KR20160071179A - Polymer resin-anchored ionic liquid catalyst and preparing method of n,n'-substituted urea using the same - Google Patents

Abstract

The present invention relates to an ionic catalyst including a nitrogen-containing organic cation chemically immobilized on a polymer resin carrier and an anion thereof and a method for selectively preparing N,N′-substituted urea by reacting an amine compound with carbon dioxide in the presence of the catalyst. The all substituted urea prepared in the present invention can be easily transformed into isocyanate via carbamate and the isocyanate can be used as an important precursor compound which can be transformed into polyurethane through the reaction with polyol. The ionic liquid-based catalyst immobilized on a polymer resin carrier of the present invention is reusable for several times, and is thus economic.

Description

TECHNICAL FIELD [0001] The present invention relates to an ionic liquid-based catalyst fixed to a polymer resin, and a method for preparing N, N'-substituted urea using the same.

The present invention relates to a process for preparing an N, N'-substituted urea by reacting an ionic liquid-phase catalyst and an amine compound and carbon dioxide in the presence of the catalyst. More specifically, the present invention relates to an ionic liquid- Liquid-phase catalyst and a method for producing N, N'-substituted urea in a high selectivity by a one-pot reaction by reacting an amine compound with carbon dioxide in the presence of the catalyst.

Generally, substituted urea is an important carbonyl compound and widely used in a variety of fields such as pesticides, pharmaceuticals, synthetic dyes, plasticizers, stabilizers, gasoline antioxidants, and amino resin additives.

Conventionally, a method of reacting an amine with phosgene has been used to prepare a substituted urea. However, since phosgene is toxic and corrosive, it is difficult to handle, and after the reaction, HCl, which is a pollutant, is produced as a by-product, which causes environmental problems. Therefore, in the United States, Japan, and Europe, methods for producing substituted urea without using harmful phosgene have been studied.

A process for producing urea using carbon monoxide or carbonyl sulfide without using phosgene has been studied. An amine is reacted with carbon monoxide and oxygen under high temperature and high pressure to prepare N, N'-substituted urea (Japanese Patent Publication 53-41123 58-144363), a method for producing urea by reacting an amine with carbon monoxide and a nitro compound using a catalyst such as rhodium or ruthenium has been studied (Japanese Patent Publication No. 62-59253 (U.S. Patent No. 2,877,268), a method in which an amine is reacted with carbon monoxide and sulfur using a tertiary amine as a catalyst (J. Org., Supra), and a method in which an amine is reacted with carbonyl sulfide to produce urea (RA Franz, 26, p3309, 1961), a method of synthesizing urea by reacting a nitro compound with water and carbon monoxide under a selenium metal catalyst No. 4,052,454), a method of producing urea in a mixed gas of carbon monoxide and oxygen by using a selenium-carbonic acid alkaline catalyst system (Korean Patent Laid-Open Publication No. 2000-0020218) and a method of mixing a mixture of carbon monoxide and oxygen using an imidazolium alkyl selenide catalyst system (U. S. Patent Application Publication No. 10-2004-0067023), and the like.

However, the method of using carbon monoxide also has various risks such as toxicity and instability of carbon monoxide, possibility of explosion due to use of oxygen gas and mixed gas, and the use of sulfur causes a byproduct such as H ₂ S And a method using a catalyst such as rhodium or ruthenium has a disadvantage in that expensive noble metal catalyst is easily decomposed due to high reaction temperature and pressure.

Studies for preparing substituted urea with environmentally friendly and high conversion and selectivity have been continuing. However, studies on the production of substituted ureas by reacting mainly amine compounds with carbon dioxide have been actively conducted. For example, a method of preparing a substituted urea by reacting an amine with carbon dioxide using a ruthenium complex or triphenylstibine oxide as a catalyst [J. Org. Chem. 56 (1991) 4456; J. Org. Chem. 57 (1992) 7339), but this method has a disadvantage in that the selectivity of the substituted urea is low and the byproducts are generated in large amounts.

