CN102391241B - Method for preparing cyclic carbonate with chitosan loading type catalyst - Google Patents
Method for preparing cyclic carbonate with chitosan loading type catalyst Download PDFInfo
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- CN102391241B CN102391241B CN201110322886.8A CN201110322886A CN102391241B CN 102391241 B CN102391241 B CN 102391241B CN 201110322886 A CN201110322886 A CN 201110322886A CN 102391241 B CN102391241 B CN 102391241B
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- ULXXSFVSTXMUSV-UHFFFAOYSA-N C1OC1Oc1ccccc1 Chemical compound C1OC1Oc1ccccc1 ULXXSFVSTXMUSV-UHFFFAOYSA-N 0.000 description 1
- MGQRAZVOQUFLOL-UHFFFAOYSA-N O=C(OC1)OC1Oc1ccccc1 Chemical compound O=C(OC1)OC1Oc1ccccc1 MGQRAZVOQUFLOL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a method for preparing cyclic carbonate with chitosan loading type catalyst. The method is characterized in that epoxy compounds and carbon dioxide are taken as raw materials, chitosan loading type catalyst is used during the reaction process, and then cyclic carbonate is synthesized under the reaction conditions of 0.1 to 10 MPa, 40 to 160 DEG C and 0.3 to 10 hours. Based on the concerted catalysis action of reactive groups in the carrier, cyclic carbonate can be synthesized with high efficiency and high selectivity under the condition that no other assistant or promoter is required to be added.
Description
Technical field:
The present invention relates to a kind of method of being prepared cyclic carbonate by epoxy compounds and carbonic acid gas cycloaddition.
Background technology:
The efficient trapping of carbonic acid gas and transform has become one of challenging problem of tool in this century.As abundant C1 resource, carbonic acid gas can synthesize multiple high added value compound, cyclic carbonate for example, methylcarbonate, isocyanic ester etc.Wherein, cyclic carbonate is the polar solvent of a kind of green, excellent property, is widely used in the synthetic of medicine and fine-chemical intermediate.
The homogeneous catalyst using in the method for the production cyclic carbonate of having reported is at present mainly the binary homogeneous catalysis system that Lewis acid metal and Lewis base form, Louis's metal of wherein using is as alkali metal halide, alkaline earth metal halide, transition metal salt, transition metal complex or tetradentate schiff base metal complexes; The Lewis base matching is as organic bases (as DMF, DBAP etc.), quaternary amines, quaternary phosphine class, pyridines, glyoxaline ion liquid etc.But there is separation difficulty in above-mentioned homogeneous catalyst, need to use noxious solvent, high in cost of production problem, urgently to be resolved hurrily.The heterogeneous catalyst of developing at present for this problem has loading type binary catalyst system (as CN1796384A), silicon dioxide carried season phosphonium salt single-component system (as JP2005003388), and metal oxide is (as MgO-Al
2o
3j.Am.Chem.Soc., 1999,121,4526), composite oxide of metal is (as Cs-P-Si composite oxides, CN1926125A), an alkali metal salt supported catalyst (KI/MgO, CN1424147A) and base-modified strong-basicity styrene ion exchange resin or macroporous strong basic styrene carried ion exchange resin Au catalyst (CN100343244C).But activity and the stability of such heterogeneous catalyst still have much room for improvement.
In recent years, ionic liquid is subject to extensive concern as a kind of emerging medium, and the exploitation that appears as new and effective catalyst system of the functionalized ion liquid that especially different functional groups is modified provides more wide space.Early-stage Study finds, hydroxyl, carboxyl or amido modified functionalized ion liquid are more competitive, active in traditional imidazoles, quaternary amines plasma liquid aspect synthetic at catalysis cyclic carbonate.Meanwhile, the carrier that contains above-mentioned functional group (as beta-cyclodextrin, Mierocrystalline cellulose, chitosan etc.) can promote the synthetic of cyclic carbonate equally preferably.But correlative study is at present still in the starting stage.Based on above-mentioned present situation, the present invention aims to provide a kind of method of the carrier loaded ionic-liquid catalyst catalytically synthesizing cyclic carbonate ester that contains hydroxyl or amino.
