CN1405140A - Method of esterifying in ion liquid [Hmim]+ BF4- - Google Patents
Method of esterifying in ion liquid [Hmim]+ BF4- Download PDFInfo
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- CN1405140A CN1405140A CN 02145086 CN02145086A CN1405140A CN 1405140 A CN1405140 A CN 1405140A CN 02145086 CN02145086 CN 02145086 CN 02145086 A CN02145086 A CN 02145086A CN 1405140 A CN1405140 A CN 1405140A
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- hmim
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- conversion rate
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- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 title claims description 16
- 150000002500 ions Chemical class 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- 239000002608 ionic liquid Substances 0.000 claims abstract description 63
- 238000005886 esterification reaction Methods 0.000 claims abstract description 36
- 230000032050 esterification Effects 0.000 claims abstract description 33
- 230000005484 gravity Effects 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 6
- 229930195729 fatty acid Natural products 0.000 claims abstract description 6
- 239000000194 fatty acid Substances 0.000 claims abstract description 6
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 2
- -1 methylimidazolium tetrafluoroborate Chemical compound 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 21
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 2
- VOIZNVUXCQLQHS-UHFFFAOYSA-N 3-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC(Br)=C1 VOIZNVUXCQLQHS-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- NDKYEUQMPZIGFN-UHFFFAOYSA-N Butyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCC NDKYEUQMPZIGFN-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229940061720 alpha hydroxy acid Drugs 0.000 description 1
- 150000001280 alpha hydroxy acids Chemical class 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- VPSLGSSVPWVZFG-UHFFFAOYSA-N butan-2-yl propanoate Chemical compound CCC(C)OC(=O)CC VPSLGSSVPWVZFG-UHFFFAOYSA-N 0.000 description 1
- UEGSDZZPMLTPSY-UHFFFAOYSA-N butyl 3-chlorobenzoate Chemical compound CCCCOC(=O)C1=CC=CC(Cl)=C1 UEGSDZZPMLTPSY-UHFFFAOYSA-N 0.000 description 1
- CDYKWPLSGKMNFW-UHFFFAOYSA-N butyl 3-hydroxybenzoate Chemical compound CCCCOC(=O)C1=CC=CC(O)=C1 CDYKWPLSGKMNFW-UHFFFAOYSA-N 0.000 description 1
- ULBTUVJTXULMLP-UHFFFAOYSA-N butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCC ULBTUVJTXULMLP-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- PEJVLWCOQVHCAF-UHFFFAOYSA-N dioctyl oxalate Chemical compound CCCCCCCCOC(=O)C(=O)OCCCCCCCC PEJVLWCOQVHCAF-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229940017144 n-butyl lactate Drugs 0.000 description 1
- SFBIZPBTKROSDE-UHFFFAOYSA-N octyl 2-hydroxypropanoate Chemical compound CCCCCCCCOC(=O)C(C)O SFBIZPBTKROSDE-UHFFFAOYSA-N 0.000 description 1
- WQNBXKKGVGKFPV-UHFFFAOYSA-N octyl 3-chlorobenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC(Cl)=C1 WQNBXKKGVGKFPV-UHFFFAOYSA-N 0.000 description 1
- VECVSKFWRQYTAL-UHFFFAOYSA-N octyl benzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1 VECVSKFWRQYTAL-UHFFFAOYSA-N 0.000 description 1
- BBZAGOMQOSEWBH-UHFFFAOYSA-N octyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCCCCCC BBZAGOMQOSEWBH-UHFFFAOYSA-N 0.000 description 1
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种离子液体[Hmim]+BF4 －，即四氟硼酸甲基咪唑盐中酯化的方法，属有机化学反应方法的技术领域，在兼作催化剂和溶剂的离子液体[Hmim]+BF4 －中，进行酯化反应的脂肪酸或芳香酸和直链醇或支链醇经过搅拌，加热，静置，重力沉降，分液得酯化产品，转化率80～100％，选择性为100％，具有高转化率，高选择性，高普适性，工艺简单，催化剂可反复循环使用，环境友好等优点。An ionic liquid [Hmim] + BF 4 － , a method for esterification in methylimidazolium tetrafluoroborate, which belongs to the technical field of organic chemical reaction methods. The ionic liquid [Hmim] + BF 4 － which doubles as catalyst and solvent In the process, the fatty acid or aromatic acid and the straight-chain alcohol or branched-chain alcohol undergoing esterification are stirred, heated, allowed to stand, settled by gravity, and liquid-separated to obtain esterified products with a conversion rate of 80-100% and a selectivity of 100%. It has the advantages of high conversion rate, high selectivity, high universality, simple process, recyclable catalyst, and environmental friendliness.
