CN1705640A - Ionic liquids containing a sulfonate anion - Google Patents

Ionic liquids containing a sulfonate anion Download PDF

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Publication number
CN1705640A
CN1705640A CNA038194058A CN03819405A CN1705640A CN 1705640 A CN1705640 A CN 1705640A CN A038194058 A CNA038194058 A CN A038194058A CN 03819405 A CN03819405 A CN 03819405A CN 1705640 A CN1705640 A CN 1705640A
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Prior art keywords
composition
charged ion
ester
negatively charged
ionic liquid
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J·H·小戴维斯
R·莫尔顿
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University of South Alabama
Sachem Inc
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University of South Alabama
Sachem Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C07C309/58—Carboxylic acid groups or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/70—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a carbon skeleton substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)
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Abstract

The present invention relates to novel ionic liquids comprising a docusate, docusate variant, or other sulfonate anion. The ionic liquids may be conveniently made via, for example, metathesis. The ionic liquids are often hydrophobic and useful in many hydrocarbon compositions, polymer compositions, and in supercritical carbon dioxide applications. The ionic liquids are capable of hindering static electricity buildup in the hydrocarbon compositions and can therefore minimize flammability and/or explosiveness.

Description

The ionic liquid that comprises azochlorosulfonate acid anion
Related application data
The application requires the right of priority of following provisional application: the U.S. provisional application No.60/404 that on August 16th, 2002 submitted to, the U.S. provisional application No.60/404 that on August 16th, 178 and 2002 submitted to, 202.
Invention field
The present invention relates to comprise ion liquid composition, this ionic liquid comprises the preparation method of many storehouses ester (docusate) negatively charged ion, many storehouses ester variant negatively charged ion or other azochlorosulfonate acid anion and said composition.
Background of invention and general introduction
Ionic liquid is to be the salt of liquid during at ambient temperature or near envrionment temperature.Ionic liquid has many purposes, and this purposes is included in chemical technology and the reaction and substitutes organic solvent, extracting of organic compounds and as the ionogen in equipment such as electrical condenser and the battery from aqueous wash streams.This be because, do not resemble common organic solvent, ionic liquid is nonvolatile and non-flammable.These performances are favourable for following aspect: help to reduce vaporization losses, eliminate the volatility organic volatile and improve safety.
Ion liquid other performance also proves favourable.For example, many ionic liquids have wide temperature range, and they remain liquid and also stable in wide pH scope in this temperature range.This is useful for the high-temperature technology that adopts high request pH.In addition, some ion liquid systems can be used as solvent and catalyzer.For example, [bmim]-Al 2Cl 7[emim]-Al 2Cl 7Can be used as solvent and catalyzer in the Friedel-Crafts reaction, wherein bmim is that 1-butyl-3 Methylimidazole and emim are 1-ethyl-3-Methylimidazoles.
For above-mentioned reasons, need to find to have the new ion liquid compound of advantageous property.Further need and to prepare such compound by simple method with waste material and the impurity that hangs down quantity.
Advantageously, found new ion liquid compound.This compound comprises many storehouses ester or other azochlorosulfonate acid anion and by the simple method preparation, this method can be produced has highly purified ionic liquid.
Detailed Description Of The Invention
" ionic liquid " expression comprises positively charged ion and anionic salt as used herein.Salt (or the hydrate of salt or solvate) is liquid (fusing point, or fusion range is lower than about 100 ℃) during at ambient temperature or near envrionment temperature.Ionic liquid can comprise the salt that two or more are different, as comprises the mixture of two or more different positively charged ions, negatively charged ion or both salt.Ionic liquid of the present invention is hydration or solvation normally.Therefore, think that hydrate and solvate both are in the definition of " ionic liquid ".
" hydrophilic ionic-liquid " expression can partially or completely mixed mutually with water ionic liquid as used herein.
" hydrophobic ionic liquid " expression and the ionic liquid of water to not mixing mutually promptly form two-phase under envrionment conditions as used herein.
" composition " comprises the mixture of following material as used herein: constitute the material of composition, and the reaction of the material by constituting composition or the product that is decomposed to form.
As used herein " derived from " material preparation or the mixing of expression from stipulating, but be not to form by the simple mixtures of those materials." derived from " material of prescribed material can be the simple mixtures of original material and the reaction product that also can comprise those materials, or even can be made up of the reaction or the degradation production of original material fully.
" halogen " represents chlorine as used herein, bromine, fluorine or iodine, arylidene is represented divalent aromatic radical such as phenylene, naphthylidene, biphenylene, anthrylene, phenanthrylene etc., inferior heteroaryl is represented divalence heteroaromatic group such as inferior pyrryl, furylidene, inferior thienyl, pyridylidene etc., alkylidene group is represented the divalence alkane group, this divalence alkane group can be by one or more heteroatomss such as nitrogen or oxygen replacement, cycloalkylidene is represented the bivalent cycloalkane group, this bivalent cycloalkane group can be by one or more heteroatomss such as nitrogen or oxygen replacement, alkenylene is represented the divalent alkylene group, and this divalent alkylene group can be by one or more heteroatomss such as nitrogen or oxygen replacement.
