CN103880677A - Method for catalyzed synthesis of n-butyl salicylate and tributyl citrate by di-sec-butylamine acidic ionic liquids - Google Patents
Method for catalyzed synthesis of n-butyl salicylate and tributyl citrate by di-sec-butylamine acidic ionic liquids Download PDFInfo
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- CN103880677A CN103880677A CN201410085355.5A CN201410085355A CN103880677A CN 103880677 A CN103880677 A CN 103880677A CN 201410085355 A CN201410085355 A CN 201410085355A CN 103880677 A CN103880677 A CN 103880677A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/04—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with only hydrogen atoms, halogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract
The technical scheme adopted by the invention is as follows: the invention discloses a method for catalyzed synthesis of n-butyl salicylate and tributyl citrate by di-sec-butylamine acidic ionic liquids, and a structural formula of the ionic liquids is as shown in the specification, wherein Y is hydrogen sulfate radical or p-toluenesulfonic acid radical. The invention develops novel varieties of acidic ion liquids, wherein the novel acidic ion liquids are dual-core high-piperidine structures which are very stable; thermal decomposition points of two ionic liquids according to a thermogravimetric analysis test are over 340 DEG C; the stability of the novel two ionic liquids is higher than that of most of ionic liquids; the two ionic liquids have stronger acidity, and the PH values are stronger than that of sulfuric acid under the same concentration. According to the invention, two ionic liquids are developed and utilized as acidic catalysts for respectively synthesizing n-butyl salicylate and tributyl citrate in a catalytic manner, so that the conversion rate of about 96% can be obtained, and ionic liquids can be recycled; compared with the normal method, the conversation rate of the n-butyl salicylate in the method disclosed by the invention is greatly improved.
Description
Technical field
The invention belongs to ionic liquid Application Areas, relate in particular to a kind of two secondary amine salt acidic ion liquid for esterification.
Background technology
Butyl salicylate is the flavouring agent that China's regulation is used, and is a kind of broad-spectrum Organic Chemicals, has fragrant, is widely used at present the field such as daily-use chemical industry and foodstuff additive.
The non-toxic plasticizer of tributyl citrate (TBC) Shi Huo FDA Food and Drug Administration (FDA) approval, there is the advantages such as consistency is good, plasticizing efficiency is high, nontoxic, volatility is little, and in resin, do not grow mould, have mould resistance, purposes is very extensive.
The method of the tradition positive butyl ester of salicylate and TBC is mainly sulphuric acid catalysis esterification process.But this technique exists that side reaction is many, product color is dark, aftertreatment technology is complicated, equipment corrosion is serious and the drawback such as spent acid environmental pollution.At present, the research of exploitation novel process of the alternative vitriol oil take hydrosulfate, hydrochloride, organic acid, solid super-strong acid, heteropolyacid etc. as catalyzer is very active, and the maximum output of butyl salicylate can reach 82%, selectivity 80%, the maximum output of TBC can reach 99%, selectivity 99%.Although these catalyzer have overcome the defect that traditional bronsted acid catalyst exists to a certain extent, they with degree have that relative reactivity is low, the easily defect such as the low and strength of acid skewness of carbon distribution, acidic site density of surface, thereby limited their application.
Ionic liquid at room temperature has the properties such as stability is high, reusable adjustable sex change energy, in a large number for catalytic esterification.At present, ionic liquid is just towards functionalization future development, become programmable green functional system, acid functionalization ionic liquid has been inherited the general advantage of ionic liquid, and can change and modified ion liquid yin, yang ion according to the needs of reaction, make it have acid adjustable sex change flexibly, and acidic site density is high, strength of acid is evenly distributed, acid being difficult for runs off, this is conducive to recycling of ionic liquid more, becomes the focus of research.In recent years, being most widely used with glyoxaline ion liquid.But prices are rather stiff for imidazoles, there is no at present large-scale commercial production, apparent availability is very little, therefore, finds and research relative low price have the more precursor that is suitable as ionic liquid positive ion of unique physical chemical property and have important scientific research and practical significance.The preparation of non-imidazoles double-core acidic ion liquid and for catalyzing and synthesizing butyl salicylate and tributyl citrate so far there are no report.
Summary of the invention
It is expensive that the present invention overcomes in prior art imidazoles double-core acidic ion liquid, is difficult to be applicable to large-scale commercial production
Deficiency, a kind of two secondary amine salt acidic ion liquids and its preparation method and application are provided.
The technical solution adopted in the present invention is: a kind of two secondary amine salt acidic ion liquids, described ionic liquid general structure
For:
wherein Y
-for bisulfate ion or tosic acid root.
