CN104725344A - Method for preparing cyclic carbonate employing catalysis of carbon dioxide and epoxide with haloid - Google Patents

Method for preparing cyclic carbonate employing catalysis of carbon dioxide and epoxide with haloid Download PDF

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Publication number
CN104725344A
CN104725344A CN201510117458.XA CN201510117458A CN104725344A CN 104725344 A CN104725344 A CN 104725344A CN 201510117458 A CN201510117458 A CN 201510117458A CN 104725344 A CN104725344 A CN 104725344A
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haloid
epoxide
cyclic carbonate
mmol
carbonic acid
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刘春�
张绍科
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Dalian University of Technology
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07D317/38—Ethylene carbonate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a method for preparing cyclic carbonate employing catalysis of carbon dioxide and epoxide with haloid, and belongs to the field of organic synthesis catalysis. According to the method, with haloid employing halogen serving as an anion as a catalyst, cycloaddition reaction employing carbon dioxide and epoxide as raw materials is catalyzed by adopting haloid which uses halogen serving as an anion as a catalyst. The catalyst is cheap and available; the production cost is reduced; the method is simple to operate in synthesis of the cyclic carbonate; the catalyst is cheap and available; the reaction condition is mild; the lowest initial reaction pressure can be as low as 0.25MPa; the catalyst is high in activity; the yield of ethylene carbonate is 99.5% under the optimal reaction condition; and with relatively environment-friendly alcohols as a solvent, the method conforms to the idea of green chemistry, and is an excellent system for preparing the cyclic carbonate.

