CN102391240A - Method for preparing cyclic carbamate by catalysis of immobilized ionic liquid - Google Patents
Method for preparing cyclic carbamate by catalysis of immobilized ionic liquid Download PDFInfo
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- CN102391240A CN102391240A CN2011102707634A CN201110270763A CN102391240A CN 102391240 A CN102391240 A CN 102391240A CN 2011102707634 A CN2011102707634 A CN 2011102707634A CN 201110270763 A CN201110270763 A CN 201110270763A CN 102391240 A CN102391240 A CN 102391240A
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- ionic liquid
- carbonic ether
- ion liquid
- cyclic carbonic
- catalytic preparation
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- AWMVMTVKBNGEAK-UHFFFAOYSA-N C1OC1c1ccccc1 Chemical compound C1OC1c1ccccc1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N CC(CO1)OC1=O Chemical compound CC(CO1)OC1=O RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- ZKOGUIGAVNCCKH-UHFFFAOYSA-N O=C(OC1)OC1c1ccccc1 Chemical compound O=C(OC1)OC1c1ccccc1 ZKOGUIGAVNCCKH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a method for preparing cyclic carbamate by catalysis of an immobilized ionic liquid. The method is characterized in that: an epoxy compound and carbon dioxide are used as raw materials, an immobilized ionic liquid catalyst is used in the reaction process, and the cyclic carbamate is synthesized under the conditions that the reaction pressure is 0.1 to 10MPa, the temperature is 80 to 150 DEG C and the reaction time is 0.5 to 6 hours. The carrier can undergo synergetic catalysis with active groups due to hydroxy, so that the cyclic carbamate can be synthesized with high efficiency and high selectivity by catalysis under the condition that other aids and cocatalyst are not added.
Description
Technical field
The present invention relates to green, clean catalysis technical field, specifically refer to a kind of by carbonic acid gas and epoxy compounds, under supported ion liquid catalysis through the cycloaddition reaction method for synthesizing carbonic ester.
Background technology
The carbonic acid gas synthesis of chemicals has become one of challenging problem of tool in this century, and synthesizing annular carbonate is exactly one of the most promising method of chemical recycling of carbon dioxide.Cyclic carbonate is a kind of extraordinary polar solvent, in the synthesizing of medicine and fine-chemical intermediate, application is more and more widely arranged.
The catalyzer of the production cyclic carbonate of having reported at present has: alkali metal halide, alkaline earth metal halide, organic bases, quaternary ammonium salt 、 quaternary alkylphosphonium salt, imidazole salts, solid alkali (like MOX); Transition metal complex, tetradentate schiff base metal complexes, crown ether or the like; These catalystsystem exist such as catalytic activity not high more or less; Stability is not high, problems such as severe reaction conditions.The heterogeneous catalyst that is used for this reaction on the other hand has the ionic liquid 、 quaternary alkylphosphonium salt of silica gel load, MOX (MgO-Al
2O
3), composite oxide of metal (the Cs-P-Si composite oxides, KI/MgO), and base-modified strong-basicity styrene ion exchange resin or big macroporous strong basic styrene ion exchange resin supported aurum catalyst etc.Although the catalyst type of report is a lot, but still exists reactive behavior low, long reaction time, active ingredient is to problems such as water sensitive, easy losses, and it is very important therefore to develop a kind of active catalystsystem high, that reaction conditions is gentle, stable.The present invention develops carrier hydroxyl supported ion liquid, aims to provide a kind of efficient, eco-friendly compound method of heterogeneous concerted catalysis synthesizing annular carbonate.
Summary of the invention
The present invention's research is under relatively mild condition, and is efficient, and highly selective is realized passing through the cycloaddition reaction method for synthesizing carbonic ester by carbonic acid gas and epoxy compounds.
Reaction expression of the present invention is:
Wherein-R is the substituting group on the epoxy compounds, for-H ,-CH
3,-CH
2Cl ,-C
2H
3,-C
4H
9With-C
6H
5A kind of.