The preparation method of above-mentioned two secondary amine salt acidic ion liquids, step is as follows:
(1) first Isosorbide-5-Nitrae-dibromobutane is joined in acetonitrile solvent, in 0 ℃ of ice-water bath, high piperidines is slowly added drop-wise to the solution that is dissolved with Isosorbide-5-Nitrae-dibromobutane in vigorous stirring simultaneously, the lower 70 ℃ of water-baths of the nitrogen protection 2～24h that refluxes; Filter gained solid, with 3～5 filtrations again of washing with acetone, then 1.33Pa, 50～70 ℃ of dry 5～8h obtain oyster white needle-like crystal and are two secondary amine salt;
(2) to the methylene dichloride adding in two secondary amine salt, it is fully dissolved, in 0 ℃ of ice-water bath, slowly drip wherein HY acid, logical nitrogen, 20～40 ℃ of water-baths backflow 5～48h, revolve to steam and remove methylene dichloride, again revolve steaming, then 1.33Pa 2～3 times by washed with dichloromethane, 50～70 ℃ of dry 6～8h obtain orange thick pair of secondary amine salt acidic ion liquid, and described HY acid is sulfuric acid or tosic acid.
Further, the Isosorbide-5-Nitrae-dibromobutane described in step (1), high piperidines mol ratio are 1:2; Two secondary amine salt described in step (2) and HY acid mol ratio are 1:2.
Above-mentioned two secondary amine salt acidic ion liquids can be used as catalyzer and prepare butyl salicylate, and step is as follows:
Whitfield's ointment, propyl carbinol feed intake than for 1:1.5～2 by amount of substance, reaction process Whitfield's ointment, propyl carbinol react by 1:1, excessive propyl carbinol is made band aqua, low-temperature heat is stirred, in the time that dissolving completely, Whitfield's ointment adds acidic ion liquid, the add-on of two secondary amine salt ionic liquids is sour quality 2%～6%, and temperature of reaction is 110～130 ℃, and return time is 2～5h.Reaction equation is as follows:
Above-mentioned two secondary amine salt acidic ion liquids can be used as catalyzer and prepare tributyl citrate, and step is as follows:
Citric acid, propyl carbinol feed intake than for 1:4～6 by amount of substance, reaction process citric acid, propyl carbinol react by 1:3, excessive propyl carbinol is made band aqua, low-temperature heat is stirred, in the time that dissolving completely, citric acid adds ionic liquid, the add-on of two secondary amine salt ionic liquids is sour quality 3%～5%, and temperature of reaction is 110～140 ℃, and 2～4h refluxes.Reaction equation is as follows:
The present invention compared with prior art tool has the following advantages:
(1) the present invention's preparation for catalysis butyl salicylate by two kinds of ionic liquids, very few for the report of this reaction about ionic liquid in recent years, it is all very poor for this catalytic reaction effect that many scholars attempt multiple conventional ion liquid, turns to afterwards the research of heteropolyacid, solid super strong acid as catalyst also only to obtain the transformation efficiency of 80% left and right.The catalysis of two kinds of ionic liquids of the present invention all can obtain the transformation efficiency of 96% left and right, and ionic liquid can reuse.
(2) the present invention's preparation for catalysis tributyl citrate by two kinds of ionic liquids, has avoided the disadvantageous effects of catalyzer to tributyl citrate color such as conventional ion liquid and sulfuric acid, and the tributyl citrate color and luster obtaining is better, and purity is high.
(3) in the present invention the building-up reactions of two kinds of esters finish the extraction of rear ionic liquid water and with product layering, then revolve to steam and dewater, it is convenient to reclaim, loss is few, has solved traditional high piperidines ionic liquid and has reclaimed trouble, loses a serious difficult problem.
(4) building-up process of two kinds of important esters of the present invention is made catalyzer with above-mentioned ionic liquid and has greatly been shortened the reaction times, catalyst levels is few and can be repeatedly used and still have higher transformation efficiency and selectivity, two esterifications are not all introduced new impurity purifying products conveniently with excessive reactant propyl carbinol with aqua, color and luster is good, and purity is high.
(5) the present invention has developed the new variety of acidic ion liquid, and this ionic liquid positively charged ion is the high piperidine structure of double-core, very stable, and through the thermolysis point of two kinds of ionic liquids of thermogravimetric analysis test, all more than 340 ℃, stability is higher than most ionic liquids; Two kinds of ionic liquids all have stronger acidity, and its pH value is all better than the pH value of sulfuric acid under same isoconcentration.
