CN101024612B - A kind of acidic ionic liquid catalyzed alkyd esterification method - Google Patents
A kind of acidic ionic liquid catalyzed alkyd esterification method Download PDFInfo
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- CN101024612B CN101024612B CN200710027186XA CN200710027186A CN101024612B CN 101024612 B CN101024612 B CN 101024612B CN 200710027186X A CN200710027186X A CN 200710027186XA CN 200710027186 A CN200710027186 A CN 200710027186A CN 101024612 B CN101024612 B CN 101024612B
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- 238000005886 esterification reaction Methods 0.000 title claims abstract description 43
- 230000032050 esterification Effects 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229920000180 alkyd Polymers 0.000 title claims abstract description 5
- 239000011831 acidic ionic liquid Substances 0.000 title claims abstract 3
- 239000002608 ionic liquid Substances 0.000 claims abstract description 88
- -1 α-pyrrolidone cations Chemical class 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 150000001449 anionic compounds Chemical class 0.000 claims abstract description 6
- 150000002891 organic anions Chemical class 0.000 claims abstract description 6
- 239000012024 dehydrating agents Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- 238000010992 reflux Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 claims description 2
- VOIZNVUXCQLQHS-UHFFFAOYSA-N 3-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC(Br)=C1 VOIZNVUXCQLQHS-UHFFFAOYSA-N 0.000 claims description 2
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 claims description 2
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- 150000005846 sugar alcohols Polymers 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 235000015165 citric acid Nutrition 0.000 claims 1
- PJVNDJOBKYOMBU-UHFFFAOYSA-N formic acid;phenol Chemical compound OC=O.OC1=CC=CC=C1 PJVNDJOBKYOMBU-UHFFFAOYSA-N 0.000 claims 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 29
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 239000007810 chemical reaction solvent Substances 0.000 abstract 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 25
- 230000009466 transformation Effects 0.000 description 23
- 238000000605 extraction Methods 0.000 description 22
- 238000005303 weighing Methods 0.000 description 22
- 238000013019 agitation Methods 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 230000001476 alcoholic effect Effects 0.000 description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 150000002500 ions Chemical class 0.000 description 6
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 229950004288 tosilate Drugs 0.000 description 3
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 2
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 2
- GDWRKZLROIFUML-UHFFFAOYSA-N 4-phenylbutan-2-ol Chemical class CC(O)CCC1=CC=CC=C1 GDWRKZLROIFUML-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- ULELPEYHAFTGRE-UHFFFAOYSA-N bromobenzene formic acid Chemical group C(=O)O.BrC1=CC=CC=C1 ULELPEYHAFTGRE-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 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 2
- 239000000126 substance Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- KVZLHPXEUGJPAH-UHFFFAOYSA-N 2-oxidanylpropanoic acid Chemical compound CC(O)C(O)=O.CC(O)C(O)=O KVZLHPXEUGJPAH-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NIQOQILAVJCVOU-UHFFFAOYSA-N [N+](=O)([O-])C=1C=C(C(=O)O)C=CC1.C(C1=CC=CC=C1)(=O)O Chemical compound [N+](=O)([O-])C=1C=C(C(=O)O)C=CC1.C(C1=CC=CC=C1)(=O)O NIQOQILAVJCVOU-UHFFFAOYSA-N 0.000 description 1
- 229940061720 alpha hydroxy acid Drugs 0.000 description 1
- 150000001280 alpha hydroxy acids Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 201000007386 factor VII deficiency Diseases 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YZAZXIUFBCPZGB-KVVVOXFISA-N octadec-9-enoic acid;(z)-octadec-9-enoic acid Chemical compound CCCCCCCCC=CCCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O YZAZXIUFBCPZGB-KVVVOXFISA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- SCFVLCBATVDKDN-UHFFFAOYSA-N pyrrolidin-2-one;2,2,2-trifluoroacetic acid Chemical compound O=C1CCCN1.OC(=O)C(F)(F)F SCFVLCBATVDKDN-UHFFFAOYSA-N 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Substances OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种酸性离子液体催化醇酸酯化方法，该方法采用α-吡咯烷酮阳离子与无机或有机阴离子构成的离子液体作为反应的催化剂、溶剂、脱水剂，离子液体加入量为醇和酸的总摩尔数的10～200％，在80～140℃，常压，反应0.5～8小时催化醇酸酯化反应生成酯；本发明与传统的酸催化法相比，酯化反应产物更容易分离，选择性更高，并具有高普适性；突出的特点是产物酯与催化剂可自动分相，而且离子液体经简单处理可重复使用，催化活性不变。The invention discloses an acidic ionic liquid catalyzed alkyd esterification method. The method uses an ionic liquid composed of α-pyrrolidone cations and inorganic or organic anions as a reaction catalyst, solvent, and dehydrating agent. 10-200% of the total moles, at 80-140°C, normal pressure, react for 0.5-8 hours to catalyze the esterification reaction of alkyd to generate ester; compared with the traditional acid-catalyzed method, the esterification reaction product is easier to separate, Higher selectivity and high universality; the outstanding feature is that the product ester and the catalyst can automatically separate phases, and the ionic liquid can be reused after simple treatment, and the catalytic activity remains unchanged.