The present invention relates to a kind of method of supported ion liquid catalytic preparation of cyclic carbonic ether; It is characterized in that with epoxy compounds and carbonic acid gas be raw material, is catalyzer with the ionic liquid of load, under the catalysis of supported ion liquid; At reaction pressure 0.1-10MPa; Temperature is 80 ℃-150 ℃, under the reaction times 0.5-6 hour condition, through the cycloaddition reaction synthesizing annular carbonate.Wherein carrier is selected from a kind of in molecular sieve, chitosan, Mierocrystalline cellulose and the polyoxyethylene glycol that contains hydroxyl.The ionic-liquid catalyst structure is following:
Among the last figure-R
1,-R
2,-R
3,-R
4Be substituted radical on the positively charged ion in the ionic liquid, be selected from the alkyl of carbon number between 1-12 respectively, can be identical, also can be different; Negatively charged ion X
-Be selected from Cl
-, Br
-, I
-, BF
4 -And PF
6 -In a kind of.
The invention has the advantages that, carrier contain hydroxyl can with reactive group concerted catalysis effect, efficient highly selective catalytically synthesizing cyclic carbonate ester under the condition that need not add other auxiliary agents and promotor.
Embodiment
The used supported ion liquid process for synthetic catalyst of the present invention is explained 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.
The supported catalyst preparation method: ionic liquid and carrier are removed methyl alcohol through underpressure distillation after joining by a certain percentage and mixing in the methyl alcohol, and solid was put into 100 ℃ of dryings of moisture eliminator 15 hours.
Embodiment 1
Implementation method: in the 100mL stainless steel autoclave, add the molecular sieve carried chlorination 1-butyl-3-Methylimidazole 1.74g of 4A (ionic liquid account for total catalyst weight 10%), 5.8g propylene oxide (1a); Closed reactor charges into the carbonic acid gas of 0.5MPa, slowly rises to 120 ℃ by the temperature controller controlled temperature; Controlling pressure carbon dioxide then is 2MPa, reacts 1.0 hours, is cooled to room temperature; Release; The product (2a) of gained is carried out gas chromatographic analysis, product (2a) selectivity＞99%, yield is 90%.
Embodiment 2
With embodiment 1, catalyst system therefor is for adding the molecular sieve carried chlorination 1-butyl-3-Methylimidazole 0.174g of 5A (ionic liquid account for total catalyst weight 1%), and other conditions are constant, obtain (2a) selectivity 99%, and yield is 73%.
Embodiment 3
With embodiment 1, catalyst system therefor is bromination 1-butyl-3-Methylimidazole 4.38g of adding polyoxyethylene glycol-10000 load (ionic liquid account for total catalyst weight 20%), and other conditions are constant, obtain (2a) selectivity 99%, and yield is 98%.
Embodiment 4
With embodiment 1, catalyst system therefor is for adding chitosan loaded iodate 1-butyl-3-Methylimidazole 2.66g (ionic liquid account for total catalyst weight 10%), and other conditions are constant, obtain (2a) selectivity 99%, and yield is 95%.
Embodiment 5
With embodiment 1, catalyst system therefor is 1-butyl-3-methyl imidazolium tetrafluoroborate 113g of adding the Mierocrystalline cellulose load (ionic liquid account for total catalyst weight 5%), and other conditions are constant, obtain (2a) selectivity 99%, and yield is 90%.
Embodiment 6
With embodiment 1, catalyst system therefor is 1-butyl-3-Methylimidazole hexafluorophosphate 1.42g of adding the Mierocrystalline cellulose load (ionic liquid account for total catalyst weight 5%), and other conditions are constant, obtain (2a) selectivity 99%, and yield is 88%.
Embodiment 7
With embodiment 1, catalyst system therefor is for adding the molecular sieve carried butyl-pyridinium bromine 2.16g of 5A (ionic liquid account for total catalyst weight 10%), and other conditions are constant, obtain (2a) selectivity 99%, and yield is 88%.