Summary of the invention
The object of the invention is to solve existing homogeneous catalyst and be difficult to separated problem, providing a kind of is the ionic-liquid catalyst catalysis epoxidation compound of carrier chemical load and the method that cyclic carbonate is prepared in carbonic acid gas cycloaddition by renewable resources chitosan, to reduce cost of investment, simplify the operation.
Object of the present invention can realize by following measures: selecting reproducible chitosan is carrier, by the active group on this carrier framework, directly carrying out quaternized Huo quaternary phosphine reacts, generation is with the chitosan chemical load type catalyzer of quaternary ammonium salt Huo quaternary alkylphosphonium salt group, and catalyzer corresponding construction formula is as follows:
The de-acetyl rate of carrier chitosan is 70～90%, and relative molecular weight is 2 * 10
4～5 * 10
5, n value scope is 124～3100; Substituent R ' be selected from a kind of in the alkyl of phenyl or carbon number≤8; Substituent R is selected from a kind of in the alkyl of phenyl or carbon number≤10, and the charge capacity of active ingredient on carrier is 1～4mmol/g.
The reaction expression relating in the present invention is:
Wherein the structural formula of epoxy compounds used is:
M=1,2 in structural formula, 3 or 4, n=0,1,2,3 or 4.
The method of preparing cyclic carbonate with chitosan loading type catalyst, is characterized in that at reaction conditions be 0.1～10MPa, and 40～160 ℃, 0.3～10 hour, catalyst levels be take 0.4～6mol% that ionic liquid cubage is epoxy compounds.
Chitosan loaded type method for preparing catalyst of the present invention:
1) ionic liquid preparation: in there-necked flask, tertiary amine or tertiary phosphine compounds are slowly dropped in the alkylene dihalide of three times of molar equivalents, stir 24～48h and carry out quaternized or quaternary phosphineization reaction at 50～80 ℃.After stopped reaction, the solid product of generation is with after washing with acetone suction filtration three times, and vacuum-drying 6～12h at 50～75 ℃, is used to get step ready;
2) chitosan chemical load: by 4～6g chitosan (deacetylation 70-90%, molecular-weight average 2 * 10
4～5 * 10
5), the there-necked flask that the ionic liquid aqueous solution (60-80wt%) of 10～30g step 1 preparation and 30～60mL Virahol join 100mL, stirring reaction 24～48h at 60～100 ℃.After stopped reaction, after pH value of reaction system is adjusted to 6～7, add ethanol to be settled out product, washing with acetone obtains product at 50～75 ℃ after vacuum-drying 12～24h.It is 1～4mmol/g that analysis and characterization records charge capacity scope.
Embodiment
The present invention illustrates by following examples, but the present invention is not limited to following embodiment, and before and after not departing from, under the scope of described aim, change is included in technical scope of the present invention.
Embodiment 1
Chitosan loaded glyoxaline ion liquid preparation method:
1) 1-(2-bromotrifluoromethane)-3-methyl bromination imidazoles (a, m=2, X=Br) ionic liquid preparation: in there-necked flask, N-Methylimidazole is slowly dropped in the glycol dibromide of three times of molar equivalents, at 50 ℃ of lower magnetic force stirring reaction 24h.After stopped reaction, solid product is with after washing with acetone suction filtration three times, and vacuum-drying 6h at 50 ℃ is stand-by;
2) chitosan chemical load: 4g chitosan (deacetylation 80%, molecular-weight average 5 * 10
4), 15g1-(2-bromotrifluoromethane)-3-methyl bromination imidazoles the aqueous solution (60wt%) and 30mL Virahol join the there-necked flask of 100mL, stirring reaction 24h at 75 ℃.After stopped reaction, after pH value of reaction system is adjusted to 6, add ethanol to be settled out product, through washing, after oven dry, obtain product.Analysis and characterization records charge capacity and is about 3mmol/g.
Chitosan loaded quaternary amines (c) or pyridines (d) ionic liquid preparation method can be referring to said process.