Description
Technical field
The present invention relates to the organic chemical reactions method, particularly relate to a kind of method for catalyzing alcohol acid esterization by acidic ion liquid.
Background technology
Carboxylic acid ester compound has the wide industrial purposes, much is important chemical product.Traditional alcoholic acid esterification technology is used the inorganic acid as catalyst of severe corrosive such as the vitriol oil usually, exist that selectivity is low, product is coloured, be difficult to separate with product, problems such as etching apparatus and contaminate environment, it is therefore industrial that exploitation is had the novel alcoholic acid esterification system demand of environmental benefit and economic benefit is very urgent.Advantages such as the ionic liquid that is liquid state under the room temperature is the novel material that receives much attention in recent years, has good stability, and is non-volatile, and solvability and acidity are adjustable are showing excellent characteristic as novel green catalyst and solvent in a lot of acid catalyzed reactions.Deng You congruence (CN1247856) is used alkyl pyridine, the ionic liquid that phonetic azoles etc. contain nitric heterocyclic compound and metal or non-metallic halide formation carries out catalyst for esterification and solvent as alcohol and acid, realized the alcoholic acid esterification reaction, but shortcomings such as this class ionic liquid existence is stable inadequately to water and air, the stable deficiency of repeated use; (CN1405140 is CN1528733) with ionic liquid [Hmim] BF for He Mingyuan etc.
4, Fang Yanxiong etc. (CN1880295) is cationic ionic liquid with the pyrrolidone that the N-alkyl or alkenyl replaces, and as the catalyzer and the solvent of alcoholic acid esterification, successively realized the esterification of alcohol with acid.The small molecules ester of low carbon number is at [Hmim] BF
4System (CN1405140, CN1528733) in phase-splitting automatically, thereby can not prepare by separatory, must be by distillation preparation (CN1528733).The present invention is that the ionic liquid that constitutes with alpha-pyrrolidone positively charged ion and inorganic or organic anion is as alcoholic acid esterification catalyst for reaction, solvent, dewatering agent, have advantages of high catalytic activity and universality, just can realize automatic phase-splitting by simply being separated with esterification products, and can be recycled, catalytic activity is constant substantially, therefore is expected to substitute in chemical industry do not meet traditional severe corrosive acid catalytic materials such as the vitriol oil that Green Chemistry requires.
Summary of the invention
The objective of the invention is to replace the reaction of traditional inorganic acids catalyst alcoholic acid esterification, realize the alcoholic acid esterification of the green high-efficient under the mild reaction conditions with acidic ion liquid.
The present invention realizes by following scheme:
In the there-necked flask that magnetic stirring apparatus, thermometer, reflux condensing tube are housed, add the ionic liquid and the alcohol, sour of certain proportioning, through reacting by heating, cooling, standing demix while stirring, processes such as separatory realize esterification; Or ionic liquid mixed with alkyd, through after the reacting by heating while stirring, straight run distillation goes out ester products.Ionic liquid can be reused after simply dewatering and keep catalytic activity constant.
The inventive method feature is the ionic liquid that constitutes with alpha-pyrrolidone positively charged ion and inorganic or organic anion catalyzer, solvent, the dewatering agent as esterification, add-on is 10～200% of alcohol, a sour total mole number, 80～140 ℃ of temperature of reaction, normal pressure, 0.5～8 hour reaction times.
The described alpha-pyrrolidone cationic structural of the inventive method formula is as follows:
The described inorganic or organic anion of the inventive method is chlorine, bromine, iodine, sulfate radical, bisulfate ion, nitrate radical, dihydrogen phosphate, acetate, tetrafluoroborate, tosic acid root, trifluoromethanesulfonic acid root, trifluoroacetic acid radical ion.
The described reactant alcohol of the inventive method is C
1～C
12The saturated or unsaturated fatty alcohol of the monobasic of straight or branched, aromatic alcohol, polyvalent alcohol, C
3～C
12Alicyclic ring alcohol.
