CN102586799A - Method for preparing carbonate ester by means of electrolysis - Google Patents
Method for preparing carbonate ester by means of electrolysis Download PDFInfo
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Abstract
The invention provides a method for preparing carbonate ester by means of electrolysis of carbon dioxide and alcohol. The method comprises the following steps of: reducing the alcohol and the carbon dioxide at a cathode in an electrolytic tank with supporting electrolyte and organic solvents; and esterifying electrolyte by means of an alkylate reagent. According to the method, the constant-current electrolysis is preferably selected for electrolysis; the carbonate ester can be economically and conveniently prepared by synthetizing the alcohol and the carbon dioxide at high yield rate by means of the electrolysis under normal pressure and circumstance of without metal catalysts, particularly carbonate alkylidene ester is prepared from the carbon dioxide and alkane glycol, and linear diester carbonate such as dimethyl carbonate and the like is prepared from the carbon dioxide and monohydric alcohol.
Description
Invention field
The present invention relates to a kind of method for preparing organic carbonate through electrolysis by carbonic acid gas and alcohol.Prepared the method for cyclic carbonate and through electrosynthesis by carbonic acid gas and alcohol prepared linear carbonates by carbonic acid gas and glycol said being comprised through electrosynthesis by carbonic acid gas and the pure method for preparing organic carbonate.
Background technology
Organic carbonate is a very important compounds, has purposes widely, is applied to many fields of chemistry and pharmaceutical industry.
Wherein, Cyclic carbonate is the important chemical product; NSC 11801 in the cyclic carbonate (EC) is widely used in industries such as chemical fertilizer, fiber, pharmacy and organic synthesis; And propylene carbonate (PC) promptly is a kind of broad-spectrum organic raw material; Also be a kind of organic solvent of excellent property, be used widely in fields such as organic synthesis, gas delivery, electrochemistry and metal extractions, especially NSC 11801 and propylene carbonate the two can be used as the organic solvent of nonaqueous electrolytic solution secondary batteries such as lithium ion battery.
In addition, as a kind of important organic carbonate, methylcarbonate (DMC) is a kind of eco-friendly Organic Chemicals, and it can be used as fuel dope, carbonylation agent, alkylating reagent and polar solvent.In addition, DMC was widely used in synthesizing of polycarbonate and urethane.
Use because organic carbonate has widely, its compound method obtains further investigation, and the oxidisability carbonylation of phosgenation technology, carbonic ether permutoid reaction, alcohol and the reaction of urea and alcohol etc. are for example arranged.
WO2008031864 has described a kind of through in the presence of water and catalytic compound, making the corresponding alkylene oxide hydrocarbon contact the method for preparing alkylene carbonates with carbonic acid gas; Said catalytic compound comprises the organic bases that has neutralized with hydrogen halide; In the method; Organic bases comprises carbon group compound, and this carbon group compound contains one or more and brings to less the right nitrogen-atoms of a pair of free electron and/or one or more right phosphorus atom of a pair of free electron that brings to less, and the pKa of organic bases is greater than 8.
WO2009141377 has described a kind of through carbonic acid gas and 1, and the 2-epoxy alkane contacts with carbonation catalyst and prepares carbonic acid 1, the method for 2-alkylene ester.
Alkylene carbonates also can be by carbonic acid gas and glycol preparation.
JP 2008001659 has described a kind of by glycol or USP Kosher and CO
2Carried out at the activated metal catalyzer with by the water that in cyclization process, generated water with or the material of hydrolysis in the presence of prepare the method for cyclic carbonate.
CN101029039 has described a kind of through adjacent glycol and CO
2The method that in acetonitrile, in the presence of the Zn catalyzer, prepares five-membered ring carbonate ester.
In addition, as the commercial methods of Synthesis of dimethyl carbonate, the several different methods such as methyl alcohol depolymerization, oxidization of methanol property carbonylation method and transesterification reaction that comprise phosgene have been developed.Yet all these methods are all used deleterious, corrosive, inflammable and explosion gas, like phosgene, hydrogenchloride and carbon monoxide.
Japanese documentation JP2009242306A disclose a kind of comprise metallic compound, and can comprise arbitrarily acidic cpd catalyzer in the presence of prepare the method for methylcarbonate by methyl alcohol and carbonic acid gas.