" many storehouses ester " represents the negatively charged ion of two (2-ethylhexyl) esters of sulfo-succinic acid as used herein.The chemical formula of many storehouses ester (negatively charged ion) is C 20H 37O 7S -" many storehouses ester variant " is used to comprise the compound of being described by following chemical structural formula I and III and comprises the negatively charged ion of two (organic) ester derivatives of sulfo-succinic acid and the negatively charged ion of two (organic amide) derivatives of sulfo-succinic acid as used herein.
This any numerical value of enumerating comprise from than low value to high value all numerical value with a unit increment, condition is the separation that has at least 2 units between than low value and any high value any.As an example, if the numerical example of statement component quantity or process variable such as temperature, pressure, time etc. 1-90 in this way, preferred 20-80, more preferably 30-70 thinks so and list numerical value such as 15-85 clearly in this specification sheets, 22-68,43-51,30-32 etc.For less than one numerical value, think suitably that then a unit is 0.0001,0.001,0.01 or 0.1.These only are concrete examples of wishing, and think and stated clearly in a similar manner that in this application the Schwellenwert listed and the institute of the numerical value between the maximum might make up.
Ionic liquid of the present invention comprises one or more compounds.Therefore, ionic liquid can be that pure compound maybe can be the mixture of compound.Every kind of compound comprises negatively charged ion or anion mixture and the positively charged ion or the cation mixt of the following stated.
R 1-O-C (O)-CH (SO 3 -)-R 3-C (O)-O-R 2With
I
Figure A0381940500101
Negatively charged ion
The illustration negatively charged ion of The compounds of this invention comprises having those that are selected from chemical structural formula, the R in above structural formula I and II 1, R 2, R 4And R 5Be independently selected from and replace or not substituted alkyl or thiazolinyl.R 1, R 2, R 4And R 5Alkyl or alkenyl should contain the carbon atom of enough numbers so that ionic liquid has required performance.For example, hydrophobic ionic liquid if desired, then in the ionic liquid overall number of carbon atom usually greater than the situation of hydrophilic ionic-liquid if desired.Yet if there is too many carbon atom in negatively charged ion, because the decline of performance such as vapour pressure, moment of dipole, polarity etc., ionic liquid may can not be used as ionic liquid.
For hydrophobic ionic liquid, R 1, R 2, R 4And R 5Preferably be independently selected from and contain have an appointment five or more a plurality of carbon atom, the alkyl of about 18 carbon atoms of preferably about 6-.R 1, R 2, R 4And R 5A preferred group be-CH 2-CH (CH 2CH 3) (CH 5CH 2-CH 3).The performance that this group provides to ionic liquid for it and be useful for its cost and easily manufactured property.
R among the structural formula I 3Be replacement or unsubstituting alkylidene, inferior heteroaryl, arylidene or cycloalkylidene.Preferably, R 3Be replace or unsubstituting alkylidene and even more preferably, R 3Be-(CH 2) n-, wherein n is the integer of about 1-about 10.
R 6, R 7And R 8Be independently selected from hydrogen (H) or another kind of substituting group, for example alkyl, NO 2, halogen, cyano group, silyl and OH.Preferably, R 6, R 7And R 8Be H.
In some cases, two or more adjacent substituting groups such as R 1And R 2, R 4And R 5, R 6And R 7, and/or R 7And R 8Can be combined together to form ring as 5-7 unit carbocyclic ring.Such isocyclic example comprises cyclopentyl and cyclohexyl ring.
R 1, R 2, R 3, R 4, R 5, R 5, R 7And R 8Can randomly replace by one or more substituting groups.Substituent type is not crucial especially, as long as the mixture of compound or compound has required ionic liquid performance.Therefore, substituting group generally includes typical case and atypical organic substituent as being selected from following those: alkyl, NO 2, halogen, cyano group, silyl, OH and other suitable substituents.Substituting group self is further branching usually.
Can be used for preparing ion liquid another kind of illustration negatively charged ion is the many storehouses ester variant with following chemical structural formula:
R 1-N(R 2)-C(O)-CH(SO 3 -)-R 3-C(O)-N(R 4)-R 5
III
R in the chemical structure formula III 1, R 2, R 3, R 4And R 5Can be independently selected from hydrogen atom (H) or carbon-containing group, as alkyl, thiazolinyl, alkynyl, aryl, benzyl, alkyl oxide etc.
In one embodiment, negative ion source is a 2-ethylhexyl amidosulfonic acid sodium salt, and it can use the known technology with this specification sheets benefit synthetic.For example, preparation has the negatively charged ion of above chemical structure formula III, wherein R 1And R 5Each is the 2-ethylhexyl, R 2And R 4Each is a hydrogen atom, and R 3It is methylene radical.Use this negatively charged ion by at first it being separated with sodium salt, with its different cationic source reaction, prepare two kinds of different ionic liquids then with two kinds.Positively charged ion in a kind of ionic liquid is the TBuA positively charged ion.Positively charged ion in another kind of ionic liquid is 1-methyl-3-hexyl imidazoles.
In other test, preparation has second negatively charged ion of above chemical structure formula III, wherein R 1And R 5Each is the 2-ethylhexyl, R 2And R 4Each is an ethyl, and R 3It is methylene radical.Use two kinds of other ionic liquids of this negatively charged ion preparation, wherein by at first it being separated with sodium salt, then (in independent test) with it and above-mentioned identical two kinds of cationic sources, promptly TBuA positively charged ion and 1-methyl-3-hexyl imidazoles reacts.
