
Height, but there are catalyst the problems such as being detached with product difficulty, is seriously polluted.Although and heterogeneous catalyst can solve separation difficulty
Problem, but since the exposure level of active component and reaction substrate is relatively low, its catalytic activity is caused generally to be less than homogeneous catalyst.
Therefore, developing novel efficient green acid catalyst becomes the main direction of studying of researcher.
Acid poly ion liquid is a kind of polymer material containing acidic functionality, has highdensity reaction active site
Point, the structure that can design modulation and acidity and the characteristics such as can be recycled, turn in organic chemical reactions, electrochemistry and biomass
The fields such as change suffer from application (Chemical Reviews 116 (2016) 6133-6183).However, when acid poly ion liquid
When as acid catalyst, since its catalytic active center cannot be fully exposed in reaction substrate so that their catalysis is lived
Property usually less than corresponding homogeneous ionic liquid.
Recently, a kind of alkaline poly ion liquid being swollen in reaction substrate of document report is as effective catalyst catalysis
Aniline and ethylene carbonate (5 (2016) 435-438 of ACS Macro Letters), phenylamino alcohol and ethylene carbonate
(ChemistrySelect 2 (2017) 9443-9449) and ethylene carbonate and water (Green Chemistry 20 (2018)
Reaction 1594-1601).This kind of alkalinity swelling poly ion liquid can be swollen in reaction substrate, increased alkali center and reacted
The exposure level of substrate, to improve the catalytic activity of alkaline poly ion liquid.However, this kind of alkalinity swelling poly ion liquid
Catalytic activity is still difficult to reach the catalytic activity of homogeneous catalyst, and most this kind of catalyst are catalyzed after the completion of reaction
The phenomenon that agent inactivates.
Invention content
The purpose of the present invention is intended to provide a kind of acid swelling poly ion liquid catalysis hexamethylene esters compound hydrolysis reaction
The method for preparing cyclohexanol passes through free radical polymerization and sulphur first using ionic liquid and sodium p styrene sulfonate as polymerized monomer
Acid acidification, the acid poly ion liquid being swollen in water；It is swollen in reaction substrate using acidity swelling poly ion liquid
Special performance and the advantages such as the highdensity reactivity site of poly ion liquid and good stability, in temperate condition
Lower catalysis hexamethylene esters compound hydrolysis reaction prepares cyclohexanol, to realize the Efficient Conversion of reaction.Acid provided by the invention
Property swelling poly ion liquid catalyst catalytic activity be higher than homogeneous catalyst (sulfuric acid, p-methyl benzenesulfonic acid and ionic liquid 1- second
Alkenyl -3- (3 '-sulfonic group) propyl imidazole disulfate etc.) and heterogeneous catalyst (molecular sieve, heteropoly acid and sulfonate resin
Deng), and stability it is good, it is easily separated, can be recycled for multiple times.
Realize the specific technical solution of the object of the invention：
A kind of method that acid swelling poly ion liquid catalysis hexamethylene esters compound hydrolysis reaction prepares cyclohexanol, feature
It is：Ionic liquid and sodium p styrene sulfonate are acidified through free radical polymerization and sulfuric acid, the acid polyion being swollen in water
Liquid is used as the hydrolysis of catalyst hexamethylene ester type compound, generates target product cyclohexanol；Specifically include with
Lower step：Step 1：Prepare acid swelling poly ion liquid
By polymerized monomer (ionic liquid and sodium p styrene sulfonate), crosslinking agent and initiator azodiisobutyronitrile (AIBN)
Be distributed in aqueous solution, transparent solid obtained through thermal initiation free radical polymerization, then by transparent solid be distributed to 0.5~3 mole/
In the aqueous sulfuric acid risen, reaction is stirred at room temperature 12~48 hours, after reaction, is repeatedly washed with deionized water until washing
Liquid is in neutrality, and obtains acid swelling poly ion liquid, and chemical structural formula is：
In formula, n be 3 to 4 integer；Wherein：
Ionic liquid of the present invention is 1- vinyl -3- (3 '-sulfonic group) propyl imidazole salt or 1- vinyl -3-
(4 '-sulfonic group) butyl imidazole salt.
