CN112337507B - Application of cyclodextrin inclusion compound in catalyzing CO2Application in cycloaddition reaction - Google Patents
Application of cyclodextrin inclusion compound in catalyzing CO2Application in cycloaddition reaction Download PDFInfo
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- CN112337507B CN112337507B CN202011267725.9A CN202011267725A CN112337507B CN 112337507 B CN112337507 B CN 112337507B CN 202011267725 A CN202011267725 A CN 202011267725A CN 112337507 B CN112337507 B CN 112337507B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J31/065—Cyclodextrins
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- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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- 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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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a cyclodextrin inclusion compound for catalyzing CO2Application in cycloaddition reaction of cyclodextrin and vitamin B1Cyclodextrin inclusion compound obtained after mixed reaction of hydrochloride and alkali metal halide for catalyzing CO2And epoxide cycloaddition reaction to synthesize the cyclic carbonate. The cyclodextrin inclusion compound can efficiently and selectively catalyze CO under mild conditions and without any solvent or auxiliary agent2And epoxide cycloaddition reaction to synthesize cyclic carbonate, and the activity of the catalyst is almost unchanged after the catalyst is recycled for many times.
Description
Technical Field
The invention belongs to CO2The technical field of cycloaddition, in particular to a cyclodextrin inclusion compound for catalyzing CO2And epoxide cycloaddition cyclic carbonates.
Background
With waste CO2The cyclic carbonate synthesized by cycloaddition reaction with epoxide changes waste into valuable, has the advantages of high atom utilization rate, less by-products and the like, and conforms to the principle of green chemistry. The process has important significance for relieving greenhouse effect from the viewpoint of replacing the original carbonate synthesis process. There are a large number of cycloaddition catalysts including homogeneous catalysts such as metal salts, organic bases, ionic liquids and metal complexes, heterogeneous catalystsAgents such as metal oxides, polyionic liquids, supported catalysts, organometallic framework materials, and carbon materials have been reported in succession. The homogeneous catalyst has high catalytic activity, but the catalyst is difficult to recover, and the product needs to be purified by distillation; although the heterogeneous catalyst is simple to separate, the heterogeneous catalyst generally has the defects of harsh reaction conditions, requirement of solvents and/or auxiliaries, incapability of obtaining activity and mechanical properties and/or stability and the like, and the preparation process is complex. Easy large-scale preparation, low price, and high-efficiency catalysis of CO under mild condition without solvent and auxiliary agent2The development of a heterogeneous catalyst with good stability for cycloaddition reaction becomes the core of a process for synthesizing carbonic ester.
Earlier studies found vitamin B1(VB1) Can catalyze CO2The cycloaddition reaction has unsatisfactory catalytic activity and stability, and the activity and stability are remarkably improved but are still unsatisfactory after the graphene oxide and the graphene oxide are adopted to form a composite material. In addition, the graphene oxide preparation process is complex, serious in pollution and high in cost. Aiming at the problems, the cyclodextrin and VB which are cheap, easy to obtain and renewable are adopted1Complexing to form inclusion compound, protecting active center in cyclodextrin cavity with core, and increasing VB1Stability of (2). The cyclodextrin inclusion compound is rich in hydroxyl group and is beneficial to the activation of epoxide, and the cyclodextrin inclusion compound is mixed with VB1The halogen anion in the composition can promote CO2And (3) performing cycloaddition reaction.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a cyclodextrin inclusion compound which is cheap, easy to obtain, efficient and stable and can be used for catalyzing CO2The cyclodextrin inclusion compound can efficiently and selectively catalyze CO under mild conditions and without any solvent or auxiliary agent2And epoxide cycloaddition reaction to synthesize the cyclic carbonate, and the activity of the catalyst is almost unchanged after the catalyst is recycled for many times.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
application of cyclodextrin inclusion compound in catalyzing CO2Use in cycloaddition reactions to convert cyclicDextrin and vitamin B1Cyclodextrin inclusion compound obtained after mixed reaction of hydrochloride and alkali metal halide for catalyzing CO2And epoxide cycloaddition reaction to synthesize the cyclic carbonate.
Preferably, the specific preparation process of the cyclodextrin inclusion compound is as follows: mixing vitamin B1Adding hydrochloride and alkali metal halide into cyclodextrin water solution, stirring at room temperature for reaction, evaporating for crystallization to obtain white solid, washing with anhydrous ethanol, and vacuum drying.