Embodiment 2
Chitosan loaded quaternary phosphine class ionic liquid preparation method:
1) (R ' is phenyl to (3-chloropropyl) triphenyl phosphonium chloride for b, x=3, X=Cl) ionic liquid preparation: in there-necked flask, triphenylphosphine is slowly added to 1 of its three times of molar equivalents, in 3-propylene dichloride, at 80 ℃ of lower magnetic force stirring reaction 24h.After stopped reaction, solid product is with after washing with acetone suction filtration three times, and vacuum-drying 6h at 50 ℃ is stand-by;
2) chitosan chemical load: 4g chitosan (deacetylation 80%, molecular-weight average 5 * 10
4), 20g(3-chloropropyl) the triphenyl phosphonium chloride aqueous solution (80wt%) and 40mL Virahol join the there-necked flask of 100mL, stirring reaction 48h at 80 ℃.After stopped reaction, after pH value of reaction system is adjusted to 7, add ethanol to be settled out product, through washing, after oven dry, obtain product.Analysis and characterization records charge capacity and is about 2.5mmol/g.
Embodiment 3
Implementation method: in 100mL stainless steel autoclave, add successively chitosan (chitin deacetylase degree 80%, abbreviation deacetylation 80%) 1-methyl-3-ethyl bromination imidazoles (a of load, m=2, X=Br) 0.5g(1.5mmol), (0.14mol), closed reactor, is filled with the CO of appropriate pressure to 10mL propylene oxide (1a)
2, by temperature controller, control temperature and slowly rise to 120 ℃, then controlling reaction pressure is 2.5MPa, reacts 4 hours.After reaction, reactor is cooled to room temperature, slowly emits excessive CO
2, filter to isolate after catalyzer, the product of gained (2a) is used to gas chromatograph-mass spectrometer quantitative analysis, selectivity > 99.8%, and yield is 96%.
Embodiment 4
With embodiment 3, used catalyst is 1-methyl-3-ethyl imidazolitm chloride (a, m=2, X=Cl) 0.4g(1mmol of chitosan (deacetylation 90%) load), other conditions are constant, obtain product (2a) selectivity 98.5%, and yield is 75%.
Embodiment 5
With embodiment 3, used catalyst is 1-methyl-3-propyl group iodate imidazoles (a, m=3, X=I) 0.5g(1.5mmol of chitosan (deacetylation 80%) load), other conditions are constant, obtain (2a) selectivity 99%, and yield is 99%.
Embodiment 6
With embodiment 3, used catalyst is that (R ' is phenyl for b, x=2 for the propyl group triphenyl phosphonium chloride of chitosan (deacetylation 80%) load, X=Cl) 1g(2.5mmol), temperature is 130 ℃, and the reaction times is 10 hours, other are constant, obtain (2a) selectivity 99.8%, and yield is 90%.
Embodiment 7
With embodiment 3, used catalyst is that (R is ethyl for c, y=2 for the etamon chloride of chitosan (deacetylation 70%) load, X=Cl) 2.7g(5mmol), temperature is 100 ℃, and the reaction times is 8 hours, other are constant, obtain (2a) selectivity 99.7%, and yield is 90%.
Embodiment 8
With embodiment 3, used catalyst is decyl pyridinium bromide (d, the z=10 of chitosan (deacetylation 70%) load, X=Br) 2g(3mmol), temperature of reaction is 110 ℃, and the reaction times is 4 hours, other are constant, obtain (2a) selectivity 99.8%, and yield is 86%.
Embodiment 9
With embodiment 3, catalyst levels is 1.0g, and temperature of reaction is 110 ℃, and the reaction times is 3 hours, and other are constant, obtains (2a) selectivity 99.8%, and yield is 95%.
Embodiment 10
With embodiment 3, catalyst levels is 2g(6mmol), temperature of reaction is 40 ℃, and reaction pressure is 5MPa, and the reaction times is 8 hours, and other are constant, obtain (2a) selectivity 100%, and yield is 95%.
Embodiment 11
With embodiment 3, catalyzer is used after five times, obtains (2a) selectivity 99.5%, and yield is 90%.
