CN102416348A - Polymer supported imidazole ion catalyst as well as preparation method and application thereof - Google Patents
Polymer supported imidazole ion catalyst as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a polymer supported imidazole ion catalyst as well as a preparation method and application thereof. The preparation method is characterized in that a polymer supported imidazole ion liquid catalyst is prepared by utilizing a chemical method; and cyclic carbonate is prepared at high selectivity through a cycloaddition reaction of CO2 and epoxide under the conditions that initial CO2 pressure is 1-3.5MPa, reaction temperature is 110-170 DEG C and reaction time is 1-8 hours. The catalyst can be simply prepared and has good hydrothermal stability and mild cycloaddition reaction condition in no need of adding any organic solvents and co-catalysts; and the selectivity of obtained cyclic carbonate is high, and the catalyst can be repeatedly utilized. The method is expected to have wide application prospect in the field of industrial catalysis.
Description
[technical field]
The present invention relates to the organic synthesis field, relate in particular to a kind of imidazole-like ionic Catalysts and its preparation method and application in the cycloaddition reaction of epoxides of polymer load.
[background technology]
Carbon dioxide (the CO that fossil fuel (coal, oil, natural gas) burning produces
2) be topmost greenhouse gases on the present earth.Along with the industrialized process of the mankind, greenhouse effects have proposed serious challenge to human existence and development.Simultaneously, CO
2Be cheapness and rich in natural resources the most in the C1 family, its phosphorus content is coal, oil, the natural gas three big energy 10 times.From the dual consideration of the environmental protection and the energy, at present with CO
2Be feedstock production organic chemical industry product, become the focus of global common concern.
Cyclic carbonate is a kind of good aprotic, polar type solvent, has application widely aspect medicine and the fine chemistry industry.By CO
2Prepare cyclic carbonate with the cycloaddition reaction of epoxides, process is simple, and productive rate is high, receives extensive concern.This reaction is the reaction of heat release, volume-diminished, so high pressure, cryogenic conditions help the carrying out that react.Selecting appropriate catalyst is to react the key of carrying out smoothly, this has been carried out a large amount of research both at home and abroad at present, mainly contains homogeneous catalysis system and heterogeneous catalytic system.Wherein homogeneous catalyst mainly comprises: alkali metal and organic phosphine, organic base, metal complex, (J Org Chem58 (1993) 6198 such as ionic liquid; J Org Chem 68 (2003) 6705; J Catal 232 (2005) 80; J Mol Catal A256 (2006) 295; Chem Commun 36 (2000) 2089; Tetrahedron Lett 44 (2003) 2931; J Mol Catal A 312 (2009) 87; J Am Chem Soc 126 (2004) 3732; Tetrahedron Lett48 (2007) 297; J Am Chem Soc 123 (2001) 11498; Green Chem 11 (2009) 1754; Chem Commun 39 (2003) 896; Green Chem 5 (2003) 92; Green Chem 6 (2004) 613; Tetrahedron Lett 49 (2008) 3588; Appl Catal A 341 (2008) 106; Catal Today 131 (2008) 130; Tetrahedron Lett 50 (2009) 423; US20050014956; WO05003113); Heterogeneous catalytic system mainly comprises: metal oxide catalyst, molecular sieve and clay class catalyst, (Appl Catal A 219 (2001) 259 such as loaded catalyst; J Am Chem Soc 121 (1999) 4526; J Mol Catal A258 (2006) 165; Appl Catal A 298 (2006) 177; Microporous Mesoporous Mater76 (2004) 177; J Phys Chem B 109 (2005) 2315; J Catal 233 (2005) 1; Microporous Mesoporous Mater 90 (2006) 314; J Mol Catal A 266 (2007) 69; J Mol Catal A242 (2005) 32; Chem Commun 11 (2009) 43; Appl Catal A 368 (2009) 97; Green Chem 10 (2008) 337; Angew Chem Int Ed 46 (2007) 7255; Appl Catal A347 (2008) 192; Catal Commun 10 (2009) 659; Appl Catal A 365 (2009) 88; CIESCJournal 60 (2009) 1471; CN101318949A; CN101280042A; US20050070724).The major defect of homogeneous catalysis system is exactly that the Preparation of Catalyst cost is high, is difficult to reclaim, and needs to add solvent or/and co-catalyst; Heterogeneous catalyst then exists catalytic activity low, poor selectivity, and stability is bad, problems such as severe reaction conditions.So the exploitation component is simple, be easy to separate, effective catalyst capable of being industrialized is the emphasis of current research.