Preferably, the cyclodextrin is selected from one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
Preferably, the alkali metal halide is selected from one of NaBr, NaI, KBr and KI.
Preferably, the vitamin B is1The molar ratio of the hydrochloride to the cyclodextrin is 1: 0.2 to 5.
Preferably, the vitamin B is1The molar ratio of the hydrochloride to the alkali metal halide is 1: 2 to 5.
Preferably, the epoxide is one of ethylene oxide, epichlorohydrin, propylene oxide, butylene oxide, cyclohexene oxide, cyclopentene oxide and styrene oxide.
Preferably, the molar ratio of the cyclodextrin inclusion compound to the epoxide is 0.005-0.05: 1.
compared with the prior art, the invention has the technical effects that:
1) the cyclodextrin inclusion compound disclosed by the invention is simple in preparation process, the raw materials belong to renewable resources, are cheap and non-toxic, and meanwhile, the cyclodextrin inclusion compound belongs to a metal-free heterogeneous catalyst, and can efficiently catalyze CO under the conditions of no solvent, no auxiliary agent and mild conditions2And (3) performing cycloaddition reaction.
2) The invention uses cyclodextrin cavity to coat active center vitamin B1And an internal hydrophobic microenvironment is formed, so that the hydrolysis reaction of the epoxide can be inhibited, and the selectivity of the catalyst is improved.
3) The invention uses active center vitamin B1Cyclodextrin cavity coated on surface and rich in hydroxylNot only can protect the active center and improve the stability of the catalyst, but also the hydroxyl on the surface of the cyclodextrin can promote CO2The cycloaddition reaction is carried out, and the catalytic activity is high.
4) The cyclodextrin inclusion compound belongs to a metal-free heterogeneous catalyst, and the activity of the cyclodextrin inclusion compound is almost unchanged after repeated recycling.
Detailed Description
The technical scheme of the invention is further explained by combining the embodiment as follows:
the analysis of selectivity and yield of the target products in the following examples and comparative examples of the invention employed Agilent 7820A, a gas chromatograph manufactured by Agilent corporation equipped with a TCD detector and RTX-1 capillary chromatography 0(30 m. times.0.25 mm. times.0.25 μm).
Example 1
(1) Preparing a catalyst: 9.73g (10mmol) of alpha-cyclodextrin are dissolved ultrasonically in 500mL of water at 50 ℃ and 3.37g (10mmol) of vitamin B are added1Hydrochloride and 5.1g NaBr (50mmol), stirring at room temperature for 12h, evaporating to crystallize, washing the solid with absolute ethyl alcohol for 3 times, and vacuum drying at 60 ℃ for 12h to obtain the product of alpha-CD-Br.
(2) And (3) cycloaddition reaction: at room temperature, 0.143mmol of alpha-CD-Br, 0.15g of internal standard substance biphenyl and 28.6mmol of propylene oxide are sequentially added into a 30mL high-pressure reaction kettle, and 2MPa CO is introduced into the kettle under the condition of room temperature stirring2Then putting the high-pressure reaction kettle into an oil bath reactor with magnetic stirring to react for 6 hours at the temperature of 100 ℃, putting the high-pressure reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 99.8% with a selectivity of 99.9%.
Example 2
(1) Preparing a catalyst: 5.67g (5mmol) of beta-cyclodextrin are dissolved in 500mL of water with ultrasound at 30 ℃ and then 8.42g (25mmol) of vitamin B are added1Hydrochloride and 75g NaI (50mmol), stirring at room temperature for 12h, evaporating and crystallizing, washing the solid with absolute ethyl alcohol for 3 times, and vacuum drying at 60 ℃ for 12h to obtain the product which is recorded as beta-CD-I.
(2) And (3) cycloaddition reaction: at room temperature, sequentially adding beta into a 30mL high-pressure reaction kettle0.72mmol of-CD-I, 0.15g of biphenyl as an internal standard substance and 28.6mmol of epichlorohydrin, and introducing 2MPa CO under the condition of stirring at room temperature2Then putting the high-pressure reaction kettle into an oil bath reactor with magnetic stirring to react for 6 hours at the temperature of 80 ℃, putting the high-pressure reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 99.6% with a selectivity of 99.9%.
