CN1243119A - Method for purifying N, N-dimethylaniline by acid anhydride - Google Patents
Method for purifying N, N-dimethylaniline by acid anhydride Download PDFInfo
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- CN1243119A CN1243119A CN 99114288 CN99114288A CN1243119A CN 1243119 A CN1243119 A CN 1243119A CN 99114288 CN99114288 CN 99114288 CN 99114288 A CN99114288 A CN 99114288A CN 1243119 A CN1243119 A CN 1243119A
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- accelerine
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Abstract
The method for purifying N, N-dimethylaniline is characterized by making N, N-dimethylaniline crude product and organic acid anhydride produce acylation reaction, the ratio of the molar weight of added organic acid anhydride and the molar total weight of N-methylaniline and aniline being in the N, N-dimethylaniline is 1 : 0.5-1.5, the temperature of acylation reaction is controlled at 20-100 deg.C, reaction time is 5-60 min., then making said reaction mixture and alkaline aqueous solution produce neutralization reaction, and the equipment number of alkaline matter in the alkaline aqueous solution is 0.9-2 times mole number of the added organic acid anhydride, after said reaction is completed, separating out water phase to obtain the invented N, N-dimethylaniline semifinished product, finally making distillation treatment to obtain the invented finished product.
Description
The present invention relates to a kind of method of purification of fine chemical material, particularly N, the method for purification of accelerine.
N, accelerine (hereinafter to be referred as DMA) are a kind of important meticulous Organic Chemicals, are widely used in the manufacturing of dyestuff, medicine, spices and explosive and thiofide, and are used for pesticide producing as solvent and acid binding agent.The common manufacture method of DMA is with aniline, methyl alcohol and sulfuric acid mix by a certain percentage, in autoclave, under the condition of 200-230 ℃ and 3.0-4.0MPa, react, generate DMA, because this reaction is reversing process, and through intermediate N monomethylaniline (hereinafter to be referred as MA), be subjected to the influence of the equilibrium constant, in the DMA crude product, contain a certain amount of unreacted raw material aniline (hereinafter to be referred as An) and intermediate MA usually, the China standard HG2-375-83 of the Ministry of Chemical Industry regulation, in the DMA first grade content of MA necessary≤0.5% (w/w, down with), An content must meet chlorinated lime touchstone (the 2.4th of HG2-375-83, be equivalent to≤0.03%).Nippon Standard JIS K4112 also has with standard laid down by the ministries or commissions of the Central Government HG2-375-83 identical regulation to the MA in the DMA finished product with An content with Taiwan standard C NS12196-K2180.(be respectively 192.5 ℃, 190 ℃ and 184 ℃ because the boiling point of DMA, MA, An is close, rectificating method with routine is difficult to separate, in actual production, for the content that makes MA and An up to standard, three kinds of methods of general employing: 1, (theoretical value is 2: 1 to the molar feed ratio of increase methyl alcohol and aniline, and actual value can reach 3.5-4.5: 1); 2, prolong the reaction times (will be controlled in the reaction times 6-8 hour usually); 3, use above two kinds of methods simultaneously.Common shortcoming of these methods is the throughput that has reduced this key equipment of autoclave, increased production cost, method 1 also might cause reaction pressure to raise, autoclave manufactured and designed the corresponding raising of standard, and will strengthen the workload that reclaims excessive methanol, simultaneously, owing to lack reliable monitoring means, content fluctuation with MA and An in the DMA crude product of aforesaid method production is bigger, causes the waste and the quality accident of throughput easily.
Purpose of the present invention is exactly in order to address the above problem, propose a kind ofly to shorten the reaction times significantly, and make that quality product is effectively controlled with the acid anhydrides N that purifies, the method for accelerine.