The general formula of the described aromatic alcohol of the inventive method is:
Wherein R is C
1～C
4Alkyl.
The described polyvalent alcohol of the inventive method is ethylene glycol, glycerol, tetramethylolmethane.
Monocarboxylic acid, di-carboxylic acid, lactic acid, citric acid that the described reactant acid of the inventive method is straight or branched, phenylformic acid, salicylic acid, m-Salicylic acid, P-hydroxybenzoic acid, 0-chloro-benzoic acid, m-chlorobenzoic acid, Chlorodracylic acid, o-bromobenzoic acid, m-bromobenzoic acid, parabromobenzoic acid.
The monocarboxylic general formula of the described straight or branched of the inventive method is R ＇ COOH, and R is H atom, C
1～C
17Alkyl, C
2～C
17Thiazolinyl; The general formula of di-carboxylic acid is HOOC (CH
2)
nCOOH, n=O, 1-6.
In the method for the invention, the addition sequence in the reaction process between alcohol, acid and the ionic liquid three without limits.
In the method for the invention, stir reflux certain hour down in the reaction process, reaction afterreaction liquid leaves standstill separatory, tells upper organic phase and gets esterified prod; Or reaction afterreaction liquid directly distill esterified prod.
The inventive method is compared with background technology, and beneficial effect is:
1. used acidic ion liquid promotes medium as alcoholic acid esterification catalyst for reaction or reaction, the phase-splitting automatically of esterification reaction product and ionic liquid, and the purity height is simplified separation process.
2. transformation efficiency height, selectivity 100%.
3. reacted ionic-liquid catalyst can use repeatedly through simple vaccum dewatering, and catalytic activity is constant, and product is colourless.When the ionic liquid usage quantity is big, can dewater and use repeatedly continuously.
4. such ionic liquid is compared cheap with traditional imidazoles, pyridines ionic liquid.Because the ionic liquid steam forces down, and is non-volatile, so this catalyst system is eco-friendly.
5. universality is good.Saturated fatty acid, unsaturated fatty acids, alpha hydroxy acid, diprotic acid, aromatic acid, phenylformic acid, substituted benzoic acid can generate ester with above-mentioned reactant alcohol.
Embodiment
Following embodiment is to the further specifying of the inventive method, and is not limitation of the invention.
Embodiment one: take by weighing acetate 0.1mol respectively, ethanol 0.1mol, ionic liquid alpha-pyrrolidone hydrosulfate 0.1mol; Ionic liquid, ethanol, acetate are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and 80 ℃ of heating reflux reactions 0.5 hour; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 90.3%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment two: take by weighing acetate 0.1mol respectively, propyl carbinol 0.1mol, ionic liquid alpha-pyrrolidone nitrate 0.02mol; Ionic liquid, propyl carbinol, acetate are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, and 100 ℃ of lower magnetic force stirring reactions 1 hour; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 75.8%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment three: take by weighing acetate 0.1mol respectively, n-Heptyl alcohol 0.1mol, ionic liquid alpha-pyrrolidone hydrochloride 0.01mol; Ionic liquid, n-Heptyl alcohol, acetate are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 140 ℃, reacted 2 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 71.7%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment four: take by weighing acetate 0.1mol respectively, lauryl alcohol (lauryl alcohol) 0.1mol, ionic liquid alpha-pyrrolidone hydrobromate 0.1mol; Ionic liquid, lauryl alcohol, acetate are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 130 ℃, reacted 2 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 65.2%, selectivity 100%.Ionic liquid is reused after vacuum hydro-extraction.
