CN1243713C - Method for synthesizing ethyl ester linoleic acid by catalyzing S 04/T102 solid super strong acid - Google Patents
Method for synthesizing ethyl ester linoleic acid by catalyzing S 04/T102 solid super strong acid Download PDFInfo
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- CN1243713C CN1243713C CN 200310107645 CN200310107645A CN1243713C CN 1243713 C CN1243713 C CN 1243713C CN 200310107645 CN200310107645 CN 200310107645 CN 200310107645 A CN200310107645 A CN 200310107645A CN 1243713 C CN1243713 C CN 1243713C
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- ethyl linoleate
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- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 title claims abstract description 35
- 239000007787 solid Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000002253 acid Substances 0.000 title abstract description 15
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 title abstract 4
- 235000020778 linoleic acid Nutrition 0.000 title abstract 4
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- 125000004494 ethyl ester group Chemical group 0.000 title 1
- FMMOOAYVCKXGMF-MURFETPASA-N ethyl linoleate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC FMMOOAYVCKXGMF-MURFETPASA-N 0.000 claims abstract description 35
- 229940031016 ethyl linoleate Drugs 0.000 claims abstract description 34
- FMMOOAYVCKXGMF-UHFFFAOYSA-N linoleic acid ethyl ester Natural products CCCCCC=CCC=CCCCCCCCC(=O)OCC FMMOOAYVCKXGMF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 229960004232 linoleic acid Drugs 0.000 claims description 31
- 239000003930 superacid Substances 0.000 claims description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005886 esterification reaction Methods 0.000 abstract description 30
- 230000032050 esterification Effects 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 abstract 1
- 239000003377 acid catalyst Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- -1 stirring heating Chemical compound 0.000 description 7
- 238000004448 titration Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 150000002632 lipids Chemical class 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 206010003210 Arteriosclerosis Diseases 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- 206010008132 Cerebral thrombosis Diseases 0.000 description 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 201000001429 Intracranial Thrombosis Diseases 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 208000011775 arteriosclerosis disease Diseases 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 1
- 229940093471 ethyl oleate Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003053 immunization Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000009637 wintergreen oil Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a method for synthesizing ethyl linoleate by catalyzing SO4<2->/TiO2 solid super strong acid, and the present invention relates to an ethyl linoleate synthesizing method which uses linoleic acid and anhydrous alcohol as raw materials and is catalyzed by SO4<2->/TIO2 solid super strong acid. The existing SO4<2->/TIO2 solid super strong acid and esterification process used for esterifying high aliphatic acids, such as linoleic acid, etc. are not reported by documents. According to the method, anhydrous alcohol and linoleic acid are respectively added into a reactor according to a molar ratio of 1 to 10:1, an SO4<2->/TIO2 solid super strong acid catalyst which takes 0.5 to 6% of the weight of the linoleic acid is added into the reactor, and the mixture is stirred and heated under the protection of nitrogen to react for 2 to 10 hours at return temperature. Product is decompressed and refined at-98.6 to-99.4 kPa, 158 to 172 DEG C of distillation cut is collected, and then ethyl linoleate is obtained. The method of the present invention has the advantages of high reaction activity, simple operation, easy product separation, repeated catalyst use and little environmental pollution.
Description
Technical field: the present invention relates to be a kind of with linolic acid and dehydrated alcohol be raw material, with SO
4 2-/ TiO
2The method of the synthetic ethyl linoleate of solid superacid as catalyst.