Description

The method of cyclic carbonate prepared by haloid catalysis carbonic acid gas and epoxide
Technical field
The present invention relates to the method that cyclic carbonate prepared by haloid catalysis carbonic acid gas and epoxide, it belongs to organic synthesis catalytic field.
Background technology
Along with the aggravation of " Greenhouse effect ", the chemical reaction effectively utilizing the carbonic acid gas of inertia to realize green is focus (the J. Am. Chem. Soc. 2014,136,6142-6147 of people's research in recent years; J. Am. Chem. Soc. 2013,135,11996-12003).
Cyclic carbonate is the solvent of the broad-spectrum chemical of a class and high boiling point high polarity, has been applied to the numerous areas (Green Chem. 2010,12,1514-1539) such as organic synthesis intermediate, battery electrolyte, metal extraction agent.
CO 2carry out with epoxide the Atom economy that reaction that cycloaddition prepares cyclic carbonate has 100%, be the reaction of typical atom economy type, meet the developing direction of Green Chemistry.Report multiple for CO in prior art 2with the catalyst system of epoxide synthesizing annular carbonate, the number of patent application of Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences's application is in the patent of 201110442303.5, is for catalyzer with the two quaternized ionic liquid of Silicage-polymer-bonded phase; The number of patent application of Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences's application is in the patent of 201110062979.1, and be take metal molybdate as catalyzer, organic quaternary ammonium salt or alkali metal halide are promotor; Also have (J. Am. Chem. Soc., 2013,135,18497-18501 such as some other metal oxide, metal complexes and organic inorganic hybridization catalyzer; J. Am. Chem. Soc. 2013,135,11,996 2003), but these catalyst systems are all comparatively complicated or expensive.
Halogen cheap and easy to get is that the salt of negatively charged ion is also used to catalysis CO 2with epoxide synthesizing annular carbonate, but under condition of no solvent its catalysis CO 2with the reaction effect difference (Tetrahedron Lett., 2008,49,3588-3591) of epoxide synthesizing annular carbonate.Therefore, to develop with the halogen of the cheapness salt that is negatively charged ion be catalyst preparing cyclic carbonate, and efficient catalytic reaction system has significant application value.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of in alcoholic solution haloid catalysis carbonic acid gas and epoxide prepare the method for cyclic carbonate, to provide a kind of cheap and easy to get catalyzer preparing cyclic carbonate and simple catalytic environment.
The method of cyclic carbonate prepared by haloid catalysis carbonic acid gas and epoxide, and being solvent with alcohol, take haloid as catalyzer, with carbonic acid gas and epoxide for initiator prepares cyclic carbonate, comprises the following steps:
(1) join in autoclave by haloid, epoxide and solvent, the consumption of haloid is the 0.05-5.0 % of epoxide amount; The salt of described haloid to be halogen be negatively charged ion, described haloid is potassiumiodide, sodium iodide, Potassium Bromide, Sodium Bromide, Tetrabutyl amonium bromide or tetrabutylammonium iodide; Described epoxide is oxyethane, propylene oxide, Styrene oxide 98min. or phenyl glycidyl ether; Described solvent selected from methanol, ethanol, n-propyl alcohol or Virahol;
(2) in autoclave, passing into carbonic acid gas to original pressure is 0.25-3.0 MPa, reacts at temperature of reaction 80-160 DEG C.
Implementation process of the present invention is (taking oxyethane as initiator): in 75 mL autoclaves, add oxyethane (14.3 mmol), salt (1.43 mmol), ethanol (71.5 mmol) and biphenyl (0.5 mmol that halogen is negatively charged ion, internal standard substance), then pass into carbonic acid gas, system pressure is made to reach 0.5 MPa, 120 ° of C react for some time, are obtained the productive rate of propylene carbonate by gas chromatographic analysis.
The invention has the beneficial effects as follows: the method employing is the haloid of negatively charged ion with halogen is catalyzer, and the cycloaddition reaction that catalysis is raw material with carbonic acid gas and epoxide, this catalyzer is cheap and easy to get reduces production cost.The method reaction conditions is gentle, and minimum initial reaction pressure can be low to moderate 0.25 MPa; Under the reaction conditions optimized, NSC 11801 productive rate 99.5%.With the alcohols of relative environmental protection for solvent, meet the theory of Green Chemistry.
Embodiment
In order to understand the present invention better, set forth further below in conjunction with embodiment, but these embodiments should not be construed as any limitation of the invention.
embodiment 1
Ethanol (71.5 mmol), oxyethane (14.3 mmol), potassiumiodide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 0.5 MPa, 120 ° of C react 1 hour, are obtained the productive rate 99.5% of product NSC 11801 by gas chromatogram fixative quantitative analysis.
embodiment 2
Ethanol (71.5 mmol), propylene oxide (14.3 mmol), potassiumiodide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 0.5 MPa, 120 ° of C react 1 hour, are obtained the productive rate 93.6% of product propylene carbonate by gas chromatogram fixative quantitative analysis.
embodiment 3
Ethanol (71.5 mmol), propylene oxide (14.3 mmol), tetrabutylammonium iodide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 0.5 MPa, 120 ° of C react 1 hour, are obtained the productive rate 88.0% of product propylene carbonate by gas chromatogram fixative quantitative analysis.
embodiment 4
Ethanol (71.5 mmol), propylene oxide (14.3 mmol), potassiumiodide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 3.0 MPa, 120 ° of C react 1 hour, are obtained the productive rate 94.5% of product propylene carbonate by gas chromatogram fixative quantitative analysis.
embodiment 5
Ethanol (71.5 mmol), propylene oxide (14.3 mmol), potassiumiodide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 0.25 MPa, 120 ° of C react 1 hour, are obtained the productive rate 87.9% of product propylene carbonate by gas chromatogram fixative quantitative analysis.
embodiment 6
Ethanol (71.5 mmol), propylene oxide (14.3 mmol), potassiumiodide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 0.5 MPa, 160 ° of C react 1 hour, are obtained the productive rate 90.9% of product propylene carbonate by gas chromatogram fixative quantitative analysis.
embodiment 7
Ethanol (71.5 mmol), propylene oxide (14.3 mmol), potassiumiodide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 0.5 MPa, 80 ° of C react 1 hour, are obtained the productive rate 89.5% of product propylene carbonate by gas chromatogram fixative quantitative analysis.
embodiment 8
Ethanol (71.5 mmol), propylene oxide (14.3 mmol), tetrabutylammonium iodide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 0.5 MPa, 120 ° of C react 1 hour, are obtained the productive rate 91.5% of product propylene carbonate by gas chromatogram fixative quantitative analysis.
embodiment 9
Ethanol (71.5 mmol), propylene oxide (14.3 mmol), sodium iodide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 0.5 MPa, 120 ° of C react 1 hour, are obtained the productive rate 92.4% of product propylene carbonate by gas chromatogram fixative quantitative analysis.
embodiment 10
Ethanol (71.5 mmol), propylene oxide (14.3 mmol), Potassium Bromide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 0.5 MPa, 120 ° of C react 1 hour, are obtained the productive rate 87.6% of product propylene carbonate by gas chromatogram fixative quantitative analysis.
embodiment 11
Ethanol (71.5 mmol), propylene oxide (14.3 mmol), Sodium Bromide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 0.5 MPa, 120 ° of C react 1 hour, are obtained the productive rate 89.5% of product propylene carbonate by gas chromatogram fixative quantitative analysis.
embodiment 12
Ethanol (71.5 mmol), Styrene oxide 98min. (14.3 mmol), potassiumiodide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 0.5 MPa, 120 ° of C react 1 hour, are obtained the productive rate 85.6% of product by gas chromatogram fixative quantitative analysis.
embodiment 13
Ethanol (71.5 mmol), phenyl glycidyl ether (14.3 mmol), potassiumiodide (1.43 mmol) is added in 75 mL autoclaves, then pass into carbonic acid gas, system pressure is made to reach 0.5 MPa, 120 ° of C react 1 hour, are obtained the productive rate 88.2% of product by gas chromatogram fixative quantitative analysis.
Above content is the further description done the present invention in conjunction with optimal technical scheme, can not assert that specific embodiment of the invention is only limitted to these explanations.Concerning general technical staff of the technical field of the invention, under the prerequisite not departing from design of the present invention, simple deduction and replacement can also be made, all should be considered as protection scope of the present invention.