In order to increase the conversion and selectivity of substituted urea, a process for preparing substituted urea through a catalyst system using a liquid has been studied. A process for preparing substituted ureas using an ionic liquid as a catalyst and a solvent and using CsOH as a catalyst [ Angew. Chem. Int. Ed. 42 (2003) 3257; Chinese Patent 1209347], a method using a base containing Cs ⁺ ions as a catalyst [Green Chem. 9 (2007) 158], a method of introducing various ionic liquids as catalysts [Phys. Chem. Chem. Phys. 13 (2011) 6197] were studied. However, in these methods, the selectivity of the substituted urea can be increased, but the recovery of the catalyst is not easy and the catalyst is difficult to be reused. On the other hand, conventionally, substituted ureas are synthesized under solvent-free conditions through the reaction of an amine compound with carbon dioxide using an ionic liquid such as [1-butyl-3-methylimidazolium] OH (hereinafter also referred to as [Bmim] OH) Method [Green Chem. (Bmim) Acetate and [Bmim] Cl catalysts have been found to have hygroscopicity in the case of [Bmim] OH, [Bmim] Acetate and [Bmim] Cl catalysts. There is a disadvantage that it is easily decomposed by hydrolysis when water is present in the reactor.

Accordingly, there is a demand for development of a new catalyst system capable of increasing the conversion and selectivity of the substituted urea and having high stability and facilitating the recovery and reuse of the catalyst.

The present invention relates to a novel catalyst system capable of producing substituted urea at a high conversion and a high selectivity, capable of reuse after separation with high stability, and which does not remarkably reduce conversion and selectivity even in the case of reuse, And a method for producing the urea.

As a result of intensive studies to solve the above problems, the present inventors have found that an ionic catalyst composed of a nitrogen-containing organic cation and a bicarbonate (HCO ₃ ^- ) chemically fixed on a polymer resin carrier is replaced with an amine compound and carbon dioxide Urea, the conversion and selectivity of substituted urea are higher than those in the conventional case, and it is a heterogeneous catalyst which is high in stability and does not dissolve in an organic solvent and can be easily reused after being easily separated through a filter or the like, And that it is possible to maintain the conversion rate / selectivity at the time.

That is, the present invention provides an ionic liquid-based catalyst comprising a nitrogen-containing organic cation chemically immobilized on a polymeric resin carrier and a bicarbonate anion:

Wherein the nitrogen-containing organic cation comprises at least one kind of cation represented by the following general formula (1) or (2)

[Chemical Formula 1]

(2)

은 고분자 수지 담지체를 나타낸다).Wherein R ¹ to R ³ are each independently selected from the group consisting of quaternary ammonium, imidazolium, pyridinium, pyrazolium, piperidinium, pyrrolidinium, triazolium, oxazolium, Thiazolium, pyridinium, pyrimidinium and pyridazinium, n is an integer of 1 or more and 10 or less,

Represents a polymer resin carrier).

In a preferred embodiment, the ionic liquid-based catalyst comprises at least one member selected from the group consisting of compounds represented by the following formulas (3) to (7)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

는 고분자 수지 담지체를 나타낸다).(Wherein R ⁴ to R ¹⁷ each represent an alkyl group having 1 to 12 carbon atoms, n is an integer of 1 or more and 6 or less,

Represents a polymer resin carrier).

Representative examples of the compounds represented by the above formulas (3) to (7) include the following compounds:

,

,

,

,

,

,

,

,

는 고분자 수지 담지체를 나타낸다).(Wherein Bu represents a butyl group,

Represents a polymer resin carrier).

As a preferred embodiment, the polymeric resin used in the production of the ionic liquid-based catalyst of the present invention may be a polymeric resin in which a functional group is bonded to the terminal of the resin carrier and nitrogen-containing organic materials can be easily fixed to the polymeric resin through the functional group There are no special restrictions. The polymer resin may be a substituted / unsubstituted polystyrene or a derivative thereof, and it is most preferable to use a chloromethylated polystyrene resin. In addition, a polystyrene resin having an alkyl halide end or a polystyrene resin having a hydroxymethyl terminated end may be used.

