• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von symmetrischen 1,3-disubstituierten Harnstoffen durch Umsetzung von Harnstoff mit primären Aminen. Dabei werden Harnstoff und Amin im Molverhältnis 1:2,2 bis 1 : in einem Reaktor mit aufgesetzter Kolonne bei einerTemperatur im Bereich zwischen 150 und 250°C und bei einem Druck im Bereich zwischen 10 und 60 bar umgesetzt, und das entstehende Ammoniak wird, gegebenenfalls zusammen mit nicht umgesetztem Amin, am Kolonnenkopf abgenommen. Nach diesem Verfahren lassen sich Harnstoffe der Formel in der R einen unverzweigten oder verzweigten Alkylrest mit 1 bis 20 Kohlenstoffatomen, der durch Phenyl oder Phenoxy einfach oder mehrfach substituiert sein kann, einen unverzweigten oder verzweigten Alkoxyalkylrest mit 2 bis 20 Kohlenstoffatomen, einen Monocycloalkylrest mit3 bis 8 Kohlenstoffatomen oder einen Bicycloalkylrest mit bis 12 Kohlenstoffatomen bedeutet, herstellen; sie sind wertvolle Ausgangsstoffe für die Synthese von Farbstoffen und Pflanzenschutzmitteln.
    公开号:SU1060105A3
    申请号:SU792834292
    申请日:1979-10-15
    公开日:1983-12-07
    发明作者:Верц Отто；Блок Ульрих；Фишер Роман；В.Ротермунд Герхард
    申请人:Басф Аг (Фирма)；
    IPC主号:
    专利说明:

    about
    SP The invention relates to an improved process for the preparation of symmetric 1,3-disubstituted urea samples of the formula R-NH-CO-NH-R, where R is unbranched or branched C-alkyl. A method of producing substituted urea of the general formula 1 is known by reacting urea with an amine, i.e. by transamination of urea at 150-200 ° C without pressure, without solvent, and without excess amine 1. At these temperatures, the reactions of all the ureas have significant sublimation vapor pressures, which cause great technical problems, since 2 mol of ammonia is formed per 1 mol of U3 displaced urea. This off-gas is usually absorbed by water, which requires a 20-25% ammonia solution. Disposal of this solution, contaminated with urea and amine, is problematic. Finally, it should also be borne in mind that the boiling point of most amines required for transamination is well below 150-200 C. The consequence of this is I; the fact that the concentration of amines in the melt is inevitably very low, this leads to poor time / yield volumes. The duration of the process is 20 hours. The closest in technical essence and the achieved effect to the proposed is a method of obtaining substituted urea of the general formula by reacting urea with an amine without pressure and without solvent in a reaction column with cap plates that has at least two temperature ranges at the bottom of the column 120-140 and top 160-18.5 C. Reaction time 30 hours. Reagent molar ratio 1: 2 The disadvantage of the known method is the duration of the process. Taking into account the long residence time of the gas phase available for the reaction column, this in technical scale tables leads to practically. unsatisfactory reactor volumes. In addition, a complex multi-stage reactor is required. The purpose of the invention is to simplify the process. The goal has been achieved by a process for the preparation of symmetrical 1,3-substituted ureas of the general formula by reacting the urea with an amine of the general formula R-NHa,. . J where R has the indicated values, at 150-250 ° C and a pressure of 14-27 atm with a molar ratio of starting reagents of 1: 2.2-1: 6 in a packed-column reactor, the ammonia and unreacted amine formed are removed in the head of the prick Usually the process is carried out continuously. Suitable for exchange reaction reactors are vessels with internal or external heating devices that can be equipped with mixing devices such as a mechanical stirrer or jet-jet stirrer. The column mounted on the reactor is equipped with conventional installations of metal or ceramic, and predominantly nozzle elements can be used, such as, for example, saddle-shaped and shaped rings, or sieve, cap and valve plates. The exchange reaction can also be carried out in several reactors in cascade order. Urea and amine are charged to the reactor in a molar ratio of 1: 2.21: 6, preferably 1: 3 - 1: 4. The exchange reaction is carried out at a temperature in the range of 150-250 ° C, preferably 195-210 ° C, and at a pressure in the range of 10-60 atm, preferably 15-25 atm. In order to achieve an exchange of at least 95%, under these conditions, an average residence time in the reactor is from 0.5 to 4 hours. The exchange can be determined analytically by high-pressure liquid chromatography. During the exchange reaction, ammonia is distilled off at the head of the column. Depending on the boiling point and the excess of amine in the head of the column, the mixture of ammonia and amine is also removed. This mixture can be easily