Embodiment five: take by weighing acetate 0.1mol respectively, phenylcarbinol 0.1mol, ionic liquid alpha-pyrrolidone hydriodate 0.05mol; Ionic liquid, phenylcarbinol, acetate are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 110 ℃, reacted 2 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 84.7%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment six: take by weighing acetate 0.1mol respectively, phenylpropyl alcohol 0.1mol, ionic liquid alpha-pyrrolidone acetate 0.02mol; Ionic liquid, phenylpropyl alcohol, acetate are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 120 ℃, reacted 8 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 73.2%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment seven: take by weighing acetate 0.1mol respectively, 4-phenyl-2-butanols 0.1mol, ionic liquid alpha-pyrrolidone trifluoroacetate 0.02mol; Ionic liquid, 4-phenyl-2-butanols, acetate are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 140 ℃, reacted 8 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 51.3%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment eight: take by weighing acetate 0.2mol respectively, ethylene glycol 0.1mol, ionic liquid alpha-pyrrolidone tosilate 0.02mol; Ionic liquid, ethylene glycol, acetate are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 120 ℃, reacted 1 hour; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 67.1%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment nine: take by weighing propionic acid 0.1mol respectively, n-propyl alcohol 0.1mol, ionic liquid alpha-pyrrolidone fluoroform sulphonate 0.01mol; Ionic liquid, n-propyl alcohol, propionic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 90 ℃, reacted 2 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 74.5%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment ten: take by weighing butanic acid 0.1mol respectively, ethanol 0.1mol, ionic liquid alpha-pyrrolidone hydrosulfate 0.02mol; Ionic liquid, ethanol, butanic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 80 ℃, reacted 2 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 79.7%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment 11: take by weighing butanic acid 0.1mol respectively, propyl carbinol 0.1mol, ionic liquid alpha-pyrrolidone a tetrafluoro borate 0.2mol; Ionic liquid, propyl carbinol, butanic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively magnetic agitation, and heating reflux reaction 1 hour; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 75.8%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment 12: take by weighing butanic acid 0.1mol respectively, the about 0.1mol of hexalin, ionic liquid alpha-pyrrolidone dihydrogen phosphate 0.04mol; Ionic liquid, hexalin, butanic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 120 ℃, reacted 2 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 53.2%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment 13: take by weighing positive enanthic acid 0.1mol respectively, methyl alcohol 0.1mol, ionic liquid alpha-pyrrolidone tosilate 0.02mol; Ionic liquid, methyl alcohol, positive enanthic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 70 ℃ of stream temperature, reacted 4 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 60.9%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment 14: take by weighing stearic acid (octadecanoic acid) 0.1mol respectively, ethanol 0.1mol, ionic liquid alpha-pyrrolidone hydrosulfate 0.1mol; Ionic liquid, ethanol, stearic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 90 ℃, reacted 8 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 42.7%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment 15: take by weighing vinylformic acid 0.1mol respectively, propyl carbinol 0.1mol, ionic liquid alpha-pyrrolidone trifluoroacetate 0.05mol; Ionic liquid, propyl carbinol, vinylformic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 100 ℃, reacted 2 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 82.5%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment 16: take by weighing oleic acid (Octadec-9-enoic Acid) 0.1mol respectively, propyl carbinol 0.1mol, ionic liquid alpha-pyrrolidone fluoroform sulphonate 0.05mol; Ionic liquid, propyl carbinol, oleic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 100 ℃, reacted 2 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 61.8%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment 17: take by weighing oxalic acid 0.1mol respectively, ethanol 0.1mol, ionic liquid α-adjoin pyrrolidone hydriodate 0.1mol; Ionic liquid, ethanol, oxalic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 80 ℃, reacted 4 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 71.3%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment 18: take by weighing Succinic Acid (succsinic acid) 11.8g (0.1mol) respectively, the about 9.260g of ethanol (0.1mol), ionic liquid alpha-pyrrolidone nitrate 0.1mol; Ionic liquid, ethanol, Succinic Acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 80 ℃, reacted 2 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 72.6%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment 19: take by weighing lactic acid (alpha-hydroxypropionic acid) 0.1mol respectively, propyl carbinol 0.1mol, ionic liquid alpha-pyrrolidone a tetrafluoro borate 0.05mol; Ionic liquid, propyl carbinol, lactic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 100 ℃, reacted 2 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 67.5%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment 20: take by weighing phenylformic acid (M-nitro benzoic acid) 0.1mol respectively, ethanol 0.1mol, ionic liquid alpha-pyrrolidone hydrosulfate 0.1mol; Ionic liquid, ethanol, phenylformic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 80 ℃, reacted 4 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 71.8%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment 21: take by weighing salicylic acid 0.1mol respectively, propyl carbinol 0.1mol, ionic liquid alpha-pyrrolidone tosilate 0.05mol; Ionic liquid, propyl carbinol, salicylic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 110 ℃, reacted 8 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 64.6%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
Embodiment 22: take by weighing adjacent bromobenzene formic acid 0.1mol respectively, propyl carbinol 0.1mol, ionic liquid alpha-pyrrolidone trifluoroacetate pyrrolidone hydrosulfate 0.05mol; Ionic liquid, propyl carbinol, adjacent bromobenzene formic acid are added in the round-bottomed flask that has agitator, thermometer, reflux condensing tube successively, magnetic agitation, and under 110 ℃, reacted 8 hours; Standing demix pipettes the upper strata esterification products, and transformation efficiency is 53.4%, selectivity 100%; Ionic liquid is reused after vacuum hydro-extraction.
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