(6) to prepare precursor salt-bis-secondary amine salt of ionic liquid be a kind of weakly alkaline secondary amine salt in the present invention, it is the good carrier of one of carried heteropoly acid, the present invention also provides the carrier of novelty in exploitation ionic liquid new variety for the load of heteropolyacid, this is the feature that traditional imidazoles, high piperidines ionic liquid do not possess.
Accompanying drawing explanation
Fig. 1 is the repeat performance of double-core ionic liquid in embodiment 6;
Fig. 2 is the repeat performance of double-core ionic liquid in embodiment 10.
Embodiment
Embodiment 1
When HY acid is sulfuric acid.
By 1,4-dibromobutane 7.10ml joins in the 250ml there-necked flask with mechanical stirring device, adds 80ml acetonitrile to make solvent, in 0 ℃ of ice-water bath, high piperidinyl-1 5.06ml is added drop-wise to 1, while vigorous stirring in 4-dibromobutane solution, the lower 70 ℃ of water-bath backflow 24h of nitrogen protection; Filter gained solid, with 3 filtrations again of washing with acetone, then 1.33Pa, 70 ℃ of dry 5h obtain oyster white needle-like crystal and are two secondary amine salt.Then getting two secondary amine salt 3.9g joins in 250ml there-necked flask, add 80ml methylene dichloride that it is fully dissolved, then by amount of substance than slow 97% the sulfuric acid 1ml that adds of 1:2, logical nitrogen, 40 ℃ of water-bath backflow 48h, revolve to steam and remove methylene dichloride, again revolve steaming by anhydrous diethyl ether washed twice, then 1.33Pa, 70 ℃ of dry 6h obtain orange thick pair of secondary amine salt acidic ion liquid two-(the high piperidines of 1-) butylidene hydrosulfate.Its 0.05molL
-1the pH value of the aqueous solution is 1.24, lower than the pH value (1.30) of the aqueous sulfuric acid of same concentration, has strongly-acid.Warp
1hNMR,
13after CNMR and infrared analysis, show that this ionic liquid structure meets two-(the high piperidines of 1-) butylidene hydrosulfate structure.The thermolysis point of testing this ionic liquid through thermogravimetric analysis is 363 ℃, shows that this ionic liquid has higher stability.
When HY acid be to and Phenylsulfonic acid.
Get 1,4-dibromobutane 7.10ml joins in the 250ml there-necked flask with mechanical stirring device, adds 80ml acetonitrile to make solvent, in 0 ℃ of ice-water bath, high piperidinyl-1 5.06ml is added drop-wise to 1, while vigorous stirring in 4-dibromobutane solution, the lower 70 ℃ of water-bath backflow 2h of nitrogen protection; Filter gained solid, with 5 filtrations again of washing with acetone, then 1.33Pa, 50 ℃ of dry 8h obtain oyster white needle-like crystal and are two secondary amine salt.Then getting two secondary amine salt 3.9g joins in 250ml there-necked flask, add 80ml methylene dichloride that it is fully dissolved, then by amount of substance than the slow tosic acid that adds of 1:2, logical nitrogen, 20 ℃ of water-bath backflow 5h, revolve to steam and remove methylene dichloride, again revolve steaming by anhydrous diethyl ether washed twice, then 1.33Pa, 50 ℃ of dry 8h obtain orange thick pair of secondary amine salt acidic ion liquid two-(the high piperidines of 1-) butylidene tosilate.Its 0.05molL
-1the pH value of the aqueous solution is 1.29, lower than the pH value (1.30) of the aqueous sulfuric acid of same concentration, has strongly-acid.Warp
1hNMR,
13after CNMR and infrared analysis, show that this ionic liquid structure meets two-(the high piperidines of 1-) butylidene tosic acid structure.The thermolysis point of testing this ionic liquid through thermogravimetric analysis is 347 ℃, shows that this ionic liquid has higher stability.
Embodiment 3
Make catalyzer with the ionic liquid in embodiment 1
Water trap is being housed, in the 250ml there-necked flask of electric mixer and thermometer, Whitfield's ointment, propyl carbinol 1:1 reaction in molar ratio, 1:1.5 feeds intake in molar ratio, excessive propyl carbinol is made band aqua, weigh Whitfield's ointment 13.83g, measure propyl carbinol 13.73ml, first by load weighted Whitfield's ointment, propyl carbinol joins in there-necked flask, low-temperature heat is stirred, in the time that Whitfield's ointment dissolves completely, add 0.2766g ionic liquid two-(the high piperidines of 1-) butylidene hydrosulfate is as catalyzer, add-on is 2% of Whitfield's ointment quality, then be warming up to 110 ℃, constant temperature backflow 4h, reaction process and time-division water.Salicylic transformation efficiency can reach 94.38%, and the selectivity of butyl salicylate is 95.14%.