separated in the second column, and the amine is recycled. The return ratio of the column can be varied from 2: 1 to 20: 1, preferably from 4: 1 to 6: 1. Despite the high temperature in the reactor, sublimation of the resulting 1,3-disubstituted urea does not interfere with rectification in the packed column. I The stated provisions relate to the industry-preferred continuous implementation of the method. The method can also be carried out periodically, and these conditions must be met. Obtained by the proposed method in accordance urea are valuable raw materials for the synthesis of dyes and chemical plant protection products. Example 1. A heated autoclave with agitators, on which a column with a nozzle (Raschig metal rings) is mounted, is continuously loaded with urea and isopropylamine in a molar ratio of .e. an excess of isopropylamine is 100%. The reaction pressure is 21 atm, the reaction temperature, the average residence time is 4 hours and the column return ratio is 4.6: 1. At the head of the column, there is a side mixture of amine and ammonia in a molar ratio of 0.9: 1. When the pressure of the discharged material is relieved, about 10% of the amine evaporates, the residue contains 99.1% diisopropyl urea and 1.3% monoisopropyl urea (determined by forced liquid chromatography). The mixture melts at 190 ° C. Example 2. In the apparatus described in example 1, urea and isopropylamine are continuously loaded in a molar ratio of 1: 4. The reaction pressure was 16 atm, the reaction temperature was 205 ° C, the average residence time was 9 hours and the return ratio of the column was 9: 1. On the head of the column comes a mixture of ag-shna and ammonia. Once loaded, the material contains, after relieving the pressure, 98.1% diisopropyl urea and 1.2% monoisopropyl urea. The mixture melts at. Example 3. The equipment described in Application 1 is loaded continuously with urea and isopropylamine in a molar ratio of 1: 4. The reaction rate is 16 atm, the reaction temperature is 205 ° C, the average residence time is 5 hours and the return ratio of the column is 4.7: 1. A mixture of amine and ammonia is released on the head of the column. The discharging material contains, after relieving the pressure, 97.2% diisopropylurea and 2.9% monoisopropylurea. The mixture melts at 190 ° C. Example 4. The apparatus described in Example 1 is loaded continuously with urea and isopropilag tires in a molar ratio of 1: 2.2, i.e. an excess of isopropylamine is 10%. The reaction pressure is 16 atm, the reaction temperature is 170-175 ° C, the average residence time is 4 hours. The return column ratio is approximately 15: 1. On the head of the column comes out a clean side-stream. The material to be discharged contains, after relieving the pressure, 90% diisopropyl urea and 10% monoisopropyl urea. O / iecb is melted at 183-185 ° C., Example 5. Circulating equipment with a packed column with packing (metal mesh rings) is loaded continuously with urea and n-propylamine in a molar ratio of 1: 4. The reaction pressure is 21 atm, the reaction temperature is 2O5®C, the average residence time is 4 hours and the return ratio of the column is 5: 1. On the head of the column goes the mixture and ammonia. Unloading material with so pl. 102-104c, after depressurization, contains more than 95% di-n-propyl urea. Example 6. In the apparatus described in Example 1, urea and isoamylamine are continuously loaded in a molar ratio of 1: 4. The reaction pressure was 16 atm, the reaction temperature was 225 ° C, the average residence time was 4 hours, and the column return ratio was 5: 1. On the head of the column there is a mixture of amine and. The discharge material contains 23% isoamylamine, which is distilled off. The distillation residue consists of more than 95% of diisoamyl urea; it melts at 43-46 ° C. Example 7. In the apparatus described in example 1, the urea and methylamine are continuously loaded in a molar ratio of 1: 4. The reaction pressure is 20 atm, the reaction temperature is 205 ° C, the average residence time is 4 hours, and the column return ratio is 5: 1. On the head of the column comes a mixture of amine and ammonia. The discharging material contains, after relieving the pressure, 98% of dimethyl urea and 1% of monomethyl urea. The product melts at 104-106 ° C. Example 8. In the apparatus described in example 1, the apparatus was loaded continuously with urea and isopropylamine in a molar ratio of 1: 4. The reaction pressure is 14 atm, the reaction temperature is 205 ° C, the average residence time is 2 hours and the reflux ratio of the column is 9: 1. A mixture of amine and ammonia is released on the head of the column. The relief material contains, after relieving pressure, 95% diisopropyl urea and 