CN102775377B - A kind of solvent-free process for catalytic synthesis of cyclic carbonate - Google Patents

A kind of solvent-free process for catalytic synthesis of cyclic carbonate Download PDF

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CN102775377B
CN102775377B CN201110430994.7A CN201110430994A CN102775377B CN 102775377 B CN102775377 B CN 102775377B CN 201110430994 A CN201110430994 A CN 201110430994A CN 102775377 B CN102775377 B CN 102775377B
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ammonium salt
carbonic acid
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CN102775377A (en
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尹双凤
邱仁华
孟振功
宋星星
邱一苗
喻琨
罗胜联
许新华
周永波
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Hunan University
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Abstract

The invention provides a kind of carbonic acid gas and the epoxide solvent-free process for catalytic synthesis by cycloaddition reaction synthesizing annular carbonate, it is characterized in that this chemical process adopts organometallic compound and quaternary ammonium salt as catalyzer, without the need to organic solvent.Organometallic complex is containing the organo-bismuth of sulphur bridge part and the title complex of antimony organic.Quaternary ammonium salt is tetraalkyl or aryl ammonium salt.This method can realize changing into the cyclic carbonate with extensive industrial use to GHG carbon dioxide recycling.This green catalysis synthetic method catalytic activity is high, and chemo-selective is high, and conversion rate is fast, and the original pressure of required carbonic acid gas is low, and reaction conditions is gentle, and energy consumption is low, and catalyzer is cheap and easy to get, preparation is simple, stability is high.The solvent-free green catalysis synthetic method of the cyclic carbonate that the present invention develops can be widely used in the recycling of the carbon dioxide greenhouse gas of catching in stack gas, synthetic ammonia, Sweet natural gas, kiln gas etc.

Description

A kind of solvent-free process for catalytic synthesis of cyclic carbonate
[technical field]
The invention belongs to organic chemical industry, green catalysis synthesis technical field, relate in particular to a kind of carbonic acid gas and the epoxide solvent-free process for catalytic synthesis by cycloaddition reaction synthesizing annular carbonate.
[background technology]
Along with a large amount of use of fossil oil and the continuous rising of demand for energy, fossil oil is just petered out, and causes " carbon source crisis ".And the various combustion of fossil fuel in the whole world is discharged into the CO in air in recent years 2amount has reached 185-242 hundred million tons/year.At present, the CO in large G&W 2total amount reaches 3.67 × 10 6hundred million tons, be equivalent to about 10 times of coal and oil carbon content; Potential CO 2the carbon content of-carbonate is higher, is about 1 × 10 8hundred million tons.Therefore, CO 2it is carbon resource inexhaustible on the earth.How to make full use of CO 2this sufficient cheap C1 resource is the important means alleviating " carbon source crisis ".
CO 2molecule is the symmetrical triatomic molecule of typical linear pattern, its structures shape it be weak electron donor (the first ionization energy 13.79ev) and strong electron acceptor (electron affinity 38ev).Comparatively speaking, CO 2the more acceptant electronics of molecule, as long as adopt suitable mode to input electronics to it, or the electronics capturing other molecule in reaction process is used, and can realize inertia CO 2the activation of molecule.At present by CO 2be converted into valuable compounds therefrom and mainly contain four kinds of approach: (i) uses the compound of high energy as reaction substrate, as: hydrogen, unsaturated compound, little membered cyclic compound and organo-metallic etc.; (ii) energy-poor compound of selective oxidation is as synthesis target, as organic carbonate; (iii) remove specific compound to carry out to product direction to make reaction; (iv) physical energy is provided to reaction, as luminous energy and electric energy.By above-mentioned approach, CO 2the multiple compounds having industrial value such as carbon, alcohol, synthetic gas, low-carbon alkene, aldehyde, acid, ether and ester can be converted into.
