KR101331168B1 - Synthesis of Phosphonium-based Ionic Liquids with Low Halide Content Using Microreactor - Google Patents

Abstract

In the present invention, there is provided a method for producing an ionic liquid having a high purity phosphonium group having a small amount of halides known as impurities in the ionic liquid as a cation. The phosphonium-based ionic liquid according to the production method of the present invention contains a halide of 20 ppm or less, has a high melting point of 330 to 511 ° C., and improves electrical characteristics. In addition, the production method according to the present invention efficiently alleviates complex reaction conditions, and eliminates the risk of reaction fever and human risk, thereby making it possible to safely and continuously produce a phosphonium-based ionic liquid.

Description

Synthesis of Phosphonium-based Ionic Liquids with Low Halide Content Using Microreactor

The present invention relates to a method for producing an ionic liquid having a high purity phosphonium group having a small amount of halides known as impurities in an ionic liquid as a cation. More specifically, the present invention relates to a method for preparing an ionic liquid having a high purity phosphonium group containing cations having a halide of 20 ppm or less using a microreactor and having a high melting point of 330 to 511 ° C and improved electrical properties. .

Phosphonium-based ionic liquids are used as carbon dioxide absorbers, for example, trialkoxyhydroxyphosphonium carboxylate (TPC).

(R1: alkyl group or aryl, R2: alkyl group, haloalkyl group or aryl group)

The trialkoxyhydroxyphosphonium carboxylate has excellent carbon dioxide absorption capability and little reduction in absorption capacity even after repeated use, and can be effectively used as a carbon dioxide absorbent due to its easy synthesis and low manufacturing cost.

Ionic liquids with phosphonium groups as cations are also good solvents for protein stabilization and crystallization. Phosphonium-based ionic liquids with esters, ethers, alcohols, and alkenes as alkyl derivatives are used for biological degradation. The phosphonium-based ionic liquid has halides, NTf ₂ , octyl sulfate, and the like as anions. In particular, phosphonium-based ionic liquids having octyl sulfate as an anion have higher biodegradability than those having octyl sulfate as an anion in cations of imidazonium or pyridinium.

The decomposition temperature of phosphonium-based ionic liquids varies depending on the anion, and many kinds are 300 ° C. or more. Thermogravimetric analysis (TGA) of trihexyl (tetradecyl) phosphonium tetrafluoroborate (Trihexyl (tetradecyl) Phosphonium tetrafluoroborate) is about 400 ° C. The phosphonium-based ionic liquid is chemically and thermally stable to enable reuse of a solvent.

To date, ammonium-based ionic liquids have been mainly studied, and phosphonium-based ionic liquids are still rarely studied:

1) Used as solvent in droformylation of Tetraalkylphosphonium tosylate

2) Used as a solvent for the palladium catalyzed Heck reaction of Tetraalkylphosphonium halide

3) Solvent of palladium mediated Suzuki cross-coupling reaction of Trihexyl (tetradecyl) Phosphonium chloride

4) Extraction of Metal Ions from Aqueous Solution

The use of the ^{reported-recently} trialkyl phosphonium salts ^{(trialkylphosphonium salt) [HPR3] +} [X] on.

Accordingly, there is a need in the art for improved synthesis of phosphonium-based ionic liquids, which are expanding their range of application.

An object of the present invention is to provide a method for producing an ionic liquid having a high purity phosphonium group as a cation with a residual halide content of 20 ppm or less, a decomposition temperature of 300 ° C. or higher, and improved electrical properties by using a microreactor.

In order to achieve the object of the present invention, the present invention is a method for preparing an ionic liquid having a high purity phosphonium group as a cation, comprising a cation-providing phosphonium compound and dimethyl sulfate, trifluoromethane sulfate, and iodine alkanes Provided is a method comprising reacting in an microreactor one anion-providing compound selected from the group consisting of:

The ionic liquid synthesized in the production method of the present invention may be further concentrated under reduced pressure.

In the production method of the present invention, the cation-providing phosphonium compound includes alkyl phosphines such as trimethyl phosphine, triethyl phosphine, tripropyl phosphine and tributyl phosphine; And phenyl phosphines such as triphenyl phosphine.

Anion-providing compounds include dimethyl sulfate; Trifluoromethane sulfate; And iodine alkanes such as iodine methane, iodine ethane, iodine propane and iodine butane.