The molar ratio of ionic liquid of the present invention and the sodium p styrene sulfonate is 1~5:5~1.
Crosslinking agent of the present invention is [EG3(Vim)2]Br、[O(Vim)2] Br, divinylbenzene (DVB) or dimethyl propylene
Olefin(e) acid glycol ester (EGDMA)；Wherein, [EG3(Vim)2]Br、[O(Vim)2] Br chemical structural formulas are：
The mole dosage of crosslinking agent of the present invention accounts for the 1~20% of the polymerized monomer total moles dosage.
The mole dosage of initiator A IBN of the present invention account for the polymerized monomer and crosslinking agent total moles dosage 1~
10%.
Water of the present invention and the mass ratio of polymerized monomer are 2.5~10:1.
The reaction temperature of thermal initiation free radical polymerization of the present invention is 60~100 DEG C.
The reaction time of thermal initiation free radical polymerization of the present invention is 12~24 hours.
Step 2：Hexamethylene esters compound hydrolysis reaction prepares cyclohexanol
In autoclave, acid swelling poly ion liquid catalyst, hexamethylene ester type compound and water are sequentially added, is filled
Nitrogen to pressure is 0.01~1.0 megapascal, and reaction temperature is controlled at 60~120 DEG C, is stirred 1~24 hour, is obtained after reaction
To target product cyclohexanol, wherein acid swelling poly ion liquid catalyst repetitive cycling after simple separation recycles uses,
Specifically reaction equation is：
Hexamethylene ester type compound of the present invention is selected from cyclohexyl formate, cyclohexyl acetate, cyclohexyl propionate, butyrate
Ester, pentanoic acid cyclohexyl ester, caproic acid cyclohexyl, 2- cyclohexyl acrylates or benzoate ester.
The molar ratio of hexamethylene ester type compound of the present invention and the water is 1:1~50.
The mole dosage of acid swelling poly ion liquid catalyst of the present invention accounts for the hexamethylene ester type compound mole
The 0.5~10% of dosage.
The present invention has the following advantages：The present invention designs for the first time has synthesized the acid poly ion liquid with swelling behavior.
This acid swelling poly ion liquid has the special performance being swollen in water and the highdensity reaction active site of poly ion liquid
The advantages such as point and good stability, can be catalyzed hexamethylene esters compound hydrolysis reaction and prepare ring under mild conditions
Hexanol, and catalytic activity is considerably higher than the homogeneous and heterogeneous catalyst of known references report.In addition, molten through disappearing after reaction
Swollen and centrifugation, you can realize recycling and the cycling and reutilization of catalyst.Find that such acidity swelling is poly- by circulation experiment
Ionic liquid has an excellent recycling performance, and catalytic activity is without substantially changeing after cycle 10 times.
Specific implementation mode
In conjunction with following specific examples, the present invention is described in further detail, and of the invention protects content not limit to
In following embodiment.Without departing from the spirit and scope of the invention, those skilled in the art it is conceivable that variation and excellent
Point is all included in the present invention, and using appended claims as protection domain.Implement the present invention process, condition,
Reagent, experimental method etc. are among the general principles and common general knowledge in the art, this hair in addition to the following content specially referred to
It is bright that content is not particularly limited.