Description
Technical Field
The invention relates to an ionic liquid [ Hmim]]+BF4 -Namely a method for esterifying tetrafluoroborate methylimidazolium salt, belonging to the technical field of organic chemical reaction methods.
Background
Esters are important intermediates in the industrial and pharmaceutical industries. Esterification processes of the background art are mostly carried out using mineral acids as catalysts. However, a large amount of organic solvent is required, and the residual waste acid after the reaction causes environmental pollution. The ionic liquid is an environment-friendly new material which is greatly concerned in recent years, and has the advantages of good stability, no volatilization, adjustable compatibility with organic matters and the like. Fraga-Dubreuil et al reported a method of catalytic esterification using ionic liquids in Catalysis Communications 2002, but the method uses ionic liquids whose synthesis is complicated, still needs a large amount of organic solvents, and the conversion rate of esterification reaction is not high.
Ionic liquid [ Hmim]]+BF4 -The catalyst is very simple and convenient to synthesize, has acidity, and can be used as an acidic catalyst and an environment-friendly solvent.
Disclosure of Invention
The invention aims to solve the technical problem of providing an esterification method which is environment-friendly, high in conversion rate and selectivity and simple in process. The invention solves the technical problem by the following scheme: ionic liquid [ Hmim]]+BF4 -The method of medium esterification is characterized in that the ionic liquid [ Hmim []]+BF4 -Andplacing fatty acid or aromatic acid and straight chain alcohol or branched chain alcohol in a reaction bottle, stirring, heating, standing, gravity settling, separating, and obtaining esterification product, ionic liquid [ Hmim]with high conversion rate and high selectivity]+BF4 -The catalyst and the solvent are used simultaneously, and the esterification reaction has the simple formula:
R＝Alkyl(C2～C20)，
CH2＝CH-(CH2)8-
HOOC-，
R′＝Alkyl(C1-C10). Ionic liquid [ Hmim]]+BF4 -Can be recycled after simple dehydration.
The present invention will now be described in detail. Ionic liquid [ Hmim]]+BF4 -The method for medium esterification is characterized in that,
the implementation steps are as follows:
22 parts by weight of an ionic liquid [ Hmim]]+BF4 -And 9-28.4 parts by weight of fatty acid or aromatic acid and 7-26 parts by weight of straight chain alcohol or branched chain alcohol are placed into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 2-12 hours, the reaction liquid is kept stand and is subjected to gravity settling, an upper organic layer is separated through liquid separation, and an esterified product is obtained, wherein the conversion rate is 80-100%, and the selectivity is 100%.
The ionic liquid in the lower layer can be recycled after simple dehydration.
Compared with the background art, the invention has the following advantages: 1. ionic liquid [ Hmim]]+BF4 -The synthesis method is particularly simple and convenient, and the cost is low. 2. Ionic liquid [ Hmim]]+BF4 -Is not required in the synthesis and esterification reactionThe method has the advantages that the method uses organic solvents, really realizes clean production.3. the ester compounds can be synthesized in the environment-friendly medium ionic liquid with high conversion rate and high selectivity.4. the universality is good, and the saturated fatty acid, the unsaturated fatty acid, α -hydroxy acid, dibasic acid, aromatic acid, substituted aromatic acid and the like can generate corresponding esters with primary alcohol and secondary alcohol with high conversion rate.