Cyclic carbonate is the chemical products with good biological degradability, can be used as clean polar solvent, also can be used for that resol is produced, thermosetting resin synthesis, thermal recording material synthesis, and as the electrolytic solution of high-energy-density battery (as lithium ion battery) and electric capacity, metal extraction agent, cosmetics additive and chemical intermediate etc.Main purposes is exactly polycarbonate (PC) synthesis.The synthetic method of cyclic carbonate mainly contains phosgenation and non-phosgene.Non-phosgene, namely adopts carbonic acid gas as the method for carbonylation agent, obtains the extensive concern of people because of its " green chemistry process process ".Epoxide and the carbonic acid gas product circular carbonic ether that direct initial ring addition reaction obtains 100% Atom economy under the catalysis of catalyzer is current study hotspot.At present, adopt organometallic complex to catalyze and synthesize for cyclic carbonate and have been reported, mainly concentrate on the title complexs such as Salen aluminium, manganese, and the concern that the title complex such as organo-metallic bismuth and organo-metallic antimony is subject to is less; The title complex of the bismuth-containing mainly synthesized and antimony is unstable, responsive to water and air, is more impossiblely exposed to inside sour gas.Applicant its in publication number disclosed in 15 days June in 2011 be CN102091504A, it is entitled as in the patent application of " chemical process of a kind of trapping, fixing and purification of carbon dioxide, sulfurous gas, sulphur trioxide and oxynitride ", describe a kind of novel organo-bismuth of sulphur bridge part and the sulfide of antimony organic, find that this kind of title complex can well be used for trapping, fixing and purification of carbon dioxide, sulfurous gas, sulphur trioxide and oxynitride under the acting in conjunction of solvent.But this application is only inquired into the trapping of greenhouse gases, fixing and purification, and does not study the recycling of the carbon dioxide trapped.Here, we by the series of this new synthesis to air-stable containing 5,6,7,12-[c, f] organo-bismuth (antimony) title complex of [1,5]-sulphur bismuth (antimony) octene skeleton is used for, in the cycloaddition reaction of carbonic acid gas and epoxide synthesizing annular carbonate, obtaining good catalytic effect.Find based on existing bibliographical information and our research, this kind of compound containing above-mentioned skeleton is applied to CO at imagination by us 2recycling, realizes collecting carbonic anhydride, fixes, purifies and the whole technical process of recycling.
Applicant its in the patent being entitled as " organic bismuth ion compound and preparation and application thereof containing bridge sulphur atom ligand " that is CN101508703A of publication number disclosed in 19 days Augusts in 2009 and its in publication number disclosed in 30 days September in 2009 be CN101544671A be entitled as in the patent application of " antimony organic ionic compound and preparation and application thereof containing bridge sulphur atom ligand ", describe the muriatic synthesis of two kinds of organometallic complexs, react using the muriate of these two kinds of title complexs and corresponding mineral alkali and can obtain double-core organo-bismuth stibium complex in the application as CO 2being catalytically converted into the Primary Catalysts of the effective catalyst of cyclic carbonate with epoxide, developing a kind of process for catalytic synthesis of brand-new cyclic carbonate, theory and practice is all feasible.
[summary of the invention]
The object of the present invention is to provide the solvent-free process for catalytic synthesis of a kind of brand-new catalysis transform of carbon dioxide carbonic ether circlewise, to improve the transformation efficiency of epoxide, improve the selectivity of cyclic carbonate, reduce the energy consumption in carbon dioxide conversion process, improve selectivity of catalyst.
To achieve the above object of the invention, the present invention proposes following technical scheme:
Brand-new carbonic acid gas and epoxide are catalytically converted into a solvent-free process for catalytic synthesis for cyclic carbonate, be with double-core containing the organo-bismuth of bridge sulphur atom ligand and organic stibium complex for Primary Catalysts, quaternary ammonium salt is promotor.