Embodiment 1：Prepare acid swelling poly ion liquid catalyst P-VSIm48.75-HSS43.75-[EG3(Vim)2]SS2.5
By ionic liquid 1- vinyl -3- (3 '-sulfonic group) propyl imidazole salt (1.054g, 4.875mmol), to benzene second
Alkene sodium sulfonate (1.005g, 4.875mmol), crosslinking agent [EG3(Vim)2] Br (0.116g, 0.25mmol) and initiator A IBN
(0.112g, 0.682mmol) is distributed in the reaction bulb containing 5 milliliters of aqueous solution, after deoxygenation 30 minutes, in a nitrogen atmosphere
It is reacted 24 hours in 80 DEG C.After reaction, sediment water and methanol repeatedly wash, dry, obtain transparent solid.It will be transparent
Solid is distributed in the aqueous sulfuric acid of 100 milliliters of a concentration of 1 mol/Ls, is stirred at room temperature 24 hours, after reaction, is spent
The multiple washing copolymer of ionized water, until cleaning solution is in neutrality.Polymer is dried in vacuo, you can obtain acid swelling polyion
Liquid, and it is named as P-VSIm48.75-HSS43.75-[EG3(Vim)2]SS2.5.It is tested through swellbility, acidity swelling poly ion liquid
P-VSIm48.75-HSS43.75-[EG3(Vim)2]SS2.5Swellbility in water is 25.
Embodiment 2：Prepare acid swelling poly ion liquid catalyst P-VSIm48.75-HSS43.75-[O(Vim)2]SS2.5
By ionic liquid 1- vinyl -3- (3 '-sulfonic group) propyl imidazole salt (1.054g, 4.875mmol), to benzene second
Alkene sodium sulfonate (1.005g, 4.875mmol), crosslinking agent [O (Vim)2] Br (0.115,0.25mmol) and initiator A IBN
(0.112g, 0.682mmol) is distributed in the reaction bulb containing 5 milliliters of aqueous solution, after deoxygenation 30 minutes, in a nitrogen atmosphere
It is reacted 24 hours in 80 DEG C.After reaction, sediment water and methanol repeatedly wash, dry, obtain transparent solid.It will be transparent
Solid is distributed in the aqueous sulfuric acid of 100 milliliters of a concentration of 1 mol/Ls, is stirred at room temperature 24 hours, after reaction, is spent
The multiple washing copolymer of ionized water, until cleaning solution is in neutrality.Polymer is dried in vacuo, you can obtain acid swelling polyion
Liquid, and it is named as P-VSIm48.75-HSS43.75-[O(Vim)2]SS2.5.It is tested through swellbility, acidity swelling poly ion liquid P-
VSIm48.75-HSS43.75-[O(Vim)2]SS2.5Swellbility in water is 14.
Embodiment 3：Acidity swelling poly ion liquid catalyst P-VSIm48.75-HSS43.75-[EG3(Vim)2]SS2.5Catalysis
Acid cyclohexyl ester hydrolysis reaction prepares cyclohexanol
Sequentially added into 50 milliliters of autoclaves equipped with magneton the acid swelling that swellbility in water is 25 gather from
Sub- liquid catalyst P-VSIm48.75-HSS43.75-[EG3(Vim)2]SS2.5(0.205g), cyclohexyl formate (1.281g,
10mmol) with water (4.505g, 250mmol), it is filled with the nitrogen of 0.1 megapascal, after being heated to 100 DEG C, is stirred to react 7 hours.Instead
After answering, be cooled to room temperature, into reaction solution be added internal standard compound biphenyl, using Shimadzu gas chromatograph GC-2014 to its into
Row quantitative analysis determines that the conversion ratio of cyclohexyl formate is 84%, the selective ＞ 99% of target product cyclohexanol.Cyclohexanol