Japanese documentation JP2009132673A discloses a kind of at ZrO
2Or CeO
2The method that in acetonitrile, prepares methylcarbonate under the existence of catalyzer by methyl alcohol and carbonic acid gas.
American documentation literature US2008300419A has described a kind of method for preparing organic carbonate; It is included under the existence of carbon monoxide and liquid-phase catalysis system and makes alkylol cpd carry out the oxidisability carbonylation reaction; Form organic carbonate; In the method, the liquid-phase catalysis system comprises at least a catalyzer, at least a additive and at least a ionic liquid that is made up of positively charged ion with nitrogen heterocyclic ring structure and negatively charged ion.
Chinese patent document CN1733696A provides the method for a kind of co-producing dimethyl carbonate and divalent alcohol, and it comprises epoxy alkane and carbon dioxide reaction formation cyclic carbonate, carries out transesterify with methyl alcohol then, generates target compound.For example, oxyethane and carbonic acid gas are reacted in reactor drum, generate NSC 11801.In the presence of sodium methylate, resulting NSC 11801 is handled with methyl alcohol in rectifying tower, generated methylcarbonate and 1.
Japanese documentation JP2006289157A has described solid catalyst that a kind of usefulness has Lewis acid position or protonic acid position is prepared organic carbonate by carbonic acid gas and methyl alcohol method.
Chinese patent document CN1485313A relates to a kind of method for preparing methylcarbonate; It is included in the cycloaddition reaction that under the existence of catalyzer carbonic acid gas and oxyethane was carried out 0.5～4 hour; Carry out transesterify with methyl alcohol then; Through separating, obtain methylcarbonate, terepthaloyl moietie and NSC 11801.
In aforesaid method, the Greenhouse effect in view of carbonic acid gas utilize the chemical research of carbonic acid gas to receive extensive concern in recent years.Carbonic acid gas and epoxide reaction generation cyclic carbonate have caused the interest that people are very big as a kind of effective way of chemical fixation carbonic acid gas.
In addition, also receive highly expectation by methyl alcohol and the direct Synthesis of dimethyl carbonate of carbonic acid gas, because such method is environmental protection in essence.
But, above-mentioned all prepare in the method for carbonic ether, a shortcoming of existence is, needs to use expensive with complicated catalyst compound, and need under high pressure or high temperature, carry out.
The present technique field needs a kind ofly can be under mild conditions easyly to prepare organic carbonate economically and need not to use the method for expensive metal catalysis salts.
Electroorganic synthesis is a kind of Green Chemistry, with " conventional " use the solution-type redox reaction of homogeneous phase or heterogeneous catalyst to compare, it has some tangible advantages.In fact, from 1978, just begin one's study and come synthesizing organic carbonic ether (for example referring to U.S. Pat 4,131,521) through electrosynthesis.But in this USP, organic carbonate prepares with pure and mild carbon monoxide.The main drawback of this method is to use carbon monoxide, and carbon monoxide toxicity is very big, can react with oxygen under certain condition, sets off an explosion.
In view of the foregoing; The present inventor has carried out deep research; Prepare the method for carbonic ether through electrosynthesis by carbonic acid gas alcohol with further improvement, especially comprise by carbonic acid gas and the pure method for preparing linear carbonates and prepare alkylene carbonates by carbonic acid gas and glycol.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing carbonic ether through electrolysis by carbonic acid gas and alcohol; It is included in the electrolyzer that comprises supporting electrolyte, organic solvent pure and mild carbonic acid gas is reduced at negative electrode, then with alkylating reagent with the electrolytic solution esterification.
In the said method, preferably, said electrolysis is carried out with continuous current.
In the said method, preferably, said solvent is an organic solvent, and more preferably, said organic solvent is selected from acetonitrile and N.
In the said method, preferably, said supporting electrolyte is a tetraalkylammonium salt, more preferably tetraethyl-ammonium salt, especially preferably tetraethyl ammonium iodide or tetraethylammonium bromide.
In the said method, preferably, use Graphite Electrodes as anode.