Cation-providing phosphonium compounds and anion-providing compounds can be synthesized on the reaction solvent. Reaction solvents that may be used include alcohol solvents such as ethanol, methanol, propanol, ethylene glycol, methyl acetate, ethyl acetate, propyl acetate, γ-butyrolactone, ester solvents such as propion carbonite, acetonitrile, propionitrile, and the like. Nitrile solvents, aromatic solvents such as benzene, toluene, xylene, N, N-dimethylformamide, dimethyl sulfoxide, methylene chloride and the like. The reaction solvent is used alone or as a mixture of any two or more kinds.

The reaction is done in a microreactor. The microreactor has several micrometers for the flow path of the fluid, rapid heating and cooling, laminar flow, and large surface area per unit volume, so that the diffusion of the material is short. It is characterized by (FIGS. 2 and 3). In the present invention, a conventionally used microreactor having safety in chemical reactions may be used (FIG. 1).

In the production method of the present invention, the use concentration of the cation-providing phosphonium compound is preferably from 0.0002 mol to 1.0 mol, and if it exceeds 1.0 mol, a product does not participate, and if less than 0.0002 mol, the reaction is not completed and the yield is low. do. The flow rate to the microreactor is preferably 0.11ml / min ~ 13.0ml / hr. If the amount exceeds 13.0ml / hr, the flow rate is increased, so that unreacted substances are generated and must be reacted again. If the amount is less than 0.11ml / min, the flow rate is too slow, and it takes a long time to complete the reaction.

The use concentration of the anion-providing compound is preferably 0.0002 moles to 1.0 mole, and when it exceeds 1.0 mole, a product that does not participate in the reaction becomes a by-product to be removed, and when it is less than 0.0002 mole, the reaction completeness is low and the yield is low. The flow rate flowing to the microreactor is preferably 0.01ml / min ~ 2.0ml / min. If the amount exceeds 2.0ml / hr, the flow rate is increased, so unreacted substances are generated and must be re-reacted. If the amount is less than 0.01ml / min, the flow rate is too slow to complete the reaction.

The reaction temperature including the microreactor is preferably 0 to 100 ° C. If the temperature exceeds 100 ° C, the formation of by-products and decomposition products is promoted, and the color becomes dark and difficult to remove. If the temperature is less than 0 ° C, the excess amount is unreacted and the yield is low. The reaction time is preferably 10 to 30 minutes. If it is more than 30 minutes, by-products are formed and the color becomes dark and difficult to remove. The decomposition product is accelerated, and in less than 10 minutes, unreacted material is present and reaction completion is low.

Further reduced pressure concentration of the product may be carried out for 1 to 2 hours at an internal temperature of 50-60 ° C under 1 atmosphere. When concentrated, 755 ~ 760torr should be maintained. If the internal temperature of the concentrate is high, the compound with low thermal stability will produce decomposition products and become dark in color.The compound with low thermal stability will produce decomposition products or color even if the concentration is long. This will darken. When the concentration is lower than 755torr, the concentration efficiency is lowered, and the residual solvent and water remain, and the residual solvent and water remain, even when the inner temperature of the concentrate is low or the concentration time is short.

According to the production method of the present invention, a highly purified phosphonium-based ionic liquid having a halide content of 20 ppm or less and having a very high melting point of 330 to 511 占 폚 was continuously obtained safely with a microreactor.

According to the production method of the present invention, an ionic liquid having a high-purity phosphonium group as a cation having a residual halide content of 20 ppm or less can be continuously and safely produced by a microreactor.

The phosphonium-based ionic liquid according to the present invention not only has high purity, but also has a high melting point of 330 to 511 ° C due to improved thermal stability, and excellent electrical conductivity.

In addition, the production method of the ionic liquid of the present invention is to relax the reaction conditions required to obtain a solid phase and a liquid phase, improve the stability of the reaction, easy to scale up, reduced design, investment and operating costs, raw materials, Reducing solvent, waste and energy results in improved synthetic yields, improved chemical purity and reduced production costs.

Figure 1 shows the overall arrangement of the microreactor synthesis apparatus.
2 is a synthetic circuit diagram showing the process of passing the reagents A and B through the syringe pump to the microreactor through the micro mixer to become a target compound.
3 shows Y type, Helix type and Static type, which are types of micromixers.
4 is a 716 DMS Titrino ion analyzer which is a halide measuring apparatus.