The present invention also relates to a process for the preparation of N, N'-substituted ureas using the above ionic liquid system catalyst, wherein an amine compound and carbon dioxide are reacted in the presence of the ionic liquid system catalyst to produce N , ≪ / RTI > N'-substituted ureas:

In the above formula, R is an aliphatic alkyl group having 2 to 10 carbon atoms or an aliphatic alkyl group having 4 to 10 carbon atoms (the terminal of these alkyl groups may be substituted with a hydroxyl group, an acyl group, a carboxyl group, a halogen atom or an -NH ₂ group) .

Wherein the amine compound is a compound represented by the formula R ¹ -NH ₂ wherein R ¹ is an aliphatic alkyl group having 2 to 10 carbon atoms or an aliphatic alkyl group having 4 to 10 carbon atoms and the terminal of the alkyl group is a hydroxyl group, , A carboxyl group, a halogen atom or an -NH ₂ group, and examples of the amine compound include methylamine, ethylamine, isopropylamine, butylamine, isobutylamine, hexylamine, dodecylamine, hexa Cyclohexylamine, cycloheptylamine, cyclooctylamine, cyclododecylamine, 1,4-diaminocyclohexane, 4, 4-diaminocyclohexane, 4, 4'-methylenebis (cyclohexylamine), and the like, but are not limited thereto. However, it is preferable to use alicyclic primary amines such as cyclobutylamine, cyclopentylamine, cycloheptylamine and the like in view of higher conversion and selectivity.

Reaction of an amine compound with carbon dioxide using an ionic liquid-based catalyst comprising a nitrogen-containing organic cation and a bicarbonate anion chemically immobilized on the polymer resin carrier yields the desired N, N'-substituted urea in a high exchange rate and high selectivity can do.

Regarding the preferable reaction conditions in the reaction of the amine compound and carbon dioxide in the presence of the ionic liquid system catalyst of the present invention, a reaction temperature and pressure higher than a certain level are required to improve the selectivity and conversion of the substituted urea, If the pressure becomes too high, the conversion rate will be reduced due to the reverse reaction. If the reaction temperature or pressure becomes too high, the economical efficiency of the process will deteriorate due to problems such as reduction in conversion / selectivity due to the reverse reaction at high temperature, A problem arises. In order to further improve the conversion and the selectivity of the substituted urea production method, the preferable temperature range is 170 to 190 占 폚, and the preferable (carbon dioxide) pressure range is 800 to 1400 psig.

The reaction time is preferably about 4 to 6 hours because the conversion and the selectivity of the substituted urea are improved.

The molar ratio of the amine compound to the ionic liquid system catalyst is from 5000: 1 to 50: 1, preferably from 2500: 1 to 100: 1. If the molar ratio is too low, it is not economically advantageous to use a large amount of the ionic liquid system catalyst. Conversely, when the molar ratio is excessively high, the conversion rate is undesirably decreased.

The reaction may be carried out in the absence of a solvent or in the presence of an alcohol having 1 to 6 carbon atoms such as tetrahydrofuran (THF), dimethylformamide (DMF), N, N'-dimethylpropyleneurea (DMPU), N-methylpyrrolidone NMP), dimethylsulfoxide (DMSO), acetonitrile, toluene, and dioxane, and the reaction is carried out in the presence of a one- pot reaction. More specifically, when the process of the present invention is carried out in the presence of a solvent, it is stable at high temperatures such as N, N'-dimethylpropylene urea (DMPU) or N-methylpyrrolidone (NMP) polar aprotic solvent is preferably used.

According to the present invention, an amine compound and carbon dioxide can be reacted with an ionic liquid-phase catalyst chemically immobilized on a polymeric resin carrier to produce substituted urea with high conversion and selectivity.

All of the substituted ureas prepared in the present invention can be easily converted to isocyanate via carbamate, and the isocyanate can be used as an important precursor compound which can be converted to a polyurethane through reaction with a polyol.

On the other hand, the ionic liquid-based catalyst fixed to the polymer resin in the present invention has an additional advantage of being economical because it is stable and can be reused many times.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are intended to further illustrate the present invention, and the scope of the present invention is not limited thereto.

[ Manufacturing Example  1 ~ 5] Ionic Liquid system  Preparation of Catalyst PS - IL , Compounds 1 to 5)

The ionic liquid system catalyst compound of the present invention was synthesized by using Merrifield resin (3.5-4.5 mmol of Cl group / g) having a Cl functional group bonded to a polystyrene carrier as a starting material. The synthesis steps of the ionic liquid system catalyst compounds of the present invention (representative examples of the compounds represented by the above formulas 3 to 7) are summarized in the following table.

