CN102391241A - 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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- CN102391241A CN102391241A CN2011103228868A CN201110322886A CN102391241A CN 102391241 A CN102391241 A CN 102391241A CN 2011103228868 A CN2011103228868 A CN 2011103228868A CN 201110322886 A CN201110322886 A CN 201110322886A CN 102391241 A CN102391241 A CN 102391241A
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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 for preparing cyclic carbonate by epoxy compounds and carbonic acid gas cycloaddition.
Background technology:
The efficient capture 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 or the like.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 that uses in the method for the production cyclic carbonate of having reported at present mainly is the binary homogeneous catalysis system that Lewis acid metal and Lewis base are formed; Wherein employed Louis's metal such as alkali metal halide; Alkaline earth metal halide; Transition metal salt, transition metal complex or tetradentate schiff base metal complexes; Lewis base that matches such as organic bases (like DMF, DBAP etc.), quaternary amines, quaternary phosphine class, pyridines, glyoxaline ion liquid or the like.But there is separation difficulty in above-mentioned homogeneous catalyst, needs to use noxious solvent, and problems such as cost height need to be resolved hurrily.The heterogeneous catalyst of developing at present to this problem has loading type binary catalyst system (like CN1796384A), silicon dioxide carried season phosphonium salt single-component system (like JP2005003388), and MOX is (like MgO-Al
2O
3, J.Am.Chem.Soc., 1999; 121; 4526), composite oxide of metal is (like the 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 the activity of such heterogeneous catalyst and stability still remain to be improved.
In recent years, ionic liquid receives extensive concern as a kind of emerging medium, and especially the exploitation that appears as new and effective catalystsystem of the functionalized ion liquid of different functional groups modification 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 the catalysis cyclic carbonate.Simultaneously, the carrier (like beta-cyclodextrin, Mierocrystalline cellulose, chitosan or the like) that contains above-mentioned functional group can promote the synthetic of cyclic carbonate equally preferably.But correlative study still is in the starting stage at present.Based on above-mentioned present situation, the present invention aims to provide a kind of method that contains the carrier loaded ionic-liquid catalyst catalytically synthesizing cyclic carbonate ester of hydroxyl or amino.
Summary of the invention
The objective of the invention is to solve existing homogeneous catalyst and be difficult to isolating problem; Providing a kind of is the ionic-liquid catalyst catalysis epoxidation compound of carrier chemical load and the method that the carbonic acid gas cycloaddition prepares cyclic carbonate by the renewable resources chitosan; To reduce cost of investment, simplify the operation.
The object of the invention can be realized through following measure: selecting reproducible chitosan is carrier; Directly carry out the reaction of quaternized Huo quaternary phosphine through the reactive group on this carrier framework; Generate the chitosan chemical load type catalyzer of band quaternary ammonium salt Huo quaternary alkylphosphonium salt group, catalyzer corresponding construction formula is following:
It is 70～95% that the carrier chitosan takes off the acetyl rate, 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 that relates among the present invention is:
Wherein the structural formula of used epoxy compounds is:
M=1,2,3 or 4 in the structural formula, n=0,1,2,3 or 4.
The method of chitosan loaded type Preparation of Catalyst cyclic carbonate is characterized in that at reaction conditions be 0.1～10MPa, and 40～160 ℃, 0.3～10 hour, catalyst levels was 0.4～6mol% of epoxy compounds with the ionic liquid cubage.
Chitosan loaded type method for preparing catalyst according to the 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 down at 50～80 ℃ and carry out quaternized or the quaternary phosphine reaction.Behind the stopped reaction, the solid product of generation with washing with acetone and suction filtration three times after, at 50～75 ℃ of following vacuum-drying 6～12h, use to get the step ready;
2) chitosan chemical load: with 4～6g chitosan (deacetylation 70-95%, 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 is at 60～100 ℃ of following stirring reaction 24～48h.Behind the stopped reaction, pH value of reaction system transferred to 6～7 after, add ethanol sedimentation and go out product, washing with acetone, behind 50～75 ℃ of following vacuum-drying 12～24h product.It is 1～4mmol/g that analysis and characterization records the charge capacity scope.