Embodiment 12
With embodiment 3, epoxy compounds used is oxyethane (1b), and temperature of reaction is 110 ℃, and the reaction times is 3 hours, and other are constant, obtain (2b) selectivity 99%, and yield is 96%.
Embodiment 13
With embodiment 3, epoxy compounds used is epoxy chloropropane (1c), and in 4 hours reaction times, other conditions are constant, obtain (2c) selectivity 92%, and yield is 92%.
Embodiment 14
With embodiment 3, epoxy compounds used is epoxy styrene (1d), and other conditions are constant, obtains (2d) selectivity 99%, and yield is 90%.
Embodiment 15
With embodiment 3, epoxy compounds used is phenoxy group oxyethane (1e), catalyst levels 2mmol, and other conditions are constant, obtain (2e) selectivity 99%, and yield is 90%.
Embodiment 16
With embodiment 3, epoxy compounds used is allyl group oxyethane (1f), catalyst levels 2mmol, and other conditions are constant, obtain (2f) selectivity 99%, and yield is 93%.
Claims (4)
1. chitosan loaded type catalyst is prepared the method for cyclic carbonate, it is characterized in that take that epoxy compounds and carbonic acid gas are as raw material, in reaction process, use chitosan chemical load type catalyzer, at reaction conditions, be 0.1～10MPa, 40～160 ℃, synthesizing annular carbonate under the condition of 0.3～10 hour, catalyst structure is as follows:
The de-acetyl rate of carrier chitosan is 70～95%, and relative molecular weight is 2 * 10
4～5 * 10
5, n span is 124～3100; Substituent R ' be selected from a kind of in the alkyl of phenyl or carbon number≤8; Substituent R is selected from a kind of in the alkyl of phenyl or carbon number≤10.
2. chitosan loaded type catalyst according to claim 1 is prepared the method for cyclic carbonate, and the charge capacity of active ingredient on carrier is 1～4mmol/g.
3. chitosan loaded type catalyst according to claim 1 is prepared the method for cyclic carbonate, and the structural formula of epoxy compounds is as follows:
M=1,2,3 or 4, n=0,1,2,3 or 4 wherein.
4. chitosan loaded type catalyst according to claim 1 is prepared the method for cyclic carbonate, and catalyst levels be take 0.4～6mol% that ionic liquid cubage is epoxy compounds.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102838583A (en) * | 2012-09-10 | 2012-12-26 | 南昌航空大学 | Method for preparing cyclic carbonate by using functionalized quaternary phosphonium salt ionic liquid |
| CN104276987B (en) * | 2014-09-28 | 2016-08-17 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of mercaptan compound |
| CN104646055B (en) * | 2014-11-21 | 2017-01-18 | 常州大学 | Method for preparing immobilized ionic liquid catalyst |
| CN104974128B (en) * | 2015-07-24 | 2017-12-26 | 大连理工大学 | A kind of method of support type quaternary alkylphosphonium salt catalyst preparation cyclic carbonate |
| CN107417534B (en) | 2017-06-20 | 2021-01-29 | 中国科学院过程工程研究所 | System and process for co-producing dimethyl carbonate and ethylene glycol |
| CN112142872B (en) * | 2020-09-08 | 2022-05-31 | 常州大学 | Alkaline ionic liquid grafted chitin, and preparation method and application thereof |
Citations (2)
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| CN1343668A (en) * | 2001-10-10 | 2002-04-10 | 中国科学院兰州化学物理研究所 | Process for synthesizing cyclic carbonate |
| CN1796384A (en) * | 2004-12-24 | 2006-07-05 | 中国科学院兰州化学物理研究所 | Method for synthesizing cyclic carbonate from carbon dioxide and epoxy compound through reaction of cycloaddition |
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| CN1343668A (en) * | 2001-10-10 | 2002-04-10 | 中国科学院兰州化学物理研究所 | Process for synthesizing cyclic carbonate |
| CN1796384A (en) * | 2004-12-24 | 2006-07-05 | 中国科学院兰州化学物理研究所 | Method for synthesizing cyclic carbonate from carbon dioxide and epoxy compound through reaction of cycloaddition |
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