JP2006510581A - Ionic liquids containing sulfonate cations - Google Patents

Abstract

The present invention relates to novel ionic liquids containing docusate, docusate variants or other sulfonate anions. The ionic liquid of the present invention can be easily produced by, for example, metathesis. Ionic liquids are often hydrophobic and are useful in many hydrocarbon compositions, polymer compositions, and supercritical carbon dioxide applications. The ionic liquid can avoid static buildup in the hydrocarbon composition and thus minimize flammability and / or explosiveness.

Description

(Related application data)
This application claims priority to US Provisional Patent No. 60 / 404,178 (filed 16 August 2002) and US Provisional Patent 60 / 404,202 (filed 16 August 2002).

(Field of Invention)
The present invention relates to compositions comprising an ionic liquid comprising a docusate anion, a docusate variant anion, or other sulfonate anion, and a process for making the composition.

(Background and Summary of the Invention)
An ionic liquid is a salt that is a liquid at or near atmospheric temperature. Ionic liquids have numerous uses, including replacement of organic solvents in chemical processes and reactions, extraction of organic compounds from aqueous waste streams, and electrolytes in devices such as capacitors and batteries. Can be used. This is because, unlike conventional organic solvents, ionic liquids are non-volatile and non-flammable. These properties are advantageous in that they help reduce loss to evaporation, eliminate volatile organic emissions, and increase safety.

Other properties of ionic liquids have also proven advantageous. For example, many ionic liquids have a wide temperature range that remains liquid and are also stable over a wide pH range. This is advantageous for high temperature processes at severe pH. In addition, some ionic liquid systems can be used as both solvents and catalysts. For example, [bmim] -Al ₂ Cl ₇ and [emim] -Al ₂ Cl ₇ can be used as solvents and catalysts in the Friedel-Crafts reaction, where bmim is 1-butyl-3-methylimidazolium. And emim is 1-ethyl-3-methylimidazolium.

  For the above reasons, it is desirable to find new ionic liquid compounds with favorable properties. This ionic liquid is even more desirable when such compounds can be made by a simple process with small amounts of waste and impurities.

  Advantageously, new ionic liquid compounds have been discovered. This compound contains either docusate or other sulfonate anions and is made by a simple process that can produce a high purity ionic liquid.

(Detailed description of the invention)
As used herein, “ionic liquid” means a salt comprising a cation and an anion. Salts (or salt hydrates or solvates) are liquids (ie, having a melting point or solubility range of less than about 100 ° C.) at or near atmospheric temperature. The ionic liquid can include two or more different salts (eg, a mixture of salts containing two or more different cations, anions, or both). The ionic liquids of the present invention are often hydrates and solvates. Thus, both hydrates and solvates are considered within the definition of “ionic liquid”.

  As used herein, “ionic liquid” means an ionic liquid that is partially or completely miscible with water.

  As used herein, “hydrophobic ionic liquid” means an ionic liquid that is relatively immiscible with water (ie, forms two phases at atmospheric conditions).

  As used herein, a “composition” includes a mixture of materials that make up the composition, as well as products formed by reaction or decomposition of materials that comprise the composition.

  As used herein, “derived from” means made or mixed from specific materials, but need not consist of simple mixing of these materials. Certain material “derived” substances may be simple mixtures of the original substances and may also contain reaction products of these substances or reaction products of the original substances. Product or decomposition product.

  As used herein, “halo” means chloro, bromo, fluoro or iodo and arylene is a divalent aromatic such as phenylene, naphthylene, biphenylene, anthracenylene, phenanthrenylene, and the like. Refers to a group, heteroarylene refers to a divalent heteroaromatic group such as pyrrolene, furanylene, thiophenylene, pyridinylene, etc., and alkylene is substituted with one or more heteroatoms (eg, nitrogen or oxygen) Means a divalent alkane group, cycloalkylene means a divalent cycloalkene group, which can be substituted with one or more heteroatoms (eg nitrogen or oxygen), alkenylene is one or more Means a divalent alkene group that can be substituted with a heteroatom such as nitrogen or oxygen.

As used herein, “docusate” is the anion of the bis (2-ethylhexyl) ester of sulfosuccinic acid. Formula docusate (anion) _{is, C 20 H 37 O 7 S} - a. As used herein, “docusate variants” include the compounds illustrated by the chemical structures I and III described below, and anions of bis (organo) ester derivatives of sulfosuccinic acid and It is believed to contain the anion of a bis (organoamino) derivative of sulfosuccinic acid.

  Any numerical value reiterated in this document is all from the lowest value in 1 unit increments to the highest value, assuming that there is a separation of at least 2 units between any lowest value and any highest value. Contains the value of. As an example, the amount of a component or the value of a process variable (eg, temperature, pressure, time, etc.) is suggested to be, for example, 1-90, preferably 20-80, more preferably 30-70. In some cases, values such as 15-85, 22-68, 43-51, 30-32, etc. are intended to be explicitly recited herein. For values less than 1, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are just examples specifically intended and all possible combinations of numerical values between the lowest and highest values listed are considered to be expressly presented in this application in a similar manner. Should.

