CN111362800A - Method for preparing organic carbonate at normal temperature and pressure - Google Patents
Method for preparing organic carbonate at normal temperature and pressure Download PDFInfo
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- CN111362800A CN111362800A CN202010252771.5A CN202010252771A CN111362800A CN 111362800 A CN111362800 A CN 111362800A CN 202010252771 A CN202010252771 A CN 202010252771A CN 111362800 A CN111362800 A CN 111362800A
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Abstract
The invention relates to the technical field of organic synthesis, and provides a method for preparing organic carbonate at normal temperature and normal pressure, wherein carbon dioxide is introduced into imidazole ionic liquid to obtain a mixture; then mixing the obtained mixture with alcohol and halogenated hydrocarbon, and making addition-substitution reaction to obtain organic carbonate, and making the whole reaction process be implemented at normal temperature and normal pressure. The invention utilizes the imidazole ionic liquid and the halohydrocarbon to reduce the activation energy of the reaction, and finally realizes the utilization of CO under the conditions of normal temperature and normal pressure2Preparing the organic carbonate.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for preparing organic carbonate at normal temperature and normal pressure.
Background
Organic carbonates are important organic synthetic intermediates and have been widely used as alkylating, alkoxylating and carbonylating reagents. Organic carbonates are also green aprotic solvents, good oil additives, and ideal electrolytes for lithium ion batteries.
By using CO2The preparation of organic carbonates as starting material is one of the possible methods, usually by means of CO under high temperature and pressure conditions2And the alcohol is prepared under the action of a metal solid catalyst, and the method has the advantages of wide raw material source, low price and high atom utilization rate, and conforms to the principles of sustainable development and economy. However, the prior art uses CO2Method for preparing organic carbonates due to CO2Since the low self-reactivity is required to be carried out under high temperature and high pressure, the reaction temperature and pressure are disadvantageously high.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing organic carbonate under normal temperature and pressure conditions, which can prepare organic carbonate under normal temperature and pressure conditions.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing organic carbonate at normal temperature and normal pressure, which comprises the following steps:
(1) introducing carbon dioxide into the imidazole ionic liquid to obtain the ionic liquid containing the carbon dioxide;
(2) mixing the ionic liquid containing carbon dioxide obtained in the step (1) with alcohol and halogenated hydrocarbon, and carrying out addition-substitution reaction to obtain organic carbonate;
the step (1) and the step (2) are carried out under the conditions of normal temperature and normal pressure.
Preferably, the alcohol is a monohydric alcohol and/or a dihydric alcohol.
Preferably, the structure of the cation in the imidazole ionic liquid is shown as a formula I or a formula II:
in the formula I, R1And R2Independently is C2～C16An alkyl group of (a); in the formula II, R3Is C2～C16Alkyl radical of (2), R4NH2Is C2～C16An aminoalkyl group of (a); the anion of the imidazole ionic liquid in the step (1) comprises bicarbonate ions, acetate ions, propionate ions, n-butyl acid ions, isobutyrate ions, pivaloate ions, levulinate ions or 1,2, 4-triazole ions.
Preferably, said R is1、R2And R3Independently an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a 2-methylpentyl group, or a 3-methylpentyl group; the R is4NH2Is an amine ethyl group, an amine n-propyl group, an amine isopropyl group, an amine n-butyl group, an amine isobutyl group, an amine n-pentyl group, an amine isopentyl group, an amine n-hexyl group, an amine 2-methylpentyl group or an amine 3-methylpentyl group.
Preferably, the imidazole-based ionic liquid comprises at least one of 1-ethyl-3-methylimidazole hydrogen carbonate, 1-butyl-3-methylimidazole hydrogen carbonate, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole levulinic acid salt, 1-butyl-3-methylimidazole levulinic acid salt, 1-ethyl-3-methylimidazole triazoium salt and 1-butyl-3-methylimidazole triazoium salt.
Preferably, the alcohol includes at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, n-hexanol, 2-hexanol, 3-hexanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 3-octanol, 4-octanol, ethylene glycol, 1, 2-propanediol, and 1, 2-butanediol.