In the following Examples, the present invention will be described in more detail, but the present invention is not limited thereto.

<Device used>

The microreactor used Keychem L of YMC, Japan, and the MRSY04-40 was used for the cylinder pump, and the Helix type was used for the micromixer.

<Measurement of Residual Halides>

Metrohm 716 DMS Titrino ion spectrometer was used, and the residual halide was measured by the standard method.

<Production Example>

Example  One: Methyltriphenylphosphonium Methylsulfonate  synthesis

1.0 g of triphenylphosphine was diluted in methanol (0.0038 mol) to 7.9 ml / hr, and 0.48 g of dimethylsulfonate was diluted to 0.0038 mol (0.038 mol) in methanol to 0.053 ml / min. I sent it through that pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain methyltriphenylphosphonium methylsulfonate as a solid. Yield was 0.38 g (yield: 82%). The analysis results of the obtained ionic liquid are as follows:

Residual Halogen: 7.4 ppm, Electrical Conductivity: 1.384 mS / cm, Melting Point: 367 ° C (dec.)

Example  2: Tributylmethylphosphonium Methylsulfonate  synthesis

3.0 g of tributylphosphine was diluted in methanol (0.0148 mol) at 8.2 ml / hr, and 1.87 g of dimethylsulfonate was diluted in methanol (0.0148 mol) at 0.053 ml / min. I sent it through that pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain tributylpropylphosphonium methylsulfonate as a liquid. Yield was 7.99 g (yield: 82%). The analysis results of the obtained ionic liquid are as follows:

Residual Halogen: 12.5 ppm, Conductivity: 1.540 mS / cm, Melting Point: 340 ° C (dec.)

Example  3: Tripropylmethylphosphonium Methylsulfonate  synthesis

3.0 g of tripropylphosphine was diluted in methanol (0.0187 mol) at 12.6 ml / hr, and 2.36 g of dimethylsulfonate was diluted in methanol (0.0187 mol) at 0.1 ml / min. I sent it through that pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain tripropylmethylphosphonium methylsulfonate as a liquid. Yield was 1.1 g (yield: 48%). The analysis results of the obtained ionic liquid are as follows:

Residual Halogen: 2.4ppm, Electrical Conductivity: 2.152 mS / cm, Melting Point: 345 ℃ (dec.)

Example  4: Triethylmethylphosphonium Methylsulfonate  synthesis

2.0 g of triethylphosphine was diluted in methanol (0.0169 mol) at 4.7 ml / hr, and 2.13 g of dimethylsulfonate was diluted in methanol (0.0169 mol) at 0.053 ml / min. I sent it through that pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain triethylmethylphosphonium methylsulfonate as a solid. Yield was 2.0 g (yield 67%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 3.7ppm, electrical conductivity: 2.369 mS / cm, melting point: 337 캜.

Example  5: Tetramethylphosphonium Methylsulfonate  synthesis

2.0 ml of trimethylphosphine diluted in methanol (0.0262 mol) to 4.7 ml / hr, 3.31 g of dimethylsulfonate diluted to methanol (0.0262 mol) to 0.053 ml / min, adjusted to 40 ° C. in a microreactor Spent through the pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain triethylmethylphosphonium methylsulfonate as a solid. Yield was 4.3 g (89% yield). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 9.3 ppm, electrical conductivity: 1.781 mS / cm, melting point: 390 ° C.

Example  6: Methyltriphenylphosphonium Of trifluoromethanesulfonate  synthesis

0.5 g of triphenylphosphine was diluted (0.002 mol) in acetonitrile, and 12.6 ml / hr and 0.34 g of methyl triflomethanesulfonate were diluted (0.002 mol) in acetonitrile to 60 ° C. at 0.11 ml / min. Flow through the cylinder pump to a controlled microreactor. The solution which passed the microreactor was collected, and it concentrated under reduced pressure (1 atmosphere, 50 degreeC, 1 hour), and obtained the methyl tripetyl phosphonium triflo methanesulfonate as a solid. Yield was 0.5 g (yield: 60%). The analysis results of the obtained ionic liquid are as follows:

Residual Halogen: 4.2ppm, Electrical Conductivity: 1.266 mS / cm, Melting Point: 424 ℃ (dec.)