  The ionic liquid of the present invention is composed of one or more compounds. Thus, the ionic liquid can be a pure compound or a mixture of compounds. Each compound comprises an anion or a mixture of anions and a cation or a mixture of cations as described below.

R ₁ —O—C (O) —CH (SO ₃ ^— ) ^— R ₃ —C (O) —O—R ₂ I; and

.

(Anion)
Exemplary anions of the compounds of the present invention include those having a chemical structure selected from R ₁ , R ₂ , R ₄ and R ₅ in structures I and II above, independently substituted or unsubstituted alkyl And those selected from the group consisting of a group or an alkenyl group. The alkyl or alkenyl group of R ₁ , R ₂ , R ₄ and R ₅ should have a sufficient number of carbon atoms so that the ionic liquid has the desired properties. For example, when a hydrophobic ionic liquid is desired, the total number of carbon atoms in the ionic liquid is typically greater than when a hydrophilic ionic liquid is desired. However, if there are too many carbon atoms in the anion, the ionic liquid may become less useful as an ionic liquid due to reduced properties such as vapor pressure, dipole moment, polarity, and the like.

For hydrophobic ionic liquids, R ₁ , R ₂ , R ₄ and R ₅ are preferably independently selected from alkyl groups having about 5 or more carbon atoms, preferably about 6 to about 18 carbon atoms. Is done. One preferred group for R ₁ , R ₂ , R ₄ and R ₅ is —CH ₂ —CH (CH ₂ CH ₃ ) (CH ₅ CH ₂ —CH ₃ ). This group gives properties to the ionic liquid, is also useful in terms of cost, and is convenient to manufacture.

R ₃ in the above structure I is a substituted or unsubstituted alkylene group, heteroarylene group, arylene group, or cycloalkylene group. Preferably, R ₃ is a substituted or unsubstituted alkylene group, and even more preferably R ₃ is — (CH ₂ ) _n —, where n is an integer from about 1 to about 10. is there.

R ₆ , R ₇ and R ₈ are independently hydrogen (H) or selected from other substituents such as, for example, alkyl, NO ₂ , halo, cyano, silyl and OH. Preferably R ₆ , R ₇ and R ₈ are H.

In some examples, two or more adjacent substituents (eg, R ₁ and R ₂ , R ₄ and R ₅ , R ₆ and R ₇ , and / or R ₇ and R ₈ ) are taken together. Thus forming a ring such as a 5- to 7-membered carbocyclic ring. Examples of such carbocyclic rings include cyclopentyl and cyclohexyl rings.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ can be optionally substituted with one or more substituents. The type of substituent is not particularly important as long as the compound or mixture of compounds has the desired ionic liquid properties. Thus, the substituents typically include representative and non-representative organic substituents such as those selected from the group consisting of alkyl, NO ₂ , halo, cyano, silyl, OH and other suitable substituents. Can be mentioned. The substituent itself can often be further branched.

Another exemplary anion that can be used to make an ionic liquid is the following chemical structure:
^{_{R 1 -N (R 2) -C}} (O) -CH (SO 3 -) -R 3 -C (O) -N (R 4) -R 5 III
A docusate variant having

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in chemical structure III are independently a hydrogen atom (H) or a carbon-containing group (eg, alkyl, alkenyl, alkynyl, aryl, benzyl, alkyl-ether) Etc.).

In certain embodiments, the source of the anion is the sodium salt of 2-ethylhexylamide sulfonate salt, which can be synthesized using known techniques having the benefits of this specification. For example, an anion having the above chemical structure III in which R ₁ and R ₅ are each a 2-ethylhexyl group, R ₂ and R ₄ are each a hydrogen atom, and R ₃ is a methylene group was prepared. Two different ionic liquids were prepared with this anion by first isolating as a sodium salt and then reacting with a source of two different cations. The cation in one ionic liquid was a tetrabutylammonium cation. The cation in the other ionic liquid was 1-methyl-3-hexylimidazolium.

In another experiment, a second anion having the above chemical structure III, wherein R ₁ and R ₅ are each a 2-ethylhexyl group, R ₂ and R ₄ are each an ethyl group, and R ₃ is a methylene group Was prepared. Two or more ionic liquids are first isolated as sodium salts and then (in separate experiments) then the same source of the two cations (ie, tetrabutylammonium and 1-methyl-3-hexylimidazolium) Prepared with this anion by reacting with.