[summary of the invention]
The present invention provides a kind of imidazole-like ionic catalyst of polymer load, and it can and not add under the condition of any organic solvent at the reaction condition of gentleness, realizes that efficient, highly selective is by CO
2Prepare the method for cyclic carbonate with the cycloaddition reaction of epoxides.
The structure of the imidazole-like ionic catalyst of polymer load provided by the invention is:
Polymer wherein is the polydivinylbenezene of imidazolesization; The load capacity of the polydivinylbenezene of imidazolesization is 0.5-2.5mmol/g.
The present invention also provides the imidazole-like ionic Preparation of catalysts method of above-mentioned polymer load, may further comprise the steps:
S1: with imidazoles polydivinylbenezene and 3-bromo-propionic acid with 1: the mixed in molar ratio of [1-3], vacuumize, the 5-10 with imidazoles polydivinylbenezene mole under the inert gas shielding extraordinarily goes into 1; 1; 1 ,-trichloroethanes is as solvent, reaction system heating reflux reaction 20-30h.
S2: after stopping reaction, be cooled to room temperature, filter, solvent is removed in washing, and vacuum drying obtains light yellow solid, promptly gets.
Its synthetic route is following:
The present invention also provides a kind of imidazole-like ionic with above-mentioned polymer load to be applied to prepare the method for cyclic carbonate, is at CO
2Initial pressure is 1～3.5MPa, and reaction temperature is 110～170 ℃, and the reaction time is under the condition of 1～8h, through CO
2Prepare cyclic carbonate with the cycloaddition reaction highly selective of epoxides.This Preparation of Catalyst is simple, and load is firm, good hydrothermal stability; The cycloaddition reaction mild condition need not added any organic solvent and co-catalyst, and the selectivity of gained cyclic carbonate is high, can repeatedly reuse, and is with a wide range of applications in the Industrial Catalysis field.
The general formula of above-mentioned cycloaddition reaction is:
The used epoxides of the present invention is expoxy propane, epoxychloropropane, 1,2-epoxy butane, 7-oxa-bicyclo[4.1.0.
The present invention compared with prior art has following advantage:
(1) the Preparation of catalysts method is simple, is easy to reclaim, and can be repeatedly used;
(2) catalyst system and catalyzing need not add organic solvent or/and co-catalyst, water, Heat stability is good;
(3) catalyst is to epoxides and CO
2Between cycloaddition reaction have very high catalytic activity and selectivity, and reaction condition is gentle, is fit to large-scale production, has a wide range of applications in the Industrial Catalysis field.
[specific embodiment]
Preparation of Catalyst:
Embodiment 1
S1: with imidazoles polydivinylbenezene and 3-bromo-propionic acid with 1: the mixed in molar ratio of [1-3], vacuumize, inert gas shielding add down imidazoles polydivinylbenezene mole 5-10 doubly 1; 1; 1 ,-trichloroethanes is as solvent, reaction system heating reflux reaction 20-30h.
S2: after stopping reaction, be cooled to room temperature, filter, solvent is removed in washing, and vacuum drying obtains light yellow solid, promptly gets.
The preparation of cyclic carbonate:
Embodiment 2
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl are as internal standard compound, and the 2mL expoxy propane feeds CO under the room temperature
22.0MPa, place the oil bath reactor of 140 ℃ of band magnetic agitation to react, behind the reaction 4h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 96.5%, and selectivity is 99.8%.
Embodiment 3
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl are as internal standard compound, and the 2mL expoxy propane feeds CO under the room temperature
22.5MPa, place the oil bath reactor of 160 ℃ of band magnetic agitation to react, behind the reaction 6h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 98.8%, and selectivity is 99.6%.