Example 3
(1) Preparing a catalyst: 12.97g (10mmol) of gamma-cyclodextrin are dissolved ultrasonically in 500mL of water at 30 ℃ and 0.67g (2mmol) of vitamin B is added1The hydrochloride and 1.029g NaBr (10mmol) are stirred at room temperature for 12h, the solid after evaporation crystallization is washed with absolute ethyl alcohol for 3 times, and the product is dried in vacuum at 60 ℃ for 12h and is recorded as gamma-CD-Br.
(2) And (3) cycloaddition reaction: at room temperature, 1.43mmol of gamma-CD-Br, 0.15g of internal standard substance biphenyl and 28.6mmol of epoxy butane are sequentially added into a 30mL high-pressure reaction kettle, and 2MPa CO is introduced into the reaction kettle under the condition of room temperature stirring2Then putting the high-pressure reaction kettle into an oil bath reactor with magnetic stirring to react for 6 hours at the temperature of 80 ℃, putting the high-pressure reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 95.3% with a selectivity of 99.8%.
Comparative example 1
(1) Preparing a catalyst: at 30 deg.C, add 8.42g (25mmol) of vitamin B1Dissolving hydrochloride and 75g NaI (50mmol) in 500mL of water, stirring at room temperature for 12h, washing the solid after evaporation crystallization with absolute ethyl alcohol for 3 times, drying at 60 ℃ in vacuum for 12h, and recording the product as VB1-I。
(2) And (3) cycloaddition reaction: sequentially adding VB into a 30mL high-pressure reaction kettle at room temperature10.72mmol of-I, 0.15g of biphenyl as an internal standard substance and 28.6mmol of epichlorohydrin, and introducing 2MPa CO under stirring at room temperature2Then putting the high-pressure reaction kettle into an oil bath reactor with magnetic stirring to react for 6 hours at the temperature of 80 ℃, putting the high-pressure reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, and taking the supernatantGC analysis: the yield of propylene carbonate was 63.8% with a selectivity of 99.4%.
Comparative example 2
The catalyst is beta-cyclodextrin.
And (3) cycloaddition reaction: at room temperature, 0.72mmol of beta-cyclodextrin, 0.15g of internal standard substance biphenyl and 28.6mmol of epichlorohydrin are sequentially added into a 30mL high-pressure reaction kettle, and 2MPa CO is introduced into the kettle under the condition of room temperature stirring2Then putting the high-pressure reaction kettle into an oil bath reactor with magnetic stirring to react for 6 hours at the temperature of 80 ℃, putting the high-pressure reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 0.6% with a selectivity of 89.2%.
Comparative example 3
(1) Preparing a catalyst: 5.67g (5mmol) of beta-cyclodextrin are dissolved in 500mL of water with ultrasound at 30 ℃ and 1.68g (5mmol) of vitamin B are added1Hydrochloride and 0.595g of KBr (5mmol) are stirred at room temperature for 12h, the solid after evaporative crystallization is washed 3 times with absolute ethanol and dried under vacuum at 60 ℃ for 12h, and the product is recorded as beta-CD-Br-Cl.
(2) And (3) cycloaddition reaction: at room temperature, 0.72mmol of beta-CD-Br-Cl, 0.15g of internal standard substance biphenyl and 28.6mmol of epoxy chloropropane are sequentially added into a 30mL high-pressure reaction kettle, and 3MPa CO is introduced into the kettle under the stirring of room temperature2Then putting the high-pressure reaction kettle into an oil bath reactor with magnetic stirring to react for 6 hours at the temperature of 80 ℃, putting the high-pressure reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 84.5% with a selectivity of 99.8%.
Example 4
(1) Preparing a catalyst: 5.67g (5mmol) of beta-cyclodextrin are dissolved in 500mL of water with ultrasound at 30 ℃ and then 8.42g (25mmol) of vitamin B are added1Hydrochloride and 75g NaI (50mmol), stirring at room temperature for 12h, evaporating to crystallize, washing the solid with anhydrous ethanol for 3 times, and vacuum drying at 60 ℃ for 12h to obtain the product which is recorded as beta-CD-I.
(2) Cycloaddition reaction: at room temperature, sequentially adding beta-CD-I0.72 into a 30mL high-pressure reaction kettlemmol, internal standard substance biphenyl 0.15g, epichlorohydrin 28.6mmol, 7.2mmol H2O, introducing 2MPa CO under stirring at room temperature2Then putting the high-pressure reaction kettle into an oil bath reactor with magnetic stirring to react for 6 hours at the temperature of 80 ℃, putting the high-pressure reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 98.6% with a selectivity of 99.1%.