Example  7: Tributylmethylphosphonium Of trifluoromethanesulfonate  synthesis

1.16 g of tributylphosphine was diluted in methylene chloride (0.005 mol) to 6.6 ml / hr, and 0.94 g of methyl triflomethanesulfonate was diluted to 0.001 mol in methylene chloride (0.05 mol) at 40 ° C. Flow through the cylinder pump to a controlled microreactor. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain tributylmethylphosphonium triflomethanesulfonate as a solid. Yield was 0.9 g (yield 43%). The analysis results of the obtained ionic liquid are as follows:

Residual halide: 9.8 ppm, electrical conductivity: 0.384 mS / cm, melting point: 365 deg.

Example  8: Methyltripropylphosphonium Of trifluoromethanesulfonate  synthesis

2.19 g of tributylphosphine was diluted in methylene chloride (0.013 mol) to 5.3 ml / hr, and 2.23 g of methyl triflomethanesulfonate was diluted in methylene chloride (0.013 mol) to 0.05 ml / min at 40 ° C. Flow through the cylinder pump to a controlled microreactor. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain methyltripropylphosphonium triflomethanesulfonate as a solid. Yield was 4.0 g (yield: 90%). The analysis results of the obtained ionic liquid are as follows:

Residual halide: 9.2 ppm, electrical conductivity: 0.986 mS / cm, melting point: 511 캜.

Example  9: Triethylmethylphosphonium Of trifluoromethanesulfonate  synthesis

0.88 g of triethylphosphine was diluted in methanol (0.007 mol) to 3.9 ml / hr, and 1.22 g of methyl trifluoromethanesulfonate was diluted to 0.007 mol in methanol to 0.053 ml / min. Spilled to microreactor. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain triethyl (methyl) phosphonium triflomethanesulfonate as a solid. Yield was 0.6 g (yield: 68%). The analysis results of the obtained ionic liquid are as follows:

Residual halide: 5.9 ppm, electrical conductivity: 3.029 mS / cm, melting point: 388 ° C (dec.)

Example  10: Tetramethylphosphonium Of trifluoromethanesulfonate  synthesis

1.12 g of trimethylphosphine diluted in methanol (0.014 mol) to 2.7 ml / hr, 2.4 g of methyl triflomethanesulfonate diluted to methanol (0.014 mol) and adjusted to 0.053 ml / min at 40 ° C. Spilled to the reactor. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain tetramethylphosphonium triflomethanesulfonate as a solid. Yield was 2.5 g (yield: 70%). The analysis results of the obtained ionic liquid are as follows:

Residual halide: 7.2 ppm, electrical conductivity: 2.211 mS / cm, melting point: 366 ° C (dec.)

Example  11: Butyltrimethylphosphonium  Iodine Synthesis

1.27 g of trimethylphosphine was diluted in methylene chloride (0.0167 mol) to 2.7 ml / hr, and 3.07 g of 1-iodobutane was diluted in methylene chloride (0.0167 mol) to 0.053 ml / min and adjusted to 40 ° C. Flowed through the cylinder pump to the reactor. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain butyltrimethylphosphonium iodine as a solid. Yield was 2.7 g (yield 63%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 10.01 ppm, electrical conductivity: 0.789 mS / cm, melting point: 435 ° C.

Example  12: Trimethylpropylphosphonium  Iodine Synthesis

1.19 g of trimethylphosphine diluted in methylene chloride (0.0157 mol) to 3.1 ml / hr, 2.66 g of 1-iodine propane diluted to methylene chloride (0.0157 mol) to 0.053 ml / min, controlled at 40 ° C Spent through the cylinder pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain trimethylpropylphosphonium iodine as a solid. Yield was 3.0 g (yield: 80%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 3.18 ppm, electrical conductivity: 2.170 mS / cm, melting point: 485 캜.

Example  13: Ethyltrimethylphosphonium  Iodine Synthesis

Microreactor adjusted to 40 ° C. by adjusting 1.11 g of trimethylphosphine in methylene chloride (0.0146 mol) to 3.8 ml / hr, and 2.27 g of 1-iodine ethane in methylene chloride (0.0146 mol) to 0.053 ml / min. Spent through the cylinder pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain ethyltrimethylphosphonium iodine as a solid. Yield was 3.0 g (yield: 88%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 2.81 ppm, Electrical conductivity: 2.172 mS / cm, Melting point: 452 캜.

