CN111909094A - Multi-active center ionic liquid, preparation method and method for catalytically synthesizing cyclic carbonate by using multi-active center ionic liquid - Google Patents
Multi-active center ionic liquid, preparation method and method for catalytically synthesizing cyclic carbonate by using multi-active center ionic liquid Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 35
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000004593 Epoxy Substances 0.000 claims abstract description 20
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- -1 dicarboxyl imidazole dibromide Chemical compound 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 5
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- YHCVRAUCGVYFQA-UHFFFAOYSA-N ethyl bromate Chemical compound CCOBr(=O)=O YHCVRAUCGVYFQA-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- SODVIWFIWHJBNS-UHFFFAOYSA-N 1H-imidazole dihydrobromide Chemical compound Br.Br.C1=CNC=N1 SODVIWFIWHJBNS-UHFFFAOYSA-N 0.000 claims description 2
- 150000005690 diesters Chemical class 0.000 claims description 2
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical group CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 37
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000001514 detection method Methods 0.000 description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
-
- 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
- B01J31/0279—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 cationic portion being acyclic or nitrogen being a substituent on a ring
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- Catalysts (AREA)
Abstract
The invention relates to a novel multi-active center ionic liquid, which has the following structural formula:
wherein n =1, 2 or 3. The invention also provides a method for synthesizing cyclic carbonate by using the ionic liquid catalyst. The invention solves the problem of the prior utilization of CO2With catalysts present in the process for the synthesis of cyclic carbonates with epoxy compounds, which catalysts are not very high in performance, are harsh in reaction conditions, and use organic solvents or co-catalystsThe problem is that the novel multi-active center ionic liquid is used as a catalyst to catalyze epoxy compounds and CO at the temperature of 30-80 ℃ under the pressure of 0.1-0.5 MPa2The cycloaddition reaction is carried out to generate the cyclic carbonate, and the highest yield can reach 98.5 percent.
Description
Technical Field
The invention belongs to the technical field of environment-friendly catalysis, and particularly relates to a novel multi-active-center ionic liquid, a preparation method and application of the ionic liquid in catalyzing carbon dioxide and an epoxy compound to react and synthesize cyclic carbonate.
Background
CO2As a cheap, rich, nontoxic and renewable C1 resource, the material can replace CO or phosgene to synthesize a plurality of chemical products with high added value, such as urea, methanol, cyclic carbonate and the like, which has great significance from the perspective of green sustainability. In a large number of CO2In the conversion utilization pathway, CO2The cycloaddition reaction with epoxy compounds is the most effective and widely used method, on one hand, the cycloaddition reaction belongs to atom economy type reaction, the by-products are negligible, on the other hand, the generated cyclic carbonate has wide application, and can be used as polar aprotic solvent, electrolyte of fuel cells or lithium ion batteries and various medical intermediates.
Since cyclic carbonates have important economic potential and broad application prospects, further improvement in catalyst performance is required to improve yield and reduce cost. Among the various catalysts, ionic liquids have been reported to stand out among numerous catalysts with their unique advantages. In recent decades, various ionic liquids have been developed, such as functionalized ionic liquids, dicationic ionic liquids, and bifunctional ionic liquids, but general ionic liquids may still have one or more disadvantages of low catalytic activity, harsh catalytic conditions, and low reusability. Therefore, it is necessary to search for a high-efficiency ionic liquid having high catalytic activity under mild conditions.
Disclosure of Invention
In order to solve the technical problems of low catalyst activity, harsh reaction conditions, use of organic solvents and the like in the conventional method for synthesizing the cyclic carbonate, the invention aims to provide a novel multi-active-center ionic liquid, which is used for catalyzing and synthesizing the cyclic carbonate under the conditions of normal temperature and normal pressure, has high catalytic activity and does not need any metal cocatalyst or organic solvent.
The invention also provides a preparation method of the novel multi-active-center ionic liquid.
In order to achieve the purpose, the invention adopts the following technical scheme:
a novel multi-active center ionic liquid has a structural formula as follows:
The invention provides a preparation method of the ionic liquid with multiple active centers, which comprises the following steps:
1) reacting imidazole with ethyl bromate to generate ester imidazole, which specifically comprises the following steps: imidazole and ethyl bromate in CH2Cl2、KOH、K2CO3Carrying out reflux reaction for 6-10h in the presence of tetrabutylammonium bromide, and carrying out post-treatment after the reaction is finished; the ethyl bromoate is BrCH2COOEt、BrCH2CH2COOEt or BrCH2CH2CH2COOEt；
2) Ester imidazole and CH2Br2Reacting for 0.5-5 h at 90-100 ℃, obtaining solid diester imidazole dibromide salt after the reaction is finished, and obtaining dicarboxyl imidazole dibromide after hydrolysis and water removal by hydrobromic acid;
3) and (3) stirring and reacting the dicarboxylimidazole dibromic acid and 1,1,3, 3-tetramethylguanidine at room temperature for 6-18 h in the presence of a solvent, and performing rotary evaporation, washing and drying after the reaction is finished to obtain the product.