In above-mentioned synthetic method, described double-core organo-bismuth antimony sulfide is organo-bismuth title complex and the organic stibium complex with structural formula I:
Wherein, described title complex be a class novel containing the organometallic complex of bridge sulphur atom ligand, the structural formula of described part is [(R 1) (R 2) (R 3) (R 4) PhCH 2] S [CH 2ph (R 5) (R 6) (R 7) (R 8)], wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8for identical on phenyl ring or not identical any group; Metal center (M 3+) be bismuth (Bi 3+) and antimony (Sb 3+).M 3+with M 3+be connected by oxygen family element; And in such title complex, M 3+except being formed except covalent linkage with the carbon atom of two in part, also form coordinate bond with the sulphur atom in part, with M 3+covalent linkage is formed with chalcogen atom.The substituent R of described part 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R ' is identical on phenyl ring or not identical alkyl (C0-C20) or aryl (C6-C20), wherein preferably H, methyl, ethyl, the tertiary butyl, cyclohexyl, phenyl or naphthyl.Described oxygen family element are oxygen, sulphur, selenium and tellurium (O, S, Se, Te), wherein preferred oxygen and sulphur.
In above-mentioned synthetic method, described organo-metallic bismuth stibium complex catalyzer, its particular compound and preparation method thereof, please refer to applicant its publication number disclosed in the 15 days June in 2011 be CN102091504A, it is entitled as the patent application of " chemical process of a kind of trapping, fixing and purification of carbon dioxide, sulfurous gas, sulphur trioxide and oxynitride ".
In above-mentioned synthetic method, the organometallic complex of described preparation is the Primary Catalysts that carbonic acid gas and epoxide cycloaddition reaction prepare cyclic carbonate, and quaternary ammonium salt is the composition catalyst system of promotor.
In above-mentioned synthetic method, described quaternary ammonium salt (R 4nX) be any quaternary amine, wherein R is the fatty substituents of C1 to C20 and the aromatic substituent of C5-C20, preferable methyl, ethyl, butyl, phenyl; The preferred fluorine of X, chlorine, bromine, iodine, BF 4, PF 6, C nh 2n+1sO 3(n=1-20), C nf 2n+1sO 3(n=1-20), C 6h 5sO 3, C 6f 5sO 3, wherein preferred bromine and iodine.
In above-mentioned synthetic method, it is temperature of reaction 20-180 DEG C that described catalyst system is used as the reaction conditions that carbonic acid gas and epoxide cycloaddition reaction prepare cyclic carbonate, reaction times 0.5-24h, the original pressure of carbonic acid gas is 0.5-10MPa, the consumption 0.1-10mol% of Primary Catalysts, the consumption of promotor is 0.1-10mol%; Wherein preferable reaction temperature is 110-140 DEG C, reaction times preferred 6-24h, and the original pressure of carbonic acid gas is 2.0-4.0MPa, the consumption 0.2-2mol% of Primary Catalysts, and the consumption of promotor is 0.1-2mol%.
In above-mentioned synthetic method, the structural formula of described epoxide is II, wherein R 1, R 2for identical or not identical alkyl (C0-C20) or aryl (C5-C20), or other any heteroatom substituting group.
The catalyst system of double-core organo-bismuth stibium complex of the present invention and quaternary ammonium salt composition is to CO 2the catalytic being catalytically converted into cyclic carbonate is fast, and the reaction times is short, regeneration temperature and regeneration energy consumption low, to equipment free of losses, and catalyzer is cheap and easy to get, nontoxic pollution-free, preparation is simple, stability is high and can repeatedly use.The present invention can be widely used in the CO of greenhouse gases 2recycling and change into catalyzing and synthesizing of cyclic carbonate.
[accompanying drawing explanation]
CO provided by the invention shown in Fig. 1 2the solvent-free process for catalytic synthesis of cyclic carbonate is catalytically converted into epoxide.