5% monoisopropyl urea. The product melts at 185s. Example 9. The apparatus described in Example 1 was loaded continuously with urea and ethylamine in a molar ratio of 1: 4. The reaction pressure was 23 atm, the reaction temperature was 220 ° C, the average residence time was 4 hours, and the return ratio of the column was 5.5: 1. A mixture of amine and ammonia is released on the head of the column. The discharged material contains, after relieving the pressure, 98.4% diethyl urea and 1.2% monoethyl urea. The product melts at 106-109 ° C. Example 10. In the apparatus described in Example 1, urea and methylamine are continuously loaded in a molar ratio of 1: 6. The reaction pressure is 27 atm. The reaction temperature is -205 ° C, the average residence time is 1 hour and the return ratio of the column is 5: 1. On the head of the colony there is a blemish of YMIA. and ammonia. The discharge material contains, after relieving the pressure, 98.2 dimethyl urea and 1.3% monomethyl urea. The product melts at. Example 11. In the apparatus described in Example 1, the equipment is continuously fed with urea and methylamine in a molar ratio of 1: 4. The reaction pressure is 25 atm, the reaction temperature is 150-160 ° C, the average residence time is 8 hours, and the column return ratio is 5: 1. A mixed mixture of amine and ammonia is released on the head of the column. The discharge material contains, after relieving the pressure, 93.7% of dimethyl urea and 4.0 monomethyl urea. The product melts at 103 ° C. Example 12. The apparatus described in Example 1 is continuously fed with urea and n-heptadecylamine in a molar ratio of 1: 4. The reaction pressure is 20 atm, the reaction temperature is approximate, the average residence time is 4 hours and the column return ratio is 5: 1. On the head of the column comes a mixture of ammonia and ammonia. The unloading material contains, after depressurization, 96.3% di-n-heptadecyl urea and 2.1% monoheptadoyl urea. The product melts at 70-73 ° C. Example 13. The apparatus described in example i is continuously loaded with urea and isopropylamine in a molar ratio of 1: 4. The reaction pressure is 18 atm, the reaction temperature is 240-250 ° C, the average residence time is 2 hours and the return ratio of the column is 5: 1. On the head of the column comes a blend of amine and cUviMHaKa. The discharge material contains, after relieving, 98.6% diisopropyl urea and 1.2% monoisopropyl urea. The product melts at 187-188 ° C. Thus, the proposed method allows the process to be carried out in just 0.5-4 hours and a very simple, single-stage reactor can be used. Solved the problem of waste disposal, i.e. The ammonia gas obtained as a result of the reaction does not contain urea, and can be used in chemical production without additional purification.
    权利要求:
    Claims (2)
    [1]
    (577 1. METHOD FOR PRODUCING SIM
    METRIC 1, 3-DOUBLASTED UREA of the general formula
    R-NH-CO-NH-R, where R is unbranched or branched C ^ -C ^ ralkyl, by reacting urea with an amine of the general formula
    RNh 2 , where R has the indicated meanings, at elevated temperature, with the fact that, in order to simplify the process, the starting reagents are used in a molar ratio of 1:: 2.2 - 1: 6 and the process is carried out at 150-250 ° C and a pressure of 14-27 atm in a reactor with a packed column, and the formed ammonia and unreacted amine are removed in the head of the column.
    [2]
    2. The method of pop. 1, excellent,. and the fact that the process is carried out continuously.
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE896640C|1942-05-13|1953-11-12|Knoll Ag|Process for the production of mono- or symmetrical dimethyl urea|
    DE855551C|1942-05-13|1952-11-13|Knoll Ag|Process for the production of mono- or symmetrical dimethyl urea|
    US3937727A|1974-07-05|1976-02-10|Ashland Oil, Inc.|Process for preparing n, n-dimethylurea|NZ225165A|1987-06-25|1990-09-26|Lilly Co Eli|Carbamate preparation|
    ES2062248T3|1989-11-10|1994-12-16|Agrolinz Agrarchemikalien|PROCEDURE FOR OBTAINING PURE UREAS, ASYMMETRICALLY DISUBSTITUTED.|
    DE3940261A1|1989-12-06|1991-06-13|Agrolinz Agrarchemikalien Muen|Prodn. of di:substd. urea herbicides and fungicides, e.g. fenuron - by reacting amine with N-alkyl- or N,N-di:alkyl-urea in presence of corresp. alkyl- or di:alkylamine|
    GB9312881D0|1993-06-22|1993-08-04|Jefferson Roger L|Boiler treatment and novel compounds therfor|
    DE4432637A1|1994-09-14|1996-03-21|Huels Chemische Werke Ag|Polyamines containing new urea groups|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19782844962|DE2844962A1|1978-10-16|1978-10-16|METHOD FOR PRODUCING SYMMETRIC 1,3-DISUBSTITUTED UREAS|
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