Embodiment 8
With embodiment 1, catalyst system therefor is the Tetrabutyl amonium bromide 3.22g that adds the Mierocrystalline cellulose load (ionic liquid account for total catalyst weight 10%), and other conditions are constant, obtain (2a) selectivity 99%, and yield is 88%.
Embodiment 9
With embodiment 1, catalyst system therefor is the dotetracontane base base brometo de amonio 0.818g that adds polyoxyethylene glycol-2000 load (ionic liquid account for total catalyst weight 1%), and other conditions are constant, obtain (2a) selectivity 99%, and yield is 82%.
Embodiment 10
With embodiment 1, catalyst system therefor is for adding chitosan loaded hexadecyl tributyl phosphonium bromide 0.507g (ionic liquid account for total catalyst weight 1%), and other conditions are constant, obtain (2a) selectivity 99%, and yield is 76%.
Embodiment 11
With embodiment 1, reaction pressure is 10MPa, and the reaction times is 0.5 hour, and other conditions are constant, obtains (2a) selectivity 99%, and yield is 86%.
Embodiment 12
With embodiment 1, reaction pressure is 0.5MPa, and the reaction times is 6 hours, and other conditions are constant, obtains (2a) selectivity 99%, and yield is 88%.
Embodiment 13
With embodiment 1, used epoxy compounds is epoxy chloropropane (1b), and other conditions are constant, obtains (2b) selectivity 93%, and yield is 90%.
Embodiment 14
With embodiment 1, used epoxy compounds is oxyethane (1c), 80 ℃ of temperature of reaction, and in 8 hours reaction times, other conditions are constant, obtain (2c) selectivity 99%, and yield is 98%.
Embodiment 15
With embodiment 1, used epoxy compounds is epoxy styrene (1d), 150 ℃ of temperature of reaction, and other conditions are constant, obtain (2d) selectivity 99%, and yield is 87%.
Embodiment 16
With embodiment 1, used epoxy compounds is epoxy styrene (1e), 150 ℃ of temperature of reaction, and other conditions are constant, obtain (2e) selectivity 99%, and yield is 87%.
Claims (7)
1. the method for a supported ion liquid catalytic preparation of cyclic carbonic ether; It is characterized in that with epoxy compounds and carbonic acid gas be raw material, is catalyzer with the ionic liquid of load, at reaction pressure 0.1-10MPa; 80 ℃-150 ℃ of temperature; Under the reaction times 0.5-6 hour condition, through the cycloaddition reaction synthesizing annular carbonate, wherein ion liquid structure is following:
Among the last figure-R
1,-R
2,-R
3,-R
4Be substituted radical on the positively charged ion in the ionic liquid, be selected from the alkyl of carbon number between 1-12 respectively, can be identical, also can be different; Negatively charged ion X
-Be selected from Cl
-, Br
-, I
-, BF
4 -And PF
6 -In a kind of.
2. the method for a kind of supported ion liquid catalytic preparation of cyclic carbonic ether according to claim 1 is characterized in that catalyzer adopts physical load.
3. the method for a kind of supported ion liquid catalytic preparation of cyclic carbonic ether according to claim 1 is characterized in that carrier is selected from a kind of in molecular sieve, chitosan, Mierocrystalline cellulose and the polyoxyethylene glycol.
4. the method for a kind of supported ion liquid catalytic preparation of cyclic carbonic ether according to claim 1 is characterized in that carrier contains hydroxyl.
5. the method for a kind of supported ion liquid catalytic preparation of cyclic carbonic ether according to claim 1 is characterized in that the structure of raw materials used epoxy compounds is:
Wherein-R is the substituting group on the epoxy compounds, for-H ,-CH
3,-CH
2Cl ,-C
2H
3,-C
4H
9, and-C
6H
5In a kind of.
6. the method for a kind of supported ion liquid catalytic preparation of cyclic carbonic ether according to claim 1 is characterized in that negatively charged ion X
-Be selected from Cl
-, Br
-And I
-In a kind of.