As first aspect of the present invention, the present invention provides a kind of and prepares the method for alkylene carbonates through electrolysis by carbonic acid gas and glycol, and said electrolytic reaction is as shown in the formula shown in (1),
In the formula,
R1, R2 are independently selected from hydrogen or can any substituted low alkyl group or aryl; Preferably; R1 representes Wasserstoffatoms, and R2 representes to be selected from any in hydrogen, C1-C6 alkyl, the substituted C1-C3 alkyl of monohydroxy and the phenyl, and especially preferred R1 of being and R2 represent hydrogen or methyl independently;
R ' is a low alkyl group, preferable methyl or ethyl, especially preferable methyl;
X is a halogen, preferred iodine or bromine, especially preferred iodine.
In said first aspect of the present invention, especially preferred acetonitrile is as organic solvent.
As second aspect of the present invention, the present invention provides a kind of and prepares the method for linear carbonates through electrolysis by carbonic acid gas and alcohol, and said electrolytic reaction is as shown in the formula shown in (2),
In the formula,
R
3Expression can substituted C1-C8 alkyl, the C3-C12 alicyclic radical, preferably, and R
3Expression can be by the substituted C1-C6 alkyl of aliphatic aryl, C4-C8 naphthenic base, especially preferably can be by the substituted C1-C5 alkyl of phenyl, C4-C6 naphthenic base;
R
4Expression C1-C6 alkyl, preferred C1-C3 alkyl, especially preferable methyl;
X representes halogen, preferred bromine or iodine, especially preferred iodine.
In said method of the present invention, especially preferred N is as organic solvent.
With respect in the electrolyzer that comprises supporting electrolyte, organic solvent with adding alcohol and its reaction after the carbonic acid gas electrolysis again; In the present invention; Pure and mild carbonic acid gas is reduced at negative electrode, can further improve the productive rate of title product carbonic ether.
And, of the present inventionly can under normal pressure and temperature, carry out by carbonic acid gas and the method that alcohol prepares carbonic ether through electrolysis.
Embodiment
The present invention a kind ofly prepares the method for carbonic ether through electrolysis by carbonic acid gas and alcohol, and it is included in the electrolyzer that comprises supporting electrolyte, organic solvent pure and mild carbonic acid gas is reduced at negative electrode, then with alkylating reagent with the electrolytic solution esterification.
In the present invention, the carbon dioxide as raw material is not particularly limited.Said carbonic acid gas can be by limestone kiln gas, coke combustion gas, heavy oil combustion gas, volatile oil splitting gas, crack crude gas etc. contain in the gas of great amount of carbon dioxide separate, purifying obtains, also can be by dilutions such as rare gas elementes such as nitrogen.But in order not increase the capacity of carbonic ether manufacturing installation, be advisable to use highly purified carbonic acid gas, carbon dioxide purity should be more than 95%, and is preferred more than 99%.
In the present invention, use the diaphragmless cell that comprises metal ring negative electrode and anode bar.Said anode is connected with D.C. regulated power supply with anode.Dioxide gas infeeds in the electrolytic solution through the pressure regulating device that is connected with supply container.
The negative electrode that can use in the present invention must be stablized under reaction conditions.Its representational example is many metallic substance, for example stainless steel, platinum, copper, nickel, titanium, silver etc.Wherein, preferred cathode material is copper, stainless steel, especially preferably copper.
The anode that can use in the present invention comprises the anode that those are processed by the sufficiently stable material under electrolytic condition or the material that in electrolytic process, can be consumed.The representative example of suitable anode material comprises graphite, platinum, copper and magnesium.Wherein, the anode of preferably processing by sufficiently stable material under electrolytic condition, like the anode of processing by platinum or graphite, especially preferred graphite anode.
In the present invention, electrolytic solution comprises alcohol, carbonic acid gas and supporting electrolyte, also comprises solvent.Suitable solvent has aprotic solvent.Its example has methyl-sulphoxide, methane amide, ethanamide, N, acetonitrile, propionitrile, Nitromethane 99Min., Methylal(dimethoxymethane), methyl sulfolane and ionic liquid BMIMBF
4Deng.Wherein, considering from economic and practical angle, is good with organic solvent, and especially with acetonitrile (MeCN) and N, dinethylformamide (DMF) is good.In the present invention, usually using single solvent to be advisable, but for the solubleness that increases supporting electrolyte or increase the solvability of carbonic acid gas in solvent, also can use the mixed solvent of two kinds or more kinds of solvent compositions.