Structure determines through NMR spectrum and mass spectrum,1H NMR(400MHz,CDCl3 ,TMS)3.64-3.63(m,1H),2.01-1.84
(m,2H),1.81-1.71(m,2H),1.62-1.53(m,1H)1.36-1.10(m,5H)；13C NMR(100MHz,CDCl3,
TMS)δ70.3,35.5,25.4,24.1；MS(EI):M/z (%):100[M]+(7),82(89),57(100)。
Embodiment 4：Acidity swelling poly ion liquid catalyst P-VSIm48.75-HSS43.75-[O(Vim)2]SS2.5It is catalyzed second
Sour hexamethylene ester hydrolysis reaction prepares cyclohexanol
Sequentially added into 50 milliliters of autoclaves equipped with magneton the acid swelling that swellbility in water is 14 gather from
Sub- liquid catalyst P-VSIm48.75-HSS43.75-[O(Vim)2]SS2.5(0.201g), cyclohexyl acetate (1.426g, 10mmol)
With water (4.505g, 250mmol), it is filled with the nitrogen of 0.1 megapascal, after being heated to 100 DEG C, is stirred to react 7 hours.Reaction terminates
Afterwards, it is cooled to room temperature, internal standard compound biphenyl is added into reaction solution, it is quantified using Shimadzu gas chromatograph GC-2014
Analysis determines that the conversion ratio of cyclohexyl acetate is 73%, the selective ＞ 99% of target product cyclohexanol.The structure of cyclohexanol passes through
NMR spectrum and mass spectrum determination,1H NMR(400MHz,CDCl3 ,TMS)3.64-3.63(m,1H),2.01-1.84(m,
2H),1.81-1.71(m,2H),1.62-1.53(m,1H)1.36-1.10(m,5H)；13C NMR(100MHz,CDCl3,TMS)δ
70.3,35.5,25.4,24.1；MS(EI):M/z (%):100[M]+(7),82(89),57(100)。
Embodiment 5：Acidity swelling poly ion liquid catalyst P-VSIm48.75-HSS43.75-[EG3(Vim)2]SS2.5Catalysis
Ethyl cyclohexyl ester hydrolysis reaction prepares cyclohexanol
Sequentially added into 50 milliliters of autoclaves equipped with magneton the acid swelling that swellbility in water is 25 gather from
Sub- liquid catalyst P-VSIm48.75-HSS43.75-[EG3(Vim)2]SS2.5(0.205g), cyclohexyl acetate (1.426g,
10mmol) with water (4.505g, 250mmol), it is filled with the nitrogen of 0.1 megapascal, after being heated to 100 DEG C, is stirred to react 7 hours.Instead
After answering, be cooled to room temperature, into reaction solution be added internal standard compound biphenyl, using Shimadzu gas chromatograph GC-2014 to its into
Row quantitative analysis determines that the conversion ratio of cyclohexyl acetate is 80%, the selective ＞ 99% of target product cyclohexanol.Cyclohexanol
Structure determines through NMR spectrum and mass spectrum,1H NMR(400MHz,CDCl3 ,TMS)3.64-3.63(m,1H),2.01-1.84
(m,2H),1.81-1.71(m,2H),1.62-1.53(m,1H)1.36-1.10(m,5H)；13C NMR(100MHz,CDCl3,
TMS)δ70.3,35.5,25.4,24.1；MS(EI):M/z (%):100[M]+(7),82(89),57(100)。
Embodiment 6：Comparative example
Present embodiments provide the method that different acid catalyst catalysis ethyl cyclohexyl ester hydrolysis reactions prepare cyclohexanol.
Acid catalyst (sour total amount is identical), cyclohexyl acetate are sequentially added into 50 milliliters of autoclaves equipped with magneton
(1.426g, 10mmol) and water (4.505g, 250mmol), is filled with the nitrogen of 0.1 megapascal, after being heated to 100 DEG C, is stirred to react 7
Hour.After reaction, it is cooled to room temperature, internal standard compound biphenyl is added into reaction solution, utilizes Shimadzu gas chromatograph GC-2014
Quantitative analysis is carried out to it, the results are shown in Table 1.