Comparative example 4
(1) Preparing a catalyst: at 30 deg.C, add 8.42g (25mmol) of vitamin B1Dissolving hydrochloride and 75g NaI (50mmol) in 500mL of water, stirring at room temperature for 12h, washing the solid after evaporation crystallization with absolute ethyl alcohol for 3 times, drying at 60 ℃ in vacuum for 12h, and recording the product as VB1-I。
(2) And (3) cycloaddition reaction: at room temperature, sequentially adding VB into a 30mL high-pressure reaction kettle1-I0.72 mmol, internal standard substance biphenyl 0.15g, epichlorohydrin 28.6mmol, 7.2mmol H2O, introducing 2MPa CO under stirring at room temperature2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 6 hours at 80 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 57.4% with a selectivity of 78.2%.
As can be seen from examples 2, 4, 1 and 4, the catalytic performance and product selectivity of beta-CD-I are not greatly affected by adding a certain amount of water into the reaction substrate, but VB1After water is added into a system with the catalyst of-I, the selectivity of the product is sharply reduced, which shows that VB1The water resistance of the product after the-I is complexed with the beta-CD is improved.
Performance experiments were repeated with the catalysts of example 2 and comparative example 1 (the catalysts were washed with alcohol and dried for reuse) and the product yield data are shown in table 1.
TABLE 1 evaluation of catalyst Recycling Properties
| Circulating for 1 time | Circulating for 2 times | Circulating for 3 times | Circulating for 4 times | Circulating for 5 times | |
| Example 2 catalyst | 99.6％ | 98.9％ | 99.2％ | 99.3％ | 99.2％ |
| Comparative example 1 catalyst | 63.8％ | 58.45 | 53.5 | 47.2 | 36.1％ |
The reaction conditions are as follows: catalyst 0.72mmol, epichlorohydrin 28.6mmol, 2MPa CO2， 80℃，6h
As can be seen from Table 1, VB after five cycles1The activity of the-I catalyst decreases sharply, while the beta-CD-I activity is hardly changed. And VB1During the recycling process of-I, the reaction liquid turns red to indicate VB1The decomposition of the compound I takes place,the product obtained in the circulation process of the beta-CD-I is colorless all the time, which indicates that VB1The stability of the-I is obviously improved after the-I is complexed with the beta-CD.
Claims (5)
1. Application of cyclodextrin inclusion compound in catalyzing CO2The application in the cycloaddition reaction is characterized in that: cyclodextrin and vitamin B1Cyclodextrin inclusion compound obtained after mixed reaction of hydrochloride and alkali metal halide for catalyzing CO2And epoxide cycloaddition reaction to synthesize cyclic carbonate;
the preparation process of the cyclodextrin inclusion compound comprises the following steps: mixing vitamin B1Adding hydrochloride and alkali metal halide into cyclodextrin water solution, stirring at room temperature for reaction, evaporating for crystallization to obtain white solid, washing with anhydrous ethanol, and vacuum drying to obtain the final product;
the vitamin B1The molar ratio of the hydrochloride to the cyclodextrin is 1: 0.2 to 5;
the vitamin B1The molar ratio of the hydrochloride to the alkali metal halide is 1: 2 to 5.
2. The cyclodextrin inclusion compound of claim 1 for catalyzing CO2The application in the cycloaddition reaction is characterized in that: the cyclodextrin is selected from one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
3. The cyclodextrin inclusion compound of claim 1 in catalyzing CO2The application in the cycloaddition reaction is characterized in that: the alkali metal halide is selected from one of NaBr, NaI, KBr and KI.
4. The cyclodextrin inclusion compound of claim 1 in catalyzing CO2The application in the cycloaddition reaction is characterized in that: the epoxide is one of ethylene oxide, epichlorohydrin, propylene oxide, butylene oxide, cyclohexene oxide, cyclopentene oxide and styrene oxide.
5. The method of claim 1Application of cyclodextrin inclusion compound in catalyzing CO2The application in the cycloaddition reaction is characterized in that: the molar ratio of the cyclodextrin inclusion compound to the epoxide is 0.005-0.05: 1.
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