Make catalyzer with the ionic liquid in embodiment 1
Water trap is being housed, in the 250ml there-necked flask of electric mixer and thermometer, Whitfield's ointment, propyl carbinol 1:1 reaction in molar ratio, 1:1.7 feeds intake in molar ratio, excessive propyl carbinol is made band aqua, weigh Whitfield's ointment 13.83g, measure propyl carbinol 15.55ml, first by load weighted Whitfield's ointment, propyl carbinol joins in there-necked flask, low-temperature heat is stirred, in the time that Whitfield's ointment dissolves completely, add the upper ionic liquid of 0.4149g two-(the high piperidines of 1-) butylidene hydrosulfate is as catalyzer, add-on is 3% of Whitfield's ointment quality, then be warming up to 120 ℃, constant temperature backflow 3.5h, reaction process and time-division water.Salicylic transformation efficiency can reach 95.77%, and the selectivity of butyl salicylate is 96.23%.
Embodiment 5
Make catalyzer with the ionic liquid in embodiment 2
Water trap is being housed, in the 250ml there-necked flask of electric mixer and thermometer, Whitfield's ointment, propyl carbinol 1:1 reaction in molar ratio, 1:1.9 feeds intake in molar ratio, excessive propyl carbinol is made band aqua, weigh Whitfield's ointment 13.83g, measure propyl carbinol 17.41ml, first by load weighted Whitfield's ointment, propyl carbinol joins in there-necked flask, low-temperature heat is stirred, in the time that Whitfield's ointment dissolves completely, add 0.5532g ionic liquid two-(the high piperidines of 1-) butylidene tosilate is as catalyzer, add-on is 4% of Whitfield's ointment quality, then be warming up to 130 ℃, constant temperature backflow 2h, reaction process and time-division water.Salicylic transformation efficiency can reach 96.78%, and the selectivity of butyl salicylate is 96.97%.
Make catalyzer with the ionic liquid in embodiment 1
Water trap is being housed, in the 250ml there-necked flask of electric mixer and thermometer, Whitfield's ointment, propyl carbinol 1:1 reaction in molar ratio, 1:2 feeds intake in molar ratio, excessive propyl carbinol is made band aqua, weigh Whitfield's ointment 13.83g, measure propyl carbinol 18.31ml, first by load weighted Whitfield's ointment, propyl carbinol joins in there-necked flask, low-temperature heat is stirred, in the time that Whitfield's ointment dissolves completely, add 0.8298g ionic liquid two-(the high piperidines of 1-) butylidene hydrosulfate is as catalyzer, add-on is 6% of Whitfield's ointment quality, then be warming up to 130 ℃, constant temperature backflow 5h, reaction process and time-division water.Salicylic transformation efficiency can reach 97%, and the selectivity of butyl salicylate is 96.81%.After finishing, reaction need to add a small amount of water that two-(the high piperidines of 1-) butylidene hydrosulfate is extracted, this ionic liquid is after 12 times are reused, Whitfield's ointment transformation efficiency, all in 96% left and right (see figure 1), shows that two-(the high piperidines of 1-) butylidene hydrosulfate has good repeat performance.
Embodiment 7
Make catalyzer with the ionic liquid in embodiment 1.
Water trap is being housed, in the 250ml there-necked flask of electric mixer and thermometer, citric acid, propyl carbinol 1:3 reaction in molar ratio, 1:4 feeds intake in molar ratio, excessive propyl carbinol is made band aqua, weigh citric acid 10.51g, measure propyl carbinol 18.31ml, first load weighted citric acid and propyl carbinol are added in there-necked flask, low-temperature heat is stirred, in the time that citric acid dissolves completely, add 0.3153g ionic liquid two-(the high piperidines of 1-) butylidene hydrosulfate is as catalyzer, add-on is 3% of citric acid quality, then be warming up to 110 ℃, constant temperature backflow 2h, reaction process and time-division water.The transformation efficiency of citric acid can reach 97.18%, tributyl citrate selectivity be 98.23%.
Make catalyzer with the ionic liquid in embodiment 1.