  Based on experiments where an ionic liquid was made from an anion having the chemical structure III, each of the R groups in the chemical structure III varies in length or composition, as in docusate salts and derivatives and variants thereof. And, when combined with an appropriate cation (eg, onium cation), it is still believed to produce an ionic liquid.

(Cation)
As long as the ionic liquid has properties suitable for its intended use, the cation of the produced ionic liquid is not particularly important. Representative useful cations include, for example, “onium” cations. Onium cations include substituted or unsubstituted cations such as ammonium, phosphonium and sulfonium cations. Preferred onium cations include, for example, substituted or unsubstituted N-alkyl or N-arylpyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, triazolium, imidazolinium, methylpyrrolidinium, isothiazolium , Isoxazolium, oxazolium, pyrrolium and thiophenium. Substituents include one or more of the following groups: halo, alkyl groups, and aryl groups such as phenyl. In addition, two adjacent substituents can be taken together to form an alkylene radical, thereby forming a ring structure centered on N. Alkyl radicals, phenyl radicals and alkylene radicals can be further substituted. Another particularly preferred cation is an ammonium cation substituted with one or more groups (eg, an alkyl group and an aryl group such as phenyl). Many such cations and substituted cations are described in US Pat. Nos. 5,827,602 and 5,965,054, which are incorporated by reference in their entirety.

  Other suitable cations include BMIM, tetrabutylammonium, tributylmethylammonium, tetrabutylphosphonium, tetraethylammonium, N, N-dialkylpyrrolidinium, trimethyl-2-hydroxyethylammonium, N, N′-dialkylimidazolium, N-alkylpyridinium or a mixture thereof may be mentioned. The cation can be an onium cation, optionally containing 4 or more carbon atoms.

(Processes for making compounds having structures I-III, and mixtures thereof)
The ionic liquid compounds of Structures I-II can be conveniently made by a number of different processes. One process suitable for making the hydrophobic or hydrophilic ionic liquids or mixtures of the present invention uses metathesis (ie, a double decomposition reaction), whereby two or more compounds react with two. Including the step of forming one or more new compounds, one of which is an ionic liquid. For example, reacting [bmim] Cl with sodium docusate yields [bmim] docusate and NaCl. The two or more compounds produced by the metathesis reaction can then be separated by any means.

  The manner in which two or more compounds are contacted to form an ionic liquid is not particularly important as long as the desired reaction occurs. In general, the compounds can be mixed in any order and formed in situ, or can be mixed with a solvent such as water that is at least partially miscible and does not significantly react with any compound.

  Starting compounds are often readily available, and many syntheses are available to those skilled in the art to make the desired starting compounds. Mixing conditions can vary depending on the particular compound used and the desired product. In most instances, the compound and any solvent (eg, water or dichloromethane) at atmospheric pressure and high enough to cause the reaction, but not high enough to decompose or boil any starting compound. In contact is acceptable. In general, the contact temperature can range from about 75 ° C to about 110 ° C, preferably from about 85 ° C to about 100 ° C. When water is used as the solvent, temperatures of about 75 ° C to about 110 ° C are sometimes preferred. This is because there is a tendency to break the emulsion that typically forms between the ionic liquid and water. On the other hand, when the solvent is organic (eg, dichloromethane), the preferred temperature is typically low, substantially around normal room temperature (eg, 25 ° C.) or slightly above room temperature.

  The manner in which the elevated temperature is achieved and maintained is not particularly important. Often, any heating element can be used such that the compounds are mixed or the starting compounds can be heated separately and then mixed. Similarly, any vessel or reactor can be used as long as it is the appropriate size and material. Often it is advantageous to use a stirring means to facilitate the reaction.

  In general, the elevated temperature is maintained for at least a sufficient time until the desired reaction occurs to the desired extent. In some instances, it may be desirable to maintain the elevated temperature for a longer time than the time required for the reaction to complete. In this manner, any low-boiling compounds that are formed as water or as a by-product or present as a solvent can be removed by boiling.

  The amount of each of the starting materials can vary depending on the desired yield. In general, high yields are often obtained by using approximately stoichiometric amounts of reactants (ie, a ratio of about 1: 1). However, as those skilled in the art will appreciate, different reaction conditions may alter the ratio of reactants that yields the optimum yield.

  If it is desired to make a mixture of ionic liquids containing two or more different salts, it can be achieved by using a mixture of three or more different compounds to form various salts. If desired, the resulting ionic liquid salt mixture can then be used as a mixture and the individual salts can be separated by conventional means.

  If necessary, the ionic liquid or ionic liquid mixture can be removed from the solvent and / or reaction mixture by any suitable means, the maximum efficiency of which varies depending on the type of ionic liquid or mixture and the desired purity. obtain. Suitable recovery means include rotary evaporation or distillation, azeotropic distillation, ion chromatography, liquid-liquid extraction, crystallization, pervaporation, desiccant and reverse osmosis.