According to preparing ion liquid test from negatively charged ion therein with chemical structure formula III, believe, under the situation of many storehouses ester salt and their derivative and variant, each R group in the chemical structure formula III can variation length or composition and still produce ionic liquid when combining with suitable positively charged ion such as positively charged ion.
Positively charged ion
The ion liquid positively charged ion of producing is not crucial especially, as long as ionic liquid has and makes it be applicable to the performance of its required purposes.Typical useful positively charged ion comprises, for example " " positively charged ion.Positively charged ion comprises that positively charged ion is as replacing or unsubstituted An, Phosphonium and sulfonium cation.Preferred cation comprises, for example replaces or unsubstituted N-alkyl or N-aryl-pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles, thiazole, oxazole, triazole, tetrahydroglyoxaline, crassitude, isothiazole, isoxazole, oxazole, pyrroles and thiophene.Substituting group comprises one or more following groups: halogen, alkyl and aryl such as phenyl.In addition, two adjacent substituting groups can be combined together to form alkylidene group, therefore are formed on N and go up the ring structure that merges.Alkyl, phenyl and alkylidene group can further be substituted.Another kind of particularly preferred positively charged ion is the ammonium cation by one or more groups such as alkyl and aryl such as phenyl replacement.The many such positively charged ions and the positively charged ion of replacement are described in U.S. patent Nos.5, and 827,602 and 5,965,054, they are incorporated herein by reference in full at this.
Other suitable positively charged ion comprises BMIM, TBuA, tributyl-methyl phosphonium ammonium, 4-butyl-phosphonium, tetraethyl ammonium, N, N-dialkyl group tetramethyleneimine, trimethylammonium 2-hydroxyethyl ammonium, N, N '-dialkylimidazolium, N-alkyl pyridine or its mixture.Positively charged ion can be positively charged ion and randomly comprise more than 4 carbon atoms.
Preparation method with compound and composition thereof of structural formula I-III
The ion liquid compound of structural formula I-II can be easily by many diverse ways preparations.A kind of method that is applicable to preparation hydrophobicity of the present invention or hydrophilic ionic-liquid or mixture comprises the use replacement(metathesis)reaction, i.e. replacement(metathesis)reaction, and the reaction of two or more compounds forms two or more new compounds thus, and wherein a kind of is ionic liquid.For example, reaction [bmim] Cl and Docusate Sodium can obtain [bmim] many storehouses ester and NaCl.Can separate two or more compounds of producing by replacement(metathesis)reaction by any measure then.
Contacting two or more compounds is not particularly important to form ion liquid mode, as long as required reaction takes place.Generally speaking, compound can be adopted any order to mix, can original position form, or can mix with solvent such as water, water to small part can mix indistinctively mutually reacts with any compound.
Initial compounds obtains usually easily, and in addition, those skilled in the art can utilize many synthesizing to prepare required initial compounds.Mixing condition can be dependent on the specific compound of employing and required product and changes.In most of the cases, acceptable be environmental stress with contact compound and optional solvent such as water or methylene dichloride at a certain temperature, this temperature is enough high to allow reaction effectively take place but not too high to decomposing or any initial compounds that seethes with excitement.Generally speaking, the contact temperature can be about 110 ℃ of about 75-, about 100 ℃ of preferably about 85-.When water was used as solvent, because this tends to destroy the emulsion that forms usually between ionic liquid and water, therefore the about 110 ℃ temperature of about 75-was preferred sometimes.On the other hand, when solvent is organically when (as methylene dichloride), preferred temperature is general obvious lower, usually near room temperature as 25 ℃ or a little more than room temperature.
The mode of the temperature that reaches therein and keep increasing is not crucial especially.When mixing cpd or can heat separately and then when mixing initial compounds, can adopt any heating unit usually.Similarly, can adopt any container or reactor, as long as it has suitable size and material.Usually useful is to adopt whipping appts to promote reaction.
Generally speaking, keeping the temperature that increases at least, time enough occurs to required degree up to required reaction.In some cases, may need to keep the temperature that increases than finishing the required longer time of reaction.So, can remove any water or the low boiling component that forms as by product or exist as solvent by boiling.
The quantity of every kind of initial compounds can be dependent on required yield and changes.Generally, obtain high yield by promptly about 1: 1 ratio of reactant of using about stoichiometric usually.Yet such as understood by a person skilled in the art, different reaction conditionss can change the reactant ratio that produces optimum yield.
If people need prepare the ionic liquid mixture that comprises two or more different salt, then it can be finished by following mode: adopt the mixture of three kinds or more kinds of different compounds to make and form various salt.The ionic liquid salt mixture that obtains can be used as mixture then and uses, or if desired, single salt can be separated by conventional measure.
If desired, can adopt any suitable measure to reclaim ionic liquid or ionic liquid mixture from solvent and/or reaction mixture, wherein effective measures can be dependent on the type of ionic liquid or mixture and required purity and change.Suitable recovery measure comprises rotary evaporation or distillation, component distillation, chromatography of ions, liquid-liquid extraction, crystallization, pervaporation, siccative and reverse osmosis.