[embodiment]
CO provided by the present invention 2be catalytically converted into the solvent-free process for catalytic synthesis of cyclic carbonate with epoxide, refer to accompanying drawing 1: adopt autoclave stainless steel high-pressure reactor (volume 30mL) to investigate CO 2with the cycloaddition reaction of epoxide.Typical operational procedure is: add in still by a certain amount of double-core organo-bismuth stibium complex catalyst I (0.1-10mol%) and promotor quaternary ammonium salt (0.1-10mol%) and epoxide (25mmol) and interior mark biphenyl (about 200mg), sealing final vacuum 30min, to remove air in still, backfills CO 2to CO 2original pressure 0.5-10MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 20-180 DEG C; Reaction times is 5min-24h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Product adopt GC-MS (Agilent6890-5973MSDGC-MS gas chromatograph-mass spectrometer (GC-MS)) and 1hNMR (Bruck-400 type NMR spectrometer with superconducting magnet, TMS is interior mark) carries out qualitative analysis.Quantitative analysis adopts Agilent6890N gas chromatograph, analytical procedure is marker method, analysis condition is: fid detector, sampler temperature 250 DEG C, detector temperature 250 DEG C, post case temperature are that (40 DEG C keep 2min in temperature programming, 15 DEG C/min is warming up to 220 DEG C, keep 10min), Rtx-wax capillary chromatograph (30m × 0.25mm × 0.25 μm).
Below in conjunction with concrete preparation example, the present invention will be further described:
embodiment 1
By binuclear organometallic complexes catalyst I (R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be hydrogen, X is oxygen, M is bismuth) (0.1mol%) and promotor tetrabutyl iodate amine (0.1mol%) and oxyethane (25mmol) and interior mark biphenyl (about 200mg) adds in still, sealing final vacuum 30min, to remove air in still, backfills CO 2to CO 2original pressure 3.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 140 DEG C; Reaction times is 6h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 100%, selectivity 98.2%.
embodiment 2
By binuclear organometallic complexes catalyst I (R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be hydrogen, X is oxygen, M is antimony) (0.2mol%) and promotor tetrabutyl iodate amine (0.1mol%) and propylene oxide (25mmol) and interior mark biphenyl (about 200mg) adds in still, sealing final vacuum 30min, to remove air in still, backfills CO 2to CO 2original pressure 3.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 140 DEG C; Reaction times is 6h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 99.7%, selectivity 100%.
embodiment 3
By binuclear organometallic complexes catalyst I (R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be hydrogen, X is oxygen, M is bismuth) (0.2mol%) and promotor tetrabutyl iodate amine (0.1mol%) and epoxy chloropropane (25mmol) and interior mark biphenyl (about 200mg) adds in still, sealing final vacuum 30min, to remove air in still, backfills CO 2to CO 2original pressure 3.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 140 DEG C; Reaction times is 6h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 100%, selectivity 100%.
embodiment 3
By binuclear organometallic complexes catalyst I (R 1, R 2, R 3, R 4, R 5, R 6, R 7, be hydrogen, R 8for methyl, X is oxygen, M is bismuth) (0.5mol%) and promotor tetrabutyl iodate amine (0.1mol%) and epoxy chloropropane (25mmol) and interior mark biphenyl (about 200mg) adds in still, sealing final vacuum 30min, to remove air in still, backfills CO 2to CO 2original pressure 3.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 140 DEG C; Reaction times is 6h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 98.1%, selectivity 99.3%.
embodiment 4
By binuclear organometallic complexes catalyst I (R 1, R 2, R 4, R 5, R 6, R 7, R 8be methyl, R 3for ethyl, X is oxygen, M is antimony) and promotor tetrabutyl iodate amine (1mol%) and epoxy hexane (25mmol) and interior mark biphenyl (about 200mg) add in still, sealing final vacuum 30min, remove air in still, backfills CO 2to CO 2original pressure 3.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 140 DEG C; Reaction times is 6h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 70.1%, selectivity 99.3%.
embodiment 5
By binuclear organometallic complexes catalyst I (R 1, R 2, R 3, R 4be H, R 5, R 6, R 7, R 8be ethyl, X is oxygen, M is bismuth) and promotor tetrabutyl iodate amine (1mol%) and epoxy styrene (25mmol) and interior mark biphenyl (about 200mg) add in still, sealing final vacuum 30min, remove air in still, backfills CO 2to CO 2original pressure 3.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 140 DEG C; Reaction times is 6h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 99.5%, selectivity 99.5%.