  Although the above procedure can be used to make hydrophobic or hydrophilic ionic liquids, in some applications it is preferred to make hydrophobic ionic liquids. This is because hydrophobic ionic liquids are often less soluble in water, which is often used as a reaction medium. Thus, simple liquid-liquid extraction can be used to separate hydrophobic ionic liquids from soluble byproducts. In contrast, hydrophilic ionic liquids are often miscible with by-products. As a result, different separation methods (eg, solvent extraction) can be used. For example, it may be desirable or necessary to extract the ionic liquid using a hydrophobic solvent such as an alkyl chloride (eg, methylene chloride).

(Characteristics and use of the ionic liquid of the present invention)
The purity of the ionic liquid produced by the process of the present invention can often be 55% or more, preferably 60% or more, more preferably 70% or more, and most preferably 80% or more. This is advantageous for processes that require high purity materials such as electrical engineering. Ionic liquids are also preferably hydrophobic and are therefore useful in many processes as a substitute for organic solvents and in mixtures with catalysts such as ZnCl ₂ , CuCl ₂ , AlCl ₃ and organic catalysts.

  The ionic liquids of the present invention are also often useful in mixtures with hydrocarbons such as alkanes (eg, hexane). This mixture often does not retain an electrostatic charge and therefore does not easily ignite or explode.

(Docusate and modified docusate in supercritical CO ₂ application)
Tetrabutylammonium docusate has been found to be soluble in supercritical carbon dioxide (CO ₂ ). Supercritical applications using CO ₂ typically operate at temperatures above about 32 ° C. and pressures above about 1,070 psi. Docusate and docusate variant based ionic liquids are believed to be useful adjuvants, additives and surfactants for addition to supercritical CO ₂ for washing, synthesis and separation applications.

(Docusate as antistatic agent and modified docusate)
Docusate and docusate variant-based ionic liquids are believed to be useful antistatic additives for fuel and polymer applications. Docusate and docusate variant-based ionic liquids tend to be partially or fully miscible with hydrocarbons (eg, alkanes such as hexane) and can be added to the fuel as an antistatic additive. These ionic liquids can also be added to polymers such as polyvinyl acetate as antistatic additives.

(Docusate and modified docusate in ionic liquid blend)
In one embodiment, two or more ionic liquids are blended together to form an improved reaction solvent. Lewis acid ionic liquids are advantageously blended with ionic liquids based on docusate or docusate variants to provide better mixing between reactants to form an improved reaction solvent that improves reaction kinetics. obtain. Because ionic liquids of docusate and docusate variant tend to be at least relatively miscible with the hydrocarbon stream, they tend to inhibit the formation of two phases and improve mixing and contact between the reactants. Examples of Lewis acid ionic liquids believed to be useful for making blends with sulfonate anions (eg, docusate and docusate variants) ionic liquids of the present invention were filed in August 2003, Disclosed in a pending US patent (serial number not currently known) of the title "Lewis Acid Ionic Liquids" invented by Roger Mullton, as if fully set forth herein Is incorporated by reference.

  Exemplary Lewis acid ionic liquids useful in these blends include (i) cations selected from ammonium cations, sulfonium cations and phosphonium cations and having less than 14 total carbon atoms; and (ii) having the formula AlyR3y + 1. Here, y is 0 or more, and R is an ionic liquid having an anion selected independently from the group consisting of an alkyl group and a halogen group. A suitable anion for the Lewis acid ionic liquid in the blend is the aluminum chloride anion.

  A suitable cation for the Lewis acid ionic liquid is tetraalkylammonium. Depending on the desired ionic liquid properties, it may be advantageous for one or more alkyl groups to be optionally substituted with one or more suitable substituents. Suitable substituents include, for example, halogen (eg, chloride, bromide or iodide). Particularly preferred tetraalkylammonium cations include trimethylethylammonium, trimethylchloromethylammonium, trimethylbutylammonium and tributylmethylammonium.

Another suitable cation for the Lewis acid ionic liquid is an N-alkyl substituted, saturated heterocycle (eg, piperidinium and morpholium). In particular, piperidinium substituted on the nitrogen with an alkoxy or alkyl group (eg — (CH ₂ ) ₂ OMe, butyl or propyl) is preferably advantageous. Pyrrolidine-based cations can also be used. The cation can include an ether functionality (eg, NCH ₂ CH ₂ OCH ₃ ⁺ ). The cation may comprise a halogenated alkyl group.

Exemplary Lewis acid ionic liquids for blends include ammonium salts (eg, MeBu ₃ NCl, Me ₃ pentyl NCl, Me ₃ butyl NCl, MeEt ₃ NCl, Me ₂ Et ₂ NCl, Cl—CH ₂ —NMe). ₃ Cl or N-methyl N-butylpyrrolidinium Cl) is a source, and ionic liquids with anions and cations of ammonium chloride are mentioned. Other exemplary Lewis acid ionic liquids include N-alkyl substituted piperidinium heptachlorodialuminate, trimethylchloromethylammonium heptachlorodialuminate, trimethylbutylammonium heptachlorodialuminate, and tributylmethylammonium Heptachlorodialuminate is mentioned.