Preparation of compounds 1, 2 and 3

Compounds 1 to 3 were prepared in the following three steps.

(i) Merrifields resin (1% crosslinked, 3.5-4.5 mmol Cl / g) and bis (2-chloroethyl) amine (2.45 g, 12 mmol) were added to a 100 mL round flask Purified 35 mL of acetonitrile is added to the reaction solvent and refluxed in an argon atmosphere for 12 hours. After the reaction was completed, the reaction product was cooled at room temperature, and the product was collected by filtration, washed with a sufficient amount of methanol and acetone, and dried in a vacuum oven at 80 DEG C to obtain a yellow solid.

(ii) The obtained 2 g of yellow solid was dispersed in 35 mL of dimethylformamide and 1-methylimidazole (2.56 mL, 32 mmol) was added. After stirring the mixture vigorously in an argon atmosphere at 80 < 0 > C for 24 h, the solid product obtained was washed with acetone to remove residual 1-methylimidazole. After removing the 1-methylimidazole, the obtained solid was dried in a vacuum at a temperature of 80 ° C to obtain a yellow solid.

(iii) To replace the chloride anion with a bicarbonate species, sodium bicarbonate (2.69 g, 32 mmol) and the solid obtained in step (ii) were added to 35 mL of purified methanol and mixed together . The mixture was stirred at room temperature for 24 hours under an argon atmosphere. Thereafter, the solid was filtered, washed with secondary distilled water until neutral, and dried in a vacuum oven at a temperature of 80 ° C to synthesize Compound 1. As a comparison experiment, instead of bicarbonate anions other anions were prepared by adding a derivative of Compound 1 with a variety of anions using _{^{(Br -, NTf 2 -,}} OMs - -, OTs). Compound 2 and Compound 3 were also prepared by the same method as above except that Compound 2 was synthesized by using pyridine instead of 1-methylimidazole and Compound 3 was synthesized by using tetra-n-butylamine.

Production methods of compounds 4 and 5

(vi) Merryfield resin (2g) and imidazole (1.1g, 16mmol) were added, and then refluxed with 35mL of acetonitrile as a reaction solvent. Then, the mixture was refluxed at 100 for 24 hours under an argon atmosphere. After the reaction, the reaction mixture was filtered under reduced pressure. The obtained solid was washed with acetone, 0.1 mol / L hydrochloric acid and secondary distilled water, and dried at 80 ° C. under vacuum to obtain a yellow solid.

(vii) 1,4-Dibromobutane (1.45 ml, 12 mmol) and 2 g of the yellow solid obtained in the above step (iv) were stirred in 30 ml of 1,4-dichloromethane and the mixture was stirred for 24 hours in an argon atmosphere Lt; / RTI > After cooling to room temperature, the product was collected by filtration and washed with a sufficient amount of methanol and acetone. It was then dried in a vacuum oven at 80 DEG C to give 2 g of a dark yellow solid.

(iv-v) The above 2 g solid and tributylamine (3.82 ml, 16 mmol) were added to 35 mL of purified dimethylformamide and stirred at 80 < 0 > C for 24 h under an argon atmosphere. Thereafter, after cooling at room temperature, the solid was collected by filtration, washed with acetone and dried at 80 ° C under reduced pressure to give a product containing two bromine anions. The final product, Compound 4, could be synthesized by replacing the bromide anion (Br ^- ) with a bicarbonate anion according to the same procedure (iii) as described above. Compound 5 was prepared in the same manner as above, but was synthesized by reacting pyridine instead of tributylamine.

The synthesis procedures of the above compounds 1 to 5 are shown collectively as shown in Table 1 below. (Steps (i to vii) shown below correspond to those of the steps described in the above-mentioned production method)

[ Manufacturing Comparative Example  1 ~ 2] Catalyst Synthesis Si -10, Si -11)

An ionic liquid catalyst using a silica-based carrier was synthesized by the following method. Mesoporous silica type MCM-41 and SBA-15 (Si-10, 11) were used as the silica-based support, and the ionic liquid described above was fixed.