The different acid catalyst catalysis ethyl cyclohexyl ester hydrolysis reactions of table 1 prepare cyclohexanol
As seen from Table 1, under the same conditions, acid swelling poly ion liquid P-VSIm48.75-HSS43.75-[EG3(Vim)2]
SS2.5Catalytic activity be considerably higher than homogeneous catalyst (sulfuric acid, p-methyl benzenesulfonic acid and ionic liquid 1- vinyl -3- (3 '-sulphurs
Acidic group) propyl imidazole disulfate) and heterogeneous catalyst (Amberlite IR 120), this illustrates acid swelling polyion liquid
Swelling character of the body in reaction substrate greatly improves the catalytic activity of acid poly ion liquid.
Embodiment 7：Acidity swelling poly ion liquid catalyst P-VSIm48.75-HSS43.75-[EG3(Vim)2]SS2.5Follow
Ring recycles situation
Acidity swelling poly ion liquid catalyst P-VSIm48.75-HSS43.75-[EG3(Vim)2]SS2.5It is catalyzed ethyl cyclohexyl
After ester hydrolysis reaction, through deswelling and centrifugation, recycling is realized, (3 × 5 milliliters) washings of acetone are used in combination, then through vacuum
It is dry, it is added in autoclave, into catalytic cycle next time.With described in embodiment 5, cycle the results are shown in Table other steps
2。
2 catalyst P-VSIm of table48.75-HSS43.75-[EG3(Vim)2]SS2.5Recycling situation
| Cycle-index | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Ethyl cyclohexyl ester conversion rate/% | 79.7 | 80.4 | 82.9 | 81.4 | 79.9 | 81.0 | 80.0 | 78.3 | 79.3 | 77.6 |
| Cyclohexanol selectivity/% | ＞ 99 | ＞ 99 | ＞ 99 | ＞ 99 | ＞ 99 | ＞ 99 | ＞ 99 | ＞ 99 | ＞ 99 | ＞ 99 |
From table 2 it can be seen that acidity swelling poly ion liquid catalyst P-VSIm48.75-HSS43.75-[EG3(Vim)2]
SS2.5After 10 cycles, for catalytic activity without substantially changeing, it is good that this illustrates that such acidity swelling poly ion liquid has
Stability can be recycled for multiple times.
Claims (3)
1. a kind of method that acid swelling poly ion liquid catalysis hexamethylene esters compound hydrolysis reaction prepares cyclohexanol, feature
Be, ionic liquid and sodium p styrene sulfonate are acidified through free radical polymerization and sulfuric acid, the acidity being swollen in water gather from
Sub- liquid is used as the hydrolysis of catalyst hexamethylene ester type compound, generates target product cyclohexanol；It specifically includes
Following steps：
Step 1：Prepare acid swelling poly ion liquid
Polymerized monomer, crosslinking agent and initiator azodiisobutyronitrile (AIBN) are distributed in aqueous solution, through thermal initiation free radical
Polymerization obtains transparent solid, then transparent solid is distributed in the aqueous sulfuric acid of 0.5~3 mol/L, and reaction 12 is stirred at room temperature
It~48 hours, after reaction, is repeatedly washed with deionized water until cleaning solution is in neutrality, obtains acid swelling polyion liquid
Body, chemical structural formula are：
In formula, n be 3 to 4 integer；Wherein：
The polymerized monomer is ionic liquid and sodium p styrene sulfonate, and the molar ratio of ionic liquid and sodium p styrene sulfonate is
1~5:5~1；
The mole dosage of the crosslinking agent accounts for the 1~20% of the polymerized monomer total moles dosage；
The mole dosage of the initiator A IBN accounts for the 1~10% of the polymerized monomer and crosslinking agent total moles dosage；
The water and the mass ratio of polymerized monomer are 2.5~10:1；
The reaction temperature of the thermal initiation free radical polymerization is 60~100 DEG C；Reaction time is 12~24 hours；
Step 2：Hexamethylene esters compound hydrolysis reaction prepares cyclohexanol
In autoclave, acid swelling poly ion liquid catalyst, hexamethylene ester type compound and water, inflated with nitrogen are sequentially added
It is 0.01~1.0 megapascal to pressure, reaction temperature controls at 60~120 DEG C, stirs 1~24 hour, obtain mesh after reaction
Mark product cyclohexanol；Wherein：
The hexamethylene ester type compound is selected from cyclohexyl formate, cyclohexyl acetate, cyclohexyl propionate, cyclohexyl butyrate, valeric acid ring
Own ester, caproic acid cyclohexyl, 2- cyclohexyl acrylates or benzoate ester；
The molar ratio of the hexamethylene ester type compound and the water is 1:1~50；
The mole dosage of the acid swelling poly ion liquid catalyst account for the hexamethylene ester type compound mole dosage 0.5~
10%；
Acid swelling poly ion liquid catalyst repetitive cycling after separation and recovery uses.