The synthetic route of the multi-active center ionic liquid is as follows:
specifically, in the preparation method of the ionic liquid with multiple active centers, ester imidazole and CH2Br2The molar ratio of (A) to (B) is 1-1.5: 0.5; the molar ratio of the dicarboxylimidazole dibromic acid to the 1,1,3, 3-tetramethylguanidine is 1: 2-2.5; the solvent is methanol, ethanol, etc.
The invention provides a method for catalytically synthesizing cyclic carbonate by using the multi-active center ionic liquid, which comprises the steps of adding the multi-active center ionic liquid and an epoxy compound into a reaction kettle according to the mol ratio of 2-35: 100, and synthesizing the cyclic carbonate by performing cycloaddition reaction for 1-10 hours under the conditions that the reaction pressure is 0.1-0.5 MPa and the reaction temperature is 30-80 ℃.
Specifically, the epoxy compound is a compound with any one of the following structures:
further preferably, the molar ratio of the multi-active center ionic liquid to the epoxy compound is 1-2: 20.
Further preferably, the temperature of the cycloaddition reaction is 30 to 60 ℃.
The invention provides a method for catalyzing CO by using novel multi-active-center ionic liquid2And a method for preparing cyclic carbonate by using an epoxy compound, namely using a novel multi-active center ionic liquid as a catalyst, and enabling CO to react under mild conditions without using a cocatalyst or a solvent2And an epoxy compound to synthesize a cyclic carbonate through a cycloaddition reaction. CO 22The reaction equation for preparing cyclic carbonates by cycloaddition with epoxy compounds is as follows:
wherein R is-CH2Cl、-CH2OH、-C6H5、-CH2OCH2CH＝CH2or-CH2OC6H5And the like.
Compared with the prior art, the invention has the following beneficial effects:
1) the novel multi-active-center ionic liquid provided by the invention can efficiently catalyze CO under the conditions of mildness (normal temperature and pressure), no cocatalyst and no organic solvent2And an epoxy compound to form a cyclic carbonate. The catalyst can catalyze different epoxidationsThe compound and CO2The cycloaddition reaction shows excellent universality;
2) the novel multi-active-center ionic liquid of the invention catalyzes CO2And the epoxy compound can be recycled for many times, the cyclic carbonate can be easily separated under the condition of adding ethyl acetate after being catalytically generated, the solid ionic liquid can be obtained again through simple washing and rotary evaporation, the recycling performance is good, and the cost is reduced. The catalyst catalyzes CO2High activity in cycloaddition reaction with epoxy compounds, mild reaction conditions, no metal or solvent, high operation safety and good industrial application prospect.
Drawings
FIG. 1 is C [ CMImBrTMG ] prepared in example 1]2Nuclear magnetic resonance hydrogen spectrum of the catalyst;
FIG. 2 is C [ CMImBrTMG ] prepared in example 1]2Nuclear magnetic resonance carbon spectrum of the catalyst;
C[CMImBrTMG]2the data for the hydrogen and carbon spectra of nmr are as follows:1H NMR(400MHz,D2O)7.87(s,1H),7.65(s,1H),6.82(s,1H),4.94(s,2H),3.38(s,1H),3.00(s,12H).13C NMR(101MHz,D2o)171.43,137.89,124.87,121.75,59.03,52.45,48.90, 38.91; from fig. 1 and 2 and the corresponding nuclear magnetic data analysis, it is understood that the synthesized catalyst is the target catalyst.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, and the following examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
The structural formula of the novel multi-active-center ionic liquid catalyst prepared in the example is as follows:
First, 6.8g (0.10mol) of imidazole and 75mL of CH were added to a 250mL three-necked flask2Cl2，8.4g(0.15mol)KOH、13.8g(0.10mol)K2CO3And 0.79g (0.002mol) of tetrabutylammonium bromide, stirred at room temperature for 30min, and 16.7g (0.1mol) of BrCH was added dropwise2And (5) after the COOEt is dripped for about 30min, continuously stirring and refluxing for 6-10 h. After the reaction is finished, stopping heating, cooling to room temperature, filtering, and precipitating with CH2Cl2Washing (40 mL. times.3), washing the filtrate with saturated NaCl solution and rotary evaporation of the organic phase to give a wine-red liquid I-esterimidazole.