(viii) All silica materials were pre-activated at 100 DEG C by depressurization for 8 hours before use. To a 100 mL round flask was added 2 g of activated SBA-15 (or MCM-41) and chloropropyltrimethoxysilane (CPTMS) (3 mL, 16 mmol), which had been activated, to 35 mL of purified toluene and mixed. After addition of the mixture under argon atmosphere, the silica was separated by filtration, washed with toluene and dichloromethane, and Soxhlet extracted with dichloromethane for 24 hours to remove unreacted CPTMS. The solid was filtered again and the CPTMS / silica product was dried in a vacuum oven at a temperature of 60 to obtain an intermediate as follows. Thereafter, the following silica-based catalysts Si-10 and Si-11 were obtained by using the production methods (i, ii, iii) of the polystyrene-based catalyst.

[N, N'-substituted Urea  Produce]

The reaction for preparing N, N'-substituted urea is shown in the following reaction scheme.

[Reaction Scheme 1]

In the above Reaction Scheme 1,

R is as described in the formula of the N, N'-substituted urea,

Cat refers to the ionic liquid system catalysts of the present invention, T denotes the reaction temperature, P denotes the pressure, t denotes the reaction time, and S denotes the organic solvent. These catalyst systems and reaction conditions are as described above.

As can be seen from the above reaction scheme 1, in the present invention, N, N'-substituted urea is produced by reacting carbon dioxide with an amine compound as a starting material.

After completion of the reaction in the present invention, the insoluble substituted urea is filtered and dried, and the weight is measured to obtain the yield. The conversion of the amine compound can be confirmed by gas-liquid chromatography. In addition, the conversion of the amine compound can be calculated by analyzing the filtrate by gas chromatography after removing the substituted urea.

When the reaction of the present invention is completed, the substituted urea, which is the main target compound, is dissolved by using hot methanol to easily separate from the heterogeneous catalyst through filtration, and the catalyst of the present invention is also dissolved in most organic solvents It can be easily separated through a filter as a catalyst and then reused to carry out the reaction several times, which is economical.

[ Example  1] High pressure reaction DCU  Produce

(4.26 g, 43 mmol) of cyclohexylamine (CHA, also referred to as "CyNH ₂ "), Compound 1 (0.25 g) prepared in Preparation Example 1 and N-methylpiperazine pyrrolidone (NMP) (10mL) and the filled cooling was substituted, one of the typical general process conditions for producing the urea reaction temperature 170 ℃, 4 hours at CO ₂ pressures 1200psig reaction mixture was cooled to room temperature with external standards (external standard (2 mL) was added and the solid product was isolated. At this time, the separated solid product was washed with distilled water 2-3 times to remove the cyclohexylcarbamate salt (CyNH ₃ ⁺ CyNHCOO ₃ ^- ), further washed with THF 2 to 3 times, and then completely dried in a vacuum oven. The yield of DCU was calculated by measuring the weight of N, N'-dicyclohexylurea (N, N'-dicyclohexylurea, DCU) produced after drying. The conversion rate (%) of CHA and the yield of DCU (1) and (2).

[Equation 1]

&Quot; (2) "

&Quot; (3) "

On the other hand, the solid product was separated and the remaining filtrate was analyzed by gas chromatography, and the conversion ratio was calculated by quantitative analysis using unreacted CHA using an external standard. As a result of the GC analysis using the FID as described above, the CHA conversion was 60.4%, the DCU yield was 59.6%, and the selectivity was 98.7%.

[ Example  2 to 5, Comparative Example  1-2]

Experiments were carried out under the same conditions as Example 1, but the results are shown in Table 2 while varying the type of catalyst.

division catalyst CHA
Conversion Rate (%) DCU
Selectivity (%) Example 1 Compound 1 (Formula 3) 60.4 98.7 Example 2 Compound 2 (Formula 4) 54.1 96.5 Example 3 Compound 3 (Formula 5) 52.5 98.8 Example 4 Compound 4 (Formula 6) 49.5 99.2 Example 5 Compound 5 (Formula 7) 48.0 99.5 Comparative Example 1 Si-10 48.5 98.6 Comparative Example 2 Si-11 49.6 98.3

The conversion of CHA by the Si-10 and Si-11 catalysts prepared in Comparative Examples 1 and 2 was almost similar to the CHA conversion by the catalyst of the present invention. However, according to further studies by the present inventors, 11 is difficult to synthesize, and when the catalyst is reused after the use of the catalyst several times, the activity of the catalyst is remarkably lowered, which is unsuitable as a catalyst for preparing substituted ureas.