In the present invention, the solvent of use is normally dielectric, and therefore, general other adding supporting electrolyte is to increase the electroconductibility of solution.Suitable supporting electrolyte has tetraalkylammonium salt.The representative example of the tetraalkylammonium salt that can use in the present invention comprises tetraethyl ammonium iodide (TEAI), tetraethylammonium bromide (TEABr), etamon chloride (TEACl), tetraethyl-ammonium tetrafluoroborate (TEABF
4), tetrabutylammonium iodide (TBAI), Tetrabutyl amonium bromide (TBABr), tetrabutylammonium perchlorate (TBAP).Wherein, preferred tetraethyl-ammonium salt, especially preferred tetraethyl ammonium iodide and tetraethylammonium bromide.The concentration of supporting electrolyte can suitably be adjusted according to the electroconductibility of required electrolytic solution.Usually, the concentration of supporting electrolyte is 0.01～5mol/L, is 0.05～1mol/L better, especially being good about 0.1mol/L.
In the present invention, during electrolysis, and the amount of the alcohol of carbonic acid gas generation electrochemical reaction is usually between 0.01-2.0mol/L, preferred 0.05-0.4mol/L, especially preferred 0.10-0.25mol/L.Because used alcohol is liquid, therefore, in the present invention, the usage quantity of alcohol can account for the 0.001-60 volume % of electrolytic solution total amount, even more.That is, in the present invention, but as the liquid alcohol of reactant also double as solvent, to improve operation efficiency.
In the present invention, the electrosynthesis reaction is carried out through in electrolytic solution, importing carbonic acid gas.The electrosynthesis reaction can be carried out under normal pressure, also can add to depress and carry out, but for reducing facility investment, preferably under normal pressure, carry out.
On the other hand, in the present invention, also can use constant potential to carry out electrolysis.When adopting the potentiostatic deposition method, current potential can-1.7V～-3.0V vs Ag/AgI/I-between, preferred-2.3V.But with respect to potentiostatic deposition, carry out electrolysis with continuous current, more convenient operation, productive rate is higher.
Because electrochemistry is redox reaction, carry out for making reaction, use electronics as reagent.Therefore, through the electric charge of electrolyzer, that is the amount of electronics can influence the degree of carrying out of electrochemical reaction.Because electronics is a kind of reagent, therefore, in case the electrochemical synthesis reaction, will take place through electrochemical cell in it.In the present invention; The electrolysis of passing through as one aspect of the invention is the single electron reduction reaction by the reaction of carbonic acid gas and glycol carbonate synthesis alkylene ester with as the electrolysis of passing through of another aspect of the present invention by the reaction of carbonic acid gas and alcohol preparation linear carbonates; Therefore, being used for electrolytic theoretical electric weight is 1.0F/mol.The phenomenon that can increase along with the increase of energising amount with product productive rate in the reaction of general electrosynthesis is different, when electrolysis electricity during obviously greater than theoretical electric weight productive rate but descend on the contrary.This possibly be because of CO in the electrolysis
2The radical anion CO that reduces and generate
2 -Can generate oxalic acid through linked reaction, along with the increase of electric weight, reaction times lengthening, more CO
2 -Product can coupling become oxalic acid, is unfavorable for generating as the carbonic ether of title product.Therefore, among the present invention, electrolysis electricity is 0.5-2.0F/mol, is preferably 0.8-1.5F/mol.
Among the present invention, " productive rate " speech is meant the electrolysate of actual generation and the per-cent of expected theoretical value." current efficiency " speech is meant when the electric weight through electrolyzer is 1 faraday, the actual electrolysate that generates and the per-cent of expected theoretical value.Wherein, 1 faraday is equivalent to 96500 coulombs.
As first embodiment of the present invention, what the present invention provided that a kind of following formula representes prepares the method for alkylene carbonates by carbonic acid gas and glycol:
In the formula, R1, R2 are independently selected from hydrogen or can any substituted C1-C3 alkyl or aryl, and R ' is a low alkyl group, and X is a halogen; Be preferably, R1 representes Wasserstoffatoms, and R2 representes to be selected from any in hydrogen, methyl and the phenyl; R ' is methyl or ethyl, and X is iodine or bromine, is more preferably; R1 and R2 all represent hydrogen, and R ' is a methyl, and X is an iodine.