Background technology: ethyl linoleate (9,12-octadecadienoic acid ethyl ester) has the effects such as immunizing power of anticancer, atherosclerosis, regulation and control metabolism, enhancing body, particularly as preventing and treating cerebral thrombosis, the lipid level capsule and pill of diseases such as arteriosclerosis, the main medicine material of Maitong capsule and pill, have excellent curative effect, have broad application prospects in fields such as medicine, healthcare products, food and feed additives.Ethyl linoleate is normally made by linolic acid and dehydrated alcohol esterification under sulphuric acid catalysis, because linolic acid contains unsaturated link(age), easily dewater in the esterification reaction process, side reaction such as oxidation, charing, two keys among the saboteur, influence quality product and curative effect of medication, and also there is the aftertreatment technology complexity in sulfuric acid catalysis, to problem such as production unit seriously corroded, acid waste water quantity discharged be big, its use is subjected to more restrictions.SO
4 2-/ TiO
2Solid super acid catalyst has the acidity stronger than 100% sulfuric acid, because of have the reactive behavior height, high temperature resistant, easy to prepare, reusable, reduce environmental pollution, simplify advantages such as product separation technology, solid super-strong acid shows good catalytic activity to acid catalyzed reactions such as esterifications, has obtained people's extensive concern.Hino M and Arata K. etc. (Appl.Catal, 1985,18:401～404) have made SO with the titanium salt hydrolysis method
4 2-/ TiO
2Super acids, be respectively applied for the preparation of dinoctyl phthalate, ethyl propenoate and wintergreen oil, esterification for different carboxylic acids and alcohol, catalytic effect shows bigger difference: be used for ethyl propenoateization, the esterification yield that reacts acid in 4 hours is 88%, 8 hours esterification yield is 97%, and is used for the synthetic of the bigger dimixo-octyl phthalate of molecule, and the esterification yield of phthalic acid has only 78% after 4 hours.Appoint (petrochemical complex Journal of Chinese Universities, 2002,15 (4): 34～36) investigated acetic acid, butanic acid and butanols, amylalcohol respectively such as found a state at SO
4 2-/ TiO
2The result of esterification under the solid super acid catalyst effect, butanic acid and Pentyl alcohol reaction, the esterification yield of butanic acid only is 76.13%.Experimental result shows that along with the carbonatoms increase of lipid acid, the esterification yield of lipid acid descends.This is because the sterically hindered increase of lipid acid and Fatty Alcohol(C12-C14 and C12-C18) molecule has reduced the rate of migration of surfactivity intermediate on catalyst surface, thereby reduces the esterification yield of reactivity worth and lipid acid.At present, solid super acid catalyst and the esterification technique that is used for higher aliphatic acid esterifications such as linolic acid do not seen bibliographical information.
Summary of the invention: the object of the present invention is to provide a kind of SO of using
4 2-/ TiO
2Solid super-strong acid successively joins dehydrated alcohol and linolic acid in reactor in molar ratio as the method for the synthetic ethyl linoleate of catalyzer at 1～10: 1, adds the SO that accounts for linolic acid quality 0.5～6% again
4 2-/ TiO
2Solid super acid catalyst, stirring heating under nitrogen protection was reacted 6～10 hours down in reflux temperature; Product-98.6～-99.4kPa under rectification under vacuum, collect 158～172 ℃ cut, promptly obtain the ethyl linoleate product.The representative of the ethyl linoleate that obtains with present method consists of: soft-ethyl ester accounts for 7.5% of total mass, and ethyl oleate accounts for 23.5%, and ethyl linoleate accounts for 59.7%, and linolenic acid accounts for 4.8%.The leading indicator of product ethyl linoleate is: outward appearance: faint yellow oily clarified liq; Acid number (mgKOH/g): be not more than 1; Saponification value (mgKOH/g): 175～185; Iodine number (g/100g): be not less than 136; Relative density: 0.875～0.886; Refractive index (30 ℃): 1.455～1.460.Method of the present invention has reactive behavior height, easy and simple to handle, product separation is easy, catalyzer is reusable and environmental pollution is little advantage.