Although aforesaid method can be used for preparing hydrophobicity or hydrophilic ionic-liquid, preferred preparation hydrophobic ionic liquid in some applications.This is because hydrophobic ionic liquid is not dissolved in the water that is commonly used for reaction medium usually very much.Therefore, simple liquid-liquid extraction can be used for hydrophobic ionic liquid and solvability separation of by-products.On the contrary, hydrophilic ionic-liquid is usually mixed mutually with by product.So can adopt different separation methods, as solvent extraction.For example, use hydrophobic solvent, for example alkyl chloride may be desirable or necessary as methylene dichloride with extracting ionic liquid.
Ion liquid characteristic of the present invention and purposes
The ion liquid purity of being produced by the inventive method can be preferably greater than 60% usually greater than 55%, more preferably greater than 70%, most preferably greater than 80%.For the technology that requires high purity material as this is normally favourable in electronic industry.Therefore ionic liquid is also preferably hydrophobic, can be used in many technologies as the surrogate of organic solvent and is used to contain the mixture of following material: catalyzer such as ZnCl 2, CuCl 2, AlCl 3, and organic catalyst.
Ionic liquid of the present invention also is generally used for containing hydrocarbon, for example the mixture of alkane such as hexane.Mixture is static electrification lotus not usually, therefore is not easy to light or explode.
OvercriticalCO 2 Many storehouses ester in the application and Duo Ku ester variant
Find that many storehouses of TBuA ester is dissolved in supercritical co (CO 2).Use CO 2Overcritical application be higher than under 32 ℃ the temperature and greater than about 1, the pressure of 070psi is operation down usually.Believe that the ionic liquid based on many storehouses ester and Duo Ku ester variant is to join the supercritical CO that is used to clean, synthesize and separate application 2In used additives, additive and washing composition arranged.
Many storehouses ester and Duo Ku ester variant as static inhibitor
Believe that the ionic liquid based on many storehouses ester and Duo Ku ester variant is the useful anti static additive that is used for fuel applications and polymer application.Tend to partially or completely can be used as anti static additive and join in the fuel based on the ionic liquid of many storehouses ester and Duo Ku ester variant with hydrocarbon (for example alkane such as hexane) is mixed mutually.These ionic liquids also can be used as anti static additive and join in polymkeric substance such as the polyvinyl acetate (PVA).
Many storehouses ester in the ionic liquid blend and Duo Ku ester variant
In one embodiment, with two or more ionic liquid blend together to form improved reaction solvent.Believe can with Lewis acidic ionic liquid with based on the advantageously blend of ionic liquid of many storehouses ester or many storehouses ester variant, forming improved reaction solvent, this reaction solvent is provided at better mixing between the reactant to improve reaction kinetics.Because many storehouses ester and Duo Ku ester variant ionic liquid tend to mix mutually relatively with hydrocarbon stream at least, they tend to suppress biphase form and improve between the reactant mixing with contact.Believe that can be used for the example of Lewis acidic ionic liquid that preparation contains the ion liquid blend of azochlorosulfonate acid anion of the present invention (as many storehouses ester and Duo Ku ester variant) is disclosed in exercise question in " Lewis acidic ionic liquid ", that on August 15th, 2003 submitted to and the common unsettled U.S. application (series number is unknown at present) by Roger Moulton invention, the document is introduced into as a reference as illustrating fully at this.
The illustration Lewis acidic ionic liquid that is used for these blends comprises such ionic liquid, and promptly this ionic liquid contains (i) and is selected from ammonium, Liu He phosphonium cation and contains the positively charged ion of total less than 14 carbon atoms; (ii) has general formula Al yR 3y+1Negatively charged ion, wherein y greater than 0 and R be independently selected from alkyl and halogen group.The suitable anion that is used for the blend Lewis acidic ionic liquid is the aluminum chloride negatively charged ion.
The suitable cation that is used for Lewis acidic ionic liquid is a tetra-allkylammonium.Depend on required ionic liquid performance, advantageously one or more alkyl are randomly replaced by one or more suitable substituents.Suitable substituents comprises, for example halogen such as chlorine, bromine or iodine.Particularly preferred tetraalkylammonium cation comprises trimethylammonium ethyl ammonium, trimethylammonium chloromethyl ammonium, trimethylammonium butyl ammonium and tributyl-methyl phosphonium ammonium.
The another kind of suitable cation that is used for Lewis acidic ionic liquid is saturated heterocyclic such as piperidines and the morpholine that the N-alkyl replaces.Especially, on nitrogen by alkoxyl group or alkyl as-(CH 2) 2The piperidines that OMe, butyl or propyl group replace is useful especially.Also can adopt positively charged ion based on tetramethyleneimine.Positively charged ion can comprise that ether functional group is (as NCH 2CH 2OCH 3 +).Positively charged ion can comprise haloalkyl.
The illustration Lewis acidic ionic liquid that is used for blend comprises such ionic liquid, and promptly this ionic liquid contains aluminum chloride negatively charged ion and the positively charged ion that is derived from following ammonium salt: MeBu 3NCl, Me 3Amyl group NCl, Me 3Butyl NCl, MeEt 3NCl, Me 2Et 2NCl, Cl-CH 2-NMe 3Cl or N-methyl-N-butyl pyrrolidine Cl.Other illustration Lewis acidic ionic liquid comprises heptachlor two aluminic acid piperidines, heptachlor two aluminic acid trimethylammonium chloromethyl ammoniums, heptachlor two aluminic acid trimethylammonium butyl ammoniums and the heptachlor two aluminic acid tributyl-methyl phosphonium ammoniums that the N-alkyl replaces.