In first embodiment of the present invention, because of the saturation concentration of carbonic acid gas in acetonitrile is higher than the saturation concentration in DMF, and, acetonitrile molecule CO easily and in the electrolytic process
2The radical anion CO that reduces and generate
2 -In conjunction with, it is more stably existed, help participating in reaction, therefore, usually preferred acetonitrile.
Because the saturation concentration of carbonic acid gas in acetonitrile depends on temperature usually, therefore, temperature is low more, and the carbonic acid gas that may be dissolved in the acetonitrile is also many more.Because carbonic acid gas is the key reagents of reaction, therefore, receive gas concentration lwevel about temperature can influence the productive rate of alkylene carbonates.On the other hand, temperature can influence the overpotential and the speed of reaction of electrochemical reaction, thereby influences the alkylene carbonates productive rate.Therefore, in first embodiment of the present invention, electrolysis temperature is generally-10～45 ℃, and preferred 15～35 ℃, especially preferred 25-35 ℃.
In first embodiment of the present invention, electrolysis with current density usually with 1.81-6.46mA/cm
2For good, preferred 3.67-5.53mA/cm
2, especially preferred 3.67mA/cm
2
In first embodiment of the present invention, the preferred 1.0-2.0F/mol of electrolysis electricity, especially preferred 1.0F/mol.
In first embodiment of the present invention, after the electrolytic synthesis alkylene carbonates, can select conventional treatment method known in the art from electrolytic solution, to separate carbonic ether according to the characteristic of the carbonic ether that generates.Suitable treatment step for example comprises that (i) adds Anhydrous potassium carbonate and methyl iodide in electrolytic solution, with the electrolytic solution esterification, stirred 5 hours at 50 ℃ then; (ii) add HCl solution, with the reaction soln hydrolysis; (iii) with ETHYLE ACETATE or ether extraction carbonic ether 3 times; (iv) wash organic layer, (v) organic layer is dry with sal epsom, boil off organic solvent, obtain alkylene carbonates.
As second embodiment of the present invention, the present invention provides a kind of and prepares the method for linear carbonates through electrolysis by carbonic acid gas and alcohol, and said electrolytic reaction is as shown in the formula shown in (2),
In the formula,
R
3Expression can substituted C1-C8 alkyl, the C3-C12 alicyclic radical, preferably, and R
3Expression can be by the substituted C1-C6 alkyl of aliphatic aryl, C4-C8 naphthenic base, especially preferably can be by the substituted C1-C5 alkyl of phenyl, C4-C6 naphthenic base;
R
4Expression C1-C6 alkyl, preferred C1-C3 alkyl, especially preferable methyl;
X representes halogen, preferred bromine or iodine, especially preferred iodine.
In second embodiment of the present invention, preferred N is as organic solvent.
In second embodiment of the present invention, electrolysis is preferably 2.74-5.07mA/cm with current density
2, especially preferred 3.67-4.14mA/cm
2
In second embodiment of the present invention, electrolysis is preferably 15-45 ℃ with temperature, especially is preferably 25-30 ℃.
In second embodiment of the present invention, be preferably 0.15-0.20mol/L as the concentration of the alcohol of reaction raw materials.
Embodiment
Through embodiment the present invention is specifically described below, but these embodiment should not think the qualification to embodiment of the present invention.
Embodiment 1
Under 1 normal atmosphere, use the Room type glass electrolyzer of capacity as 15mL.Make anode with graphite rod, copper ring is made negative electrode.In electrolyzer, pack into, be blown into CO under the normal atmosphere as electrolytical 0.3152g (0.0015mol) tetraethylammonium bromide, 15mL acetonitrile and 209 μ L (0.00376mol) terepthaloyl moietie
2, until saturated.15 ℃ feed constant current 3.67mA/cm down
2, electrolysis to the electric weight that 0.00376 faraday (1F/mol) is arranged passes through.