Example  14: Tetramethylphosphonium  Iodine Synthesis

Microreactor adjusted to 40 ° C at 0.053 ml / min by diluting 0.73 g of trimethylphosphine in methylene chloride (0.0093 mol) to 4.9 ml / hr, and 1.32 g of 1-iomethane in methylene chloride (0.0093 mol). Spent through the syringe pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain tetramethylphosphonium iodine as a solid. Yield was 0.7 g (yield 37%). The analysis results of the obtained ionic liquid are as follows.

Residual halogen: 4.18 ppm, electrical conductivity: 0.729 mS / cm, melting point: 486 캜.

Example  15: Butyltriethylphosphonium  Iodine Synthesis

0.85 g of triethylphosphine was diluted in methanol (0.0076 mol) to 3.8 ml / hr, and 1.33 g of 1-iodine butane was diluted to 0.0076 mol in methanol to 0.053 ml / min. Spent through the cylinder pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain butyltriethylphosphonium iodine as a solid. Yield was 1.3 g (yield 63%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 4.07 ppm, electrical conductivity: 0.492 mS / cm, melting point: 409 캜.

Example  16: Triethylpropylphosphonium  Iodine Synthesis

1.44 g of triethylphosphine was diluted in methanol (0.0122 mol) at 4.5 ml / hr, and 2.07 g of 1-iodine propane was diluted in methanol (0.0122 mol) at 0.05 ml / min. Spent through the cylinder pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain triethylpropylphosphonium iodine as a solid. Yield was 2.8 g (yield: 82%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 5.11 ppm, electrical conductivity: 1.308 mS / cm, melting point: 411 캜.

Example  17: Tetraethylphosphonium  Iodine Synthesis

1.13 g of triethylphosphine was diluted in ethanol (0.0096 mol) at 5.5 ml / hr, and 1.49 g of 1-iodine ethane was diluted (0.0096 mol) in ethanol at 0.053 ml / min. Spent through the cylinder pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain tetraethylphosphonium iodine as a solid. Yield was 2.2 g (yield: 86%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 9.18 ppm, electrical conductivity: 1.436 mS / cm, melting point: 420 캜.

Example  18: Triethylmethylphosphonium  Iodine Synthesis

1.43 g of triethylphosphine was diluted in ethanol (0.0121 mol) to 7.1 ml / hr, and 1.72 g of 1-iodine methane (0.0121 mol) was diluted to 0.053 ml / min using a microreactor adjusted to 80 ° C. Spent through the cylinder pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain triethylmethylphosphonium iodine as a solid. Yield was 2.9 g (yield 94%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 3.18 ppm, electrical conductivity: 0.865 mS / cm, melting point: 433 캜.

Example  19: Butyl tripropyl phosphonium  Iodine Synthesis

1.21 g of tripropylphosphine was diluted in methylene chloride (0.0076 mol) to 5.24 ml / hr, and 1.39 g of 1-iodine butane was diluted (0.0076 mol) in methylene chloride to 0.053 ml / min. Flowed through the cylinder pump to the reactor. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain butyltripropylphosphonium iodine as a solid. Yield was 1.1 g (yield 42%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 12.4 ppm, electrical conductivity: 0.998 mS / cm, melting point: 387 캜.

Example  20: Tetrapropylphosphonium  Iodine Synthesis

3.0 g of tripropylphosphine was diluted in methylene chloride (0.018 mol) to 6.1 ml / hr, and 3.18 g of 1-iodine propane was diluted (0.018 mol) in methylene chloride to 0.05 ml / min. Flow through the cylinder pump to the reactor. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain tetrapropylphosphonium iodine as a solid. Yield was 3.6 g (yield: 60%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 3.9 ppm, electrical conductivity: 0.392 mS / cm, melting point: 387 캜.