7. the method for a kind of supported ion liquid catalytic preparation of cyclic carbonic ether according to claim 1 is characterized in that ionic liquid loaded amount is lower than 20wt%.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570640A (en) * | 2012-07-30 | 2014-02-12 | 华东师范大学 | Carbon dioxide one-pot method for directly preparing oxazolidine-2-one compounds |
| CN104056661A (en) * | 2014-06-23 | 2014-09-24 | 内蒙古鄂尔多斯电力冶金股份有限公司氯碱化工分公司 | Mesoporous carbon cmk-3 supported ionic liquid catalysis method for preparation of cyclic carbonate |
| CN104341369A (en) * | 2013-08-01 | 2015-02-11 | 华东师范大学 | Preparing method of oxazolidine-2-one compounds |
| 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 |
| CN105153104A (en) * | 2015-08-18 | 2015-12-16 | 广西大学 | Method for synthesizing propylene carbonate |
| CN105294643A (en) * | 2014-07-24 | 2016-02-03 | 中国石油化工股份有限公司 | Catalyst and method for preparing ethylene carbonate from oxirane and carbon dioxide |
| CN105732566A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Method of producing ethylene carbonate |
| CN106916108A (en) * | 2017-01-19 | 2017-07-04 | 河南大学 | A kind of pyrazolium ion liquid and the method using its catalytically synthesizing cyclic carbonate ester |
| CN110152731A (en) * | 2019-05-28 | 2019-08-23 | 中国科学院过程工程研究所 | A kind of load type polymerization ionic-liquid catalyst and its preparation method and application |
| CN114433229A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst for preparing alkylene carbonate and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2011
- 2011-09-14 CN CN2011102707634A patent/CN102391240A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 张建新: "负载离子液体催化制备环状碳酸酯的研究", 《中国优秀硕士学位论文全文数据库 》, 19 August 2010 (2010-08-19), pages 12 - 15 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570640A (en) * | 2012-07-30 | 2014-02-12 | 华东师范大学 | Carbon dioxide one-pot method for directly preparing oxazolidine-2-one compounds |
| CN104341369A (en) * | 2013-08-01 | 2015-02-11 | 华东师范大学 | Preparing method of oxazolidine-2-one compounds |
| CN104056661A (en) * | 2014-06-23 | 2014-09-24 | 内蒙古鄂尔多斯电力冶金股份有限公司氯碱化工分公司 | Mesoporous carbon cmk-3 supported ionic liquid catalysis method for preparation of cyclic carbonate |
| CN105294643A (en) * | 2014-07-24 | 2016-02-03 | 中国石油化工股份有限公司 | Catalyst and method for preparing ethylene carbonate from oxirane and carbon dioxide |
| CN105294643B (en) * | 2014-07-24 | 2018-07-13 | 中国石油化工股份有限公司 | Ethylene oxide and carbon dioxide prepare the catalyst and its method of ethylene carbonate |
| CN105732566A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Method of producing ethylene carbonate |
| 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 |
| 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 |
| CN105153104A (en) * | 2015-08-18 | 2015-12-16 | 广西大学 | Method for synthesizing propylene carbonate |
| CN106916108A (en) * | 2017-01-19 | 2017-07-04 | 河南大学 | A kind of pyrazolium ion liquid and the method using its catalytically synthesizing cyclic carbonate ester |
| CN106916108B (en) * | 2017-01-19 | 2019-10-25 | 河南大学 | A kind of pyrazolium ion liquid and the method using its catalytically synthesizing cyclic carbonate ester |
| CN110152731A (en) * | 2019-05-28 | 2019-08-23 | 中国科学院过程工程研究所 | A kind of load type polymerization ionic-liquid catalyst and its preparation method and application |
| CN114433229A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst for preparing alkylene carbonate and preparation method and application thereof |
| CN114433229B (en) * | 2020-10-20 | 2024-01-30 | 中国石油化工股份有限公司 | Catalyst for preparing alkylene carbonate, and preparation method and application thereof |
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Application publication date: 20120328 |