(1A 120V) supplies with by D.C. regulated power supply QJ12001X with electric current in electrolysis.In the electrolytic process, electrolytic solution is remained on 15 ℃.When electrolysis finishes, add Anhydrous potassium carbonate and methyl iodide, 50 ℃ were stirred 5 hours.Use ethyl acetate extraction then, use gas chromatographic analysis.The result shows, generates 0.0755g (0.8573mmol) NSC 11801, and productive rate is about 22.8%.
On the other hand, suppose that the electrolytic reaction of being carried out is an electronic processes, then the NSC 11801 that generated of per unit faraday is 88.06g, can calculate thus, and current efficiency also is 22.8%.Isolate NSC 11801, confirm with GC-MS (U.S. HP6890/5973N of Agilent company type GC-MS).
Embodiment 2
Use with embodiment 1 identical method and apparatus and prepare NSC 11801; Different is, with 15mLDMF as solvent, with 0.5540g (0.0015mol) tetrabutylammonium iodide as ionogen; Terepthaloyl moietie is 84 μ L (0.0015mol), and the current density of 25 ℃ of following feeding electrolyzers is 5.53mA/cm
2Obtain NSC 11801 0.0144g, productive rate and current efficiency are 10.9%.
Embodiment 3
Use with embodiment 1 identical method and apparatus to prepare NSC 11801, different is, terepthaloyl moietie is 84 μ L (0.0015mol), and as anode, the current density of 25 ℃ of following feeding electrolyzers is 5.53mA/cm with platinum
2Obtain NSC 11801 0.0195g, productive rate and current efficiency are 14.8%.
Embodiment 4
Use with embodiment 3 identical method and apparatus to prepare NSC 11801, different is that as anode, the total electric weight that feeds electrolyzer is 0.003 faraday (2F/mol) with graphite.Obtain NSC 11801 0.0149g, productive rate is 11.3%, and current efficiency is 5.7%.
Embodiment 5
Use with embodiment 2 identical method and apparatus to prepare propylene carbonate, different is, replaces terepthaloyl moietie as reagent with Ucar 35 110 μ L (0.0015mol), and with tetraethylammonium bromide as ionogen.Obtain propylene carbonate 0.0158g, productive rate and current efficiency are 10.3%.
Embodiment 6
Use with embodiment 5 identical method and apparatus to prepare propylene carbonate, different is, with the 15mL acetonitrile as solvent, with 0.3857g (0.0015mol) tetraethyl ammonium iodide as ionogen.Obtain propylene carbonate 0.0208g, productive rate and current efficiency are 13.6%.
Embodiment 7
Use with embodiment 6 identical method and apparatus to prepare propylene carbonate, different is that electrolysis is carried out at 35 ℃.Obtain propylene carbonate 0.0216g, productive rate and current efficiency are 14.1%.
Embodiment 8
Use with embodiment 6 identical method and apparatus to prepare propylene carbonate, different is, with 3mL Ucar 35,12mL acetonitrile and 0.3857g (0.0015mol) tetraethyl ammonium iodide as electrolytic solution.The total electric weight that feeds electrolyzer is 0.0015 faraday.The result shows that the productive rate of propylene carbonate is 3.8%, obtains propylene carbonate 0.1586g, and current efficiency is 100%.
Embodiment 9
Being that anode, metal ring are the mixing solutions 15mL that adds in the room type electrochemical pond of negative electrode by acetonitrile that contains TEAI (0.1mol/L) and Ucar 35 with graphite, slowly be blown into CO
2Air-flow to 1 normal atmosphere, and feed constant current 5.53mA/cm
2, pass through to the electric charge of 1F/mol, carry out constant-current electrolysis thus.After the electrolysis, add Anhydrous potassium carbonate (0.2mol/L) and methyl iodide (0.5mol/L), and mixed solution was stirred 5 hours at 50 ℃, thus with the electrolytic solution esterification.Then, with the solution hydrolysis, use ether extraction.With sal epsom that organic phase is dry again, get the product propylene carbonate.The result sees the following form 1.
Table 1
* a: electrolysis is at-2.3V vs Ag/Ag
+The constant potential condition under carry out.
