KR20110088749A

KR20110088749A - Method for preparing aliphatic diureas

Info

Publication number: KR20110088749A
Application number: KR1020100008396A
Authority: KR
Inventors: 김훈식; 정민석; 누엔딘콴; 심유나
Original assignee: 경희대학교 산학협력단
Priority date: 2010-01-29
Filing date: 2010-01-29
Publication date: 2011-08-04
Also published as: KR101137499B1

Abstract

The present invention relates to a method for environmentally friendly production of aliphatic diurea by using water as a reaction solvent and a catalyst in preparing aliphatic diurea by reacting aliphatic diamine with urea. According to the production method of the present invention, by using water as a reaction solvent and catalyst, not only can be prepared in high yield and high selectivity diurea under mild conditions, but also a problem of the process using a conventional organic solvent and metal catalyst There is no need for separation of the catalyst and solvent, which greatly simplifies the purification of the product.

Description

Method for Preparing Aliphatic Diurea {Method for Preparing Aliphatic Diureas}

The present invention relates to a process for producing aliphatic diurea. More specifically, the present invention relates to a method for producing aliphatic diurea in a high yield in an aqueous solution without using an organic solvent and a metal catalyst in preparing aliphatic diurea by reacting aliphatic diamine with urea.

Isocyanates, which have been used as intermediates for the production of polyurethanes, adhesives and pesticides, have been synthesized from amines and phosgene, but this method requires the use of highly toxic phosgene, as well as by-products of large quantities of pollutant hydrogen chloride (HCl). There are drawbacks and new environmentally friendly methods that do not use phosgene have been required. As a part of this method, a method of preparing carbamate first and pyrolyzing it to prepare an isocyanate is mainly studied.

Methods for preparing carbamate include reacting a nitro compound or amine with carbon monoxide and alcohol at high temperature and high pressure in the presence of a catalyst, synthesizing carbamate from the reaction of amine with dialkyl carbonate, and reacting amine with ethylene or propylene carbonate. Method and the like.

U.S. Patent Nos. 3,461,149 and 3,979,427 used metal halide salts such as iron chloride as cocatalysts to increase reaction rates with palladium or rhodium-based catalysts when carbamate was prepared using nitro or amine compounds. Excess promoters are not only difficult to separate after the reaction, but also cause corrosion problems of the device.

U.S. Patent No. 4,178,455 describes that the reaction rate and selectivity can be increased by adding a primary amine when preparing a carbamate from an aromatic nitro compound using a catalyst such as platinum. Since iron chloride is used as the redox active metal halide, this method also has problems with separation and corrosion.

In order to solve this corrosion problem, U.S. Patent Nos. 4,169,269, 4,219,661, 4,262,130, and 4,339,592, etc., add a tertiary amine such as pyridine to the reaction without the use of redox-active metal halides to remove from aromatic nitro compounds. Carbamate was prepared. As the catalyst, palladium, platinum, and other Group VIII elements may be used, and under the same conditions, US Pat. Nos. 3,338,956, 3,993,685, 4,705,883 and the like used a carbonyl compound of rhodium or ruthenium as a catalyst. The pyridine used at this time is in excess of the catalyst used, and sometimes used as a reaction solvent. However, this method is not economically feasible due to the difficulty of using pyridine with inverse smell and recovery of precious metal catalyst.

US Pat. Nos. 4,297,502, 4,304,992 and 4,474,978 use carbamate by reacting a primary amine or urea with an aromatic nitro compound in the presence of CO and alcohol using palladium containing PdCl ₂ and a phosphine ligand as a catalyst. Although there is a method for preparing the catalyst, there is a problem that the catalyst is too expensive and the catalyst recovery after the reaction is not easy.

Japanese Patent Application Laid-Open No. 54-145601 discloses a method of using a transition metal compound such as palladium, a palladium compound as a catalyst, a method of using palladium, ruthenium, rhodium and Lewis acid, and a tertiary amine as a catalyst, but such a method is known. They have a problem that they require low catalyst activity and use expensive precious metal catalysts, as well as by-products of urea compounds and N-alkylated amines in large quantities.

Chemistry Letters (1972) 373-374 describe a method for synthesizing carbamate by carbonylating an amine on a selenium catalyst, but using an equivalent amount of selenium results in high catalyst loss and aromatic amine as a raw material. When used, there is a drawback that the reaction hardly proceeds.

As a method for solving this problem, a method of reacting dialkyl carbonate and amine under relatively mild conditions has been proposed. For example, Japanese Patent Laid-Open No. 51-33095 describes a method of using Lewis acids such as uranyl acetate and antimony trichloride as a catalyst. However, these catalysts promote the alkylation reaction of amines with diester carbonate in addition to the carbamate formation reaction, so that by-products of N-alkylated amines are increased. In addition, the uranium compound gives a relatively good result, but the handling of the radioactive element is difficult, so there is no practical use.