Embodiment
The present invention explains with following embodiment, but the present invention is not limited to following embodiment, before and after not breaking away from, under the scope of said aim, changes and implements to be included in the 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, the N-Methylimidazole is slowly dropped in the glycol dibromide of three times of molar equivalents, at 50 ℃ of lower magnetic force stirring reaction 24h.Behind the stopped reaction, solid product with washing with acetone and suction filtration three times after, 50 ℃ of following vacuum-drying 6h, for use;
2) chitosan chemical load: 4g chitosan (deacetylation 80%, molecular-weight average 5 * 10
4), 15g 1-(2-bromotrifluoromethane)-3-methyl bromination imidazoles aqueous solution (60wt%) and 30mL Virahol join the there-necked flask of 100mL, at 75 ℃ of following stirring reaction 24h.Behind the stopped reaction, pH value of reaction system transferred to 6 after, add ethanol sedimentation and go out product, through washing, after the oven dry 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) (b, x=3, R ' are phenyl to (3-chloropropyl) triphenyl phosphonium chloride, X=Cl) ionic liquid preparation: in there-necked flask, triphenylphosphine is slowly added 1 of its three times of molar equivalents, in the 3-propylene dichloride, at 80 ℃ of lower magnetic force stirring reaction 24h.Behind the stopped reaction, solid product with washing with acetone and suction filtration three times after, 50 ℃ of following vacuum-drying 6h, for use;
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, at 80 ℃ of following stirring reaction 48h.Behind the stopped reaction, pH value of reaction system transferred to 7 after, add ethanol sedimentation and go out product, through washing, after the oven dry product.Analysis and characterization records charge capacity and is about 2.5mmol/g.
Embodiment 3
Implementation method: in the 100mL stainless steel autoclave; 1-methyl-3-ethyl bromination imidazoles (a, the m=2 that adds chitosan (chitin deacetylase degree 80% is called for short deacetylation 80%) load successively; X=Br) 0.5g (1.5mmol); 10mL propylene oxide (1a) (0.14mol), closed reactor charges into the CO of an amount of pressure
2, slowly rise to 120 ℃ by the temperature controller controlled temperature, controlling reaction pressure then is 2.5MPa, reacts 4 hours.After the reaction reaction kettle is cooled to room temperature, slowly emits excessive CO
2, filter to isolate catalyzer after, the product (2a) of gained is used the gas chromatograph-mass spectrometer quantitative analysis, selectivity＞99.8%, yield are 96%.
Embodiment 4
With embodiment 3, catalyst system therefor be chitosan (deacetylation 90%) load 1-methyl-3-ethyl imidazolitm chloride (a, m=2, X=Cl) 0.4g (1mmol), other conditions are constant, obtain product (2a) selectivity 98.5%, yield is 75%.
Embodiment 5
With embodiment 3, catalyst system therefor be chitosan (deacetylation 80%) load 1-methyl-3-propyl group iodate imidazoles (a, m=3, X=I) 0.5g (1.5mmol), other conditions are constant, obtain (2a) selectivity 99%, yield is 99%.
Embodiment 6
With embodiment 3, catalyst system therefor be chitosan (deacetylation 80%) load the propyl group triphenyl phosphonium chloride (b, x=2, R ' they are phenyl; X=Cl) 1g (2.5mmol), temperature is 130 ℃, the reaction times is 10 hours; Other are constant, obtain (2a) selectivity 99.8%, and yield is 90%.
Embodiment 7
With embodiment 3, catalyst system therefor be chitosan (deacetylation 70%) load etamon chloride (c, y=2, R are ethyl; X=Cl) 2.7g (5mmol), temperature is 100 ℃, the reaction times is 8 hours; Other are constant, obtain (2a) selectivity 99.7%, and yield is 90%.