Embodiment 10
Be that anode, copper ring are to add solution 15mL (Ucar 35 double as solvent and the reactant be made up of acetonitrile and Ucar 35 (PG) that contains 0.1mol/L TEAI in the room type electrochemical pond of negative electrode with graphite; Its volume is as shown in the table; Surplus is an acetonitrile), slowly be blown into CO
2Air-flow is until CO
2Pressure reaches 1 normal atmosphere, and feeds constant current 5.53mA/cm
2, pass through until 144.75 coulombs electric charge, carry out constant-current electrolysis thus.After the electrolysis, add Anhydrous potassium carbonate (0.2mol/L) and methyl iodide (0.5mol/L), and mixed solution was stirred 5 hours at 50 ℃, thus with the electrolytic solution esterification.Then, with the solution hydrolysis, use ether extraction.With sal epsom that organic phase is dry again, get the reaction product propylene carbonate.The result sees the following form 2.
Table 2
Embodiment 11
Be that anode, copper ring are to add the acetonitrile 15mL that contains 0.1mol/LTEABr in the room type electrochemical pond of negative electrode with graphite, and adding the 0.25mol/L glycol, slowly be blown into CO
2Air-flow is until CO
2Pressure reaches 1 normal atmosphere, and feeds constant current 3.67mA/cm
2, pass through until the electric charge of 1F/mol, carry out constant-current electrolysis at 25 ℃ thus.After the electrolysis, add Anhydrous potassium carbonate (0.2mol/L) and methyl iodide (0.5mol/L), and mixed solution was stirred 5 hours at 50 ℃, thus with the electrolytic solution esterification.Then, with the solution hydrolysis, use ether extraction.With sal epsom that organic phase is dry again, get the reaction product alkylene carbonates.The result sees the following form 3.
Table 3
* b: the diol concentration as reactant is 0.1M.
Embodiment 12
Under 1 normal atmosphere, use the Room type glass electrolyzer of capacity as 15mL.Make anode with graphite rod, copper ring is made negative electrode.In electrolyzer, pack into, be blown into CO under the normal atmosphere as electrolytical 0.3857g (0.0015mol) tetraethyl ammonium iodide, 15mL N and 61 μ L (0.0015mol) methyl alcohol
2, until saturated.25 ℃ feed constant current 3.67mA/cm down
2, electrolysis to the electric weight that 0.0015 faraday (1F/mol) is arranged passes through.
(1A 120V) supplies with by D.C. regulated power supply QJ 12001X with electric current in electrolysis.In the electrolytic process, electrolytic solution is remained on 25 ℃.When electrolysis finishes, through adding Anhydrous potassium carbonate and methyl iodide and making the electrolytic solution esterification in 5 hours 50 ℃ of stirrings.Distill electrolytic solution then, obtain methylcarbonate.Use gas chromatographic analysis.The result shows, generates 0.0500g (0.555mmol) methylcarbonate, and productive rate is about 37.0%.
On the other hand, suppose that the electrolytic reaction of being carried out is an electronic processes, then the methylcarbonate that generated of per unit faraday is 90.07g, can calculate thus, and current efficiency also is 37.0%.Isolate methylcarbonate, confirm with GC-MS.
Embodiment 13
Use with embodiment 12 identical method and apparatus to prepare methylcarbonate, different is, as solvent, etamon chloride is a supporting electrolyte with the 15mL acetonitrile, and the current density of feeding is for being 3.67mA/cm
2Generate methylcarbonate 0.0147g, productive rate and current efficiency are 10.9%.
Embodiment 14
Use with embodiment 12 identical method and apparatus to prepare methylcarbonate, different is, with 0.5540g (0.0015mol) tetrabutylammonium iodide as ionogen.Generate methylcarbonate 0.0397g, productive rate and current efficiency are 29.4%.
Embodiment 15
Use with embodiment 12 identical method and apparatus to prepare methylcarbonate, different is, with platinum as anode.Generate methylcarbonate 0.0351g, productive rate and current efficiency are 26.0%.
Embodiment 16
Use with embodiment 12 identical method and apparatus to prepare methylcarbonate, different is that current density is 4.14mA/cm
2Generate methylcarbonate 0.0712g, productive rate and current efficiency are 52.7%.