Example  21: Ethyltripropylphosphonium  Iodine Synthesis

2.39 g of tripropylphosphine diluted to methylene chloride (0.014 mol) to 7.5 ml / hr, 2.32 g of 1-iodine ethane to methylene chloride (0.014 mol) to 0.053 ml / min, adjusted to 40 ° C Flowed through the cylinder pump to the reactor. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain ethyltripropylphosphonium iodine as a solid. Yield was 2.8 g (yield: 60%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 8.2 ppm, electrical conductivity: 0.880 mS / cm, melting point: 394 캜.

Example  22: Methyltripropylphosphonium  Iodine Synthesis

2.51 g of tripropylphosphine was diluted in methylene chloride (0.015 mol) to 9.6 ml / hr, and 2.22 g of 1-iomethane was diluted to methylene chloride (0.015 mol) to 0.05 ml / min. Flowed through the cylinder pump to the reactor. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain methyltripropylphosphonium iodine as a solid. Yield was 3.5 g (yield: 75%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 8.9 ppm, electrical conductivity: 1.555 mS / cm, melting point: 399 캜.

Example  23: Tetrabutylphosphonium  Iodine Synthesis

0.42 g of tributylphosphine was diluted in methylene chloride (0.0002 mol) to 6.6 ml / hr, and 0.38 g of 1-iodine butane in methylene chloride (0.002 mol) to 0.053 ml / min. Flow through the cylinder pump to the reactor. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain tetrabutylphosphonium iodine as a solid. Yield was 0.8 g (yield: 40%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 6.4pm, electrical conductivity: 0.930 mS / cm, melting point: 389 ° C.

Example  24: Tributylpropylphosphonium  Iodine Synthesis

3.15 g of tributylphosphine was diluted in ethanol (0.015 mol) to 5.1 ml / hr, and 2.63 g of 1-iodine propane was diluted to 0.053 ml / min in ethanol (0.015 mol) in a microreactor adjusted to 70 ° C. Spent through the cylinder pump. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain tributylpropylphosphonium iodine as a solid. Yield was 4.1 g (yield 71%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 9.1 ppm, electrical conductivity: 0.748 mS / cm, melting point: 382 ° C.

Example  25: Tributylethylphosphonium  Iodine Synthesis

1.17 g of tributylphosphine was diluted in methylene chloride (0.0058 mol) to 9.4 ml / hr, and 0.90 g of 1-iodine ethane to methylene chloride (0.058 mol) in 0.053 ml / min, adjusted to 40 ° C. Flowed through the cylinder pump to the reactor. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain tributylethylphosphonium iodine as a solid. Yield was 0.8 g (yield: 38%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 4.4 ppm, electrical conductivity: 1.359 mS / cm, melting point: 389 캜.

Example  26: Tributylmethylphosphonium  Iodine Synthesis

1.56 g of tributylphosphine was diluted in methylene chloride (0.0052 mol) to 12.0 ml / hr, and 1.09 g of 1-iodine methane was diluted (0.0052 mol) in 0.053 ml / min to 40 ° C. Flow through the cylinder pump to the reactor. The solution passed through the microreactor was collected and concentrated under reduced pressure (1 atm, 50 ° C, 1 hour) to obtain tributylmethylphosphonium iodine as a solid. Yield was 1.6 g (yield 63%). The analysis results of the obtained ionic liquid are as follows:

Residual halogen: 9.1 ppm, electrical conductivity: 1.9340 mS / cm, melting point: 395 ° C.

Claims (7)

In the method for producing a high purity phosphonium-based ionic liquid,
Cation-providing phosphonium compounds selected from the group consisting of trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine and triphenylphosphine;
Reacting with a microreactor one anion-providing compound selected from the group consisting of dimethyl sulfate, trifluoromethane sulfate, and iodine alkanes,
The flow rate of the cation-providing phosphonium compound in the microreactor is 0.11 to 13.0 ml / hr, the flow rate of the anion-providing compound is 0.01 to 2.0 ml / hr, and the reaction temperature including the microreactor is 40 to 100 ° C. And a halide content of the phosphonium ionic liquid of 12.4 ppm or less and a melting point of 330 ° C to 511 ° C. delete The method of claim 1, further comprising the step of concentrating the ionic liquid reacted separately under reduced pressure. The method according to claim 1 or 3, wherein the use concentration of the cation-providing phosphonium compound is 0.0002 to 1.0 mole, and the use concentration of the anion-providing compound is 0.0002 to 1.0 mole.
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