Embodiment 8
With embodiment 3, catalyst system therefor be chitosan (deacetylation 70%) load the decyl pyridinium bromide (d, z=10, X=Br) 2g (3mmol), temperature of reaction is 110 ℃, the reaction times is 4 hours, other are constant, obtain (2a) selectivity 99.8%, 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), and 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 obtains (2a) selectivity 99.5% after using five times, and yield is 90%.
Embodiment 12
With embodiment 3, used epoxy compounds 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, used epoxy compounds 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, used epoxy compounds is epoxy styrene (1d), and other conditions are constant, obtains (2d) selectivity 99%, and yield is 90%.
Embodiment 15
With embodiment 3, used epoxy compounds is phenoxy oxyethane (1e), catalyst levels 2mmol, and other conditions are constant, obtain (2e) selectivity 99%, and yield is 90%.
Embodiment 16
With embodiment 3, used epoxy compounds 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 prepares the method for cyclic carbonate; It is characterized in that with epoxy compounds and carbonic acid gas be raw material; Using chitosan chemical load type catalyzer in the reaction process, is 0.1～10MPa at reaction conditions, 40～160 ℃; 0.3 synthesizing annular carbonate under～10 hours the condition, catalyst structure is following:
It is 70～95% that the carrier chitosan takes off the acetyl rate, and relative molecular weight is 2 * 10
4～5 * 10
5, the 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 prepares 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 prepares the method for cyclic carbonate, and the structural formula of epoxy compounds is following:
M=1,2,3 or 4 wherein, n=0,1,2,3 or 4.
4. chitosan loaded type catalyst according to claim 1 prepares the method for cyclic carbonate, and catalyst levels is 0.4～6mol% of epoxy compounds with the ionic liquid cubage.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104276987A (en) * | 2014-09-28 | 2015-01-14 | 黄河三角洲京博化工研究院有限公司 | Preparation method of thiol compound |
| CN104646055A (en) * | 2014-11-21 | 2015-05-27 | 常州大学 | Method for preparing immobilized ionic liquid catalyst |
| CN104974128A (en) * | 2015-07-24 | 2015-10-14 | 大连理工大学 | Method for preparing cyclic carbonate by using supported quaternary phosphonium salt catalyst |
| WO2018233093A1 (en) | 2017-06-20 | 2018-12-27 | 中国科学院过程工程研究所 | System and process for co-producing dimethyl carbonate and ethylene glycol |
| CN112142872A (en) * | 2020-09-08 | 2020-12-29 | 常州大学 | Alkaline ionic liquid grafted chitin, and preparation method and application thereof |
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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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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104276987A (en) * | 2014-09-28 | 2015-01-14 | 黄河三角洲京博化工研究院有限公司 | Preparation method of thiol compound |
| 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 |
| CN104646055A (en) * | 2014-11-21 | 2015-05-27 | 常州大学 | Method for preparing immobilized ionic liquid catalyst |
| CN104646055B (en) * | 2014-11-21 | 2017-01-18 | 常州大学 | Method for preparing immobilized ionic liquid catalyst |
| CN104974128A (en) * | 2015-07-24 | 2015-10-14 | 大连理工大学 | Method for preparing cyclic carbonate by using supported quaternary phosphonium salt 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 |
| WO2018233093A1 (en) | 2017-06-20 | 2018-12-27 | 中国科学院过程工程研究所 | System and process for co-producing dimethyl carbonate and ethylene glycol |
| CN112142872A (en) * | 2020-09-08 | 2020-12-29 | 常州大学 | Alkaline ionic liquid grafted chitin, and preparation method and application thereof |
| CN112142872B (en) * | 2020-09-08 | 2022-05-31 | 常州大学 | Alkaline ionic liquid grafted chitin, and preparation method and application thereof |
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