Detailed Description
The first embodiment is as follows: 22g of ionic liquid [ Hmim]]+BF4 -And 12.0g of acetic acid and 14.8g of n-butanol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 2 hours, the reaction solution is kept stand and gravity settling is carried out, the esterification product, namely the n-butyl acetate is separated by liquid separation, the conversion rate is 100 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example two: 22g of ionic liquid [ Hmim]]+BF4 -And 12.0g of acetic acid and 26g of n-octyl alcohol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 4 hours, the reaction solution is kept stand and is settled by gravity, the esterification product of n-octyl acetate is separated by liquid separation, the conversion rate is 99 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example three: 22g of ionic liquid [ Hmim]]+BF4 -And 20g of dodecanoic acid and 7.4g of n-butyl alcohol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 6 hours, the reaction solution is kept stand and is settled by gravity, the esterification product n-butyl dodecanoate is separated by liquid separation, the conversion rate is 98 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example four: 22g of ionic liquid [ Hmim]]+BF4 -Adding 20g of dodecanoic acid and 13g of n-octanol into a reaction bottle, stirring, heating, and controlling temperatureThe reaction is carried out for 6 hours at the temperature of 110 ℃, the reaction solution is stood and settled by gravity, the esterification product n-octyl dodecanoate is separated by liquid separation, the conversion rate is 96 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example five: 22g of ionic liquid [ Hmim]]+BF4 -And 28.4g of stearic acid and 7.4g of n-butanol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 6 hours, the reaction solution is kept stand and gravity settling is carried out, the esterification product n-butyl stearate is separated by liquid separation, the conversion rate is 92 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example six: 22g of ionic liquid [ Hmim]]+BF4 -And 28.4g of stearic acid and 13g of n-octyl alcohol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 6 hours, the reaction solution is kept stand and gravity settling is carried out, the esterification product of n-octyl stearate is separated by liquid separation, the conversion rate is 93 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example seven: 22g of ionic liquid [ Hmim]]+BF4 -And 18g of lactic acid and 14.8g of n-butanol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 4 hours, the reaction solution is kept stand and is settled by gravity, the esterification product, namely the n-butyl lactate, is separated by liquid separation, the conversion rate is 100 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example eight: 22g of ionic liquid [ Hmim]]+BF4 -And 18g of lactic acid and 26g of n-octyl alcohol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 5 hours, the reaction liquid is stood still, gravity sedimentation is carried out, the esterification product, namely the n-octyl lactate, is separated by liquid separation, the conversion rate is 96 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example nine: 22g of ionic liquid [ Hmim]]+BF4 -And 22.4g of crotonic acid and 7g of methanol are placed in a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 6 hours, the reaction solution is kept stand and gravity settling is carried out, the esterification product, namely methyl crotonate, is separated by separating, the conversion rate is 93 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example ten: 22g of ionicliquid [ Hmim]]+BF4 -And 22.4g of crotonic acid and 26g of n-octyl alcohol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 6 hours, the reaction solution is stood still and is settled by gravity, the esterification product of n-octyl crotonate is separated by liquid separation, the conversion rate is 92 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example eleven: 22g of ionic liquid [ Hmim]]+BF4 -And 9g of oxalic acid and 9.2g of ethanol are put into a reaction bottle, stirred and heated, the temperature is controlled to be 110 ℃, the reaction is carried out for 4 hours, the reaction solution is kept stand and is settled by gravity, the esterification product diethyl oxalate is separated by liquid separation, the conversion rate is 100 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example twelve: 22g of ionic liquid [ Hmim]]+BF4 -And 9g of oxalic acid and 26g of n-octyl alcohol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 5 hours, the reaction liquid is kept stand and is settled by gravity, the esterification product of di-n-octyl oxalate is separated by liquid separation, the conversion rate is 98 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example thirteen: 22g of ionic liquid [ Hmim]]+BF4 -And 20g of m-bromobenzoic acid and 7.4g of n-butanol were placed in a reaction flaskStirring and heating, controlling the temperature at 110 ℃, reacting for 12 hours, standing the reaction solution, and performing gravity settling to separate an esterification product, namely the m-butyl bromobenzoate, wherein the conversion rate is 82% and the selectivity is 100%. And the ionic liquid in the lower layer is recycled after water removal.