Embodiment one: the synthetic method of present embodiment is: dehydrated alcohol and linolic acid are successively joined in reactor in molar ratio at 1～10: 1, add the SO that accounts for linolic acid quality 0.5～6% again
4 2-/ TiO
2Solid super acid catalyst, stirring heating under nitrogen protection was reacted 2～10 hours down in reflux temperature; Product-98.6～-99.4kPa under rectification under vacuum, collect 158～172 ℃ cut, promptly obtain the ethyl linoleate product.The Orthogonal experiment results of linolic acid and dehydrated alcohol esterification shows that the factor that influences esterification yield is followed successively by catalyst levels, reaction times and acid-alcohol ratio.In reaction process, increase catalyst consumption within the specific limits and can improve linoleic esterification yield effectively, but catalyst levels increases at 3% o'clock of the linolic acid quality, increases its consumption again, the amplitude that esterification yield improves reduces.Increase acid-alcohol ratio and help improving esterification yield, when acid-alcohol ratio is increased to 4: 1 when above, continues the increase acid-alcohol ratio influence of esterification yield is reduced.In initial reaction stage, esterification reaction rate is very fast, and afterreaction speed slowed down in 6 hours, and prolonging the reaction times esterification yield after 8 hours does not again have obvious raising.Suitable esterification condition is that dehydrated alcohol and linoleic mol ratio are 2～6: 1, the SO of adding
4 2-/ TiO
2The solid super acid catalyst consumption accounts for 1～5% of linolic acid quality, and stirring heating under nitrogen protection was reacted 6～10 hours down in reflux temperature then; Product-98.6～-99.4kPa under rectification under vacuum, collect 158～172 ℃ cut, promptly obtain purified ethyl linoleate product.
Embodiment two: 27g linolic acid and 22.5ml dehydrated alcohol (ethanol and linolic acid mol ratio are 4: 1) are joined 250ml be equipped with in the four-necked bottle of water trap, add 0.81gSO then
4 2-/ TiO
2Solid super acid catalyst (catalyzer account for linolic acid quality 3%), stirring heating, nitrogen protection kept 8 hours under reflux temperature, and cooling, sampling are carried out titration with the 0.1mol/LKOH aqueous solution, and calculating linoleic esterification yield is 94.1%.Isolate catalyzer, 168～172 ℃ cut is collected in the rectification under vacuum under-98.6kPa of ethyl linoleate crude product, obtains purified ethyl linoleate product, and yield is more than 75%.The product analysis result is shown that the ethyl linoleate spectrogram in the mass spectrum of product main component and the NIST standard map is in full accord with gas-chromatography and GC-MS.The multiparity product detect mechanism's check, and the content of ethyl linoleate is 59.7%, and quality product meets the corresponding drug standard that National Drug Administration works out.
Embodiment three: 27g linolic acid and 22.5ml dehydrated alcohol (ethanol and linolic acid mol ratio are 4: 1) are joined 250ml be equipped with in the four-necked bottle of water trap, add 0.27gSO then
4 2-/ TiO
2Solid super acid catalyst (catalyzer account for linolic acid quality 1%), stirring heating, nitrogen protection kept 8 hours under reflux temperature, and cooling, sampling are carried out titration with the 0.1mol/LKOH aqueous solution, and calculating linoleic esterification yield is 85.0%.Isolate catalyzer, 158～162 ℃ cut is collected in the rectification under vacuum under-99.4kPa of ethyl linoleate crude product, obtains purified ethyl linoleate product.
Embodiment four: 27g linolic acid and 22.5ml dehydrated alcohol (ethanol and linolic acid mol ratio are 4: 1) are joined 250ml be equipped with in the four-necked bottle of water trap, add 1.35gSO then
4 2-/ TiO
2Solid super acid catalyst (catalyzer account for linolic acid quality 5%), stirring heating, nitrogen protection kept 8 hours under reflux temperature, and cooling, sampling are carried out titration with the 0.1mol/LKOH aqueous solution, and calculating linoleic esterification yield is 94.3%.Isolate catalyzer, 168～172 ℃ cut is collected in the rectification under vacuum under-98.6kPa of ethyl linoleate crude product, obtains purified ethyl linoleate product.
Embodiment five: with mol ratio is that 2: 1 dehydrated alcohol and linolic acid join 250ml and be equipped with in the four-necked bottle of water trap, adds the SO that accounts for linolic acid quality 3% then
4 2-/ TiO
2Solid super acid catalyst, stirring heating, nitrogen protection kept 8 hours under reflux temperature, and cooling, sampling are carried out titration with the 0.1mol/LKOH aqueous solution, and calculating linoleic esterification yield is 91.2%.Isolate catalyzer, 168～172 ℃ cut is collected in the rectification under vacuum under-98.6kPa of ethyl linoleate crude product, obtains purified ethyl linoleate product.