Technical solution of the present invention:
A kind of with the acid anhydrides N that purifies, the method for accelerine is characterized in that:
A, the N that will make by ordinary method, the N that the accelerine reaction mixture obtains after telling quaternary ammonium salt, accelerine crude product and organic acid anhydride carry out acylation reaction, molar weight and N that organic acid anhydride adds, the ratio of the mole total amount of methylphenylamine and aniline is 1 in the accelerine crude product: 0.5-1.5, the temperature of acylation reaction is controlled at 20-100 ℃, and the reaction times is 5-60 minute;
B, will carry out neutralization reaction by reaction mixture and the alkaline aqueous solution that a step obtains, alkaline matter equivalents in this alkaline aqueous solution be add in a step organic acid anhydride mole number 0.9-2 doubly, reaction after finishing is told water, obtain N of the present invention, the accelerine work in-process, after distillation just obtains N of the present invention, accelerine finished product.
The above-mentioned conventional N that tells quaternary ammonium salt, the accelerine crude product should wash with water earlier before carrying out acylation reaction, and the volume of its washing water is conventional N, and the 10-100% of accelerine crude product volume is preferably 20-40%, and wash temperature is 20-80 ℃.
In the above-mentioned acylation reaction, the temperature of acylation reaction is preferably 40-60 ℃, and the time of acylation reaction is preferably 10-20 minute.
The organic acid anhydride that above-mentioned acylation reaction adds can be phthalic anhydride, MALEIC ANHYDRIDE, acetic anhydride etc.The organic acid anhydride add-on preferably meets following calculation formula:
Organic acid anhydride add-on (kilogram)=9.56 * 10
-3(MA content %/107+An content %/93-0.003) wherein K is reinforced coefficient to KMV, and value 1.00-1.30 is preferably 1.05-1.15, and M is the organic acid anhydride molecular weight, and V is a DMA crude product volume (liter).
Above-mentioned acylation reaction is carried out in the used alkaline aqueous solution of neutralization reaction after finishing, and its alkaline matter can be ammonia, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate.The equivalent concentration of alkaline aqueous solution is 0.1-5.0N, is preferably 0.3-0.5N, the equivalents of alkaline matter preferably the organic acid anhydride mole number 1.2-1.5 doubly.
Main foundation of the present invention is following acylation reaction:
Before the beginning acylation reaction, earlier the DMA crude product is washed with water, and water phase separated, with remove as far as possible former process residual alkaline matter and moisture, reduce because of the acid anhydrides loss that hydrolysis causes in alkaline aqueous solution.
DMA is a tertiary amine; not with anhydride reaction; and be insoluble in water; and Compound P hN (A) COBCOONa has certain solubleness in water; thereby can MA and An content in the DMA crude product be effectively controlled with the product acid amides carboxylic acid dissolving of alkaline aqueous solution after acylation reaction is finished with reaction formula (I).
The present invention adopts aniline and the methylphenylamine in organic acid anhydride and the DMA crude product to carry out acylation reaction first; make An and MA from the DMA crude product, remove; thereby make N; reaction times in the accelerine production dropped to 2.5 hours by original 6-8 hour; production cycle obviously shortens; the throughput of key equipment utilization ratio and a whole set of DMA device increases substantially, and has reduced production cost effectively.
DMA crude product in following each embodiment obtains by following method:
With An, methyl alcohol, sulfuric acid mixed in molar ratio with 1: 3.2: 0.09, the autoclave of packing into, mixture is warming up to 210 ℃, and under 210-220 ℃, be incubated 2.5 hours, water and the excessive methanol that reaction generates told in pressure release, leftover materials are pressed in the separating still that fills a certain amount of aqueous sodium hydroxide solution in the autoclave, tell lower floor's quaternary ammonium salt aqueous solution, obtain conventional DMA crude product.
Below DMA, MA content data among each embodiment adopt the method for HG2-375-83 regulation to record, the An content data adopts the method for Nippon Standard JIS K4112 regulation to record (being vapor-phase chromatography).
Embodiment 1:
With the water washing of 202 liters of DMA crude products placing separating still with 50 liters 25 ℃; after leaving standstill branch vibration layer; under agitation in separating still, add 2.93 kilograms of phthalic anhydrides (industrial first grade, content 〉=99.0%), after stirring 15 minutes under 50 ℃; in separating still, add 53 liter of 2% aqueous sodium hydroxide solution again; continue to stir 15 minutes, leave standstill branch vibration layer, get the DMA work in-process; acylation reaction total recovery 92.6%, DMA crude product and 1
#It is constant substantially that the content of each component in the work in-process (w/w%, down together) sees Table 1. these work in-process each component content after the distillation decoking.