embodiment 6
By binuclear organometallic complexes catalyst I (R 1, R 2, R 3, R 4be H, R 5, R 6, R 7, R 8be methyl, X is sulphur, M is bismuth) and promotor tetrabutyl iodate amine (1mol%) and epoxy styrene (25mmol) and interior mark biphenyl (about 200mg) add in still, sealing final vacuum 30min, remove air in still, backfills CO 2to CO 2original pressure 3.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 140 DEG C; Reaction times is 6h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 99.5%, selectivity 99.5%.
embodiment 7
By binuclear organometallic complexes catalyst I (R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be hydrogen, X is oxygen, M is bismuth) (0.1mol%) and promotor four butyl bromation amine (0.1mol%) and oxyethane (25mmol) and interior mark biphenyl (about 200mg) adds in still, sealing final vacuum 30min, to remove air in still, backfills CO 2to CO 2original pressure 3.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 120 DEG C; Reaction times is 9h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 100%, selectivity 98.6%.
embodiment 8
By binuclear organometallic complexes catalyst I (R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be hydrogen, X is oxygen, M is antimony) (0.2mol%) and promotor four butyl bromation amine (1mol%) and propylene oxide (25mmol) and interior mark biphenyl (about 200mg) adds in still, sealing final vacuum 30min, to remove air in still, backfills CO 2to CO 2original pressure 3.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 140 DEG C; Reaction times is 6h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 99.1%, selectivity 100%.
embodiment 9
By binuclear organometallic complexes catalyst I (R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be hydrogen, X is oxygen, M is bismuth) (0.2mol%) and promotor four butyl bromation amine (0.1mol%) and epoxy chloropropane (25mmol) and interior mark biphenyl (about 200mg) adds in still, sealing final vacuum 30min, to remove air in still, backfills CO 2to CO 2original pressure 3.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 20 DEG C; Reaction times is 24h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 2%, selectivity 100%.
embodiment 10
By binuclear organometallic complexes catalyst I (R 1, R 2, R 3, R 4, R 5, R 6, R 7, be hydrogen, R 8for methyl, X is oxygen, M is bismuth) (0.5mol%) and promotor four butyl bromation amine (0.1mol%) and epoxy chloropropane (25mmol) and interior mark biphenyl (about 200mg) adds in still, sealing final vacuum 30min, to remove air in still, backfills CO 2to CO 2original pressure 3.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 120 DEG C; Reaction times is 12h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 94.1%, selectivity 99.3%.
embodiment 11
By binuclear organometallic complexes catalyst I (R 1, R 2, R 4, R 5, R 6, R 7, R 8be methyl, R 3for ethyl, X is oxygen, M is antimony) and promotor four butyl bromation amine (1mol%) and epoxy hexane (25mmol) and interior mark biphenyl (about 200mg) add in still, sealing final vacuum 30min, remove air in still, backfills CO 2to CO 2original pressure 2.5MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 110 DEG C; Reaction times is 10h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 60.5%, selectivity 94.3%.
embodiment 12
By binuclear organometallic complexes catalyst I (R 1, R 2, R 3, R 4be H, R 5, R 6, R 7, R 8be ethyl, X is sulphur, M is bismuth) and promotor four butyl bromation amine (0.5mol%) and epoxy styrene (25mmol) and interior mark biphenyl (about 200mg) add in still, sealing final vacuum 30min, remove air in still, backfills CO 2to CO 2original pressure 2.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 140 DEG C; Reaction times is 6h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 82.5%, selectivity 99.5%.