Embodiment six: with mol ratio is that 6: 1 dehydrated alcohol and linolic acid join 250ml and be equipped with in the four-necked bottle of water trap, adds the SO that accounts for linolic acid quality 3% then
4 2-/ TiO
2Solid super acid catalyst, stirring heating, nitrogen protection kept 8 hours under reflux temperature, and cooling, sampling are carried out titration with the 0.1mol/LKOH aqueous solution, and calculating linoleic esterification yield is 95.6%.Isolate catalyzer, 168～172 ℃ cut is collected in the rectification under vacuum under-98.6kPa of ethyl linoleate crude product, obtains purified ethyl linoleate product.
Embodiment seven: with mol ratio is that 4: 1 dehydrated alcohol and linolic acid join 250ml and be equipped with in the four-necked bottle of water trap, adds the SO that accounts for linolic acid quality 3% then
4 2-/ TiO
2Solid super acid catalyst, stirring heating, nitrogen protection kept 6 hours under reflux temperature, and cooling, sampling are carried out titration with the 0.1mol/LKOH aqueous solution, and calculating linoleic esterification yield is 71.8%.Isolate catalyzer, 158～162 ℃ cut is collected in the rectification under vacuum under-99.4kPa of ethyl linoleate crude product, obtains purified ethyl linoleate product.
Embodiment eight: with mol ratio is that 6: 1 dehydrated alcohol and linolic acid join 250ml and be equipped with in the four-necked bottle of water trap, adds the SO that accounts for linolic acid quality 3% then
4 2-/ TiO
2Solid super acid catalyst, stirring heating, nitrogen protection kept 2 hours under reflux temperature, and cooling, sampling are carried out titration with the 0.1mol/LKOH aqueous solution, and calculating linoleic esterification yield is 45.1%.Isolate catalyzer, 168～172 ℃ cut is collected in the rectification under vacuum under-98.6kPa of ethyl linoleate crude product, obtains purified ethyl linoleate product.
Claims (3)
1, a kind of SO
4 2-/ TiO
2The method of the synthetic ethyl linoleate of solid superacid as catalyst is characterized in that dehydrated alcohol and linolic acid are successively joined in reactor in molar ratio at 1～10: 1, adds the SO that accounts for linolic acid quality 0.5～6% again
4 2-/ TiO
2Solid super acid catalyst, stirring heating under nitrogen protection was reacted 6～10 hours down in reflux temperature; Product-98.6～-99.4kPa under rectification under vacuum, collect 158～172 ℃ cut, promptly obtain the ethyl linoleate product.
2, SO according to claim 1
4 2-/ TiO
2The method of the synthetic ethyl linoleate of solid superacid as catalyst is characterized in that described dehydrated alcohol and linoleic mol ratio are 2～6: 1.
3, SO according to claim 1
4 2-/ TiO
2The method of the synthetic ethyl linoleate of solid superacid as catalyst is characterized in that SO
4 2-/ TiO
2The ratio that solid super acid catalyst accounts for the linolic acid quality is 1～5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310107645 CN1243713C (en) | 2003-10-28 | 2003-10-28 | Method for synthesizing ethyl ester linoleic acid by catalyzing S 04/T102 solid super strong acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310107645 CN1243713C (en) | 2003-10-28 | 2003-10-28 | Method for synthesizing ethyl ester linoleic acid by catalyzing S 04/T102 solid super strong acid |
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| CN1243713C true CN1243713C (en) | 2006-03-01 |
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| CN101070282B (en) * | 2006-05-09 | 2011-06-15 | 黑龙江大学 | Process for room-temperature ion liquid-catalytic preparation of ethyl linoleate |
| CN101139288B (en) * | 2006-09-07 | 2011-06-15 | 黑龙江大学 | Method for preparating ethyl linoleate by catalysis of composite solid ultra-strong acid |
| CN103785424B (en) * | 2012-11-01 | 2015-06-17 | 中国石油化工股份有限公司 | Solid acid catalyst and preparation method thereof |
| CN105773767B (en) * | 2016-04-20 | 2018-02-13 | 江苏金聚合金材料有限公司 | A kind of method of wood acetylation and coproduction by acetic acid ester |
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