CN102260195A - Method for coproducing alkyl carbamate and alkylamide - Google Patents
Method for coproducing alkyl carbamate and alkylamide Download PDFInfo
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- CN102260195A CN102260195A CN2010101825520A CN201010182552A CN102260195A CN 102260195 A CN102260195 A CN 102260195A CN 2010101825520 A CN2010101825520 A CN 2010101825520A CN 201010182552 A CN201010182552 A CN 201010182552A CN 102260195 A CN102260195 A CN 102260195A
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Abstract
The invention discloses a method for coproducing alkyl carbamate and alkylamide. The method comprises the following steps of mixing alcohol (or phenol) and urea according to a mol ratio of 1.2-3.0 and mixing alkyl acetate and urea according to a ratio of 0.7-3.0; and reacting in a sealed way under the effect of a catalyst so as to obtain the alkyl carbamate and the alkylamide, wherein the reaction temperature is 140-190 DEG C while the reaction time is 5-25 hours. Through using the method to coproduce ethyl carbamate and acetamide, the yield of ethyl carbamate can reach 77% while the yield of acetamide can reach 49%. The method disclosed by the invention has the advantages of low energy consumption, simple equipment, no corrosion to a reaction kettle and higher economic benefits.
Description
Technical field:
The present invention relates to the method for two kinds of important chemical products of coproduction alkyl carbamate, alkylamide, especially utilize the building-up reactions of alkylamide to improve the method for alkyl carbamate productive rate.
Background technology:
Alkyl carbamate compounds (Carbamic Ester) is a very important chemical material of a class, is that intermediate product can synthesize a series of important chemical products with it.For example: by the synthetic a series of isocyanic ester of cracking alkyl carbamate, this method has replaced phosgenation synthetic route traditionally, has good environmental benefit; Carbamate and acetonyl-acetone reaction can make N-and replace 2, the 5-dimethyl pyrrole, and it has good uvioresistant performance, and has excellent compatibility with rubber plastic; Carry out transesterify with polyvalent alcohol, prepare a series of poly-amino ester compounds with aldehyde is crosslinked again, be called " nontoxic polyurethane ", be widely used as coating and tackiness agent; Urethanum is the earliest as one of tranquilizer of children, heart patient in medical treatment; Some alkyl carbamates itself have desinsection, sterilization, kill the effect of mite, weeding, are low toxicity, a big class agricultural chemicals efficiently; Butyl carbamate has the anti-contracility energy when cement dry solidification and moist curing, add a small amount of butyl carbamate, and the shrinkability of cement reduces by 50%～70%; Alkyl carbamate also has good effect at aspects such as synthetic surfactant, resin modifieds.
Alkylamide is a kind of fine chemicals of high added value.Wherein, ethanamide is mainly used in the antacid in organic solvent, softening agent, stablizer and the cosmetic industry, also can be used as wetting agent in the paper industry and the auxiliary agent in the industry such as leather, cloth and various membrane products.It is synthetic that Malonamide nitrile is mainly used in medicine, produces the third two eyeballs, fluorine pyridine acid etc.
Traditional alkyl carbamate synthetic method is to adopt phosgene and alcohol reaction, and reaction generates the carbonochloridic acid alkyl ester, carries out ammonia afterwards and solves alkyl carbamate.Another kind method is that urea and nitric acid effect are generated the urea nitrate precipitation, adds Sodium Nitrite and generates the nitrous acid urea, again with the alcohol effect, is catalyzer backflow 30h with H2SO4.Collect the cut of 146 ℃/500mmHg after the underpressure distillation, this method operation steps is numerous and diverse.
Alcoholysis of urea is the novel method for synthesizing that development in recent years is got up, and raw material is inexpensive, and reaction process is simple, is to study the main direction of alkyl carbamate synthetic at present.This method is easy, and catalyzer is generally metal oxide, separate easily.But because the ammonia that this reaction produces has suppressed balance and moved, so the productive rate of alkyl carbamate is lower.Have patent report in reaction process, to improve the productive rate of alkyl carbamate at present, but this method energy consumption is bigger, and needs the ammonia absorption tower, increased installation cost by the condensation ammonia excretion.
The present invention utilizes ammonia and alkyl acetate reaction to generate this approach of alkylamide, comes the content of ammonia in the reduction system, has both consumed the ammonia of inhibited reaction, has generated the alkylamide with higher economic worth again.And present technique is compared with the condensation ammonia excretion, has both reduced energy consumption, has saved the ammonia absorption tower again.
Summary of the invention:
The objective of the invention is to overcome the deficiency of present prior art, the method for a kind of coproduction alkyl carbamate, alkylamide is provided.
The present invention has mainly solved the phenomenon of ammonia inhibited reaction in the existing alkyl carbamate production, and ammonia is converted into the alkylamide with higher economic worth.
In order to achieve the above object, the present invention is achieved in that
Mol ratio by alcohol (or phenol) and urea is 1.2～3.0, the mol ratio of alkyl acetate and urea is 0.7～3.0 mixed, under the effect of catalyzer (its content be urea quality 4%～8%), place autoclave to react, temperature of reaction is 140-190 ℃, reaction times is 5-25 hour, and stir speed (S.S.) is 400 rev/mins, and pressure is the system autogenous pressure.