Embodiment 4
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl are as internal standard compound, and the 2mL expoxy propane feeds CO under the room temperature
23.0MPa, place the oil bath reactor of 140 ℃ of band magnetic agitation to react, behind the reaction 5h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 90.9%, and selectivity is 99.6%.
Embodiment 5
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl are as internal standard compound, and the 2mL expoxy propane feeds CO under the room temperature
21.5MPa, place the oil bath reactor of 130 ℃ of band magnetic agitation to react, behind the reaction 5h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 91.4%, and selectivity is 99.5%.
Embodiment 6
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl are as internal standard compound, and the 2mL expoxy propane feeds CO under the room temperature
21.8MPa, place the oil bath reactor of 150 ℃ of band magnetic agitation to react, behind the reaction 3h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 93.5%, and selectivity is 99.7%.
Embodiment 7
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl are as internal standard compound, and the 2mL expoxy propane feeds CO under the room temperature
21.5MPa, place the oil bath reactor of 170 ℃ of band magnetic agitation to react, behind the reaction 5h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 98.3%, and selectivity is 99.6%.
Embodiment 8
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl are as internal standard compound, and the 2mL expoxy propane feeds CO under the room temperature
23.2MPa, place the oil bath reactor of 150 ℃ of band magnetic agitation to react, behind the reaction 5h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 94.2%, and selectivity is 99.6%.
Embodiment 9
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl are as internal standard compound, and the 2mL expoxy propane feeds CO under the room temperature
21.5MPa, place the oil bath reactor of 170 ℃ of band magnetic agitation to react, behind the reaction 2h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 87.7%, and selectivity is 99.6%.
Embodiment 10
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl are as internal standard compound, and the 2mL expoxy propane feeds CO under the room temperature
22.2MPa, place the oil bath reactor of 130 ℃ of band magnetic agitation to react, behind the reaction 5h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 94.4%, and selectivity is 99.6%.
Embodiment 11
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl are as internal standard compound, and the 2mL expoxy propane feeds CO under the room temperature
21.2MPa, place the oil bath reactor of 170 ℃ of band magnetic agitation to react, behind the reaction 6h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 97.8%, and selectivity is 99.6%.
Embodiment 12
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl are as internal standard compound, and the 2.24mL epoxychloropropane feeds CO under the room temperature
21.5MPa, place the oil bath reactor of 160 ℃ of band magnetic agitation to react, behind the reaction 3h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 98.5%, and selectivity is 99.5%.
Embodiment 13
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl be as internal standard compound, 2.48mL1, and the 2-epoxy butane feeds CO under the room temperature
23.3MPa, place the oil bath reactor of 140 ℃ of band magnetic agitation to react, behind the reaction 5h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 97.0%, and selectivity is 99.9%.
Embodiment 14
The imidazole-like ionic catalyst that in the 30mL autoclave, adds the load of 0.2g polymer successively, 0.2g biphenyl are as internal standard compound, and the 2.89mL 7-oxa-bicyclo[4.1.0 feeds CO under the room temperature
22.0MPa, place the oil bath reactor of 170 ℃ of band magnetic agitation to react, behind the reaction 8h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant, get supernatant liquor after centrifugal and carry out GC and analyze: the productive rate of propene carbonate is 86.4%, and selectivity is 98.0%.In addition, under identical reaction condition, catalyst is through after recycling 5 times, and its performance is constant basically.
In order to further specify the superiority of the inventive method, select for use the catalyst of following reported in literature routine as a comparison.
Comparative Examples 1
In the 150mL autoclave, add 0.015mmolZnBr successively
2, 0.09mmol Ph
4PI, the 105mmol expoxy propane adds biphenyl as internal standard compound, feeds CO under the room temperature
22.5MPa, place the oil bath reactor of 120 ℃ of band magnetic agitation to react, behind the reaction 1h agitated reactor taking-up is placed mixture of ice and water, emit remaining CO after the cooling of question response thing
2, take out reactant and carry out the GC analysis: the conversion ratio of expoxy propane is 89.6%, selectivity＞99.0%.