Table 1
Material embodiment DMA MA An
1
#Crude product 98.709 0.977 0.312
1
#Work in-process 99.679 0.310 0.009 embodiment 2-3:
According to the operational condition of embodiment 1, change the washing water consumption into 25 liters and 150 liters respectively, work in-process content sees Table 2.
Table 2
The embodiment number washing water yield (L) DMA MA An
2
# 25 99.631 0.357 0.010
3
#150 99.694 0.295 0.009 embodiment 4-5:
According to the operational condition of embodiment 1, change crude product component and acid anhydrides consumption, the half-finished content of gained sees Table 3,4
#And 5
#The crude product composition sees Table 4.
Table 3 embodiment phthalic anhydride consumption DMA MA An acid anhydrides/impurity acidylate yield
(Kg) (mol/mol) (%) 4
#2.41 99.599 0.377 0.023 0.70 98.3 5
#5.05 99.78 0.13 0*, 1.15 81.1* null values are represented content≤0.01%, down together.
Table 4
Material DMA MA An 4
#Crude product 98.768 0.844 0.386 5
#Crude product 99.29 1.52 0.11 embodiment 6:
According to the operational condition of embodiment 5, with acidylate time lengthening to 60 minute, gained the results are shown in Table 5.
Table 5 embodiment acidylate time (min) DMA MA An acidylate yield 6
#60 99.76 0.14 0 80.3 embodiment 7-9:
According to the operational condition of embodiment 5, change the acidylate temperature, gained the results are shown in Table 6.
Table 6 embodiment acidylate temperature (℃) DMA MA An acidylate yield (%) 9
#10 99.81 0.10 0 81.9 8
#30 99.83 0.09 0 82.4 7
#70 99.63 0.23 0 75.0 embodiment 10:
With the water washing of 194 liters of DMA crude products placing separating still with 50 liters 25 ℃; after leaving standstill branch vibration layer; under agitation in separating still, add 2.15 kilograms of cis-butenedioic anhydride (industrial first grade; content 〉=99.0%); after stirring 15 minutes under 50 ℃; in separating still, add 55 liter of 2% aqueous sodium hydroxide solution again; continue to stir 15 minutes; leave standstill branch vibration layer; get the DMA work in-process; acylation reaction total recovery 87.9%, it is constant substantially that the content of each component in DMA crude product and the 10# work in-process (w/w%, down together) sees Table 7. these work in-process each component content after the distillation decoking.
Table 7 material embodiment DMA MA An10
#Crude product 98.623 1.206 0.16910
#Work in-process 99.687 0.304 0.008 embodiment 11-12:
According to the operational condition of embodiment 10, change the amount of the aqueous sodium hydroxide solution of crude product component and adding, thereby change the ratio of alkaline matter equivalents and cis-butenedioic anhydride mole number, the half-finished content of gained sees Table 8,11
#And 12
#The crude product composition sees Table 9.
Table 8 embodiment diluted alkaline volume (L) DMA MA An alkali/cis-butenedioic anhydride (equivalent/mol) 11
#42 99.665 0.320 0.015 0.9812
#63 99.600 0.390 0.009 1.46
Table 9 material DMA MA An11
#Crude product 98.365 1.144 0.22112
#Crude product 98.425 1.501 0.074 embodiment 13-14:
According to the operational condition of embodiment 1, change the equivalent concentration and the add-on of crude product component, aqueous sodium hydroxide solution, the half-finished content of gained sees Table 10,13
#And 14
#The crude product composition sees Table 11.