Example fourteen: 22g of ionic liquid [ Hmim]]+BF4 -And 20g of m-bromobenzoic acid and 13g of n-octyl alcohol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 12 hours, the reaction solution is kept stand, the reaction solution is settled by gravity, the esterification product, namely the m-bromobenzoic acid n-octyl ester, is separated, the conversion rate is 81 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example fifteen: 22g of ionic liquid [ Hmim]]+BF4 -And 15.6g of m-chlorobenzoic acid and 7.4g of n-butanol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 12 hours, the reaction solution is kept stand, gravity sedimentation is carried out, the esterification product of m-chlorobenzoic acid n-butyl ester is separated, the conversion rate is 81 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example sixteen: 22g of ionic liquid [ Hmim]]+BF4 -And 15.6g of m-chlorobenzoic acid and 13.0g of n-octyl alcohol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 12 hours, the reaction solution is stood still, the reaction solution is settled by gravity, the esterification product of m-chlorobenzoic acid n-octyl ester is separated by liquid separation, the conversion rate is 80 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example seventeen: 22g of ionic liquid [ Hmim]]+BF4 -And 13.8g of m-hydroxybenzoic acid and 7.4g of n-butanol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 10 hours, the reaction solution is kept stand, gravity sedimentation is carried out, the esterification product of m-hydroxybenzoic acid n-butyl ester is separated, the conversion rate is 93 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example eighteen: 22g of ionic liquid [ Hmim]]+BF4 -And 13.8g of m-hydroxybenzoic acid and 13g of n-octanol were put into a reaction flask, stirred and heated,controlling the temperature at 110 ℃, reacting for 10 hours, standing the reaction solution, and settling by gravity to separate out the esterification product of m-octyl hydroxybenzoate, wherein the conversion rate is 85 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example nineteenth: 22g of ionic liquid [ Hmim]]+BF4 -And 12.2g of benzoic acid and 13g of n-octyl alcohol are put into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 12 hours, the reaction solution is kept stand, gravity sedimentation is carried out, the esterification product of n-octyl benzoate is separated, the conversion rate is 80 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
Example twenty: 22g of ionic liquid [ Hmim]]+BF4 -And 14.8g of propionic acid and 14.8g of sec-butyl alcohol are added into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 4 hours, the reaction solution is kept stand and gravity settling is carried out, the esterification product sec-butyl propionate is separated by liquid separation, the conversion rate is 98 percent, and the selectivity is 100 percent. And the ionic liquid in the lower layer is recycled after water removal.
The method provided by the invention is suitable for esterification of fatty acid or aromatic acid and straight chain alcohol or branched chain alcohol, and has the advantages of high conversion rate, high selectivity, high universality, simple process, capability of repeatedly recycling the catalyst, environmental friendliness and the like.