Next, in a 100mL one-necked flask, 7.7g (0.05mol) of the synthesized wine-red liquid I and 4.35g (0.025mol) of CH were charged2Br2Heating at 96 ℃ for 4-5 h under the solvent-free condition, washing with ethyl acetate after the reaction is finished, and performing rotary evaporation to obtain a light yellow solid II diester imidazole dibromo salt. Then, 14.45g (0.03mol) of the pale yellow solid II was taken in a 100mL single-neck flask, and 10.8g (0.06mol) of 45% hydrobromic acid and 5mL of H were further added2And O, heating for 3-6 h at 80 ℃, adding 20-30 mL of cyclohexane as a water-carrying agent after the reaction is finished, heating at 110 ℃ to remove water, washing the residue with ethyl acetate, and performing rotary evaporation to obtain a light yellow solid III-dicarboximidazole hydrobromic acid.
And finally, adding 2 equivalents of 1,1,3, 3-tetramethylguanidine and 30-50 mL of methanol into a flask containing the light yellow solid III, stirring and reacting for 15-18 h at room temperature, and after the reaction is finished, performing rotary evaporation, ethyl acetate washing and drying to obtain a light yellow solid product C [ CMImBrTMG ]]2(ii) a The hydrogen spectrum and the carbon spectrum of the nuclear magnetic resonance are respectively shown in figures 1 and 2.
Referring to the above method, BrCH in the first step reaction2COOEt is replaced by BrCH respectively2CH2COOEt、BrCH2CH2CH2COOEt, finally obtaining C [ CEImBrTMG]2And C [ CPIMBrTMG ]]2N in the structural formula of the corresponding novel multi-active-center ionic liquid catalyst is 2 and 3 respectively.
Example 2
A50 mL stainless steel reactor with digital pressure gauge was charged with 0.25mmol C [ CMImBrTMG ] prepared in example 1]2Catalyst and 5mmol of epoxy chloropropane, wherein the catalyst accounts for 5mol percent of the molar content of the epoxy chloropropane, and CO is slowly introduced2Removing residual air in the reaction kettle, sealing the reaction kettle, controlling the temperature to be 30 ℃, and continuously introducing CO2Keeping the pressure of the gas at 0.1MPa, and reacting for 6 h. After the reaction is finished, ethyl acetate is added, the product is dissolved in ethyl acetate, the catalyst is separated out, and the product is analyzed by gas chromatography to obtain the product 4-chloromethyl- [1,3]The yield of the dioxolane-2-one is 70.0 percent, the selectivity is more than 99 percent, and the catalyst can be recycled for next use after being washed by ethyl acetate and dried.
Example 3
The specific experimental process and detection method are the same as example 2, except that the catalyst used accounts for 10 mol% of the molar content of the epichlorohydrin, the product yield is 76.2%, and the selectivity is more than 99%.
Example 4
The specific experimental process and detection method are the same as example 2, except that the catalyst used accounts for 15 mol% of the molar content of the epichlorohydrin, the product yield is 81.8%, and the selectivity is more than 99%.
Example 5
The specific experimental process and detection method are the same as example 2, except that the catalyst used accounts for 20 mol% of the molar content of the epichlorohydrin, the product yield is 82.5%, and the selectivity is more than 99%.
Example 6
The specific experimental process and detection method are the same as example 2, except that the reaction temperature is 50 ℃, the product yield is 98.5% and the selectivity is more than 99%.
Example 7
The specific experimental process and detection method are the same as example 6, and the difference is only that the catalyst used is C [ CEImBrTMG ]]2The product yield was found to be 88.3% with a selectivity > 99%.
Example 8
The specific experimental procedure and detection method are the same as those in example 6, except that the catalyst used is C [ CPIMBrTMG ]]2The product yield was found to be 91.4% with a selectivity > 99%.
Example 9
The specific experimental process and detection method are the same as example 6, except that the catalyst used accounts for 1 mol% of the molar content of epichlorohydrin, the product yield is 62.0%, and the selectivity is more than 99%.
Example 10
The specific experimental process and detection method are the same as example 6, except that the catalyst used accounts for 3 mol% of the molar content of the epichlorohydrin, the product yield is 88.5%, and the selectivity is more than 99%.
Example 11
The specific experimental process and detection method are the same as example 6, except that the catalyst used accounts for 7 mol% of the molar content of epichlorohydrin, the product yield is 98.3%, and the selectivity is more than 99%.
Example 12
The specific experimental process and detection method are the same as example 6, except that the reaction time is 1h, the product yield is 52.5%, and the selectivity is more than 99%.
Example 13
The specific experimental process and detection method are the same as example 6, except that the reaction time is 2h, the product yield is 64.9%, and the selectivity is more than 99%.
Example 14
The specific experimental process and detection method are the same as example 6, except that the reaction time is 3h, the product yield is 80.0%, and the selectivity is more than 99%.
Example 15
The specific experimental process and detection method are the same as example 6, except that the reaction time is 4h, the product yield is 87.3%, and the selectivity is more than 99%.