embodiment 13
By binuclear organometallic complexes catalyst I (R 1, R 2, R 3, R 4be H, R 5, R 6, R 7, R 8be methyl, X is sulphur, M is antimony) and promotor four butyl bromation amine (0.5mol%) and epoxy styrene (25mmol) and interior mark biphenyl (about 200mg) add in still, sealing final vacuum 30min, remove air in still, backfills CO 2to CO 2original pressure 3.0MPa, be finally placed in by reactor on the magnetic stirring apparatus of band oil bath heating unit, temperature of reaction is 110 DEG C; Reaction times is 8h.After question response completes, with mixture of ice and water cooling reactor to 0 DEG C, discharge residual gas, sampling utilizes gas-chromatography (GC) to carry out quantitative analysis.Transformation efficiency 73.5%, selectivity 99.5%.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (3)

1. pass through a solvent-free process for catalytic synthesis for cycloaddition reaction synthesizing annular carbonate with carbonic acid gas and epoxide, it is characterized in that adopting organometallic compound and quaternary ammonium salt R 4nX, as catalyzer, without the need to solvent, realizes synthesizing annular carbonate;
Wherein, described organometallic compound is organo-bismuth title complex and the organic stibium complex with structural formula I:
Such title complex is the organometallic complex containing bridge sulphur atom ligand, and the structural formula of its part is [(R 1) (R 2) (R 3) (R 4) PhCH 2] S [CH 2ph (R 5) (R 6) (R 7) (R 8)], wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8for identical on phenyl ring or not identical any group; Metal center M 3+bi 3+and Sb 3+; M 3+with M 3+be connected by oxygen family element; And in such title complex, M 3+except being formed except covalent linkage with the carbon atom of two in part, also form coordinate bond with the sulphur atom in part, with M 3+covalent linkage is formed with chalcogen atom;
The substituent R of described part 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8identical or not identical H, methyl, ethyl, the tertiary butyl, cyclohexyl, phenyl or naphthyl; Described oxygen family element are oxygen, sulphur, selenium or tellurium;
Described organometallic compound is Primary Catalysts, and quaternary ammonium salt is promotor;
Described quaternary ammonium salt R 4in NX, R is methyl, ethyl, butyl or phenyl; X is selected from fluorine, chlorine, bromine, iodine, BF 4, PF 6, C 6h 5sO 3, C 6f 5sO 3, C nh 2n+1sO 3or C nf 2n+1sO 3, wherein n=1 ~ 20.
2. process for catalytic synthesis according to claim 1, it is characterized in that, described catalytic reaction condition is: temperature of reaction 20-180 DEG C, reaction times 0.5-24h, the original pressure of carbonic acid gas is 0.5-10MPa, the consumption 0.1-10mol% of Primary Catalysts, the consumption of promotor is 0.1-10mol%.
3. process for catalytic synthesis according to claim 2, it is characterized in that, described catalytic reaction condition is: temperature of reaction is 110-140 DEG C, reaction times preferred 6-24h, the original pressure of carbonic acid gas is 2.0-4.0MPa, the consumption 0.2-2mol% of Primary Catalysts, the consumption of promotor is 0.1-2mol%.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1369489A (en) * 2002-01-25 2002-09-18 中国科学院上海有机化学研究所 Process for reaction of CO2 on heterocyclic compound under co-catalysis of transistion metal complex and organic alkali
CN101474576A (en) * 2009-02-12 2009-07-08 中国科学院化学研究所 Catalytic system for synthesizing annular carbonic acid ester
CN102091504A (en) * 2011-01-05 2011-06-15 湖南大学 Chemical method for gathering, fixing and purifying carbon dioxide, sulfur dioxide, sulfur trioxide and nitric oxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1369489A (en) * 2002-01-25 2002-09-18 中国科学院上海有机化学研究所 Process for reaction of CO2 on heterocyclic compound under co-catalysis of transistion metal complex and organic alkali
CN101474576A (en) * 2009-02-12 2009-07-08 中国科学院化学研究所 Catalytic system for synthesizing annular carbonic acid ester
CN102091504A (en) * 2011-01-05 2011-06-15 湖南大学 Chemical method for gathering, fixing and purifying carbon dioxide, sulfur dioxide, sulfur trioxide and nitric oxide

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