2. according to the method described in claim 1, it is characterized in that, the ionic liquid is 1- vinyl -3- (3 '-sulfonic group)
Propyl imidazole salt or 1- vinyl -3- (4 '-sulfonic group) butyl imidazole salt.
3. according to the method described in claim 1, it is characterized in that, the crosslinking agent is [EG3(Vim)2]Br、[O(Vim)2]
Br, divinylbenzene (DVB) or ethylene glycol dimethacrylate (EGDMA)；Wherein, [EG3(Vim)2]Br、[O(Vim)2]Br
Chemical structural formula is：
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810384848.7A CN108558598B (en) | 2018-04-26 | 2018-04-26 | Method for preparing cyclohexanol by catalyzing hydrolysis reaction of cyclohexyl compounds with acidic swelling polyion liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810384848.7A CN108558598B (en) | 2018-04-26 | 2018-04-26 | Method for preparing cyclohexanol by catalyzing hydrolysis reaction of cyclohexyl compounds with acidic swelling polyion liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108558598A true CN108558598A (en) | 2018-09-21 |
| CN108558598B CN108558598B (en) | 2021-05-25 |
Family
ID=63536876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810384848.7A Active CN108558598B (en) | 2018-04-26 | 2018-04-26 | Method for preparing cyclohexanol by catalyzing hydrolysis reaction of cyclohexyl compounds with acidic swelling polyion liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108558598B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109261202A (en) * | 2018-09-30 | 2019-01-25 | 中国科学院山西煤炭化学研究所 | A kind of catalyst and its preparation method and application preparing isobide for sorb dehydration of alcohols |
| CN110354899A (en) * | 2019-08-22 | 2019-10-22 | 华东师范大学 | A kind of solid acid catalyst and preparation method and the application in epoxide hydration |
| CN110975939A (en) * | 2019-12-19 | 2020-04-10 | 华东师范大学 | Ethylene carbonate hydrogenation heterogeneous catalyst, and preparation method and application thereof |
| CN114904576A (en) * | 2022-05-09 | 2022-08-16 | 河南大学 | Catalyst for glycerol condensation reaction and preparation method and application thereof |
| CN116371464A (en) * | 2023-02-10 | 2023-07-04 | 华东师范大学 | Polyionic liquid-hydrotalcite composite material, preparation method and catalytic application |
-
2018
- 2018-04-26 CN CN201810384848.7A patent/CN108558598B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109261202A (en) * | 2018-09-30 | 2019-01-25 | 中国科学院山西煤炭化学研究所 | A kind of catalyst and its preparation method and application preparing isobide for sorb dehydration of alcohols |
| CN110354899A (en) * | 2019-08-22 | 2019-10-22 | 华东师范大学 | A kind of solid acid catalyst and preparation method and the application in epoxide hydration |
| CN110975939A (en) * | 2019-12-19 | 2020-04-10 | 华东师范大学 | Ethylene carbonate hydrogenation heterogeneous catalyst, and preparation method and application thereof |
| CN114904576A (en) * | 2022-05-09 | 2022-08-16 | 河南大学 | Catalyst for glycerol condensation reaction and preparation method and application thereof |
| CN116371464A (en) * | 2023-02-10 | 2023-07-04 | 华东师范大学 | Polyionic liquid-hydrotalcite composite material, preparation method and catalytic application |
| CN116371464B (en) * | 2023-02-10 | 2024-05-17 | 华东师范大学 | Polyionic liquid-hydrotalcite composite material, preparation method and catalytic application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108558598B (en) | 2021-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108558598A (en) | A kind of method that acid swelling poly ion liquid catalysis hexamethylene esters compound hydrolysis reaction prepares cyclohexanol | |