Example 16
The specific experimental process and detection method are the same as example 6, except that the reaction time is 5h, the product yield is 98.0%, and the selectivity is more than 99%.
Example 17
The specific experimental process is the same as that of example 6, except that the epoxy compound used is epoxypropanol, the detection method is a weighing method, the product yield is 85.1%, and the selectivity is more than 99%.
WeighingThe method comprises the following steps: dissolving the product after the reaction with methanol, taking out from the reaction kettle, and carrying out rotary evaporation to obtain the product with mass m, wherein the mass of the used catalyst is m1, the mass of the substrate is m2, and the yield is calculated by
The reaction equation of the experiment is as follows:
example 18
The specific experimental procedure and detection method are the same as example 6, except that the epoxy compound used is styrene oxide, the product yield is 64.4%, and the selectivity is more than 99%.
The reaction equation of the experiment is as follows:
example 19
The specific experimental procedure and detection method are the same as example 6, except that the epoxy compound used is allyl glycidyl ether, and the product yield is 86.9% and the selectivity is more than 99%.
The reaction equation of the experiment is as follows:
example 20
The procedure is as in example 6, except that the epoxide compound used is phenyl glycidyl ether, the detection method is a gravimetric method (see example 17), and a product yield of 69.7% with a selectivity of > 99% is obtained.
The reaction equation of the experiment is as follows:
example 21
The specific experimental process and detection method are the same as those in example 6, except that the epoxy compound used is epoxycyclohexane, the reaction temperature is 80 ℃, the catalyst used accounts for 10 mol% of the molar content of the epoxycyclohexane, and CO2The pressure was 0.5MPa, the product yield was 20.0% and the selectivity was > 99%.
The reaction equation of the experiment is as follows:
examples 22 to 28
The specific experimental process and detection method are the same as example 6, and the only difference is that the catalyst used is C [ CMImBrTMG ] recovered in example 6]2The catalyst was subjected to 7 cycles of recovery under the same conditions, and the results are shown in Table 1.
TABLE 1, examples 22-28 catalyst recovery Using the catalytic results
As can be seen from Table 1, C [ CMImBrTMG ]]2After the catalyst is recycled for 4 times, the catalytic yield is only reduced by 0.2%, and after the catalyst is recycled for 7 times, the catalytic yield is still maintained to be more than 91%, which shows that the catalyst has good recycling performance.
Claims (7)
1. The multi-active center ionic liquid is characterized in that the structural formula is as follows:
2. The method for preparing the multi-active-center ionic liquid as claimed in claim 1, which is characterized by comprising the following steps:
1) reacting imidazole with ethyl bromate to generate ester imidazole; the ethyl bromoate is BrCH2COOEt、BrCH2CH2COOEt or BrCH2CH2CH2COOEt；
2) Ester imidazole and CH2Br2Reacting for 0.5-5 h at 90-100 ℃, obtaining solid diester imidazole dibromide salt after the reaction is finished, and obtaining dicarboxyl imidazole dibromide after hydrolysis and water removal by hydrobromic acid;
3) stirring the dicarboxylimidazole dibromic acid and 1,1,3, 3-tetramethylguanidine in the presence of a solvent at room temperature for 6-18 h, and performing rotary evaporation, washing and drying after the reaction is finished to obtain the dicarboxylimidazole dibromic acid.
3. The method for preparing the multi-active-center ionic liquid according to claim 2, wherein ester group imidazole and CH are used2Br2The molar ratio of (A) to (B) is 1-1.5: 0.5; the molar ratio of the dicarboxylimidazole dibromic acid to the 1,1,3, 3-tetramethylguanidine is 1: 2-2.5; the solvent is methanol or ethanol.
4. The method for catalytically synthesizing the cyclic carbonate by using the multi-active-center ionic liquid as claimed in claim 1, wherein the multi-active-center ionic liquid and the epoxy compound are added into a reaction kettle according to a molar ratio of 2-35: 100, and the cyclic carbonate is synthesized by a cycloaddition reaction for 1-10 hours under the conditions that the reaction pressure is 0.1-0.5 MPa and the reaction temperature is 30-80 ℃.
5. The method for catalytically synthesizing cyclic carbonate by using the multi-active-center ionic liquid according to claim 4, wherein the epoxy compound is a compound having any one of the following structures:
，
，
，
。
6. the method for catalytically synthesizing cyclic carbonate by using the multi-active-center ionic liquid as claimed in claim 4, wherein the molar ratio of the multi-active-center ionic liquid to the epoxy compound is 1-2: 20.
7. The method for catalytically synthesizing cyclic carbonate by using the novel multi-active-center ionic liquid as claimed in claim 4, wherein the temperature of the cycloaddition reaction is 30-60 ℃.
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