PROCESS FOR PREPARING IMIDAZOLIUM BASED IONIC LIQUIDS WITH DI-POLYMERIZED OXIRANE BASE

Abstract

The present invention relates to a process of synthesis of certain ionic liquids di-polymerized based Radziszewsky type reaction, whereby primary amines containing at least one terminal functional group, for example OH, aldehydes and a mineral or organic acid, react exothermically in a single step, thus resulting in an ionic liquid by condensation, then oxirane derivative molar quantities are added, by controlling the temperature and pressure a di-polymerized ionic liquid is obtained. The process of the present invention is advantageous because it provides a synthesis scheme for di-polymerized ionic liquids, primarily using short reaction times and high performance; this process can be further scaled for industrial production and it can accept alternative chemical precursors of lower cost.

An example of the general synthesis scheme of ionic liquids-propoxylated di (LI's) imidazolium follows:

##STR00001##

Whereby an efficiency greater than 96% of propoxylated ionic liquid is obtained, the product characterized by spectroscopic data.

Claims

1. A process for producing Ionic Liquids (IL's) with symmetrical di-polymerized imidazolium base, comprising the following steps: I). Preparation of the reaction mixture. Place the mixture in a reaction system, preferably in the following sequence: a mono-aldehyde such as poly-oxy-methylene, in conjunction with the following reagents: an organic inorganic acid (mineral) or, Amino-alkanes with a chain of 2 to 18 linear carbons, branched and/or cyclic, preferably linear amino-alkanes and branched, cyclic rings of 3 to 8 carbons (2 molar) having at least one OH terminal group, a di-aldehyde as etanedial in equimolar amounts, oxirane derivatives, preferably methyl oxirane ( molar). II). IIs obtained by following step I where the reaction mixture as obtained in step (I) is kept under stirring for 1.5 to 8 h, in the temperature range between 10 and 150 C., then it is left under stirring for a minimum period of 2 h until a single phase is obtained. The Imidazolium compounds thus obtained are purified by evaporation, frozen and lyophilized to yield the pure product. III). A preparation method and characterization of di-polymerized pure ionic liquid. The pure product described in stage II is put in a closed stainless steel reactor, with an inorganic base (pulverized), with the vacuum in the reactor having a minimum pressure of 5 psi and moisture of less than 0.1%: the reactor content is warmed to 130 C., then addition of the oxirane derivative (OD) is started, taking care that the reaction temperature is within the range between 140 and 170 C., with a maximum pressure inside the reactor of 58.8 psi (4 kg/cm.sup.2) after adjusting the cloud point, the reactor content is cooled down to 90 C. and it is connected to the vacuum system, then cooled down to 60 C. and neutralized with acetic acid; the product is characterized by spectroscopic data to verify the obtention of a di-polymerized imidazolium base ionic liquid, with an efficiency greater than 96%.

2. A process for the preparation of symmetrical di-polymerized imidazolium base ionic liquids according to claim 1, wherein the amino-alkanes have a chain of 2 to 18 carbons, as used in step I), preferably linear, branched and/or cyclic with at least one OH end group.

3. A process for the preparation of symmetrical di-polymerized imidazolium base ionic liquids according to claim 1, wherein the aldehydes used in step I) preferably are: Type 1, A Di-aldehyde, more preferably Etanedial (oxal-aldehyde) and Type 2, a mono-aldehyde, more preferably a poly-oxy-methylene.

4. A process for the preparation of symmetrical di-polymerized imidazolium base ionic liquids according to claim 1, wherein the inorganic or mineral acid used in step I), preferably hydrochloric acid in aqueous 37% or sulfuric acid 98%, nitric 95%, and/or an organic acid such as acetic acid.

5. A process for the preparation of symmetrical di-polymerized imidazolium base ionic liquids according to claim 1, wherein the oxiranes used in step 1) preferably come from methyloxirane.

6. A process for the preparation of symmetrical di-polymerized imidazolium base ionic liquids according to claim 1, where the pressure can range from 55-210 psi.

7. A process for the preparation of symmetrical di-polymerized imidazolium base ionic liquids according to claim 1, where the temperature can range from 10 to 180 C.

8. A process for the preparation of symmetrical di-polymerized imidazolium base ionic liquids according to claim 1, characterized in that in step III, wherein the molar ratio is from 1:1 to 1:50, that this interval is not limiting.