Embodiment 17
Being that anode, metal ring are to add by the DMF 15mL that contains 0.1mol/L supporting electrolyte and methyl alcohol in the room type electrochemical pond of negative electrode with graphite, slowly be blown into CO
2Air-flow is until 1 normal atmosphere, and the feeding constant current, carries out constant-current electrolysis thus.After the electrolysis, add Anhydrous potassium carbonate (0.2mol/L) and methyl iodide (0.5mol/L), mixed solution was stirred 5 hours at 50 ℃, thus with the electrolytic solution esterification.Then, with the reaction solution evaporation, obtain methylcarbonate.The result sees the following form 4.
Table 4
Embodiment 18
Be that anode, copper ring are to add by the DMF15mL that contains 0.1mol/LTEAI in the room type electrochemical pond of negative electrode with graphite, and adding alcohol, slowly be blown into CO to 0.15mol/L
2Air-flow is until 1 normal atmosphere, and feeding constant current 4.14mA/cm
2, pass through until the electric weight of 1F/mol, carry out constant-current electrolysis at 25 ℃ thus.After the electrolysis, add Anhydrous potassium carbonate (0.2mol/L) and methyl iodide (0.5mol/L), mixed solution was stirred 5 hours at 50 ℃, thus with the electrolytic solution esterification.Then, with the reaction solution evaporation, obtain carbonic diester.The result sees the following form 5.
Table 5
As stated; According to the present invention; Can under normal pressure, synthesize the preparation carbonic ether through electrolysis easily in economy under the situation of not using metal catalyst, especially prepare alkylene carbonates and prepare Linear Carbon acid diesters such as methylcarbonate by carbonic acid gas and monohydroxy-alcohol by carbonic acid gas and alkanediol by pure and mild carbonic acid gas high productivity.
Claims (15)
1. one kind prepares the method for carbonic ether through electrolysis by carbonic acid gas and alcohol, and it is included in the electrolyzer that comprises supporting electrolyte, organic solvent pure and mild carbonic acid gas is reduced at negative electrode, then with alkylating reagent with the electrolytic solution esterification.
2. method according to claim 1 is characterized in that, said electrolysis is constant-current electrolysis.
3. method according to claim 1 and 2 is characterized in that, said solvent is an organic solvent.
4. method according to claim 3 is characterized in that said organic solvent is selected from acetonitrile and N.
5. method according to claim 1 is characterized in that, said ionogen is tetraethyl ammonium iodide or tetraethylammonium bromide.
6. method according to claim 1 is characterized in that, uses graphite to be negative electrode as anode, copper ring.
7. method according to claim 1 and 2 is characterized in that, said electrolytic reaction is as shown in the formula shown in (1),
In the formula, R1, R2 are independently selected from hydrogen or can any substituted low alkyl group or aryl, and R ' is a low alkyl group, and X is a halogen.
8. method according to claim 7 is characterized in that R1 representes Wasserstoffatoms, and R2 representes to be selected from any in hydrogen, C1-C6 alkyl, the substituted C1-C3 alkyl of monohydroxy and the phenyl, and R ' is methyl or ethyl, and X is iodine or bromine.
9. method according to claim 8 is characterized in that R2 representes hydrogen or methyl, and R ' is a methyl, and X is an iodine.
10. method according to claim 7 is characterized in that, uses acetonitrile as organic solvent.
11. method according to claim 1 and 2 is characterized in that, said electrolytic reaction is as shown in the formula shown in (2),
In the formula, R
3Expression can substituted C1-C8 alkyl, the C3-C12 alicyclic radical, R
4Expression C1-C6 alkyl, X representes halogen.
12. method according to claim 11 is characterized in that, R
3Expression can be by the substituted C1-C6 alkyl of aliphatic aryl, C4-C8 naphthenic base, R
4Expression C1-C3 alkyl, X representes bromine or iodine.
13. method according to claim 12 is characterized in that, R
3Expression can be by the substituted C1-C5 alkyl of phenyl, C4-C6 naphthenic base, R
4The expression methyl, X representes bromine or iodine.
14. method according to claim 13 is characterized in that, R
3Expression methyl, R
4The expression methyl, X representes iodine.
15. method according to claim 11 is characterized in that, uses N as organic solvent.
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