[ Comparative Example  3-7]

Table 2 shows the results of the experiments conducted under the same conditions as in Example 1 for the catalysts prepared for Comparative Experiment with different anions in Production Example 1. As shown in Table 3, it was found that the highest activity was obtained when [HCO ₃ ^- ], which is an anion constituting the ionic liquid system catalyst of the present invention, was used.

division Anion CHA
Conversion Rate (%) DCU
Selectivity (%) Example 1 [HCO ₃ ^- ] 60.4 98.7 Comparative Example 3 [Cl ^-] 30.3 98.7 Comparative Example 4 [OMs ^- ] ^{* 1} 32.5 98.5 Comparative Example 5 [OTs ^- ] ^{* 2} 43.2 99.0 Comparative Example 6 [OAc ^{-] * 3} 43.5 97.8 Comparative Example 7 [NTf ₂ ^- ] ^{* 4} 43.0 98.5 * 1: Mesylate ion
* 2: Tosylate ion
* 3: Acetate ion
* 4: Bis (trifluoromethylsulfonyl) amide ion

Hereinafter, the effect of each reaction condition on the efficiency of the production method of N, N'-substituted urea will be examined.

[ Example  6 and 7]

Experiments were carried out under the same conditions as in Example 1, but the CHA conversion rates were calculated while varying the reaction time. In general, the longer the reaction time, the higher the CHA conversion and the yield / selectivity of the substituted urea. However, if the reaction time is too long, the production of by-products increases and the economical efficiency of the process deteriorates. In one embodiment of the preferred reaction time of the preparation process of the present invention, the reaction time was about 4 to 6 hours. According to the results of further studies conducted by the present inventors, the CHA conversion rate was remarkably lowered when the reaction was conducted for 3 hours or less, and when the reaction was conducted for 7 hours or more, the CHA conversion rate was maximized, but it was confirmed that the byproducts increased and the economical efficiency of the process deteriorated .

division Reaction time CHA
Conversion Rate (%) DCU
Selectivity (%) Example 1 4 60.4 98.7 Example 6 5 60.8 98.9 Example 7 6 62.4 99.2

[ Example  8-11]

Experiments were carried out in the same manner as in Example 1 except that the reaction temperature was changed. It was found that an appropriate reaction temperature range for securing a CHA conversion rate and a DCU selectivity higher than a certain level was 170 to 190 ° C. When the reaction temperature is lower than 170 ° C, the CHA conversion rate tends to be relatively decreased. According to the further research results of the present inventors, when the reaction temperature exceeds 190 ° C, the conversion rate is rather reduced due to the reverse reaction or the like.

division Temperature (℃) CHA
Conversion Rate (%) DCU
Selectivity (%)    Example 8 150 28.5 98.2    Example 9 160 40.8 99.8    Example 1 170 60.4 98.7    Example 10 180 55.6 98.7    Example 11 190 57.8 99.4

[ Example  12]

Experiments were carried out in the same manner as in Example 1 except that the kind of the solvent was changed. N, N'-substituted urea was prepared using DMPU (N, N'-Dimethylpropyleneurea) which is one of the polar aprotic solvents such as NMP used in Example 1. As shown in Table 6, high CHA conversion was obtained as in the case of using NMP.

division menstruum CHA
Conversion Rate (%) DCU
Selectivity (%)    Example 1 NMP 60.4 98.7    Example 12 DMPU 56.0 97.8

[ Example  13-17]

The procedure of Example 1 was repeated except that the kind of amine was changed. As a result, it can be confirmed that not only linear aliphatic amines such as n-butylamine but also alicyclic amines such as cyclopropylamine, cyclobutylamine and cyclopentylamine exhibit excellent conversion and selectivity. However, in the case of a diamine such as hexamethylenediamine, a polyurea having a molecular weight of 1000 to 3000 is generated, and the selectivity of the substituted urea is greatly reduced.