9. A process for the preparation of symmetrical di-polymerized imidazolium base ionic liquids according to claim 1, wherein the basic solution may be a base pka more than 8, preferably bases having pKa close to 10, particularly preferred with bases pKa (measured in water) greater than 10, where the bases used include, but are not limited to, sodium hydroxide, potassium hydroxide, lithium hydroxide.

10. A process for the preparation of symmetrical di-polymerized imidazolium base ionic liquids according to claim 1, characterized by providing a yield of at least 96%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0022] An analysis of previous results led us to disclose an original process leading to the synthesis of certain ionic liquids with symmetrical di-polymerized based compounds which uses the Radziszewski type reaction, as follows: primary amines, aldehydes and a mineral or organic acid react exothermically in a single step, thus resulting in ILs by condensation, from which molecular groups of the oxirane type are incorporated. Preferably, the ILs are derived from ethanolamine and the degree of polymerization ranges from 2 to over 50, for di-polymerized ionic liquids.

[0023] The general scheme shown above illustrates the synthesis of ILs with di-propoxylated (without limiting the use of oxirane derivatives) imidazolium based ILs.

##STR00002##

[0024] The reaction is performed following this scheme and at least 96% of the product is obtained and further characterized by spectroscopic data, which gives the following:

[0025] (1): Primary Amines (R=chains, branches and/or cycles of 2 to 18 carbons) with at least one OH end group.

[0026] (2): Etanedial (oxal-aldehyde)

[0027] (3): Poly-oxy-methylene

[0028] (4): inorganic acid (mineral), preferably hydrochloric acid, sulfuric or nitric, or an organic acid, preferably acetic.

[0029] (5): oxiranes, preferably methyloxirane

[0030] (6): inorganic base, preferably sodium hydroxide, potassium hydroxide or lithium hydroxide.

[0031] Thus, the process of the present invention comprises the following steps:

[0032] I) Preparation of the reaction mixture. A mono-aldehyde is placed in a reaction system, preferably with poly-oxy-methylene type, together with the reagents that are added preferably in the following sequence: an organic or inorganic acid (mineral) or, similar amino alkanes (2 molar) with at least one terminal OH group, and a di-aldehyde; in equimolar amounts.

[0033] II) Reaction. The reaction mixture obtained in step I is subjected to agitation for 1.5 to 5 h at a temperature ranging between 10 and 40 C., then was left for 1.5 to 3 h, preferably until forming a single phase.

[0034] III) The Purification of imidazolium type compounds was performed using a solvent or a mixture of solvents like polar aprotic, or preferably di-chloro-methane, chloroform, ethyl acetate, ethyl ether, etc., more preferably di-chloro-methane; The removal of some reaction products and unreacted materials is obtained by phase transfer at temperatures between 60 and 90 C., under reduced pressure or partial vacuum, for obtaining the pure ionic liquid, for later use.

[0035] IV) Characterization of the pure ionic liquid. It is verified that the color and impurities in the pure ILs are eliminated by dissolving it in water, preferably in a volume ratio of IL within 5, thus passing the solution through a column of active charcoal; the elution agent is frozen and lyophilized to yield pure product, thus giving a yield of at least 98% and, finally, the product is verified by spectroscopic techniques.

[0036] V) The ionic liquid obtained in previous stages (1 mol) in a closed stainless steel reactor, with an inorganic base sprayed, is placed in a sealed reactor; thus, the valve connecting the vacuum system opens and the reactor is filled for 30 min, then the vacuum in the reactor has a minimum of 5 psi pressure. The reactor is heated to 120 C. and these conditions are maintained until the moisture content is less than 0.1%; once this value is reached, the reactor contents are heated to 130 C., then at this point the heating is stopped and the addition of oxirane derivative (OD) starts, thus allowing the reactor temperature to increase after the exothermic reaction up to about 170 C.; then, a 90% load OD is added while monitoring the reaction temperature within the range between 140 and 170 C., and a maximum pressure of 58.8 psi (4 kg/cm.sup.2), with the control of temperature achieved by a cooling water jacket and by the reactor coil. After addition of 90% oxirane derivative (OD), the supply is stopped and the reaction is left for 30 min. Afterward, the other OD charge is added within a temperature range between 140 and 170 C. At this point a sampling is made along the reaction, as well as the analysis of the cloud point. Once the cloud point is adjusted, the reactor contents are cooled down to about 90 C. and the vacuum system enters to operation for 30 min. Then it follows a cooling down to about 60 C., then the vacuum is broken by allowing air inside and a neutralization with acetic acid is performed, using molar amounts relative to the base.