Table 10 embodiment alkali lye volume alkali lye equivalent concentration DMA MA An alkali/cis-butenedioic anhydride
(L) (N) (equivalent/mol) 13
#77 0.29 99.706 0.294 0 1.43 14
#42 0.91 99.664 0.323 0.012 1.69
Table 11 material DMA MA An13
#Crude product 98.945 0.962 0.09314
#Crude product 98.552 1.112 0.336
Claims (7)
1, a kind of with the acid anhydrides N that purifies, the method for accelerine is characterized in that:
A, the N that will make by ordinary method, the N that the accelerine reaction mixture obtains after telling quaternary ammonium salt, accelerine crude product and organic acid anhydride carry out acylation reaction, molar weight and N that organic acid anhydride adds, the ratio of the mole total amount of methylphenylamine and aniline is 1 in the accelerine crude product: 0.5-1.5, the temperature of acylation reaction is controlled at 20-100 ℃, and the reaction times is 5-60 minute;
B, will carry out neutralization reaction by reaction mixture and the alkaline aqueous solution that a step obtains, alkaline matter equivalents in this alkaline aqueous solution be add in a step organic acid anhydride mole number 0.9-2 doubly, reaction after finishing is told water, obtain N of the present invention, the accelerine work in-process, after distillation just obtains N of the present invention, accelerine finished product.
2, described a kind of by claim 1 with the acid anhydrides N that purifies; the method of accelerine; it is characterized in that telling the conventional N of quaternary ammonium salt; the accelerine crude product should wash with water earlier before carrying out acylation reaction; the volume of its washing water is conventional N; the 10-100% of accelerine crude product volume, wash temperature is 20-80 ℃.
3, described a kind of by claim 2 with the acid anhydrides N that purifies, the method for accelerine, the volume that it is characterized in that described washing water is conventional N, the 20-40% of accelerine crude product volume.
4, described a kind of the method for accelerine is characterized in that in the described acylation reaction that the further temperature of acylation reaction is 40-60 ℃ with the acid anhydrides N that purifies by claim 1, and the time of acylation reaction is 10-20 minute.
5, described a kind of with the acid anhydrides N that purifies by claim 1, the method for accelerine is characterized in that the organic acid anhydride that described acylation reaction adds is phthalic anhydride, MALEIC ANHYDRIDE, acetic anhydride etc., and the organic acid anhydride add-on meets following calculation formula:
Organic acid anhydride add-on (kilogram)=9.56 * 10
-3(MA content %/107+An content %/93-0.003) wherein K is reinforced coefficient to KMV, and value 1.00-1.30 is preferably 1.05-1.15, and M is the organic acid anhydride molecular weight, and V is a DMA crude product volume (liter).
6, described a kind of by claim 1 with the acid anhydrides N that purifies, the method of accelerine, it is characterized in that in the used alkaline aqueous solution of described neutralization reaction, its alkaline matter is ammonia, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, the equivalent concentration of alkaline aqueous solution is 0.1-5.0N, and the equivalents of alkaline matter is 1.2-1.5 a times of organic acid anhydride mole number.
7, described a kind of by claim 6 with the acid anhydrides N that purifies, the method for accelerine, the further equivalent concentration that it is characterized in that alkaline aqueous solution is 0.3-0.5N.
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|---|---|---|---|
| CN 99114288 CN1243119A (en) | 1999-06-28 | 1999-06-28 | Method for purifying N, N-dimethylaniline by acid anhydride |
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|---|---|---|---|
| CN 99114288 CN1243119A (en) | 1999-06-28 | 1999-06-28 | Method for purifying N, N-dimethylaniline by acid anhydride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618345B (en) * | 2009-07-22 | 2011-11-23 | 西北师范大学 | Method for static decompression recovery and recycle of catalyst in synthetic reaction of 2, 4, 6-trichloropyrimidine |
| CN105622304A (en) * | 2014-10-28 | 2016-06-01 | 天津泰普药品科技发展有限公司 | Removal method of aromatic primary amine impurities in drug or drug intermediate |
-
1999
- 1999-06-28 CN CN 99114288 patent/CN1243119A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618345B (en) * | 2009-07-22 | 2011-11-23 | 西北师范大学 | Method for static decompression recovery and recycle of catalyst in synthetic reaction of 2, 4, 6-trichloropyrimidine |
| CN105622304A (en) * | 2014-10-28 | 2016-06-01 | 天津泰普药品科技发展有限公司 | Removal method of aromatic primary amine impurities in drug or drug intermediate |
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