Japanese Laid-Open Patent Publication No. 57-82361 discloses a method using a neutral or basic compound of zinc, titanium or zirconium as a catalyst. This method has high yield of carbamate, but requires high temperature and long reaction, and it is not industrially preferable because of difficulty in separating catalyst after reaction.

Methods using Lewis acids such as aluminum chloride, tin chloride, iron chloride, zinc chloride, rhodium chloride and the like as catalysts are described in Gazz. Ital 115, 275. According to this document, reactions using these catalysts give good results, but the reaction is carried out in the presence of an excess of amines for dialkyl carbonates, which requires a lot of energy for recycling amines when it is necessary to use high boiling amines. There is a problem.

On the other hand, Japanese Patent Laid-Open No. 2-311452 discloses a method of using an alcohol of an alkali metal and an alkaline earth metal as a method of using a base as a catalyst, but a base may remain in the carbamate obtained in this method. Residual base should be removed by neutralization with acid as it may cause polymerization or coloring when converting carbamate to isocyanate.

JP-A-3-275662 discloses a method of adding 1 mol% or more of water to diester carbonate in a step of synthesizing monocarbamate by reacting ammonia or monoamine with diester carbonate. However, in the above-mentioned patent document, not only is there no mention of producing dicarbamate from diamine, but there is a lot of difficulty in separating and purifying the product because an excess amine is used together with water.

Japanese Unexamined Patent Application Publication No. 5-85854 shows that the use of excess amine for dialkyl carbonate allows the reaction to proceed rapidly even in the absence of a catalyst and to prepare carbamate with high selectivity in high yield. This method has the advantage that it is not necessary to add materials other than the reaction raw materials to the reaction system and carbamate can be obtained in a high yield in a short time, but in the case of diamine, the yield is low and the difficulty of purifying the amine used excessively is difficult. have.

Korean Patent Publication No. 1999-0079326 discloses a method for preparing carbamate in a high yield by reacting an amine with an alcohol and a mixed CO / O ₂ gas in the presence of a selenium catalyst system. There is a problem that the catalyst must be recovered.

International Patent Publication No. WO 2007/082818 discloses a method of preparing diurea by reacting diamine with urea and reacting it with alcohol at high temperature, but dicarbamate is produced in a diurea manufacturing reaction such as toluene, which is a volatile organic solvent. It is used and the reaction temperature is relatively high as 170 ~ 220 ^° C. It is economically and environmentally undesirable.

When the present inventors used as the intensive studies examine the results, a solvent water to the reaction between the aliphatic diamine and urea in order to develop environment-friendly method which can be produced in high yield and the raw material aliphatic dicarboxylic urea of the aliphatic diisocyanate 100 ^o C or less It is possible to obtain high yield of aliphatic diurea in the mild conditions of the product without the production of by-products, and to eliminate the catalyst after the reaction because the metal catalyst is not used. It has been found and completed the present invention.

Accordingly, it is an object of the present invention to provide a process for producing aliphatic diureas from aliphatic diamines and ureas in high yield and environmentally friendly.

The present invention relates to a process for producing aliphatic diurea by reacting aliphatic diamines having 2 to 8 carbon atoms with diurea, wherein water is used as a reaction solvent and a catalyst.

Aliphatic diamines having 2 to 8 carbon atoms used in the preparation method of the present invention include cycloaliphatic diamines having 2 to 8 carbon atoms, for example 1,2-ethanediamine (EDA), 1,3-propanediamine (PDA) , 1,4-butanediamine (BDA), 1,6-hexanediamine (HDA), 1,8-octanediamine (ODA), 1,2-cyclohexanediamine (1,2-CHDA), 1,3- Cyclohexane diamine (1,3-CHDA), 1,4-cyclohexane diamine (1,4-CHDA), 1,3-cyclohexane bismethylamine (1,3-CHBMA), 1,4-cyclohexane bis Methylamine (1,4-CHBMA) and the like, but are not limited thereto.

The amount of urea used is preferably 2 to 20 moles, more preferably 2.5 to 10 moles, based on 1 mole of aliphatic diamine as a starting material. If the amount of urea used is less than 2 moles, the yield of diurea is remarkably decreased. If the amount of urea exceeds 20 moles, the amount of urea to be recovered after the reaction is increased.

In the production method of the present invention, the water used as the reaction solvent and catalyst not only serves to promote the reaction, but also has a high solubility in urea, so that it is not necessary to separate the unreacted urea after the reaction, and then to the next reaction. It offers the advantages of being used as is. Furthermore, since the produced aliphatic diurea is obtained as a solid which is not dissolved in water, it can be easily recovered by filtration.

The amount of water used is preferably 0.2 to 20 moles, more preferably 2 to 10 moles, per 1 mole of aliphatic diamine as a starting material. If the amount of water used is less than 0.2 mol, the reaction proceeds too slowly, resulting in diamine conversion and diurea yield falling. If it is more than 20 mol, the amount of water to be removed after the reaction is increased. Many are uneconomical.