Comparative Examples 2
In the 100mL stainless steel cauldron, add 0.5g mesoporous material load hydroxy-functional ionic-liquid catalyst HIILsBr/MCM-41, the 10ml expoxy propane, the sealing back feeds CO
2, under 2.0MPa, in the oil bath reactor of 115 ℃ of magnetic agitation, react 4h, be cooled to room temperature, the analytical reactions mixture: the productive rate of propene carbonate is 66.0%, selectivity is 99.5%.
Claims (8)
1. the imidazole-like ionic catalyst of a polymer load, the structural formula that has is:
Wherein, said polymer is the polydivinylbenezene of imidazolesization.
2. the imidazole-like ionic catalyst of polymer load according to claim 1 is characterized in that, the load capacity of the polydivinylbenezene of imidazolesization is 0.5-2.5mmol/g.
3. the imidazole-like ionic Preparation of catalysts method of the described polymer load of claim 1 may further comprise the steps:
S1: with the polydivinylbenezene of imidazolesization and 3-bromo-propionic acid with 1: the mixed in molar ratio of [1-3], vacuumize, the 5-10 with imidazoles polydivinylbenezene mole under the inert gas shielding extraordinarily goes into 1; 1; 1 ,-trichloroethanes is as solvent, reaction system heating reflux reaction 20-30h.
S2: after stopping reaction, be cooled to room temperature, filter, solvent is removed in washing, and vacuum drying obtains light yellow solid, promptly gets.
4. the application of the imidazole-like ionic catalyst of the described polymer load of claim 1 in the preparation cyclic carbonate is characterized in that, with CO
2With epoxides be raw material, under the effect of the imidazole-like ionic catalyst of said polymer load, cycloaddition reaction prepares cyclic carbonate.
5. the application of the imidazole-like ionic catalyst of polymer load according to claim 4 in the preparation cyclic carbonate is characterized in that said epoxides is to be selected from expoxy propane, epoxychloropropane, 1,2-epoxy butane or 7-oxa-bicyclo[4.1.0.
6. the application of the imidazole-like ionic catalyst of polymer load according to claim 4 in the preparation cyclic carbonate is characterized in that said CO
2Initial pressure be 1～3.5MPa.
7. the application of the imidazole-like ionic catalyst of polymer load according to claim 4 in the preparation cyclic carbonate is characterized in that the temperature of said cycloaddition reaction is 110～170 ℃.
8. the application of the imidazole-like ionic catalyst of polymer load according to claim 4 in the preparation cyclic carbonate is characterized in that the time of said cycloaddition reaction is 1～8h.
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| CN105709821A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Low-expansion ratio resin composite catalyst and its preparation method and use |
| CN109575162A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Ion exchange resin and purposes |
| CN112159386A (en) * | 2020-09-16 | 2021-01-01 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate by mild catalysis of ionic liquid crosslinked polymer |
| CN114011342A (en) * | 2021-11-15 | 2022-02-08 | 中国科学院兰州化学物理研究所 | System and method for preparing cyclic carbonate by converting industrial tail gas carbon dioxide |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105709821A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Low-expansion ratio resin composite catalyst and its preparation method and use |
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| CN109575162A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Ion exchange resin and purposes |
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| CN112159386A (en) * | 2020-09-16 | 2021-01-01 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate by mild catalysis of ionic liquid crosslinked polymer |
| CN112159386B (en) * | 2020-09-16 | 2021-12-03 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate by mild catalysis of ionic liquid crosslinked polymer |
| CN114011342A (en) * | 2021-11-15 | 2022-02-08 | 中国科学院兰州化学物理研究所 | System and method for preparing cyclic carbonate by converting industrial tail gas carbon dioxide |
| CN114011342B (en) * | 2021-11-15 | 2022-07-22 | 中国科学院兰州化学物理研究所 | System and method for preparing cyclic carbonate by converting industrial tail gas carbon dioxide |
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