[ Example  18 ~ 21]

Experiments were carried out under the same conditions as in Example 1 except that the catalysts were separated and reused. As shown in Table 8, it can be seen that the conversion / selectivity of the substituted urea is maintained at a substantially high level even after four times of reuse.

division Reuse Count CHA
Conversion Rate (%) Substituted urea
Selectivity (%) Example 18 One 59.0 99.4 Example 19 2 55.5 99.5 Example 20 3 55.0 99.3 Example 21 4 53.2 99.7

Claims (12)

An ionic liquid system catalyst comprising a nitrogen containing organic cation and a bicarbonate anion chemically immobilized on a polymeric resin support. The method according to claim 1,
Wherein the nitrogen-containing organic cation comprises at least one cation selected from the group consisting of the following Chemical Formulas 1 and 2:
[Chemical Formula 1]

(2)

(Wherein R^One To R³Each independently represents a substituted or unsubstituted alkyl group containing a quaternary ammonium, imidazolium, pyridinium, pyrazolium, piperidinium, pyrrolidinium, triazolium, oxazolium, thiazolium, pyridinium, pyrimidyl, And n is an integer of 1 or more and 10 or less,

Represents a polymer resin carrier). The method according to claim 1,
Wherein the ionic liquid-based catalyst comprises at least one member selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 7:
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

(Wherein R ⁴ to R ¹⁷ each represent an alkyl group having 1 to 12 carbon atoms, n represents an integer of 1 or more and 6 or less,

Represents a polymer resin carrier). The method according to claim 1,
Wherein the ionic liquid-based catalyst comprises at least one member selected from the group consisting of the following compounds:

,

,
,

,

.
(Wherein Bu represents a butyl group,

Represents a polymer resin carrier). The method according to claim 1,
Wherein the polymer resin comprises any one of substituted or non-substituted polystyrene and derivatives thereof. A process for selectively producing an N, N'-substituted urea represented by the following formula by reacting an amine compound with carbon dioxide in the presence of the ionic liquid system catalyst according to any one of claims 1 to 5:

In the above formulas,
R is an aliphatic alkyl group having 2 to 10 carbon atoms or an alicyclic alkyl group having 4 to 10 carbon atoms (the terminal of these alkyl groups may be substituted with a hydroxyl group, an acyl group, a carboxyl group, a halogen atom or an -NH ₂ group). The method of claim 6,
Wherein the amine compound is a compound represented by the formula R ¹ -NH ₂ wherein R ¹ is an aliphatic alkyl group having 2 to 10 carbon atoms or an aliphatic alkyl group having 4 to 10 carbon atoms and the terminal of the alkyl group is a hydroxyl group, , A carboxyl group, a halogen atom or an -NH ₂ group. The method of claim 7,
The amine compound may be selected from the group consisting of methylamine, ethylamine, isopropylamine, butylamine, isobutylamine, hexylamine, dodecylamine, hexadecylamine, octadecylamine, benzylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine , At least one member selected from the group consisting of cyclohexylamine, cycloheptylamine, cyclooctylamine, cyclododecylamine, 1,4-diaminocyclohexane and 4,4'-methylenebis (cyclohexylamine) ≪ / RTI > substituted ureas. The method of claim 6,
Wherein the reaction is carried out under a carbon dioxide pressure of 800 to 1400 psig, a reaction temperature of 170 to 190 ° C, and a reaction time of 4 to 6 hours. The method of claim 6,
Wherein the molar ratio of the amine compound to the ionic liquid system catalyst is from 5000: 1 to 50: 1. The method of claim 6,
The reaction may be carried out without solvent,
(DMF), N, N'-dimethylpropylene urea (DMPU), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), and dimethyl sulfoxide N, N'-substituted ureas in the presence of at least one solvent selected from the group consisting of acetonitrile, toluene and dioxane. The method of claim 6,
Wherein the reaction is a one-pot reaction. ≪ RTI ID = 0.0 > 21. < / RTI >