Claims (1)

1. the method for cyclic carbonate prepared by haloid catalysis carbonic acid gas and epoxide, it is characterized in that: be solvent with alcohol, take haloid as catalyzer, with carbonic acid gas and epoxide for initiator prepares cyclic carbonate, comprises the following steps:
(1) join in autoclave by haloid, epoxide and solvent, the consumption of haloid is the 0.05-5.0 % of epoxide amount; The salt of described haloid to be halogen be negatively charged ion, described haloid is potassiumiodide, sodium iodide, Potassium Bromide, Sodium Bromide, Tetrabutyl amonium bromide or tetrabutylammonium iodide; Described epoxide is oxyethane, propylene oxide, Styrene oxide 98min. or phenyl glycidyl ether; Described solvent selected from methanol, ethanol, n-propyl alcohol or Virahol;
(2) in autoclave, passing into carbonic acid gas to original pressure is 0.25-3.0 MPa, reacts at temperature of reaction 80-160 DEG C.
CN201510117458.XA 2015-03-18 2015-03-18 Method for preparing cyclic carbonate employing catalysis of carbon dioxide and epoxide with haloid Pending CN104725344A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI601571B (en) * 2016-12-07 2017-10-11 財團法人工業技術研究院 Catalyst and method for synthesizing cyclic carbonate by the same
CN110003162A (en) * 2019-03-19 2019-07-12 武汉科技大学 A method of making catalyst synthesizing annular carbonate with lignin
CN110302813A (en) * 2019-07-24 2019-10-08 惠州宇新化工有限责任公司 A kind of catalyst of synthesizing annular carbonate and its preparation method and application
CN111393402A (en) * 2020-03-25 2020-07-10 西北大学 Br nsted acid/quaternary ammonium salt composite catalytic CO2Method for preparing cyclic carbonate by cycloaddition with epoxide
CN112337507A (en) * 2020-11-13 2021-02-09 湖南工程学院 Application of cyclodextrin inclusion compound in catalyzing CO2Application in cycloaddition reaction
JP2021506808A (en) * 2017-12-15 2021-02-22 ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ Method for producing glycerin carbonate methacrylate
CN113185490A (en) * 2021-04-15 2021-07-30 西北大学 Carboxylic acid/metal halide composite catalytic CO2Method for preparing cyclic carbonate by cycloaddition with epoxide
CN115160284A (en) * 2022-08-10 2022-10-11 嘉兴学院 Synthetic method of cyclic carbonate
CN115181087A (en) * 2022-08-25 2022-10-14 山东东岳高分子材料有限公司 Method for preparing ethylene carbonate by ionic liquid composite catalyst

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9839906B1 (en) 2016-12-07 2017-12-12 Industrial Technology Research Institute Catalyst and method for synthesizing cyclic carbonate by the same
TWI601571B (en) * 2016-12-07 2017-10-11 財團法人工業技術研究院 Catalyst and method for synthesizing cyclic carbonate by the same
JP2021506808A (en) * 2017-12-15 2021-02-22 ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ Method for producing glycerin carbonate methacrylate
JP7204751B2 (en) 2017-12-15 2023-01-16 ビーエーエスエフ ソシエタス・ヨーロピア Method for producing glycerine carbonate methacrylate
CN110003162A (en) * 2019-03-19 2019-07-12 武汉科技大学 A method of making catalyst synthesizing annular carbonate with lignin
CN110302813A (en) * 2019-07-24 2019-10-08 惠州宇新化工有限责任公司 A kind of catalyst of synthesizing annular carbonate and its preparation method and application
CN110302813B (en) * 2019-07-24 2022-08-16 惠州宇新化工有限责任公司 Catalyst for synthesizing cyclic carbonate and preparation method and application thereof
CN111393402A (en) * 2020-03-25 2020-07-10 西北大学 Br nsted acid/quaternary ammonium salt composite catalytic CO2Method for preparing cyclic carbonate by cycloaddition with epoxide
CN111393402B (en) * 2020-03-25 2023-04-07 西北大学 N & lt/EN & gt acid/quaternary ammonium salt composite catalytic CO 2 Method for preparing cyclic carbonate by cycloaddition with epoxide
CN112337507A (en) * 2020-11-13 2021-02-09 湖南工程学院 Application of cyclodextrin inclusion compound in catalyzing CO2Application in cycloaddition reaction
CN113185490A (en) * 2021-04-15 2021-07-30 西北大学 Carboxylic acid/metal halide composite catalytic CO2Method for preparing cyclic carbonate by cycloaddition with epoxide
CN115160284A (en) * 2022-08-10 2022-10-11 嘉兴学院 Synthetic method of cyclic carbonate
CN115181087A (en) * 2022-08-25 2022-10-14 山东东岳高分子材料有限公司 Method for preparing ethylene carbonate by ionic liquid composite catalyst

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Application publication date: 20150624