[0037] In this regard, it is important to note that: [0038] The amino-alkanes having a chain from 2 to 18 carbons may be employed in the process described above, these are linear, branched and/or cyclic, but amino-alkanes are preferably linear and branched amino-alkanes with cyclic rings of 3 to 8 carbons, also containing a hydroxy type functional group or any amino-alcohol with a chain of 3 to 18 carbons. [0039] The aldehydes used are preferably: [0040] A di-aldehyde such as Etanedial (oxal-aldehyde), and [0041] A mono-aldehyde as one of poly-oxy-methylene type. [0042] Inorganic or organic acids such as: [0043] Hydrochloric acid in aqueous solution at 30% [0044] Sulfuric acid 98% [0045] Nitric acid 95% [0046] Acetic Acid [0047] Polymers are of the oxirane type with functional oxi-type groups, which can be added in a molar ratio from 5 to 50 mol but this not a limiting figure when the pH is less than 10, but no less than 7.5, thus allowing that the reaction elapses at a temperature up to 180 C., but no less than 100 C., in about 1 to 6 h.

[0048] The characteristics of the synthesis products were verified by nuclear magnetic resonance (NMR) of .sup.1H and .sup.13C. For this, a Bruker Avance III machine of 300 MHz was used, with a reference of tetramethylsilane (TMS); the resonance signals of .sup.1H and .sup.13C of the solvent were used as internal references; the results are expressed by means of isomer chemical shifts (), which are expressed in parts per million (ppm), and are designated as singlet (s), doublet (d), triplet (t), multiplet (m); infrared spectroscopy (IR) was applied too for verifying the products formation, by means of a Perkin-Elmer FTIR-B, model 1600, in the region from 400 to 650 cm.sup.1 in series sapphire ATR. Also, the Mass spectra were obtained using a Bruker Instrument Compass 4.0 Data Analysis MicroTOF 10392 II-Q.

EXAMPLES

[0049] For a better understanding of the present invention but without limiting its scope, here are presented some practical examples.

Example 1

Synthesis of the Ionic Liquid Chloride N,N-polypropylene-imidazolium

[0050] In a flask is added with constant stirring the tri-mer poly-oxy-methylene (1 mol) and hydrochloric acid (1 mol) in aqueous solution at 37%, with stirring for 30 min. at 40 C. Then it was allowed to cool down in ice bath to temperatures below 10 C., then 2-aminoethanol (2 mol) was added drop-wise for about 30 min; once the mixture reach ambient temperature, stirring continues for 30 min, then ethanedial in aqueous solution (40%) is added, leaving for additional 30 min at room temperature. Then, the temperature is increased to 35-40 C. for 5 h. It is placed in the rotating evaporator (rotavapor) at 70 C. at 50 mbar. Under these conditions the yield is 96%. The product is then characterized by spectroscopic data: IR 3311, 3123, 2910, 1658, 1561, 1159, 1067 cm.sup.1; .sup.1H NMR (300 MHz, DMSO-d6) (ppm) 3.7-3.3 (m, 4H), 4.4 (m, 4H), 7.8 (d, 2H), 9.23 (s, 1H); .sup.13C NMR (300 MHz) (ppm) 51.66, 58.0, 122.6, 136.6; HRMS calculated 192.6402 C.sub.7H.sub.13ClN.sub.2O.sub.2, being 192.0775.

[0051] The ionic liquid, chloride N,N-diethanol-imidazolium (1 mol) is placed in a Parr reactor, then the valve connecting the vacuum system is open and the reactor is evacuated for 30 min, then the sodium hydroxide is loaded with the same vacuum sealing the reactor, then plugs are placed on the vent valves and sampling at the bottom allows to verify that the vacuum in the reactor is at least 5 psi. The reactor contents are heated to 120 C. for removing moisture down to less than 0.1%, thus the value of moisture is verified and the reactor contents are heated up to 140 C., once this temperature is reached, the heating is suspended and it starts the addition of propylene oxide (PO) (8 mol), thus allowing the reactor temperature to increase by the heat flow that is generated by the reaction exothermicity up to 170 C.; afterwards, there is a 90% loading of PO, always keeping the security issues until the reaction temperature is in the range between 140 and 170 C., and a maximum pressure inside the reactor of 4 Kg/cm.sup.2; in this case the temperature is controlled by introducing cooling water into the jacket and in the reactor coil. After addition of 90% charge of propylene oxide (PO), the PO supply is closed and the reaction is allowed for 30 min. Once this step occurs, the other charge of PO is allowed in at a temperature range between 140 and 170 C. After 1 h reaction, there is a take of sample and the cloud point is analyzed. Once this parameter is adjusted, the reactor content is cooled down to 90 C., then it is connected to the vacuum system to make the maximum vacuum for 30 min. Then, the system is cooled down to 60 C. and the vacuum is broken with air, then it is neutralized with acetic acid in molar amounts, relative to the soda. Under these conditions the yield is higher than 99%. The product was characterized by spectroscopic data: IR 3375, 3123, 2967, 2873, 1663, 1579, 1458, 1374, 1104 cm.sup.1; .sup.1H NMR (300 MHz, DMSO-d6) (ppm) 0.98 to 1059 (m), 2.32-2.40 (m), 3.13-3.75 (m), 7.66 (s), 7.69 (d), 7.95 (s); .sup.13C NMR (300 MHz) (ppm) 17.23, 20.18, 48.3, 54.5, 65.50, 67.32, 74.46, 76.81,121.6,172.5; Mw=487.215.