The technology of coproduction alkyl carbamate of the present invention, alkylamide comprises following processing step:
A puts into autoclave with urea, catalyzer, alkyl acetate, alcohol (or phenol), and nitrogen purge is used in sealing;
B opens stirring (400 rev/mins), is heated to temperature of reaction, treats to pick up counting after temperature rises to temperature of reaction;
C after reaction finishes, stops heating, and naturally cooling unloads still;
D with liquid filtering, the rotary evaporation that takes out, removes unreacted alcohol (or phenol), alkyl acetate;
E adds the anhydrous diethyl ether extraction in aforesaid liquid, liquid phase is the diethyl ether solution of alkyl carbamate, revolves to steam and removes ether, obtains alkyl carbamate;
G with the solid phase among the step e, adds acetone extract, and liquid phase is the acetone soln of alkylamide, revolves to steam to obtain alkylamide;
F adopts gas-chromatography (marker method, internal standard substance are methyl alcohol or ethanol) that the product that obtains is carried out quantitative analysis, obtains the productive rate of alkyl carbamate, alkylamide.
Embodiment:
In order to understand better and to implement, below in conjunction with the technology of example in detail coproduction alkyl carbamate of the present invention, alkylamide.
Example 1
Coproduction urethanum, ethanamide:
50g urea, 2.0g zinc oxide, 183g ethyl acetate, 96g ethanol are added autoclave, sealing.Use nitrogen purge.Open stirring, rotating speed is 400 rev/mins.Be warming up to 160 ℃, after the question response temperature reaches, pick up counting.After reacting 20 hours, stop heating, continue to stir, cooling naturally, still is unloaded in venting.
Take out reacted liquid, after filtration, revolve steaming, remove catalyzer and unreacted ethyl acetate, ethanol.Add the anhydrous diethyl ether extraction, the liquid phase that obtains is revolved steaming, obtains the product urethanum, and productive rate is 77%.Add acetone in the solid phase and extract, revolve steaming, obtain the product ethanamide, productive rate 49%.
Example 2
Coproduction Urethylane, ethanamide:
50g urea, 2.0g zinc oxide, 154g methyl acetate, 67g methyl alcohol are added autoclave, sealing.Use nitrogen purge.Open stirring, rotating speed is 400 rev/mins.Be warming up to 150 ℃, after the question response temperature reaches, pick up counting.After reacting 20 hours, stop heating, continue to stir, cooling naturally, still is unloaded in venting.
Take out reacted liquid, remove by filter catalyzer, adopt the gas-chromatography inner mark method ration, the productive rate that obtains the product urethanum is 52%, and the productive rate of ethanamide is 26%.
Example 3
Coproduction Urethylane, Malonamide nitrile:
50g urea, 2.0g zinc oxide, 206g methyl-cyanacetate, 67g methyl alcohol are added autoclave, sealing.Use nitrogen purge.Open stirring, rotating speed is 400 rev/mins.Be warming up to 150 ℃, after the question response temperature reaches, pick up counting.After reacting 20 hours, stop heating, continue to stir, cooling naturally, still is unloaded in venting.
Take out reacted liquid, remove by filter catalyzer, adopt the gas-chromatography inner mark method ration, the productive rate that obtains the product urethanum is 39%, and the productive rate of Malonamide nitrile is 18%.
Example 4
Coproduction phenyl carbamate, ethanamide:
50g urea, 2.0g zinc oxide, 283g phenylacetate, 196g phenol are added autoclave, sealing.Use nitrogen purge.Open stirring, rotating speed is 400 rev/mins.Be warming up to 140 ℃, after the question response temperature reaches, pick up counting.After reacting 20 hours, stop heating, continue to stir, cooling naturally, still is unloaded in venting.
Take out reacted liquid, remove by filter catalyzer, adopt the gas-chromatography inner mark method ration, the productive rate that obtains the product urethanum is 21%, and the productive rate of ethanamide is 12%.
Claims (4)
1. the method for a coproduction alkyl carbamate, alkylamide, it be by alcohol (or phenol) and urea be 1.2～3.0 in mol ratio, ester class and urea is to mix under 0.7～3.0 the ratio in mol ratio, confined reaction under the effect of catalyzer, temperature of reaction is 140～190 ℃, and the reaction times is 5～25 hours.
2. the method for coproduction alkyl carbamate according to claim 1, alkylamide is characterized in that: catalyzer is any one in metal oxide catalyst calcium oxide, the zinc oxide.
3. according to the described coproduction alkyl carbamate of claim 1, the method for alkylamide, it is characterized in that: alcohol (or phenol) is alkyl alcohols, phenol
4. according to the described coproduction alkyl carbamate of claim 1, the method for alkylamide, it is characterized in that: the ester class is an alkyl acetate, and alkyl wherein is consistent with the alkyl of alcohol (or phenol) in the claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101825520A CN102260195A (en) | 2010-05-26 | 2010-05-26 | Method for coproducing alkyl carbamate and alkylamide |
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| CN2010101825520A CN102260195A (en) | 2010-05-26 | 2010-05-26 | Method for coproducing alkyl carbamate and alkylamide |
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| CN2010101825520A Pending CN102260195A (en) | 2010-05-26 | 2010-05-26 | Method for coproducing alkyl carbamate and alkylamide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892331A (en) * | 2015-05-12 | 2015-09-09 | 中北大学 | Biodegradable organic polymeric nitrogen fertilizer and preparation method therefor |
| CN105646269A (en) * | 2015-12-31 | 2016-06-08 | 镇江高鹏药业有限公司 | Synthetic method of salicylamide |
-
2010
- 2010-05-26 CN CN2010101825520A patent/CN102260195A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892331A (en) * | 2015-05-12 | 2015-09-09 | 中北大学 | Biodegradable organic polymeric nitrogen fertilizer and preparation method therefor |
| CN104892331B (en) * | 2015-05-12 | 2017-05-17 | 中北大学 | Biodegradable organic polymeric nitrogen fertilizer and preparation method therefor |
| CN105646269A (en) * | 2015-12-31 | 2016-06-08 | 镇江高鹏药业有限公司 | Synthetic method of salicylamide |
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Application publication date: 20111130 |