Preferably, the structure of the halogenated hydrocarbon is shown as formula III, formula IV, formula V or formula VI
In the formula III, R5Is C1～C16Alkyl radical of (2), X1Is fluorine atom, chlorine atom, bromine atom or iodine atom; in the formula IV, R6Is C1～C16Alkyl radical of (2), X2And X3Independently a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; in the formula V, R7Is C1～C16Alkyl radical of (2), X4、X5And X6Independently isA fluorine atom, a chlorine atom, a bromine atom or an iodine atom; x in the formula VI7、X8、X9And X10Independently a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
Preferably, said R is5、R6And R7Independently a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a 2-methylpentyl group, or a 3-methylpentyl group.
Preferably, the halogenated hydrocarbon includes at least one of methyl chloride, methyl bromide, methyl iodide, methylene chloride, methyl bromide, methyl diiodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, ethyl monochloride, ethyl monobromide, ethyl monoiodide, 1, 2-dichloroethane, 1, 2-dibromoethane, 1, 2-diiodoethane, 1-chloropropane, 1-bromopropane, 1-iodopropane, 2-chloropropane, 2-bromopropane, 2-iodopropane, 1, 2-dichloropropane, 1, 2-dibromopropane, 1, 2-diiodopropane, 1-iodobutane, 2-iodobutane, 1-iodopentane, 1-iodohexane, 1-iodoheptane and 1-iodooctane.
Preferably, the mass ratio of the imidazole ionic liquid to the alcohol is 1: (0.1-10), wherein the mass content of the halogenated hydrocarbon in a reaction system composed of the imidazole ionic liquid, the carbon dioxide, the alcohol and the halogenated hydrocarbon is 5-90%.
The invention provides a method for preparing organic carbonate at normal temperature and normal pressure, which comprises the steps of introducing carbon dioxide into imidazole ionic liquid to obtain the ionic liquid containing the carbon dioxide; and then mixing the obtained ionic liquid containing carbon dioxide with alcohol and halogenated hydrocarbon, and carrying out addition reaction to obtain the organic carbonate, wherein the whole reaction process is carried out at normal temperature and normal pressure. The invention utilizes imidazole ionic liquid and CO2After combination, hydrogen protons on the carbon at the 2-position of imidazole ring cation are abstracted by anions, and then CO is further combined2Formation of a bond to CO2The adduct being characterised, on the one hand, by CO2The gas phase enters the liquid phase, which is beneficial to the mass and heat transfer of the subsequent reaction, and the generated CO on the other hand2Adduct CO2Original C (sp) hybridizationMode is changed to C (sp)2) Activating the reaction product and reducing the activation energy of the reaction; simultaneously utilizes the characteristics of favorable solvation effect and alkylation effect of the halogenated hydrocarbon to further reduce the activation energy of the reaction, and finally realizes the utilization of CO under the conditions of normal temperature and normal pressure2The preparation of the organic carbonate reduces the requirements of the reaction on high-temperature and high-pressure reaction conditions. Experimental results of the embodiment show that the method provided by the invention can be used for preparing the organic carbonate under normal temperature and normal pressure, and the reaction condition is mild.
Drawings
FIG. 1 is a schematic view of a process for preparing an organic carbonate under normal temperature and pressure conditions.
Detailed Description
The invention provides a preparation method of organic carbonate under normal temperature and pressure conditions, which comprises the following steps:
(1) introducing carbon dioxide into the imidazole ionic liquid to obtain the ionic liquid containing the carbon dioxide;
(2) mixing the ionic liquid containing carbon dioxide obtained in the step (1) with alcohol and halogenated hydrocarbon, and carrying out addition-substitution reaction to obtain organic carbonate;
the step (1) and the step (2) are carried out under the conditions of normal temperature and normal pressure. In the invention, the imidazole ionic liquid and the carbon dioxide can be combined to generate a carbon dioxide adduct, so that the carbon dioxide is activated, and the activation energy of the reaction is reduced; simultaneously utilizes the characteristics of favorable solvation effect and alkylation effect of the halogenated hydrocarbon to further reduce the activation energy of the reaction, and finally realizes the utilization of CO under the conditions of normal temperature and normal pressure2Preparing the organic carbonate.
According to the invention, carbon dioxide is introduced into the imidazole ionic liquid to obtain the ionic liquid containing carbon dioxide.
In the invention, the dosage relation between the imidazole ionic liquid and the carbon dioxide is determined by the absorption saturation degree of the imidazole ionic liquid to the carbon dioxide. In the invention, the molar ratio of the carbon dioxide to the imidazole ionic liquid is preferably 0.2-1.5, more preferably 0.5-1.2, and most preferably 1.03-1.1.
In the invention, the structure of the cation in the imidazole ionic liquid is preferably shown as a formula I or a formula II:
in the formula I, R1And R2Independently is preferably C2～C16More preferably C2～C10Most preferably an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a 2-methylpentyl group or a 3-methylpentyl group;
in the formula II, R3Preferably C2～C16More preferably C2～C10Most preferably an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a 2-methylpentyl group or a 3-methylpentyl group; r4NH2Preferably C2～C16More preferably C2～C110Most preferably an amine ethyl group, an amine n-propyl group, an amine isopropyl group, an amine n-butyl group, an amine isobutyl group, an amine n-pentyl group, an amine isopentyl group, an amine n-hexyl group, an amine 2-methylpentyl group or an amine 3-methylpentyl group.
In the invention, the anion of the imidazole ionic liquid preferably comprises bicarbonate ion, acetate ion, propionate ion, n-butyl acid ion, isobutyrate ion, pivalate ion, levulinate ion or 1,2, 4-triazole ion;
in the present invention, the imidazole ionic liquid more preferably comprises 1-ethyl-3-methylimidazole hydrogen carbonate, 1-butyl-3-methylimidazole hydrogen carbonate, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole levulinic acid salt, 1-butyl-3-methylimidazole levulinic acid saltAt least one of 1-ethyl-3-methylimidazolium triazoxide and 1-butyl-3-methylimidazolium triazoxide, and most preferably 1-butyl-3-methylimidazolium bicarbonate. In the invention, the ionic liquid does not change the product type, but only influences the selectivity and yield of the product, wherein the 1-butyl-3-methylimidazole bicarbonate ionic liquid has the effect on CO2The absorption capacity of (A) is the highest, and the reaction effect is the best.
The operation of introducing the carbon dioxide into the imidazole ionic liquid is not particularly specified in the invention, and a gas-introducing mode well known to those skilled in the art can be adopted.
In the invention, the time for introducing the carbon dioxide into the ionic liquid is preferably 30-480 min, more preferably 60-400 min, and most preferably 360 min. In the invention, the introduction mode of the carbon dioxide into the ionic liquid is not particularly specified, and the gas introduction mode known to those skilled in the art can be adopted. In the present invention, the condition for introducing the carbon dioxide into the ionic liquid is preferably stirring. In the present invention, the stirring rate is not particularly limited, and the absorption of carbon dioxide may be promoted. In the present embodiment, the stirring rate is preferably 350 rpm.
After the ionic liquid containing carbon dioxide is obtained, the ionic liquid containing carbon dioxide is mixed with alcohol and halogenated hydrocarbon to carry out addition reaction to obtain the organic carbonate.
In the invention, the time of the addition reaction is preferably 2-24 h, and more preferably 6-24 h.
In the invention, carbon dioxide is introduced into imidazole ionic liquid to obtain the ionic liquid containing carbon dioxide; and mixing the ionic liquid containing the carbon dioxide with alcohol and halogenated hydrocarbon, and carrying out addition reaction to obtain the organic carbonate at normal temperature and normal pressure.
In the invention, the normal temperature is preferably 15-35 ℃, and more preferably 20-30 ℃. In the present invention, the normal pressure is preferably 100 to 105kPa, and more preferably 101 to 102 kPa.
In the present invention, the ratio of the amounts of the imidazole-based ionic liquid and the alcohol is preferably 1: (0.1 to 10), more preferably 1: (0.2 to 8), and most preferably 1: (1-2). In the invention, the mass content of the halogenated hydrocarbon in the reaction system composed of the imidazole ionic liquid, the carbon dioxide, the alcohol and the halogenated hydrocarbon is preferably 5-90%, and more preferably 10-70%.
In the present invention, the alcohol is preferably a monohydric alcohol and/or a dihydric alcohol. In the present invention, when the alcohol is a monohydric alcohol, a linear organic carbonate is obtained, when the alcohol is a dihydric alcohol, a cyclic organic carbonate is obtained, and when the alcohol is a monohydric alcohol and a dihydric alcohol, a mixture of a linear organic carbonate and a cyclic organic carbonate is obtained.
In the present invention, the monohydric alcohol preferably includes at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, n-hexanol, 2-hexanol, 3-hexanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 3-octanol, 4-octanol; the diol preferably includes at least one of ethylene glycol, 1, 2-propanediol, and 1, 2-butanediol.
The structure of the halogenated hydrocarbon in the invention is preferably as shown in formula III, formula IV, formula V or formula VI
In the formula III, R5Preferably C1～C16More preferably C1～C10Most preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a 2-methylpentyl group or a 3-methylpentyl group, X1Preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom, a bromine atom or an iodine atom;
in the formula IV, R6Is C1～C16More preferably C1～C10Most preferably a methyl groupEthyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, n-hexyl group, 2-methylpentyl group or 3-methylpentyl group, X2And X3Independently preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom, a bromine atom or an iodine atom;
in the formula V, R7Is C1～C16More preferably C1～C10Most preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a 2-methylpentyl group or a 3-methylpentyl group; x4、X5And X6Independently preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom, a bromine atom or an iodine atom.
X in the formula VI7、X8、X9And X10Independently preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom, a bromine atom or an iodine atom.
In the present invention, the halogenated hydrocarbon more preferably includes at least one of monochloromethane, monobromomethane, monoiodomethane, dichloromethane, dibromomethane, diiodomethane, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, monochloroethane, monobromoethane, monoiodoethane, 1, 2-dichloroethane, 1, 2-dibromoethane, 1, 2-diiodoethane, 1-chloropropane, 1-bromopropane, 1-iodopropane, 2-chloropropane, 2-bromopropane, 2-iodopropane, 1, 2-dichloropropane, 1, 2-dibromopropane, 1, 2-diiodopropane, 1-iodobutane, 2-iodobutane, 1-iodopentane, 1-iodohexane, 1-iodoheptane and 1-iodooctane; most preferably includes methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, 1-chloropropane, 1-bromopropane, 1-iodopropane, 2-chloropropane, 2-bromopropane, 2-iodopropane.
In the present invention, when the alcohol is a monohydric alcohol for preparing a linear carbonate, the halogenated hydrocarbon preferably includes a polyhalogenated hydrocarbon and a monohalogenated hydrocarbon, and more preferably a monohalogenated hydrocarbon. In the invention, the mass content of the monohalogenated hydrocarbon in the reaction system composed of the imidazole ionic liquid, the carbon dioxide, the alcohol and the monohalogenated hydrocarbon is preferably 5-90%, more preferably 10-70%, and most preferably 20-65%. In this case, the halogenated hydrocarbon is used as both the solvent and the raw material for the addition reaction, and when the addition reaction is carried out using a monohydric alcohol corresponding to the linear carbonate and a monohalogenated hydrocarbon corresponding to the linear carbonate, the conversion and selectivity of the linear carbonate are the highest.
In the present invention, when the alcohol is a diol to prepare a cyclic carbonate, the halogenated hydrocarbon preferably includes a polyhalogenated hydrocarbon and a monohalogenated hydrocarbon, and more preferably, a polyhalogenated hydrocarbon. In the invention, the mass content of the polyhalogenated hydrocarbon in the reaction system composed of the imidazole ionic liquid, the carbon dioxide, the alcohol and the polyhalogenated hydrocarbon is preferably 5-90%, more preferably 10-70%, and most preferably 20-65%. In this case, the halogenated hydrocarbon is mainly used as a solvent for the addition reaction, and when the addition reaction is carried out by using a diol corresponding to the cyclic carbonate and a polyhalogenated hydrocarbon, the conversion rate and selectivity of the cyclic carbonate are the highest.
In the present invention, the mixing method of the carbon dioxide-containing ionic liquid, the alcohol and the halogenated hydrocarbon is not particularly limited, and a mixing method known to those skilled in the art may be used.
In the present invention, the conditions of the addition reaction are preferably stirring. The stirring rate is not particularly limited in the present invention, and the stirring rate for the reaction of the materials is well known to those skilled in the art. In the present example, the stirring rate of the addition reaction is preferably 600 rpm.
The method for analyzing the organic carbonate is not particularly limited, and the method for analyzing the organic carbonate well known to those skilled in the art may be used, and in the embodiment of the present invention, the method for analyzing the organic carbonate is preferably performed by using a gas chromatograph-mass spectrometer.
In the embodiment of the present invention, a schematic flow diagram of the preparation of organic carbonate under normal temperature and pressure conditions is shown in fig. 1, carbon dioxide is introduced into an absorption kettle containing imidazole ionic liquid to obtain ionic liquid containing carbon dioxide, and the ionic liquid is mixed with alcohol and halogenated hydrocarbon to perform an addition-substitution reaction to obtain organic carbonate.
The method provided by the invention can ensure that the whole reaction operation is carried out under the conditions of normal temperature and normal pressure, and the reaction condition is mild.
The method for producing an organic carbonate at ordinary temperature and pressure according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, and 0.64kg of methanol and 6.84kg of monoiodomethane (3L, mass fraction of monoiodomethane is 55%) were added and stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm to achieve reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that an organic carbonate product dimethyl carbonate is generated except volatile reactants; the selectivity of the obtained dimethyl carbonate can reach 99.9 percent and the yield can reach 58.4 percent through gas chromatography analysis.
Example 2
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, and 0.92kg of ethanol and 6.84kg of monoiodomethane (3L, mass fraction of monoiodomethane is 55%) were added and stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm to achieve reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that an organic carbonate product, namely methyl ethyl carbonate, is generated except volatile reactants; the selectivity of the obtained methyl ethyl carbonate can reach 99.9 percent through gas chromatography analysis, and the yield can reach 57.6 percent.
Example 3
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, and 0.92kg of ethanol and 5.85kg of monoiodoethane (3L, 50% by mass of monoiodoethane) were added, and the reaction was stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm, to achieve reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that an organic carbonate product diethyl carbonate is generated except volatile reactants; the selectivity of the obtained diethyl carbonate can reach 99.8 percent through gas chromatography analysis, and the yield can reach 55.4 percent.
Example 4
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption liquid is introduced into a reaction kettle, 1.20kg of n-propanol and 6.84kg of monoiodomethane (3L, mass fraction of monoiodomethane is 53%) are added, and the mixture is stirred and reacted for 12 hours at 25 ℃ and normal pressure, wherein the stirring speed is 600rpm, so that the reaction equilibrium is achieved.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that organic carbonate product methyl-n-propyl carbonate is generated except volatile reactants; the selectivity of the obtained methyl-n-propyl carbonate can reach 99.8 percent and the yield can reach 51.6 percent through gas chromatography analysis.
Example 5
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, and 1.20kg of isopropanol and 6.84kg of monoiodomethane (3L, mass fraction of monoiodomethane: 53%) were added thereto, and stirred at 25 ℃ and normal pressure for 12 hours at a stirring speed of 600rpm, to achieve reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that organic carbonate product methyl isopropyl carbonate is generated except volatile reactants; the selectivity of the obtained methyl isopropyl carbonate can reach 99.8 percent and the yield can reach 53.5 percent through gas chromatography analysis.
Example 6
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, 1.20kg of n-propanol and 5.85kg of monoiodoethane (3L, mass fraction of monoiodoethane is 49%) were added, and the reaction was stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm to reach reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that an organic carbonate product, namely ethyl n-propyl carbonate, is generated except volatile reactants; the selectivity of the obtained ethyl-n-propyl carbonate can reach 99.7 percent and the yield can reach 47.5 percent through gas chromatography analysis.
Example 7
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, 1.20kg of isopropanol and 5.85kg of monoiodoethane (3L, mass fraction of monoiodoethane is 49%) were added, and the reaction was stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm to reach reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that the organic carbonate product, namely the ethyl isopropyl carbonate, is generated except volatile reactants; the selectivity of the obtained ethyl isopropyl carbonate can reach 99.7 percent and the yield can reach 49.8 percent through gas chromatography analysis.
Example 8
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. Introducing the absorption liquid into a reaction kettle, adding 1.20kg of n-propanol and 5.25kg of 1-iodopropane (3L, the mass fraction of the 1-iodopropane is 46%), stirring and reacting for 12h at 25 ℃ and normal pressure, wherein the stirring speed is 600rpm, and thus the reaction equilibrium is achieved.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that dipropyl carbonate serving as an organic carbonate product is generated except volatile reactants; after gas chromatographic analysis, the selectivity of the obtained dipropyl carbonate can reach 99.8 percent, and the yield can reach 46.8 percent.
Example 9
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, and 1.48kg of n-butanol and 6.84kg of monoiodomethane (3L, mass fraction of monoiodomethane: 52%) were added and stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm to achieve equilibrium reaction.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that organic carbonate product methyl n-butyl carbonate is generated except volatile reactants; the selectivity of the obtained methyl n-butyl carbonate can reach 99.7 percent and the yield can reach 50.8 percent through gas chromatography analysis.
Example 10
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, 1.48kg of isobutanol and 6.84kg of monoiodomethane (3L, mass fraction of monoiodomethane: 52%) were added, and the reaction was stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm to reach reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that an organic carbonate product, namely methyl isobutyl carbonate, is generated except volatile reactants; through gas chromatographic analysis, the selectivity of the obtained methyl isobutyl carbonate can reach 99.6 percent, and the yield can reach 51.6 percent.
Example 11
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, and 1.48kg of n-butanol and 5.85kg of monoiodoethane (3L, mass fraction of monoiodoethane: 48%) were added and stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm to achieve reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that an organic carbonate product, namely ethyl n-butyl carbonate, is generated except volatile reactants; the selectivity of the obtained ethyl-n-butyl carbonate can reach 99.5 percent and the yield can reach 45.8 percent through gas chromatography analysis.
Example 12
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, 1.48kg of isobutanol and 5.85kg of monoiodoethane (3L, mass fraction of monoiodoethane is 48%) were added, and the reaction was stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm to reach reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that an organic carbonate product, namely ethyl isobutyl carbonate, is generated except volatile reactants; the selectivity of the obtained ethyl isobutyl carbonate can reach 99.5 percent and the yield can reach 46.7 percent through gas chromatographic analysis.
Example 13
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, and 1.48kg of n-butanol and 4.86kg of 1-iodobutane (3L, mass fraction of 1-iodobutane: 43%) were added thereto, and the mixture was stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm, to achieve equilibrium reaction.
Analyzing the reaction liquid by using a gas chromatography-mass spectrometer, and finding that organic carbonate product dibutyl carbonate is generated except volatile reactants; after gas chromatographic analysis, the selectivity of the obtained dibutyl carbonate can reach 99.6 percent, and the yield can reach 44.3 percent.
Example 14
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. Introducing the absorption liquid into a reaction kettle, adding 1.76kg of n-amyl alcohol and 4.55kg of 1-iodopentane (3L, the mass fraction of the 1-iodopentane is 41%), stirring and reacting for 12 hours at 25 ℃ and normal pressure, wherein the stirring speed is 600rpm, and thus the reaction equilibrium is achieved.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that an organic carbonate product, namely dipentyl carbonate, is generated except volatile reactants; the selectivity of the obtained dipentyl carbonate can reach 99.1 percent and the yield can reach 41.4 percent through gas chromatographic analysis.
Example 15
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. Introducing the absorption liquid into a reaction kettle, adding 2.04kg of n-hexanol and 4.31kg of 1-iodohexane (3L, the mass fraction of the 1-iodohexane is 38%), stirring at 25 ℃ and normal pressure for reaction for 12h, wherein the stirring speed is 600rpm, and thus the reaction equilibrium is achieved.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that organic carbonate product dihexyl carbonate is generated except volatile reactants; the selectivity of the obtained dihexyl carbonate can reach 98.7 percent and the yield can reach 38.5 percent through gas chromatography analysis.
Example 16
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, 2.32kg of n-heptanol and 4.14kg of 1-iodoheptane (3L, mass fraction of 1-iodoheptane is 36%) were added, and the reaction was stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm to reach reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that organic carbonate product diheptyl carbonate is generated except volatile reactants; the selectivity of the obtained diheptyl carbonate can reach 97.9 percent and the yield can reach 35.3 percent through gas chromatography analysis.
Example 17
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. Introducing the absorption liquid into a reaction kettle, adding 2.60kg of n-octanol and 3.99kg of 1-iodooctane (3L, the mass fraction of the 1-iodooctane is 35%), stirring at 25 ℃ and normal pressure for reaction for 12h, wherein the stirring speed is 600rpm, and thus the reaction equilibrium is achieved.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that organic carbonate product dioctyl carbonate is generated except volatile reactants; the selectivity of the obtained dioctyl carbonate can reach 96.5 percent and the yield can reach 31.6 percent through gas chromatography analysis.
Example 18
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, 1.24kg of ethylene glycol and 9.98kg of diiodomethane (3L, mass fraction of diiodomethane is 62%) were added, and the reaction was stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm to reach reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that organic carbonate product ethylene carbonate is generated except volatile reactants; the selectivity of the obtained ethylene carbonate can reach 95.8 percent and the yield can reach 30.2 percent through gas chromatography analysis.
Example 19
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, 1.52kg of 1, 2-propanediol and 9.98kg of diiodomethane (3L, mass fraction of diiodomethane is 61%) were added, and the reaction was stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm to reach reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that the 1, 2-propylene glycol carbonate of the organic carbonate product is generated except volatile reactants; through gas chromatographic analysis, the selectivity of the obtained 1, 2-propylene carbonate can reach 96.8 percent, and the yield can reach 36.5 percent.
Example 20
And (2) introducing 0.91kg of carbon dioxide into 4.01kg of ionic liquid 1-butyl-3-methylimidazole bicarbonate in an absorption kettle, keeping the temperature of the absorption kettle to 25 ℃, stirring and absorbing for 360min at normal pressure, wherein the stirring speed is 350rpm, and completely absorbing to obtain a mixture of the ionic liquid and the carbon dioxide adduct. The absorption solution was introduced into a reaction kettle, and 1.80kg of 1, 2-butanediol and 9.98kg of diiodomethane (3L, mass fraction of diiodomethane: 60%) were added thereto, and stirred at 25 ℃ and atmospheric pressure for 12 hours at a stirring speed of 600rpm, to achieve reaction equilibrium.
Analyzing the reaction solution by using a gas chromatography-mass spectrometer, and finding that organic carbonate product 1, 2-butenoic ester is generated except volatile reactants; the selectivity of the obtained 1, 2-butylene carbonate can reach 98.3 percent and the yield can reach 40.4 percent through gas chromatography analysis.
As can be seen from the above examples, the method provided by the invention can prepare the organic carbonate at normal temperature and normal pressure, and the reaction conditions are mild.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing organic carbonate at normal temperature and normal pressure comprises the following steps:
(1) introducing carbon dioxide into the imidazole ionic liquid to obtain the ionic liquid containing the carbon dioxide;
(2) mixing the ionic liquid containing carbon dioxide obtained in the step (1) with alcohol and halogenated hydrocarbon, and carrying out addition-substitution reaction to obtain organic carbonate;
the step (1) and the step (2) are carried out under the conditions of normal temperature and normal pressure.
2. The method according to claim 1, wherein the alcohol in the step (2) is a monohydric alcohol and/or a dihydric alcohol.
3. The method according to claim 1, wherein the structure of the cation in the imidazole-based ionic liquid in the step (1) is shown as formula I or formula II:
in the formula I, R1And R2Independently is C2～C16An alkyl group of (a);
in the formula II, R3Is C2～C16Alkyl radical of (2), R4NH2Is C2～C16An aminoalkyl group of (a);
the anion of the imidazole ionic liquid in the step (1) comprises bicarbonate ions, acetate ions, propionate ions, n-butyl acid ions, isobutyrate ions, pivaloate ions, levulinate ions or 1,2, 4-triazole ions.
4. The method of claim 3, wherein R is1、R2And R3Independently an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a 2-methylpentyl group, or a 3-methylpentyl group;
the R is4NH2Is an amine ethyl group, an amine n-propyl group, an amine isopropyl group, an amine n-butyl group, an amine isobutyl group, an amine n-pentyl group, an amine isopentyl group, an amine n-hexyl group, an amine 2-methylpentyl group or an amine 3-methylpentyl group.
5. The method of claim 4, wherein the imidazole-based ionic liquid comprises at least one of 1-ethyl-3-methylimidazole bicarbonate, 1-butyl-3-methylimidazole bicarbonate, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole levulinate, 1-butyl-3-methylimidazole levulinate, 1-ethyl-3-methylimidazole triazoium salt, and 1-butyl-3-methylimidazole triazoium salt.
6. The method according to claim 1 or 2, wherein the alcohol in the step (2) comprises at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, n-hexanol, 2-hexanol, 3-hexanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 3-octanol, 4-octanol, ethylene glycol, 1, 2-propanediol, and 1, 2-butanediol.
7. The method of claim 1, wherein the halogenated hydrocarbon in step (2) has a structure represented by formula III, formula IV, formula V or formula VI
R5-X1Formula IIIX2-R6-X3Formula IV
In the formula III, R5Is C1～C16Alkyl radical of (2), X1Is fluorine atom, chlorine atom, bromine atom or iodine atom;
in the formula IV, R6Is C1～C16Alkyl radical of (2), X2And X3Independently a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;
in the formula V, R7Is C1～C16Alkyl radical of (2), X4、X5And X6Independently a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;
x in the formula VI7、X8、X9And X10Independently a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
8. The method of claim 7, wherein R is5、R6And R7Independently a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a 2-methylpentyl group, or a 3-methyl groupA cyclopentyl group.
9. The method of claim 8, the halogenated hydrocarbon includes at least one of monochloromethane, monobromomethane, monoiodomethane, dichloromethane, dibromomethane, diiodomethane, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, monochloroethane, monobromoethane, monoiodoethane, 1, 2-dichloroethane, 1, 2-dibromoethane, 1, 2-diiodoethane, 1-chloropropane, 1-bromopropane, 1-iodopropane, 2-chloropropane, 2-bromopropane, 2-iodopropane, 1, 2-dichloropropane, 1, 2-dibromopropane, 1, 2-diiodopropane, 1-iodobutane, 2-iodobutane, 1-iodopentane, 1-iodohexane, 1-iodoheptane and 1-iodooctane.
10. The method according to claim 1, characterized in that the ratio of the amounts of the imidazole-based ionic liquid and the alcohol is 1: (0.1-10), wherein the mass content of the halogenated hydrocarbon in a reaction system composed of the imidazole ionic liquid, the carbon dioxide, the alcohol and the halogenated hydrocarbon is 5-90%.
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