Example 2

Synthesis of Acetate Ionic Liquid N,NN,N-polypropylene-imidazolium

[0052] In a flask the tri-mer poly-oxy-methylene (1 mol) is added with constant stirring and glacial acetic acid (1 mol), then it is stirred for 30 min. at 40 C., then it is allowed to cool down within an ice bath, to a temperature below 10 C.; then, 2-aminoethanol (2 mol) is added drop-wise for about 30 min., until the addition is complete after keeping under stirring for 30 minutes at room temperature, then ethanedial in aqueous solution (40%) is added left for additional 30 min., both mixtures at room temperature. When this step is complete, the temperature is increased to 35-40 C. for 5 h. Under these conditions the yield is 95%. The product was characterized by spectroscopic data: IR 3311, 3123, 2910, 1780, 1658, 1561, 1159, 1067 cm.sup.1; .sup.1H NMR (300 MHz, DMSO-d6) (ppm) 2.2 (s, 3H), 3.7-3.3 (m, 4H), 4.4 (m, 4H), 7.8 (d, 2H), 9.23 (s , 1 HOUR); .sup.13C NMR (300 MHz) (ppm) 23.4, 51.66, 58.0, 122.6, 136.6, 177.2; HRMS calculated 216.2392 C.sub.9H.sub.16N.sub.2O.sub.4, being 216.1175. The ionic liquid, acetate N,N-diethanol-imidazolium (1 mol) in a Parr reactor is placed, then the valve connecting the vacuum system is open and it is evacuated into the reactor, for 30 min., then liquid soda is added by using the same vacuum, thus sealing the reactor and placing caps on the vent valves, sampling is performed and it is verified that the vacuum in the reactor is at least 5 psi. The reactor contents are then heated to 120 C., an empty set, and these conditions are maintained for the time to remove the moisture to less than 0.1%; once the correct value of moisture is reached, the reactor contents are heated up to 130 C. and, upon reaching this temperature, the heating is suspended and the addition of propylene oxide (PO) (8 mol) is started, allowing that the reactor temperature increases by the heat generated by the exothermic reaction up to 150 C., then a 90% load of PO is added, always verifying that the reaction temperature is within a range between 140 and 150 C., and a maximum pressure inside the reactor of 4 kg/cm.sup.2; the temperature is controlled by introducing cooling water in the jacket and in the reactor coil. After addition of the 90% charge of propylene oxide (PO), PO supply is closed and the reaction is left for 30 min. Once this step is over, the other charge of PO is added at temperatures between 140 and 150 C. After 1 h reaction, it is sampled and the cloud point is measured. Once the cloud point is verified, the reactor contents are cooled down to 90 C. and the vacuum stage is connected for 30 min. Then the system is cooled down to 60 C. and the vacuum is broken with air and then neutralized with acetic acid in molar amounts, relative to the soda. Under these conditions the yield is higher than 96%. The product was characterized by spectroscopic data: IR 3375, 3123, 2967, 2873, 1780, 1663, 1579, 1458, 1374, 1104 cm.sup.1; .sup.1H NMR (300 MHz, DMSO-d6) (ppm) 0.98 to 1059 (m), 2.2 (s, 3H), 2.32-2.40 (m), 3.13-3.75 (m), 7.66 (s), 7.69 (d), 7.95 (s); 13C NMR (300 MHz) (ppm) 17.23, 20.18, 23.4, 48.3, 54.5, 65.50, 67.32, 74.46, 76.81, 121.6, 172.5, 177.2; Mw=546.255.