Claims (2)
1. Ionic liquid [ Hmim]]+BF4 -The method of medium esterification is characterized in that the ionic liquid [ Hmim []]+BF4 -Mixing with fatty acid or aromatic acid and straight chain alcohol or branched chain alcohol, stirring, heating, standing, gravity settling, separating, and high conversion rate and selectivity to obtain esterified product, ionic liquid [ Hmim]]+BF4 -The catalyst and the solvent are used simultaneously, and the esterification reaction has the simple formula:
R＝Alkyl(C2～C20)，CH2＝CH-(CH2)8-
HOOC-，
R′＝Alkyl(C1-C10)。
2. an ionic liquid [ Hmim]according to claim 1]+BF4 -The method for medium esterification is characterized in that,
the implementation steps are as follows:
22 parts by weight of an ionic liquid [ Hmim]]+BF4 -And 9-28.4 parts by weight of fatty acid or aromatic acid and 7-26 parts by weight of straight chain alcohol or branched chain alcohol are placed into a reaction bottle, stirred and heated, the temperature is controlled at 110 ℃, the reaction is carried out for 2-12 hours, the reaction liquid is kept stand and is subjected to gravity settling, an upper organic layer is separated through liquid separation, and an esterified product is obtained, wherein the conversion rate is 80-100%, and the selectivity is 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02145086 CN1187309C (en) | 2002-11-07 | 2002-11-07 | Method of esterifying in ion liquid [Hmim]+ BF4- |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02145086 CN1187309C (en) | 2002-11-07 | 2002-11-07 | Method of esterifying in ion liquid [Hmim]+ BF4- |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1405140A true CN1405140A (en) | 2003-03-26 |
| CN1187309C CN1187309C (en) | 2005-02-02 |
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Family Applications (1)
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1329491C (en) * | 2003-12-30 | 2007-08-01 | 中国科学院兰州化学物理研究所 | Ionic liquid containing phosphonate ester functional group, process for preparing same and use thereof |
| KR100746996B1 (en) | 2006-09-06 | 2007-08-08 | 인하대학교 산학협력단 | Production method of biodiesel and glycerol using ionic liquid |
| KR100782127B1 (en) | 2006-01-13 | 2007-12-05 | 한국에너지기술연구원 | Removal Method of Free Fatty Acids in Oil Using Ionic Liquid Catalyst |
| CN101070282B (en) * | 2006-05-09 | 2011-06-15 | 黑龙江大学 | Process for room-temperature ion liquid-catalytic preparation of ethyl linoleate |
| CN102146032A (en) * | 2010-02-10 | 2011-08-10 | 北京腾化技术有限责任公司 | Method for preparing methyl methacrylate |
| CN102234228A (en) * | 2010-05-05 | 2011-11-09 | 北京石油化工学院 | Method for synthesizing trimethylolpropane fatty acid ester under catalysis of ionic liquid |
| CN101735254B (en) * | 2008-11-12 | 2012-05-16 | 宁波大学 | A kind of synthetic method of borate |
| CN101709322B (en) * | 2009-11-26 | 2012-06-27 | 浙江大学 | Method for synthesizing betulic acid by carrying out biocatalysis on betulin |
| CN109400476A (en) * | 2018-12-06 | 2019-03-01 | 华东理工大学 | A kind of preparation method of long-chain ester |
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| CN100497526C (en) * | 2005-07-08 | 2009-06-10 | 中国科学院过程工程研究所 | Method for synthesizing biologic diesel oil based on ion liquid |
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- 2002-11-07 CN CN 02145086 patent/CN1187309C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329491C (en) * | 2003-12-30 | 2007-08-01 | 中国科学院兰州化学物理研究所 | Ionic liquid containing phosphonate ester functional group, process for preparing same and use thereof |
| KR100782127B1 (en) | 2006-01-13 | 2007-12-05 | 한국에너지기술연구원 | Removal Method of Free Fatty Acids in Oil Using Ionic Liquid Catalyst |
| CN101070282B (en) * | 2006-05-09 | 2011-06-15 | 黑龙江大学 | Process for room-temperature ion liquid-catalytic preparation of ethyl linoleate |
| KR100746996B1 (en) | 2006-09-06 | 2007-08-08 | 인하대학교 산학협력단 | Production method of biodiesel and glycerol using ionic liquid |
| CN101735254B (en) * | 2008-11-12 | 2012-05-16 | 宁波大学 | A kind of synthetic method of borate |
| CN101709322B (en) * | 2009-11-26 | 2012-06-27 | 浙江大学 | Method for synthesizing betulic acid by carrying out biocatalysis on betulin |
| CN102146032A (en) * | 2010-02-10 | 2011-08-10 | 北京腾化技术有限责任公司 | Method for preparing methyl methacrylate |
| CN102234228A (en) * | 2010-05-05 | 2011-11-09 | 北京石油化工学院 | Method for synthesizing trimethylolpropane fatty acid ester under catalysis of ionic liquid |
| CN109400476A (en) * | 2018-12-06 | 2019-03-01 | 华东理工大学 | A kind of preparation method of long-chain ester |
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| CN1187309C (en) | 2005-02-02 |
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