  The following examples are not intended to limit the invention, but rather are intended only to illustrate a few specific ways in which the invention can be used.

Example 1 Synthesis of Tetrabutylammonium Docusate
1 mole of sodium docusate (444 grams) was dissolved in 2 liters of water, then 1 mole of tetrabutylammonium bromide (321 grams) was added as a solid. After stirring for several minutes, stirring was stopped and the solution was separated into two layers. The upper layer was collected with a separatory funnel. This was washed twice with 1 liter of water and heated to 100 ° C. to promote layer dissociation. The resulting tetrabutylammonium docusate was heated to 110 ° C. to remove any water dissolved therein. The yield was nearly quantified (624 grams, 94% yield).

(Examples 2 to 5)
The ionic liquids of Examples 2-5 in Table 1 below were substantially the same as in Example 1 except that about 1 mole of the starting material of Table 1 was replaced with 1 mole of tetrabutylammonium bromide of Example 1. In the same manner.

  (Table 1)

(Examples 6 to 10)
The ionic liquids of Examples 6-10 in Table 2 below were made by dissolving sodium docusate in dichloromethane and dissolving the starting material in Table 2 in a separate flask in dichloromethane. The two solutions were mixed and stirred for about 12 hours. The solution was then filtered to remove the precipitated solid salt and then evaporated to a cloudy syrup. This cloudy syrup was then extracted with diethyl ether, hexane or mixtures thereof and filtered again to remove solid salts. After rotary evaporation, the residue was redissolved with hexane / ether and the filtration process was repeated until no further solid was formed (gradually using a small fraction of ether in the mixture). The resulting salt was then washed with water and dried under vacuum before affecting the final removal of inorganic salts.

  (Table 2)

  The ionic liquids of Examples 6 to 10 were generally hydrophobic ionic liquids. In the case of Example 6, i.e. 1-hexylmethylimidazolium docusate, two phases formed when contacted with less than 40% by volume of water, even after stirring. However, when 1-hexyl-3-methylimidazolium docusate was contacted with 50% by volume of water, stirring produced a firm, visible monophasic gel. Additional water was added to the gel and then stirred, again forming two phases. While not wishing to be bound by any particular logic, it is believed that some ionic liquids of the present invention can be hydrated or solvated when mixed with a proportion of water. This results in an ionic liquid that is insoluble, forms two phases when mixed with a proportion of water, and forms a single phase when mixed with other proportions of water. This inherent behavior can be very advantageous for some applications where solubility or insolubility with water is important.

(Example 11)
This example details the synthesis of a tetrabutylammonium molten salt of an amide having formula III above. 1/10 mole (50 g) of an amide-sulfonate salt sodium salt having the above chemical structure III (R ₂ and R ₄ are CH ₂ CH ₃ and R ₁ and R ₅ are each a 2-ethylhexyl group , And R ₃ is CH ₂ ) was dissolved in 250 mL of dichloromethane and 1/10 mol (32 g) of tetrabutylammonium bromide was added as a solid. The mixture was stirred for 1 day and then filtered first through filter paper and then through a short plug of silica gel. The eluted dichloromethane solution was quickly washed with water, dried over magnesium sulfate and the solvent removed under vacuum to give the desired product in high yield (64 g, 89%). The product salt is soluble in both water and some common organic solvents such as dichloromethane and acetone. The dissolution range of the obtained salt was less than about 30 ° C. This is because the product was a viscous oil at room temperature. This product salt included the bis (sulfosuccinic acid N-ethyl-N- (2-ethylhexyl) diamide) anion paired with the tetrabutylammonium cation.

(Examples 12 to 19)
These examples detail the preparation of an ionic liquid from the sodium salt of sulfosuccinate, a docusate variant. This ester was then combined with the onium cation to make an onium molten salt.

  10 grams (0.03 mole) of tetrabutylammonium bromide was dissolved in 50 mL of water and 12 grams (0.03 mole) of di-n-hexyl ester of sulfosuccinic acid was dissolved in this stirred solution as a solid. (“Di-n-hexyl ester of sulfosuccinic acid” means that the sulfosuccinic acid molecule is esterified with the two carbonyl groups of the sulfosuccinic acid molecule, not the sulfonic acid group. ). After stirring for several minutes, the aqueous layer was extracted with three successive 50 mL portions of dichloromethane, combined, dried over anhydrous magnesium sulfate, and evaporated to give the desired product (13 g, 73 %yield). The dissolution range of the obtained salt was less than about 30 ° C. this is. This is because the product was a viscous oil at room temperature.

  The same experimental procedure was used to prepare an ionic liquid of tetrabutylammonium cation and the sodium salt of the following docusate variant: (i) di-n-cyclohexyl ester of sulfosuccinic acid; (ii) di-sulfosuccinic acid di- (iii) di-n-butyl ester of sulfosuccinic acid; (iv) di-isobutyl ester of sulfosuccinic acid; (v) di-neopentyl ester of sulfosuccinic acid; (vi) di-n of sulfosuccinic acid; Heptyl ester; and (vii) di-n-heptyl ester of sulfosuccinic acid. The solubility range of the resulting salt was less than about 80 ° C and typically between about 40 ° C and 80 ° C. Octyl docusate and heptyl docusate variants had lower solubility ranges, as identified by the fact that they were viscous liquids at room temperature.

(Representative NMR data)
The structure and composition of the ionic liquid was determined by 1H-NMR spectroscopy. For all docusate salts (sulfosuccinic acid 2-ethylhexyl diester), the spectrum simply consists of resonances originating from anions that overlap the spectrum of the cation. For all docusate salts, the anion-derived resonances (with minor modifications) were within the following range: (300 Mhz, CDCl3, d: 0.73-0.83 (triplet), 1 24-1.70 (overlapping multiplets), 3.05-3-31 (complex m), 3.90-4.25 (overlapping m)
Cation resonance (300 MHz, CDCl3, d): (1-methyl-3-hexylimidazolium): 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)
(Tetraethylammonium): 1.32 (t), 3.34 (q)
(Tetrabutylammonium): 1.03 (t), 1.20-1.40 (overlapping m), 3.23 (q)
(Tetraoctylammonium): 0.86 (t), 1.18-1.50 (overlapping m), 3.25 (q)
(N- methyl _{-N- (CH 2 CH 2 OCH 2} CH 3) pyrrolidinium): 0.86 (t), 1.31 (m), 2.11 (m), 3.0-4.2 ( complex M)
(Trimethyl hexadecyl ammonium): 0.87 (t), 1.20-1.60 (overlapping m), 2.13 (s), 3.15 (q)
(Methyltributylammonium): 0.84 (t), 1.23-1.70 (overlapping m), 2.20 (s), 3.24 (m)
(1,2-bis (tributylammonium) ethane): 0.83 (t), 1.22-1.58 (overlapping m), 2.20 (s), 3.22 (m).

Several docusate variant ionic liquids were also made. The NMR spectra of these salts, like the docusate variant ionic liquid, consist of the spectrum of a specific anion overlying the spectrum of a specific cation. The following are the NMR data for the tetrabutylammonium derivatives of the three docusate variant salts. For each salt, the resonance arising from the cation is consistent with that of the docusate tetrabutylammonium cation, the values for which are listed above. The following are resonances derived from the anions of the salts of these examples (300 MHz, CDCl 3, d):
Bis (sulfosuccinic acid n-hexyl diester): 0.84 (t), 1.2-1.4 (overlapping m), 1.6 (m), 3.07 (m), 4.05-4. 22 (overlapping m)
Bis (sulfosuccinic acid cyclohexyl diester): 1.2-1.8 (complex overlapping m), 3.10 (M), 4.2-4.8 (overlapping m)
Bis (sulfosuccinic acid neopentyl diester): 0.87 (s), 0.90 (s), 3.05 to 3.25 (overlapping m), 3.78 (s), 3.80 to 3.93 (M), 4.23-4.29 (m)
Bis (sulfosuccinic acid N-ethyl-N- (2-ethylhexyl) diamide): 0.75-0.88 (triplet), 1.21-1.78 (overlapping multiplet), 2.24 (m) 3 .11-3-41 (complex m), 3.86-4.45 (overlapping m).

Claims (59)

An ionic liquid composition comprising:
(A) cation having 4 or more carbon atoms; and ^{_{(b) R 1 -O-C}} (O) -CH (SO 3 -) -R 3 -C (O) -O-R 2 I; and

An anion selected from the group consisting of wherein R ₁ , R ₂ , R ₄ and R ₅ are independently selected from the group consisting of a substituted or unsubstituted alkyl or alkenyl group;
R ₃ is a substituted or unsubstituted alkenyl group, heteroarylene group, arylene group or cycloalkylene group;
R ₆ , R ₇ and R ₈ are independently selected from H, alkyl, NO ₂ , halo, cyano, silyl and OH;
Or can R ₁ and R ₂ together form a ring;
Or can R ₄ and R ₅ together form a ring;
Or an ionic liquid composition comprising an anion wherein R ₆ and R ₇ or R ₇ and R ₈ together can form a ring. The composition of claim 1, wherein the anion has the chemical structure I. The composition of claim 2, wherein R ₁ and R ₂ are independently selected from alkyl groups having about 5 or more carbon atoms. The composition of claim 2, wherein R ₁ and R ₂ are independently selected from alkyl groups having from about 6 to about 18 carbon atoms. The composition of claim 2, wherein R ₃ is — (CH ₂ ) _n —, wherein n is an integer from about 1 to about 10. R ₁ and R ₂ are independently selected from alkyl groups having from about 6 to about 18 carbon atoms The composition of claim 5. The composition according to claim 6, wherein n is 1 and R ₁ and R ₂ are —CH ₂ —CH (CH ₂ CH ₃ ) (CH ₅ CH ₂ —CH ₃ ). The composition of claim 1, wherein the anion has the chemical structure II. The composition of claim ₈ , wherein R ₆ , R ₇ and R ₈ are H. R ₄ and R ₅ are independently selected from alkyl groups having from about 5 or more carbon atoms The composition of claim 8. R ₄ and R ₅ are independently selected from alkyl groups having from about 6 to about 18 carbon atoms The composition of claim 8. R ₄ and R ₅ are independently selected from alkyl groups having from about 5 or more carbon atoms The composition of claim 9. R ₄ and _{R 5} are _{-CH 2 -CH (CH 2 CH 3} ) (CH 2 -CH 2 -CH 3), A composition according to claim 9. The composition of claim 2 further comprising a catalyst. The composition according to claim 7, further comprising a catalyst. The composition according to claim 2, further comprising a hydrocarbon. The composition according to claim 7, further comprising a hydrocarbon. The composition according to claim 8, further comprising a catalyst. The composition according to claim 9, further comprising a catalyst. The composition according to claim 8, further comprising a hydrocarbon. Furthermore, the composition of Claim 9 containing a hydrocarbon. The composition of claim 1, wherein the cation is quaternary ammonium or quaternary phosphonium. The quaternary ammonium cation is substituted or unsubstituted pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, triazolium, imidazolinium, methylpyrrolidinium, isothiazolium, isoxazolium, oxazolium, pyrrolium, and 23. The composition of claim 22, wherein the composition is independently selected from the group consisting of thiophenium. The composition according to claim 1, wherein the cation is an ammonium cation substituted with one or more groups selected from the group consisting of an alkyl group and an aryl group. 23. The composition of claim 22, wherein the quaternary ammonium cation is BMIM. The cation is tetrabutylammonium, tributylmethylammonium, tetrabutylphosphonium, tetraethylammonium, N, N-dialkylpyrrolidinium, trimethyl-2-hydroxyethylammonium, N, N′-dialkylimidazolium, N-alkylpyridinium or these The composition of claim 1, which is a mixture of An ionic liquid composition containing at least about 55% by weight of an ionic liquid comprising:
(A) a cation; and (b) R ₁ —O—C (O) —CH (SO ₃ ^— ) ^— R ₃ —C (O) —O—R ₂ I; and

An anion selected from the group consisting of:
R ₁ , R ₂ , R ₄ and R ₅ are independently selected from the group consisting of substituted or unsubstituted alkyl or alkenyl groups;
R ₃ is a substituted or unsubstituted alkenyl group, heteroarylene group, arylene group or cycloalkylene group;
R ₆ , R ₇ and R ₈ are independently selected from H, alkyl, alkoxy, alkylthio, SO ₃ H, NO ₂ , halo, cyano, silyl and OH;
Or can R ₁ and R ₂ together form a ring;
Or can R ₄ and R ₅ together form a ring;
Or an ionic liquid composition comprising an anion wherein R ₆ and R ₇ or R ₇ and R ₈ together can form a ring. 28. The composition of claim 27, wherein the ionic liquid is hydrophobic. 30. The composition of claim 28, wherein the cation is quaternary ammonium or quaternary phosphonium. The quaternary ammonium cation is independently substituted or unsubstituted pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, triazolium, imidazolinium, methylpyrrolidinium, isothiazolium, isoxazolium, oxazolium. 30. The composition of claim 29, selected from the group consisting of, pyrrolium, and thiophenium. 31. The composition of claim 30, wherein the cation is an ammonium cation substituted with one or more groups selected from the group consisting of alkyl groups and aryl groups. 32. The composition of claim 30, wherein the quaternary ammonium cation is BMIM. The cation is tetrabutylammonium, tributylmethylammonium, tetrabutylphosphonium, tetraethylammonium, N, N-dialkylpyrrolidinium, trimethyl-2-hydroxyethylammonium, N, N′-dialkylimidazolium, N-alkylpyridinium or these 28. The composition of claim 27, which is a mixture of: 28. The composition of claim 27, wherein the anion is docusate. 28. The composition of claim 27, wherein the anion has the chemical structure I and is hydrophobic. 28. The composition of claim 27, wherein the anion has the chemical structure II and is hydrophobic. 28. The composition of claim 27, wherein the anion has the chemical structure I and is hydrophilic. 28. The composition of claim 27, wherein the anion has the chemical structural formula II and is hydrophilic. The composition of claim 1, wherein the ionic liquid is hydrophobic. The composition of claim 1, wherein the ionic liquid is hydrophilic. The anion is (i) a di-n-cyclohexyl ester of sulfosuccinic acid; (ii) a di-n-octyl ester of sulfosuccinic acid; (iii) a di-n-butyl ester of sulfosuccinic acid; An isobutyl ester; (v) a di-nepentyl ester of sulfosuccinic acid; (vi) a di-n-heptyl ester of sulfosuccinic acid; and (vii) a di-n-heptyl ester of sulfosuccinic acid. The composition according to claim 1. 42. The composition of claim 41, wherein the cation is tetrabutylammonium. An ionic liquid composition comprising:
(A) an onium cation; and (b) the following structure:
^{_{R 1 -N (R 2) -C}} (O) -CH (SO 3 -) -R 3 -C (O) -N (R 4) -R 5 III
Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ independently comprise an anion selected from the group consisting of a hydrogen atom and a carbon-containing group, An ionic liquid composition, wherein the liquid has a melting point less than about 100 ° C. R ₁ is 2-ethylhexyl, _{R 2} is ethyl, _{R 3} is a methylene group, _{R 4} is ethyl, and, _{R 5} is 2-ethylhexyl, composition according to claim 43 . 45. The composition of claim 44, wherein the cation is tetrabutylammonium. 45. The composition of claim 44, wherein the cation is 1-methyl-3-hexylimidazolium. 44. The method according to claim 43, wherein R ₁ is 2-ethylhexyl, R ₂ is a hydrogen atom, R ₃ is a methylene group, R ₄ is a hydrogen atom, and R ₅ is 2-ethylhexyl. Composition. 48. The composition of claim 47, wherein the cation is tetrabutylammonium. 48. The composition of claim 47, wherein the cation is 1-methyl-3-hexylimidazolium. 44. The composition of claim 43, further comprising a hydrocarbon. The cation and the anion form a molten salt having a melting point of less than about 100 ° C., and the molten salt is tetrabutylammonium docusate, MeBu ₃ N docusate, Me ₃ N (CH ₂ ) ₆ NMe ₃ docusate, Bu ₄ P docusate, Et ₄ N docusate, 1-hexyl-3-methylimidazolium docusate, bromide 1-octyl-3-methylimidazolium docusate, 1-butyl-3-methylimidazolium docusate and 1-methyl The composition of claim 1 selected from the group consisting of -2-ethylimidazolium docusate. A composition comprising:
An ion containing an anion selected from the group consisting of (a) (i) docusate, (ii) an anion of a bis (organo) ester derivative of sulfosuccinic acid, and (iii) an anion of a bis (organoamide) derivative of sulfosuccinic acid Liquid; and (b) CO _{2 under} supercritical conditions
Wherein the ionic liquid is dissolved in the CO ₂ . A composition comprising:
(A) a hydrocarbon fuel; and (b) (i) docusate, (ii) an anion of a bis (organo) ester derivative of sulfosuccinic acid, and (iii) an anion of a bis (organoamide) derivative of sulfosuccinic acid A composition comprising an ionic liquid containing a selected anion. A composition comprising:
(A) a polymer; and (b) (i) docusate, (ii) an anion of a bis (organo) ester derivative of sulfosuccinic acid, and (iii) an anion of a bis (organoamide) derivative of sulfosuccinic acid An antistatic additive comprising an ionic liquid containing an anion. 55. The composition of claim 54, wherein the polymer is polyvinyl acetate. An ionic liquid composition comprising:
(A) an onium cation having 4 or more carbon atoms; and (b) an anion selected from the group consisting of docusate and docusate variants. 57. The ionic liquid composition of claim 56, wherein the ionic liquid melts in a temperature range that is greater than or equal to about 40 ° C. but less than about 80 ° C. A first ionic liquid which is a composition and is combined with the following second ionic liquid:
(A) the first ionic liquid, (i) a cation selected from the group consisting of an ammonium cation, a sulfonium cation and a phosphonium cation, wherein the cation is not tetrahedrally symmetric, (ii) A first ionic liquid having the formula Al _y R _{3y + 1} , wherein y is 0 or more and R is independently selected from the group consisting of an alkyl group and a halogen group;
(B) a second ionic liquid, comprising (i) docusate, (ii) an anion of a bis (organo) ester derivative of sulfosuccinic acid, and (iii) an anion of a bis (organoamide) derivative of sulfosuccinic acid A composition comprising a second ionic liquid comprising an anion selected from: 59. The composition of claim 58, further comprising a reactant, wherein the first ionic liquid and the second ionic liquid are effective reaction solvents for the reactant.