| CN108689838B (en) | Method for preparing formic ether by catalyzing esterification of formic acid and olefin through swellable acidic polyion liquid | |
| CN110776418B (en) | Method for preparing maleic acid ester by catalyzing maleic anhydride with ionic liquid | |
| CN103638956A (en) | Catalyst for synthesizing methyl acrylate by trioxymethylene or paraformaldehyde and acetic acid and acetic acid aqueous solution, its preparation and its application method | |
| CN110372483A (en) | A kind of catalytic oxidation of cyclopentene prepares the process of glutaraldehyde | |
| CN104069891A (en) | Preparation method of polymeric-microsphere-carrier immobilized N-hydroxyphthalimide catalyst | |
| CN102627532B (en) | Use of copper alginate | |
| CN110479374A (en) | A kind of phosphorus heteropoly tungstic acid salt catalyst and preparation method thereof for synthesizing epoxy chloropropane | |
| CN107029784B (en) | A kind of Polymer-supported dual-core acidic ionic liquid catalyst and its preparation and application | |
| CN107602358B (en) | Method for preparing methoxy acetone by using micro-reaction device | |
| CN110078702A (en) | A kind of method of poly ion liquid frame catalyst preparation cyclic carbonate | |
| CN110354899A (en) | A kind of solid acid catalyst and preparation method and the application in epoxide hydration | |
| CN109746042B (en) | Catalyst for synthesizing 3-methoxy methyl acrylate and solid-supported and using method | |
| CN106378189B (en) | Catalyst and its preparation method and application for synthesizing polymethoxy dimethyl ether | |
| CN106256845A (en) | A kind of preparation method of high-molecular aliphatic polycarbonate | |
| CN107540520B (en) | Method for preparing pyromellitic acid or trimellitic acid from pinacol | |
| CN108191814A (en) | A kind of method that phosphotungstic acid titanium ammonium compound salt catalyzes and synthesizes cyclohexanone ethylene ketal | |
| CN111097516A (en) | Catalyst for synthesizing methyl methoxyacetate and preparation method thereof | |
| CN105111128B (en) | A kind of preparation method of N hydroxyphthalimides | |
| CN105712870B (en) | A kind of method that levulic acid catalytic oxidative cracking prepares succinic acid | |
| CN113578378A (en) | Preparation method of terephthalic acid based ionic liquid catalyst and application of terephthalic acid based ionic liquid catalyst in PET degradation | |
| CN108047172B (en) | Method for preparing 2-methyl-5, gamma-dioxotetrahydrofuran-2-pentanoic acid by catalyzing levulinic acid | |
| CN106632832B (en) | A kind of polymer catalyst and preparation method thereof for synthesis of isophorone | |
| CN104592034A (en) | Synthetic method of 1, 3-diamidophenyl-5, 7-dimethyl adamantane | |
| CN115350726B (en) | Catalyst for synthesizing triglyceride, preparation method thereof, triglyceride and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Gao Guohua Inventor after: Chen Bihua Inventor after: Ma Sanguan Inventor after: Zhang Yongya Inventor after: Zhang Yifeng Inventor after: Liu Bo Inventor before: Gao Guohua Inventor before: Ma Sanguan Inventor before: Chen Bihua Inventor before: Zhang Yongya Inventor before: Zhang Yifeng Inventor before: Liu Bo |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |