CN101781252A - Method for preparing functionalized acidic ionic liquid with fluorous biphasic property - Google Patents
Method for preparing functionalized acidic ionic liquid with fluorous biphasic property Download PDFInfo
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Abstract
The invention discloses a method for preparing functionalized acidic ionic liquid with fluorous biphasic property, comprising the following steps: firstly adding polyethylene glycol (PEG) into toluene to undergo azeotropic distillation at reduced pressure to remove water; under the condition of ice bath, dropwise adding thionyl chloride into mixed liquor of acid binding agents, solvents and PEG, and carrying out the reaction at normal temperature; washing the product with diethyl ether and washing the product with PEG below 1000 with acid water to obtain the PEG product with two terminals chlorinated; then reacting sodium ethylate or sodium hydride with imidazole to prepare imidazole sodium and stirring the imidazole sodium; then taking ethanol as the solvent and stirring the imidazole sodium and the PEG product with two terminals chlorinated; after pump filtration, carrying out rinsing to remove the impurities and extracting aqueous phase with dichloromethane; then taking ethanol as the solvent and dropwise adding cycloparaffin sultone into the product obtained in the previous step and stirring the mixture; taking ethanol as the solvent and dropwise adding acid into the product obtained in the previous step and stirring the mixture; and finally washing the product with diethyl ether, toluene or petroleum ether, thus obtaining the required product. The preparation method is simple to operate and high in yield rate.
Description
Technical field
The invention belongs to a kind of preparation method of acidic ion liquid, particularly a class has the preparation method of the functionalized acidic ionic liquid of fluorine two-phase character.
Background technology
The be on good terms system of formations " high temperature homogeneous phase, low temperature two-phase " of Horvath I T, et al report fluorine two makes and reacts homogeneous phase and efficiently carry out and product easily separated (Horvath I T, et al, Science, 1994,266); Joep van den Broeke, et al report fluoride ion liquid can form the temperature control two-phase system, but this fluorine-containing system structure complexity, [Joep vanden Broeke, et al, Org Lett, 2002,4 (22): 385-3854] cost an arm and a leg; The disclosed temperature control polyether-type of people such as Wei Li ionic liquid has the characteristic of " high temperature homogeneous phase, low temperature phase-splitting " in the mixed solvent of toluene, normal heptane, but this ion liquid system is to different system organic solvent proportioning differences, complicated operation (Wei Li, the doctorate paper, Dalian University of Technology, 2004); People such as the intelligent treasure of duty report acid polyethylene glycols ionic liquid, only consider the application [the intelligent treasure of duty etc., SCI, 2008,29 (10): 772-774] of PEG-200; People such as the intelligent treasure of duty are in the characteristic of reporting that synthesizing polyethylene glycol class ionic liquid and toluene exist phase splitting at room temperature, high temperature to dissolve each other, but this method needed for two steps, complicated operation, and yield is lower.(the intelligent treasure of duty etc., SCI, 2008,29 (10): 2007-2010).
Summary of the invention
The object of the present invention is to provide simple, the easy handling of a class operation, the preparation method of the product yield rate functionalized acidic ionic liquid with fluorine two-phase character high, that be convenient to promote.
The technical solution that realizes the object of the invention is: a class has the preparation method of the functionalized acidic ionic liquid of fluorine two-phase character, at first adds toluene in PEG, carries out the underpressure distillation azeotropic water removing; Under condition of ice bath, dripping thionyl chloride in the mixed solution of acid binding agent, solvent, PEG, this reaction normal temperature carries out; Use the ether cleaning product, wherein the following product of PEG1000 is washed with sour water, obtains PEG product with two terminals; Make imidazole natrium by sodium ethylate or sodium hydride and imidazoles reaction then, stir; Then make solvent, imidazole natrium and PEG product with two terminals are stirred with ethanol; Behind the suction filtration, impurity, dichloromethane extraction water are removed in washing; Make solvent with ethanol again, go on foot forward and drip the stirring of naphthenic hydrocarbon sultones in the product; Make solvent with ethanol at last, go on foot forward and drip acid in the product, stir; The functionalized acidic ionic liquid that uses ether, toluene or petroleum ether product can obtain having fluorine two-phase character at last.
The present invention compared with prior art, its remarkable advantage: it is simple to operate that the present invention has functionalized acidic ionic liquid of fluorine two-phase character and preparation method thereof, is easy to realize, the output capacity height of product has better market prospect.
Embodiment
One class has the functionalized acidic ionic liquid of fluorine two-phase character, and its molecular formula is [(CH
2)
nSO
3H) N
2C
3H
3)
2R]
2+[2A
-], structure is represented with following general formula (I):
Wherein:
R represents the inferior ethoxyl unit, is selected from-(CH
2CH
2O)
qCH
2CH
2-, wherein q=3-250 is formed by poly(oxyethylene glycol) 400-10000, and A represents mineral acid, organic acid; N representative-CH
2-number be 3～7.
R represents the inferior ethoxyl unit, is selected from-(CH
2CH
2O)
qCH
2CH
2-, wherein q=3-250 is formed by poly(oxyethylene glycol) 400-10000, and wherein preferred R represents the inferior ethoxyl unit, is selected from-(CH
2CH
2O)
qCH
2CH
2-, wherein the scope of q is 8～38, is formed by Polyethylene Glycol-600～1500; Wherein most preferably R represents the inferior ethoxyl unit, is selected from-(CH
2CH
2O)
qCH
2CH
2-, wherein q=16～28 are formed by cetomacrogol 1000.
A represents mineral acid, organic acid, can select sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid, nitric acid, carbonic acid for use when A represents mineral acid, wherein is preferably hydrochloric acid, sulfuric acid, most preferably is sulfuric acid;
N representative-CH
2-number, be 3～7, promptly 1,3-propane sultone, 1,4-butane sultones, 1,5-pentane sultones, 1,6-hexane sultones, 1,7-heptanesulfonic acid lactone, being preferably n is 3～5, promptly 1,3-propane sultone, 1,4-butane sultones, 1,5-pentane sultones, most preferably be 3 promptly with 1, the 3-propane sultone is a raw material.
One class has the functionalized acidic ionic liquid of fluorine two-phase character, and wherein R represents the inferior ethoxyl unit, is selected from-(CH
2CH
2O)
qCH
2CH
2-, wherein the scope of q is 8～38, is formed by Polyethylene Glycol-600～1500; A is a mineral acid, and n is 3～5, promptly 1, and 3-propane sultone, 1,4-butane sultones, 1,5-pentane sultones.
One class has the functionalized acidic ionic liquid of fluorine two-phase character, and wherein R represents the inferior ethoxyl unit, is selected from-(CH
2CH
2O)
qCH
2CH
2-, wherein the scope of q is 8～38, is formed by Polyethylene Glycol-600～1500; A is sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid, nitric acid or carbonic acid, A
-Be bisulfate ion, dihydrogen phosphate, chlorion, acetate, nitrate radical, bicarbonate radical, n is 3～5, promptly 1, and 3-propane sultone, 1,4-butane sultones, 1,5-pentane sultones.
A kind of functionalized acidic ionic liquid with fluorine two-phase character, wherein R represents the inferior ethoxyl unit, is selected from-(CH
2CH
2O)
qCH
2CH
2-, wherein q=16～28 are formed by cetomacrogol 1000, and A is a sulfuric acid, A
-Be bisulfate ion, n is 3, and promptly with 1, the 3-propane sultone is a raw material.
This ionic liquid self has catalytic and has excellent catalytic performance, and is difficult for running off, and recycles 10～15 activity and does not obviously reduce.
The present invention has announced that a class has the preparation method of the functionalized acidic ionic liquid of fluorine two-phase character, by sulfur oxychloride is that raw material carries out the both-end chloro to polyoxyethylene glycol, react with imidazole natrium then, again with 1,3-propane sultone reaction, what add at last that acid makes polyoxyethylene glycol series has a fluorine two-phase function acidic ion liquid.Reaction equation is as follows:
This method comprises the steps:
Step 1, in PEG, add toluene, carry out the underpressure distillation azeotropic water removing;
Step 2, in the mixed solution of acid binding agent, solvent, PEG, to dripping thionyl chloride wherein, this reaction normal temperature carries out under the condition of ice bath;
The product of step 3, usefulness ether washing step 2, wherein the following product of PEG1000 is washed with sour water, obtains PEG product with two terminals;
Step 4, make imidazole natrium by sodium ethylate or sodium hydride and imidazoles reaction;
Step 5, make solvent with ethanol, imidazole natrium that step 4 is made and step 4 make PEG product with two terminals and mix and stir;
The product of step 6, step 5 is behind suction filtration, and impurity, dichloromethane extraction water are removed in washing;
Step 7, use ethanol are made solvent, drip the naphthenic hydrocarbon sultones and stir in the product of step 6;
Step 8, use ethanol are made solvent, drip acid in the product of step 7, stir;
The product of step 9, usefulness ether, toluene or petroleum ether step 8 can make the functionalized acidic ionic liquid with fluorine two-phase character.
Acid binding agent described in present method step 3 is a pyridine; Solvent is methylene dichloride or toluene; The sulfur oxychloride that adds is 2～3.5 times of molar weights of PEG, and when the amount that adds was 2.2 times, reaction effect was best, and this step reaction was carried out under normal temperature condition 2～12 hours; The pH value of the sour water described in the step 4 is 2～6, and the effect of washing is best in the time of pH=3; The temperature of reaction of step 5 is at 30～80 ℃, and churning time is 3～7 hours; The temperature of reaction of step 6 is 30～100 ℃, and churning time is 5～10 hours; The temperature of reaction of step 8 is 40～100 ℃, and churning time is 3～6 hours, and the naphthenic hydrocarbon sultones is meant n=3～7, and that wherein more excellent is n=3,4, and optimum is that n=3 is 1, and the 3-propane sultone is a raw material; The acid that adds in the step 9 is sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid, nitric acid or carbonic acid, and wherein more excellent is phosphoric acid, sulfuric acid, and optimum is sulfuric acid, and temperature of reaction is 40～100 ℃, and churning time is 2～6 hours.
Such has the functionalized acidic ionic liquid of fluorine two-phase character, effectively reactions such as catalysis acetal, esterification, nitrated (nitre is separated), Biginelli, can obtain higher yields within a short period of time, and this ionic liquid repeatedly recycles the back catalytic activity obviously not to be reduced, the ionic liquid number of dropouts is little, and product separates by separatory.
Further specify the present invention below by embodiment.
Embodiment 1
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 6h under 70 ℃ of conditions, suction filtration, and solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, make solvent with ethanol again, add 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid PEG
1000-DAIL, productive rate 89.1%.
Its molecular formula is: [(CH
2)
3SO
3H) N
2C
3H
3)
2(CH
2CH
2O)
qCH
2CH
2]
2+[2HSO
4 -]
General formula is:
To the physicochemical characteristics of product carry out hot analysis, nuclear-magnetism, test such as infrared obtains: viscosity: 2804MPaS; 180 ℃ of heat decomposition temperatures;
1HNMR (500MHz, D
2O, TMS) δ 2.15 (t, 4H, J=7Hz, 2 * CH
2), 2.77 (m, 4H, 2 * CH
2), 3.45～3.66 (m, 90.3H, (OCH
2CH
2)
n), 3.74 (4H, 2 * CH
2), 4.21～4.30 (8H, 4 * NCH
2), 7.41 (s, 4H, 4 * CH), 8.71 (s, 2H, 2 * CH);
13C NMR (500MHz, D
2O, TMS): δ 25.2,47.7, and 47.9,49.1,68.6,68.7,69.6,122.3,123.1,136.0; PEG
1000The infrared spectrum 3849.6,3400.2,3020.3,2883.3,1731.9,1591.1,1456.1,1431,1377,1122.4,1108.9,972.1,883.3,798.5,676.9 of-DAIL, 576.7.
Embodiment 2
Get phosphoric acid 0.12mol, all the other are phosphoric acid hydrogen radical ion liquid by make negatively charged ion according to embodiment 1.This ionic liquid and toluene become homogeneous system at 80 ℃, the phase-splitting automatically of cooling back, PEG
1000-H
2PO
4Productive rate 82.1%.
Its molecular formula is: [(CH
2)
3SO
3H) N
2C
3H
3)
2(CH
2CH
2O)
qCH
2CH
2]
2+[2H
2PO
4 -]
General formula is:
The physicochemical characteristics of product is carried out tests such as nuclear-magnetism to be obtained:
1HNMR (500MHz, D
2O, TMS) δ 2.15 (t, 4H, J=7Hz, 2 * CH
2), 2.77 (m, 4H, 2 * CH
2), 3.45～3.66 (m, 90.3H, (OCH
2CH
2)
n), 3.74 (4H, 2 * CH
2), 4.21～4.30 (8H, 4 * NCH
2), 7.41 (s, 4H, 4 * CH), 8.71 (s, 2H, 2 * CH);
13CNMR (500MHz, D
2O, TMS): δ 25.2,47.7,47.9,49.1,68.6,68.7,69.6,122.3,123.1,136.0.
Embodiment 3
Polyoxyethylene glycol 800 is got 0.06mol, and all the other are by making a kind of new acidic ion liquid, productive rate 88.3% according to implementing 1.
Embodiment 4
Polyethylene Glycol-600 is got 0.06mol, and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, pH=3 acid rinsing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 89.1%.
Embodiment 5
Poly(oxyethylene glycol) 400 is got 0.06mol, and all the other are by making a kind of new acidic ion liquid, productive rate 90.2% according to implementing 1.
Embodiment 6
Get nitric acid 0.12mol, all the other are nitrate ion liquid by make negatively charged ion according to embodiment 1, productive rate 87.6%.This ionic liquid and toluene become homogeneous system at 80 ℃, the phase-splitting automatically of cooling back.
Embodiment 7
Get carbonic acid 0.12mol, all the other are bicarbonate ion liquid by make negatively charged ion according to embodiment 1, productive rate 87.6%.This ionic liquid and toluene become homogeneous system at 80 ℃, the phase-splitting automatically of cooling back.
Embodiment 8
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, 5-pentane sultones, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 83.1%.
Embodiment 9
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, 4-butane sultones, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 84.1%.
Embodiment 10
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds chloroform extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 89.1%.
Embodiment 11
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with extracted with diethyl ether and is got reddish-brown thickness acidic ion liquid, productive rate 89.1%.
Embodiment 12
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent three times with the toluene extraction and is got reddish-brown thickness acidic ion liquid, productive rate 89.1%.
Embodiment 13
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add toluene 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent three times with the toluene extraction and is got reddish-brown thickness acidic ion liquid, productive rate 89.1%.
Embodiment 14
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.132mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent three times with the toluene extraction and is got reddish-brown thickness acidic ion liquid, productive rate 92.1%.
Embodiment 15
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.21mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent three times with the toluene extraction and is got reddish-brown thickness acidic ion liquid, productive rate 88.1%.
Embodiment 16
Polyethylene Glycol-600 is got 0.06mol, and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, pH=2 acid rinsing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 87.1%.
Embodiment 17
Polyethylene Glycol-600 is got 0.06mol, and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, pH=6 acid rinsing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 86.1%.
Embodiment 18
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 30 ℃ of reaction 3h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 84.1%.
Embodiment 19
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 80 ℃ of reaction 7h, the ethanolic soln of imidazole natrium and chloro-product stir 6h, suction filtration under 70 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 88.1%.
Embodiment 20
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 5h, suction filtration under 30 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 87.1%.
Embodiment 21
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 10h, suction filtration under 100 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 88.1%.
Embodiment 22
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 10h, suction filtration under 100 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 40 ℃ of reaction 3h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 88.1%.
Embodiment 23
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 10h, suction filtration under 100 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 100 ℃ of reaction 6h, drip 0.12mol sulfuric acid again, 50 ℃ of reaction 4h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 87.1%.
Embodiment 24
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 10h, suction filtration under 100 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 40 ℃ of reaction 2h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 88.1%.
Embodiment 25
Cetomacrogol 1000 is got 0.06mol (60g), and toluene 70mL places 500mL round-bottomed flask azeotropic water removing.Add methylene dichloride 280mL then, pyridine 0.12mol (17mL), under the condition of ice bath, dripping thionyl chloride 0.12mol dropwise in the 30min, stirring reaction 4h, separatory, ether washing; Make imidazole natriums by imidazoles and sodium ethylate in 60 ℃ of reaction 4h, the ethanolic soln of imidazole natrium and chloro-product stir 10h, suction filtration under 100 ℃ of conditions, solid discards, the stillness of night washes the back with water and adds dichloromethane extraction, makes solvent with ethanol again, adds 1 of 0.12mol, the 3-propane sultone, behind 60 ℃ of reaction 4h, drip 0.12mol sulfuric acid again, 100 ℃ of reaction 6h, the gained ionic liquid is removed organic solvent for three times with petroleum ether extraction and is got reddish-brown thickness acidic ion liquid, productive rate 87.1%
Except adopting above-mentioned raw materials to prepare ionic liquid of the present invention, choose molecular weight greater than 1000 polyoxyethylene glycol, n be 6,71,6-hexane sultones, 1,7-heptanesulfonic acid lactone, acid is that raw material also can make ionic liquid of the present invention through said process for hydrochloric acid, acetic acid.
Embodiment 26
The ionic liquid that is made by embodiment 1 is used for the condensation reaction of phenyl aldehyde and ethylene glycol, and 80 ℃ of reactions can obtain 98% productive rate in 1 hour, and this ionic liquid recycles, and catalytic activity does not obviously reduce more than 5 times.
Embodiment 27
The ionic liquid that is made by embodiment 1 is used for phenylformic acid and alcoholic acid esterification, and 80 ℃ of reactions can obtain 99% productive rate in 1 hour, and this ionic liquid recycles, and catalytic activity does not obviously reduce more than 6 times.
Claims (6)
1. a class has the preparation method of the functionalized acidic ionic liquid of fluorine two-phase character, it is characterized in that this method may further comprise the steps:
Step 1, in PEG, add toluene, carry out the underpressure distillation azeotropic water removing;
Step 2, in the mixed solution of acid binding agent, solvent, PEG, to dripping thionyl chloride wherein, this reaction normal temperature carries out under the condition of ice bath;
The product of step 3, usefulness ether washing step 2, wherein the following product of PEG1000 is washed with sour water, obtains PEG product with two terminals;
Step 4, make imidazole natrium by sodium ethylate or sodium hydride and imidazoles reaction;
Step 5, use are made solvent with ethanol, and imidazole natrium and step 4 that step 4 is made make PEG product with two terminals mixing stirring;
The product of step 6, step 5 is behind suction filtration, and impurity, dichloromethane extraction water are removed in washing;
Step 7, use ethanol are made solvent, drip the naphthenic hydrocarbon sultones and stir in the product of step 6;
Step 8, use ethanol are made solvent, drip acid in the product of step 7, stir;
The product of step 9, usefulness ether, toluene or petroleum ether step 8 can make the functionalized acidic ionic liquid with fluorine two-phase character.
2. the preparation method with functionalized acidic ionic liquid of fluorine two-phase character according to claim 1 is characterized in that: the acid binding agent described in the step 3 is a pyridine; Solvent is methylene dichloride or toluene; The sulfur oxychloride that adds is 2～3.5 times of molar weights of PEG, and being reflected in this step carried out under the normal temperature condition 2～12 hours.
3. the preparation method with functionalized acidic ionic liquid of fluorine two-phase character according to claim 1 is characterized in that: the pH value of the sour water described in the step 4 is 2～6; The temperature of reaction of step 5 is at 30～80 ℃, and churning time is 3～7 hours.
4. the preparation method with functionalized acidic ionic liquid of fluorine two-phase character according to claim 1 is characterized in that: the temperature of reaction of step 6 is 30～100 ℃, and churning time is 5～10 hours.
5. the preparation method with functionalized acidic ionic liquid of fluorine two-phase character according to claim 1 is characterized in that: the temperature of reaction of step 8 is 40～100 ℃, and churning time is 3～6 hours, and the naphthenic hydrocarbon sultones is meant n=3～7.
6. the preparation method with functionalized acidic ionic liquid of fluorine two-phase character according to claim 1 is characterized in that: the temperature of reaction of step 9 is 40～100 ℃, and churning time is 2～6 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955104A (en) * | 2016-10-14 | 2018-04-24 | 南京理工大学 | One kind has acid temperature control two-phase aggretion type ionic liquid and application thereof |
| CN115125030A (en) * | 2022-08-11 | 2022-09-30 | 东北石油大学 | Polyethylene glycol porous ionic liquid and preparation method and application thereof |
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2009
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955104A (en) * | 2016-10-14 | 2018-04-24 | 南京理工大学 | One kind has acid temperature control two-phase aggretion type ionic liquid and application thereof |
| CN115125030A (en) * | 2022-08-11 | 2022-09-30 | 东北石油大学 | Polyethylene glycol porous ionic liquid and preparation method and application thereof |
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