The reaction temperature may be selected in the range of 40 to 120 ° C., but may be selected in the range of 60 to 100 ° C. in consideration of the reaction rate and the yield and selectivity of the diurea. If the reaction temperature is less than 40 ℃, the production rate and yield of diurea is lowered, if it exceeds 120 ℃ unnecessary energy is excessively consumed is uneconomical.

In addition, the reaction time may be selected in the range of 1 to 12 hours, but in consideration of the yield of the diurea and the economics of the reaction, it is preferable to select in the range of 2 to 6 hours.

According to the process for producing aliphatic diurea of the present invention, by using water as a reaction solvent and a catalyst, not only can diurea be produced in high yield and high selectivity under mild conditions, but also using existing organic solvents and metal catalysts. It does not require separation of the catalyst and solvent, which is a problem of the process, which greatly simplifies the purification of the product. In addition, since it is not necessary to use toxic phosgene or expensive metal catalysts, it is possible to produce aliphatic diurea economically and environmentally.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, it is apparent to those skilled in the art that the scope of the present invention is not limited to these examples.

Example 1:

Fill a 500 mL three neck flask with reflux and thermometer with 1,6-hexanediamine (HDA; 46.4 g, 0.4 mol), urea (60.0 g, 1.0 mol) and water (43.2 g, 2.4 mol), 80 The reaction was carried out at 4 ° C. for 4 hours. The precipitate obtained by cooling the reaction mixture to room temperature was filtered, dried, and weighed to analyze the composition by gas chromatography. As a result, the conversion rate of 1,6-hexanediamine was 100%, and diurea was obtained in a yield of 98.8%. Could.

The conversion of diamine and the yield of diurea were calculated as follows.

% Conversion of diamine = (reaction amount of diamine / amount of diamine used) × 100

Yield of Diurea (%) = (Diurea Production / Diamine Usage) × 100

Examples 2-11:

In order to determine the effect of water in the same conditions as in Example 1 fixed the molar ratio of urea and HDA to 2.5 and the reaction was performed while changing the molar ratio of water and HDA, the results are shown in Table 1 below.

Example Molar ratio (H ₂ O / HDA) HDA conversion rate (%) Diurea yield (%) 2 - 33.2 27.3 3 0.2 57.8 55.4 4 0.5 63.5 59.5 5 One 69.1 66.6 6 2 87.4 86.3 7 3 93.2 91.9 8 4 98.7 97.3 9 10: 1 100 100 10 15: 1 100 100 11 20: 1 100 100

Examples 12-16:

Under the same conditions as in Example 1, the molar ratio of water and HDA was fixed at 6, and the reaction was performed while changing the molar ratio of urea and HDA, and the results are shown in Table 2 below.

Example Molar ratio (urea / HDA) HDA conversion rate (%) Diurea yield (%) 12 2 97.3 96.9 13 4 100 100 14 8 100 100 15 10 100 100 16 20 100 100

Examples 17-21:

The reaction was performed while changing the reaction temperature under the same conditions as in Example 1, and the results are shown in Table 3 below.

Example Reaction temperature ( ^o C) HDA conversion rate (%) Diurea yield (%) 17 40 78.8 78.3 18 60 86.7 86.1 19 90 100 100 20 100 100 100 21 120 100 98.9

Examples 22-25:

The reaction was performed while changing the reaction time under the same conditions as in Example 1, and the results are shown in Table 4 below.

Example Response time (h) HDA conversion rate (%) Diurea yield (%) 22 One 75.8 74.7 23 3 92.3 91.6 24 6 100 100 25 12 100 100

Examples 26-30:

The reaction was carried out under different conditions of the diamine under the same conditions as in Example 1, and the results are shown in Table 5 below.

Example Diamine Diamine Conversion (%) Diurea yield (%) 26 EDA 100 100 27 BDA 100 100 28 ODA 96.6 96.4 29 1,2-CHDA 92.9 90.8 30 1,3-CHBMA 89.3 88.1

Claims

A process for producing aliphatic diurea by reacting aliphatic diamines having 2 to 8 carbon atoms with urea, wherein water is used as a reaction solvent and a catalyst.

The aliphatic diamine of claim 1, wherein the aliphatic diamine having 2 to 8 carbon atoms is 1,2-ethanediamine (EDA), 1,3-propanediamine (PDA), 1,4-butanediamine (BDA), 1,6-hexanediamine (HDA), 1,8-octanediamine (ODA), 1,2-cyclohexane diamine (1,2-CHDA), 1,3-cyclohexane diamine (1,3-CHDA), 1,4-cyclohexane Diamine (1,4-CHDA), 1,3-cyclohexane bismethylamine (1,3-CHBMA) or 1,4-cyclohexane bismethylamine (1,4-CHBMA).

The method according to claim 1, wherein the amount of urea used is 2 to 20 moles per 1 mole of aliphatic diamine.

The method according to claim 1, wherein the amount of water used is 0.2 to 20 moles per 1 mole of aliphatic diamine.

The production method according to any one of claims 1 to 4, wherein the reaction temperature is 40 to 120 ° C.

The production method according to any one of claims 1 to 4, wherein the reaction time is 1 to 12 hours.