In the 250ml there-necked flask that water trap, electric mixer and thermometer are housed, the 1:3 reaction in molar ratio of citric acid, propyl carbinol, 1:5 feeds intake in molar ratio, excessive propyl carbinol is made band aqua, weigh citric acid 10.51g, measuring propyl carbinol 22.88ml adds in flask, low-temperature heat is stirred, in the time that citric acid dissolves completely, add 0.4204g ionic liquid two-(the high piperidines of 1-) butylidene hydrosulfate is as catalyzer, add-on is 4% of citric acid quality, then be warming up to 120 ℃, constant temperature backflow 3h, reaction process and time-division water.The transformation efficiency of citric acid can reach 98.91%, tributyl citrate selectivity be 99.53%.
Embodiment 9
Make catalyzer with the ionic liquid in embodiment 2.
In the 250ml there-necked flask that water trap, electric mixer and thermometer are housed, the 1:3 reaction in molar ratio of citric acid, propyl carbinol, 1:6 feeds intake in molar ratio, excessive propyl carbinol is made band aqua, weigh citric acid 10.51g, measuring propyl carbinol 27.46ml adds in flask, low-temperature heat is stirred, in the time that citric acid dissolves completely, add 0.5255g ionic liquid two-(the high piperidines of 1-) butylidene tosilate is as catalyzer, add-on is 5% of citric acid quality, then be warming up to 130 ℃, constant temperature backflow 4h, reaction process and time-division water.The transformation efficiency of citric acid can reach 98.17%, tributyl citrate selectivity be 98.55%.
Make catalyzer with the ionic liquid in embodiment 2.
In the 250ml there-necked flask that water trap, electric mixer and thermometer are housed, the 1:3 reaction in molar ratio of citric acid, propyl carbinol, 1:6 feeds intake in molar ratio, excessive propyl carbinol is made band aqua, weigh citric acid 10.51g, measuring propyl carbinol 22.88ml adds in flask, low-temperature heat is stirred, in the time that citric acid dissolves completely, add 0.5255g ionic liquid two-(the high piperidines of 1-) butylidene tosilate is as catalyzer, add-on is 5% of citric acid quality, then be warming up to 140 ℃, constant temperature backflow 5h, reaction process and time-division water.The transformation efficiency of citric acid can reach 98.26%, tributyl citrate selectivity be 98.43%.After finishing, reaction need to add a small amount of water that two-(the high piperidines of 1-) butylidene tosilate is extracted, this ionic liquid is after 15 times are reused, catalytic activity, without obviously reducing (see figure 2), shows that two-(the high piperidines of 1-) butylidene tosilate has good repeat performance.
Claims (3)
1. two positive butyl esters of secondary amine salt presence of acidic ionic liquid catalyst salicylate and a tributyl citrate, is characterized in that, described ionic-liquid catalyst general structure is:
wherein Y
-for bisulfate ion or tosic acid root.
2. the according to claim 1 pair of positive butyl ester of secondary amine salt presence of acidic ionic liquid catalyst salicylate and tributyl citrate, is characterized in that, described two secondary amine salt acidic ion liquids are prepared butyl salicylate as catalyzer, and step is as follows:
Whitfield's ointment, propyl carbinol feed intake than for 1:1.5～2 by amount of substance, at 50～80 ℃, be uniformly mixed, in the time that dissolving completely, Whitfield's ointment adds acidic ion liquid, the add-on of two secondary amine salt ionic liquids is sour quality 2%～6%, temperature of reaction is 110～130 ℃, and return time is 2～5h.
3. the according to claim 1 pair of positive butyl ester of secondary amine salt presence of acidic ionic liquid catalyst salicylate and tributyl citrate, is characterized in that, described two secondary amine salt acidic ion liquids are prepared tributyl citrate as catalyzer, and step is as follows:
Citric acid, propyl carbinol feed intake than for 1:4～6 by amount of substance, at 50～80 ℃, be uniformly mixed, add ionic liquid in the time that citric acid dissolves completely, the add-on of two secondary amine salt ionic liquids is sour quality 3%～5%, temperature of reaction is 110～140 ℃, and 2～4h refluxes.
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| CN106641728A (en) * | 2016-12-28 | 2017-05-10 | 中国科学院广州能源研究所 | Compound hydrate inhibitor based on piperidine ionic liquid |
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| CN101049573A (en) * | 2007-05-15 | 2007-10-10 | 武汉大学 | Ion liquid catalyst of esterification reaction, preparation method and usage |
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| CN101049573A (en) * | 2007-05-15 | 2007-10-10 | 武汉大学 | Ion liquid catalyst of esterification reaction, preparation method and usage |
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| CN106641728A (en) * | 2016-12-28 | 2017-05-10 | 中国科学院广州能源研究所 | Compound hydrate inhibitor based on piperidine ionic liquid |
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