Do not wish that following embodiment limits the present invention, but wish that only explanation can be adopted the concrete mode of minority of the present invention.
Embodiment 1: many storehouses of TBuA ester synthetic
1 mole of Docusate Sodium (444 gram) is dissolved in 2 premium on currency, then 1 mole of Tetrabutylammonium bromide (321 gram) is added as solid.After stirring several minutes, stop stirring and solution and be divided into two-layer.In separating funnel, collect the upper strata.It is adopted 1 premium on currency washed twice, and be heated to 100 ℃ and separate mutually promoting.Many storehouses of the TBuA ester that obtains is heated to 110 ℃ to displace any dissolving water wherein.Output almost is quantitative (624 grams, 94% yield).
Embodiment 2-5
Basic adopt with embodiment 1 in identical mode prepare the ionic liquid of embodiment 2-5 in the following table 1, distinguish and be 1 mole of Tetrabutylammonium bromide in about 1 mole of parent material alternate embodiment 1 in the table 1.
Table 1
Embodiment Parent material Ionic liquid Solvability in the water
??2 ??Me(n-Bu) 3NBr ??Me(n-Bu) 3Many storehouses of N ester Hydrophobic
??3 ??Me 3N(CH 2) 6NMe 3Br ??Me 3N(CH 2) 6NMe 3Many storehouses ester Hydrophobic
??4 ??n-Bu 4PBr ??n-Bu 4Many storehouses of P ester Hydrophobic
??5 ??Et 4NBr ??Et 4Many storehouses of N ester Mix mutually
Embodiment 6-10
By dissolving Docusate Sodium in methylene dichloride and in independent flask in methylene dichloride the parent material of dissolving table 2, the ionic liquid of embodiment 6-10 in the table 2 below the preparation.Two kinds of solution are mixed and stirred about 12 hours.Then solution is filtered to remove precipitated solid salt, flash to thick slurry then.Adopt ether, hexane or its mixture to extract in thick slurry after inciting somebody to action, filter once more to remove solid salt.After rotary evaporation, resistates is dissolved in hexane/ether again and repeats filtration process (using littler gradually ether share in the mixture) up to no longer forming solid.The salt that adopts the water washing acquisition then is to carry out finally removing of inorganic salt, and is thereafter that they are dry in a vacuum.
Table 2
Embodiment Parent material Ionic liquid
??6 Bromination 1-n-hexyl-3-Methylimidazole 1-n-hexyl-many storehouses of 3-Methylimidazole ester
??7 Bromination 1-n-octyl-3-Methylimidazole 1-n-octyl-many storehouses of 3-Methylimidazole bromide ester
??8 Bromination 1-normal-butyl-3-Methylimidazole 1-normal-butyl-many storehouses of 3-Methylimidazole ester
??9 Bromination 1-methyl-2-ethyl imidazol(e) 1-methyl-many storehouses of 2-ethyl imidazol(e) ester
??10 Bromination tetra-n-butyl ammonium Many storehouses of tetra-n-butyl ammonium ester
The ionic liquid of embodiment 6-10 generally is a hydrophobic ionic liquid.Under the situation of embodiment 6, be 1-hexyl-many storehouses of 3-Methylimidazole ester, it is contacted with 40 volume percent or water still less cause biphase to form, even after stirring, also be like this.Yet,, stir and produce hard, monophasic gel visually when 1-hexyl-when many storehouses of 3-Methylimidazole ester contacts with the water of 50 volume percent.In gel, add other water, stir subsequently, cause biphase to form once more.Although do not wish to be subjected to any specific theory constraint, believe that when mixing with the water of some ratios, ionic liquids more of the present invention can hydration or solvation.This causes forming such ionic liquid, and promptly this ionic liquid does not dissolve, and when mixing, form two-phase with the water of some ratios and under other ratio for single-phase.For therein with the solvability of water or insoluble be that important some are used, this unique character can be very useful.
Embodiment 11
This embodiment describes the synthetic of acid amides TBuA fused salt with above Formulae II I in detail.Acid amides-sulfonate sodium (the R that 1/10th moles (50g) is had above chemical structure formula III 2And R 4Be CH 2CH 3, R 1And R 5Each is the 2-ethylhexyl, and R 3Be CH 2) be dissolved in the 250mL methylene dichloride and 1/10th moles of (32g) Tetrabutylammonium bromides are added as solid.Mixture was stirred one day, after this time, solution is at first passed through filter paper filtering, filter by short silica gel plug then.Adopt water to wash fast the dichloromethane solution of wash-out, use dried over mgso and, stay required product (64g, 89%) with high yield in a vacuum except that desolvating.Product salt is water-soluble and also be dissolved in several common organic solvents, as methylene dichloride and acetone.Because product at room temperature is a viscous oil, the fusion range that therefore obtains salt is lower than about 30 ℃.Product salt comprises and two (N-ethyl-N-(2-ethylhexyl) sulfo-succinic acid diamide) negatively charged ion of TBuA positively charged ion paired.
Embodiment 12-19
These embodiment describe in detail from the sodium salt of sulfosuccinic ester and prepare ionic liquid, and described sulfosuccinate is many storehouses ester variant.Then ester is combined with positively charged ion with the preparation fused salt.
10 gram (0.03mol) Tetrabutylammonium bromides are dissolved in 50mL water and add the sodium salt of 12 grams (0.03mol) as solid sulfo-succinic acid di-n-hexyl ester in the solution that stirs.(" sulfo-succinic acid di-n-hexyl ester " expression sulfosuccinic acid molecule on two carbonyls of sulfosuccinic acid molecule and not esterification on sulfo group).After stirring several minutes, water layer is adopted the dichloromethane extraction of three 50mL parts successively, then it is merged, adopt anhydrous magnesium sulfate drying, and evaporation, stay required product (13g, 73% yield).Because product at room temperature is a viscous oil, the fusion range that therefore obtains salt is lower than about 30 ℃.
Identical process of the test is used to prepare the ionic liquid of the sodium salt of TBuA positively charged ion and following many storehouses ester variant: (i) two of sulfo-succinic acid positive cyclohexyl esters; The (ii) di-n-octyl ester of sulfo-succinic acid; The (iii) di-n-butyl ester of sulfo-succinic acid; The (iv) diisobutyl ester of sulfo-succinic acid; (the v) di neo-pentyl ester of sulfo-succinic acid; (vi) two n-heptyl esters of sulfo-succinic acid; (vii) two n-heptyl esters of sulfo-succinic acid.The fusion range that obtains salt is lower than about 80 ℃ and be generally about 40 ℃-80 ℃.Octyl group and many storehouses of heptyl ester variant have lower fusion range, and this is as by shown in the following fact: they at room temperature are viscous liquid.
Representative NMR data
By the ion liquid structure of 1H-NMR spectrometry with form.For all many storehouses ester salt (2-ethylhexyl sulfosuccinic acid diesters), spectrum simply in comfortable those the cationic resonance of origin synergetic anionic resonance form.For all many storehouses ester salt, be derived from anionic resonance and be (having very little variation) in following scope: (300Mhz, CDC13, d:0.73-0.83 (three peaks), 1.24-1.70 (overlapping multimodal), 3.05-3-31 (compound m), 3.90-4.25 (overlapping m)
Positively charged ion resonance (300MHz, CDC13, d): (1-methyl-3-hexyl imidazoles): 0.79 (t), 1.21-1.27 (overlapping m), 1.80 (m), 4.03 (s), 4.22 (t), 7.35 (s), 7.49 (s), 9.50 (s).
(tetraethyl ammonium): 1.32 (t), 3.34 (q)
(TBuA): 1.03 (t), 1.20-1.40 (overlapping m), 3.23 (q)
(four octyl group ammoniums): 0.86 (t), 1.18-1.50 (overlapping m), 3.25 (q)
(N-methyl-N-(CH 2CH 2OCH 2CH 3) tetramethyleneimine): 0.86 (t), 1.31 (m), 2.11 (m), 3.0-4.2 (compound overlapping m)
(trimethylammonium cetyltrimethyl ammonium): 0.87 (t), 1.20-1.60 (overlapping m), 2.13 (s), 3.15 (q)
(methyltributylammoni,m): 0.84 (t), 1.23-1.70 (overlapping m), 2.20 (s), 3.24 (m)
(1, two (tributyl ammonium) ethane of 2-): 0.83 (t), 1.22-1.58 (overlapping m), 2.20 (s), 3.22 (m)
The ionic liquid that also prepares several many storehouses ester variant.As the NMR spectrum of many storehouses ester derivative, the NMR spectrum of these salt is by synergetic specific anionic spectrum composition on the spectrum of certain cationic.Below be the NMR data of the TBuA derivative of the variant of storehouse ester more than three kinds salt.For every kind of salt, cationic those are consistent from the cationic resonance and the TBuA of many storehouses ester, more than list their numerical value.Below be from these embodiment salt anionic resonance (300MHz, CDC13, d):
Two (n-hexyl sulfosuccinic acid diesters): 0.84 (t), 1.2-1.4 (overlapping m), 1.6 (m), 3.07 (m), 4.05-4.22 (overlapping m).
Two (cyclohexyl sulfosuccinic acid diesters): 1.2-1.8 (compound overlapping m), 3.10 (m), 4.2-4.8 (overlapping m)
Two (neo-pentyl sulfosuccinic acid diesters): 0.87 (s), 0.90 (s), 3.05-3.25 (overlapping m), 3.78 (s), 3.80-3.93 (m), 4.23-4.29 (m)
Two (N-ethyl-N-(2-ethylhexyl) sulfo-succinic acid diamide): 0.75-0.88 (three peaks), 1.21-1.78 (overlapping multimodal), 2.24 (m), 3.11-3-41 (compound m), 3.86-4.45 (overlapping m)

Claims (59)

1. ionic liquid compositions comprises:
(a) contain positively charged ion more than 4 carbon atoms; With
(b) be selected from following negatively charged ion:
With
I
Figure A038194050002C2
R wherein 1, R 2, R 4And R 5Be independently selected from and replace or not substituted alkyl or thiazolinyl;
R wherein 3Be replacement or unsubstituting alkylidene, inferior heteroaryl, arylidene or cycloalkylidene;
R wherein 6, R 7And R 8Be independently selected from H, alkyl, NO 2, halogen, cyano group, silyl and OH;
Or R 1And R 2Can be combined together to form ring:
Or R 4And R 5Can be combined together to form ring:
Or R 6And R 7Or R 7And R 8Can be combined together to form ring.
2. the composition of claim 1, wherein negatively charged ion has chemical structural formula I.
3. the composition of claim 2, wherein R 1And R 2Be independently selected from the alkyl that contains have an appointment five or more a plurality of carbon atoms.
4. the composition of claim 2, wherein R 1And R 2Be independently selected from the alkyl that contains about 18 carbon atoms of the 6-that has an appointment.
5. the composition of claim 2, wherein R 3Be-(CH 2) n-, wherein n is the integer of about 1-about 10.
6. the composition of claim 5, wherein R 1And R 2Be independently selected from the alkyl that contains about 18 carbon atoms of the 6-that has an appointment.
7. the composition of claim 6, wherein n is 1 and R 1And R 2Be-CH 2-CH (CH 2CH 3) (CH 5-CH 2-CH 3).
8. the composition of claim 1, wherein negatively charged ion has chemical structural formula II.
9. the composition of claim 8, wherein R 6, R 7And R 8Be H.
10. the composition of claim 8, wherein R 4And R 5Be independently selected from the alkyl that contains have an appointment five or more a plurality of carbon atoms.
11. the composition of claim 8, wherein R 4And R 5Be independently selected from the alkyl that contains about 18 carbon atoms of the 6-that has an appointment.
12. the composition of claim 9, wherein R 4And R 5Be independently selected from the alkyl that contains have an appointment five or more a plurality of carbon atoms.
13. the composition of claim 9, wherein R 4And R 5Be-CH 2-CH (CH 2CH 3) (CH 2-CH 2-CH 3).
14. the composition of claim 2 further comprises catalyzer.
15. the composition of claim 7 further comprises catalyzer.
16. the composition of claim 2 further comprises hydrocarbon.
17. the composition of claim 7 further comprises hydrocarbon.
18. the composition of claim 8 further comprises catalyzer.
19. the composition of claim 9 further comprises catalyzer.
20. the composition of claim 8 further comprises hydrocarbon.
21. the composition of claim 9 further comprises hydrocarbon.
22. the composition of claim 1, wherein positively charged ion is a quaternary ammonium Huo quaternary phosphine.
23. the composition of claim 22, wherein quaternary ammonium cation is independently selected from replacement or unsubstituted pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles, thiazole, oxazole, triazole, tetrahydroglyoxaline, crassitude, isothiazole, isoxazole, oxazole, pyrroles and thiophene.
24. the composition of claim 1, wherein positively charged ion is the ammonium cation that is replaced by one or more groups that are selected from alkyl and aryl.
25. the composition of claim 22, wherein quaternary ammonium cation is BMIM.
26. the composition of claim 1, wherein positively charged ion is TBuA, tributyl-methyl phosphonium ammonium, 4-butyl-phosphonium, tetraethyl ammonium, N, N-dialkyl group tetramethyleneimine, trimethylammonium 2-hydroxyethyl ammonium, N, N '-dialkylimidazolium, N-alkyl pyridine or its mixture.
27. one kind comprises the ion liquid ionic liquid compositions at least about 55wt%, this ionic liquid comprises:
(a) positively charged ion: and
(b) be selected from following negatively charged ion:
Figure A038194050004C1
With
I
Figure A038194050004C2
R wherein 1, R 2, R 4And R 5Be independently selected from and replace or not substituted alkyl or thiazolinyl;
R wherein 3Be replacement or unsubstituting alkylidene, inferior heteroaryl, arylidene or cycloalkylidene;
R wherein 6, R 7And R 8Be independently selected from H, alkyl, alkoxyl group, alkylthio, SO 3H, NO 2, halogen, cyano group, silyl and OH;
Or R 1And R 2Can be combined together to form ring;
Or R 4And R 5Can be combined together to form ring;
Or R 6And R 7Or R 7And R 8Can be combined together to form ring.
28. the composition of claim 27, wherein ionic liquid is hydrophobic.
29. the composition of claim 28, wherein positively charged ion is a quaternary ammonium Huo quaternary phosphine.
30. the composition of claim 29, wherein quaternary ammonium cation is independently selected from replacement or unsubstituted pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles, thiazole, oxazole, triazole, tetrahydroglyoxaline, crassitude, isothiazole, isoxazole, oxazole, pyrroles and thiophene.
31. the composition of claim 30, wherein positively charged ion is the ammonium cation that is replaced by one or more groups that are selected from alkyl and aryl.
32. the composition of claim 30, wherein quaternary ammonium cation is BMIM.
33. the composition of claim, wherein positively charged ion is TBuA, tributyl-methyl phosphonium ammonium, 4-butyl-phosphonium, tetraethyl ammonium, N, N-dialkyl group tetramethyleneimine, trimethylammonium 2-hydroxyethyl ammonium, N, N '-dialkylimidazolium, N-alkyl pyridine or its mixture.
34. the composition of claim 27, wherein negatively charged ion is many storehouses ester.
35. the composition of claim 27, wherein negatively charged ion has chemical structural formula I and is hydrophobic.
36. the composition of claim 27, wherein negatively charged ion has structural formula II and is hydrophobic.
37. the composition of claim 27, wherein negatively charged ion has chemical structural formula I and is hydrophilic.
38. the composition of claim 27, wherein negatively charged ion has chemical structural formula II and is hydrophilic.
39. the composition of claim 1, wherein ionic liquid is hydrophobic.
40. the composition of claim 1, wherein ionic liquid is hydrophilic.
41. the composition of claim 1, wherein negatively charged ion is to be selected from following negatively charged ion: (i) two of sulfo-succinic acid positive cyclohexyl esters; The (ii) di-n-octyl ester of sulfo-succinic acid; The (iii) di-n-butyl ester of sulfo-succinic acid; The (iv) diisobutyl ester of sulfo-succinic acid; (the v) di neo-pentyl ester of sulfo-succinic acid; (vi) two n-heptyl esters of sulfo-succinic acid; (Vii) two n-heptyl esters of sulfo-succinic acid.
42. the composition of claim 41, wherein positively charged ion is a TBuA.
43. an ionic liquid compositions comprises:
(a) positively charged ion; With
(b) have the negatively charged ion of following structure:
R 1-N(R 2)-C(O)-CH(SO 3 -)-R 3-C(O)-N(R 4)-R 5
III
R wherein 1, R 2, R 3, R 4And R 5Be independently selected from hydrogen atom and carbon-containing group;
Wherein ion liquid fusing point is lower than about 100 ℃.
44. the composition of claim 43, wherein R 1Be the 2-ethylhexyl, R 2Be ethyl, R 3Be methylene radical, R 4Be ethyl, and R 5It is the 2-ethylhexyl.
45. the composition of claim 44, wherein positively charged ion is a TBuA.
46. the composition of claim 44, wherein positively charged ion is 1-methyl-3-hexyl imidazoles.
47. the composition of claim 43, wherein R 1Be the 2-ethylhexyl, R 2Be hydrogen atom, R 3Be methylene radical, R 4Be hydrogen atom, and R 5It is the 2-ethylhexyl.
48. the composition of claim 47, wherein positively charged ion is a TBuA.
49. the composition of claim 47, wherein positively charged ion is 1-methyl-3-hexyl imidazoles.
50. the composition of claim 43 further comprises hydrocarbon.
51. the composition of claim 1, wherein positively charged ion and negatively charged ion formation fusing point is lower than about 100 ℃ fused salt, and fused salt is selected from many storehouses of TBuA ester, MeBu 3Many storehouses of N ester, Me 3N (CH 2) 6NMe 3Many storehouses ester, Bu 4Many storehouses of P ester, Et 4Many storehouses of N ester, 1-hexyl-many storehouses of 3-Methylimidazole ester, 1-octyl group-many storehouses of 3-Methylimidazole bromide ester, 1-butyl-3-Methylimidazole many storehouses ester and 1-methyl-many storehouses of 2-ethyl imidazol(e) ester.
52. a composition comprises:
(a) comprise anion ion liquid, this negatively charged ion is selected from (i) many storehouses ester, the (ii) negatively charged ion and the (iii) negatively charged ion of sulfo-succinic acid pair (organic amide) derivatives of two (organic) ester derivatives of sulfo-succinic acid; With
(b) CO under supercritical state 2
Wherein ionic liquid is dissolved in CO 2
53. a composition comprises:
(a) hydrocarbon fuel; With
(b) comprise anion ion liquid, this negatively charged ion is selected from (i) many storehouses ester, the (ii) negatively charged ion and the (iii) negatively charged ion of sulfo-succinic acid pair (organic amide) derivatives of two (organic) ester derivatives of sulfo-succinic acid.
54. a composition comprises:
(a) polymkeric substance; With
(b) comprise ion liquid anti static additive, this ionic liquid comprises negatively charged ion, and this negatively charged ion is selected from (i) many storehouses ester, the (ii) negatively charged ion and the (iii) negatively charged ion of sulfo-succinic acid pair (organic amide) derivatives of two (organic) ester derivatives of sulfo-succinic acid.
55. the composition of claim 54, wherein polymkeric substance is a polyvinyl acetate (PVA).
56. an ionic liquid compositions comprises:
(a) contain positively charged ion more than 4 carbon atoms; With
(b) be selected from the negatively charged ion of many storehouses ester and Duo Ku ester variant.
57. the ionic liquid compositions of claim 56, wherein ionic liquid fusion in following temperature range, this temperature range is higher than about 40 ℃ but be lower than about 80 ℃.
58. a composition comprises:
With first ionic liquid of second ionic liquid combination,
(a) first ionic liquid comprises:
(i) be selected from the positively charged ion of ammonium, sulfonium and phosphonium cation, this positively charged ion is that non-tetrahedron is symmetric;
(ii) has general formula Al yR 3y+1Negatively charged ion, wherein y greater than 0 and R be independently selected from alkyl and halogen group;
(b) comprise anionic second ionic liquid, this negatively charged ion is selected from (i) many storehouses ester, the (ii) negatively charged ion and the (iii) negatively charged ion of sulfo-succinic acid pair (organic amide) derivatives of two (organic) ester derivatives of sulfo-succinic acid.
59. the composition of claim 58 further comprises reactant, first and second ionic liquids are effecting reaction solvents of reactant.
CNA038194058A 2002-08-16 2003-08-15 Ionic liquids containing a sulfonate anion Pending CN1705640A (en)

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