CN1546464A - Method for synthesizing carbanilate by the reaction of aniline, urea and alcohol - Google Patents
Method for synthesizing carbanilate by the reaction of aniline, urea and alcohol Download PDFInfo
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- CN1546464A CN1546464A CNA2003101096910A CN200310109691A CN1546464A CN 1546464 A CN1546464 A CN 1546464A CN A2003101096910 A CNA2003101096910 A CN A2003101096910A CN 200310109691 A CN200310109691 A CN 200310109691A CN 1546464 A CN1546464 A CN 1546464A
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- phenyl carbamate
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Abstract
A process for synthesizing benzene carbamic acid ester from phenylamine, urea and alcohol by charging a finite amount of catalyst at suitable reaction temperature and reaction time, reacting phenylamine with urea. The advantages of the invention are mild reaction condition, simple operation process, easy available catalyst, good raw material economy and high reaction selectivity.
Description
Technical field
The invention belongs to a kind of method of synthesizing phenyl carbamate, specifically relate to a kind of method of non-phosgene route synthesizing phenyl carbamate.
Background technology
Isocyanic ester is the important organic synthesis intermediate of a class, is urethane synthetic main raw material, can be widely used in macromolecular materials such as urethane, coating, dyestuff and agricultural chemicals.Isocyanate products series mainly comprises TDI (tolylene diisocyanate), MDI (4, the 4-'-diphenylmethane diisocyanate), PI (phenyl isocyanate) etc.According to statistics, at present world TDI and MDI demand be just with annual 5.5% and 8% speed increment, and the demand of China is more with annual 7% and 10%～12% speed increment.In traditional isocyanic ester synthesis technique, most products adopt phosgenation synthetic.Shortcomings such as this synthesis technique exists that route is long, cost is high, raw material is hypertoxic, by-product hydrochloric acid etching apparatus, product residual chlorine are difficult to remove, environmental pollution is serious, along with the enhancing of environmental consciousness, phosgenation synthesizing isocyanate technology certainly will will be eliminated.The non-phosgene route has become the focus that domestic and international researcher pays close attention to, wherein with phenyl urethan as reaction intermediate, the synthesis technique of the preparing isocyanate by pyrolyzing by phenyl urethan gets most of the attention.The non-phosgene synthesising process research of phenyl urethan mainly concentrates on the following aspects: the oxidation carbonylation of aniline, reduction of nitrobenzene carbonylation reaction, aniline and carbonic ether building-up reactions.Preceding two kinds of reactions, as main catalyzer, are carried out under High Temperature High Pressure with the transition metal of group VIII or precious metal as raw material with CO, severe reaction conditions, and complicated operating process, thus limited their flow of research and industrialization progress.A kind of reaction in back with aniline and methylcarbonate as reaction raw materials, the reaction conditions gentleness, operating process is simple, but this reaction raw materials methylcarbonate consumption is big, utilization ratio is low, cost an arm and a leg, and also has certain limitation.Outside last route, coming synthesizing phenyl carbamate by aniline, urea and alcohol reaction also is a very promising non-phosgene route, and this reaction process condition gentleness, process is simple, raw material economics is good.But concentrate on synthesizing of methylcarbonate by the technical study majority that urea sets out, utilize the research report of the reaction synthesizing phenyl carbamate of aniline, urea and alcohol not see as yet so far.
Summary of the invention
The purpose of this invention is to provide a kind ofly under the reaction conditions of gentleness, utilize the most cheap reaction raw materials, the method for non-phosgene route synthesizing phenyl carbamate.
Preparation method of the present invention comprises the steps:
In autoclave, add aniline, urea, pure and mild catalyzer, logical nitrogen vacuumizes, and with the temperature rise rate of 2～10 ℃/min, is warming up to 100～200 ℃, reacts 2～8 hours;
Wherein the mol ratio of each component is: aniline: urea=1: 0.3～3
Aniline: alcohol=1: 1～10
Catalyzer: aniline=1: 5～100.
Aforesaid aniline and urea optimum mole ratio are 1: 0.6～1.5.
Aforesaid aniline and solvent optimum mole ratio are 1: 2～8.
Aforesaid catalyzer and aniline optimum mole ratio are 1: 10～50.
Aforesaid alcohol can be methyl alcohol, ethanol, n-propyl alcohol.
Aforesaid catalyzer can be PbO, KOH, ZnCl
2, Pd/C, HZSM5, HY, CH
3OK etc.
Advantage of the present invention:
Synthesising method reacting condition gentleness, the operating process of the phenyl urethan that the present invention adopts is simple, catalyzer is cheap and easy to get, raw material economics is good, reaction preference is high, is a kind of satisfy industrialization demand, novel method that practicality is stronger.
Embodiment
Embodiment 1:
At volume is in the autoclave that has induction stirring and automatic temperature control system of 150ml, adds the aniline of 0.1mol, the urea of 0.08mol, the methyl alcohol of 0.5mol, the HZSM5 of 0.06mol.After logical nitrogen vacuumized, autoclave under agitation with the heat-up rate of 4 ℃/min, was warming up to 160 ℃, reacts 4 hours.After 4 hours, the cooling autoclave, sampling is carried out GC and is analyzed.Result: transformation efficiency 15%, selectivity 86%.
Embodiment 2:
At volume is in the autoclave that has induction stirring and automatic temperature control system of 150ml, adds the aniline of 0.1mol, the urea of 0.12mol, the n-propyl alcohol of 0.6mol, the Pd/C of 0.08mol.After logical nitrogen vacuumized, autoclave under agitation with the heat-up rate of 6 ℃/min, was warming up to 180 ℃, reacts 3 hours.After 3 hours, the cooling autoclave, sampling is carried out GC and is analyzed.Result: transformation efficiency 12%, selectivity 78%.
Embodiment 3:
At volume is in the autoclave that has induction stirring and automatic temperature control system of 150ml, adds the aniline of 0.1mol, the urea of 0.1mol, the ethanol of 0.4mol, the ZnCl of 0.04mol
2After logical nitrogen vacuumized, autoclave under agitation with the heat-up rate of 10 ℃/min, was warming up to 150 ℃, reacts 5 hours.After 5 hours, the cooling autoclave, sampling is carried out GC and is analyzed.Result: transformation efficiency 17%, selectivity 65%.
Embodiment 4:
At volume is in the autoclave that has induction stirring and automatic temperature control system of 150ml, adds the aniline of 0.1mol, the urea of 0.1mol, the methyl alcohol of 0.7mol, the KOH of 0.07mol.After logical nitrogen vacuumized, autoclave under agitation with the heat-up rate of 8 ℃/min, was warming up to 160 ℃, reacts 5 hours.After 5 hours, the cooling autoclave, sampling is carried out GC and is analyzed.Result: transformation efficiency 11%, selectivity 72%.
Embodiment 5:
At volume is in the autoclave that has induction stirring and automatic temperature control system of 150ml, adds the aniline of 0.1mol, the urea of 0.08mol, the ethanol of 0.4mol, the PbO of 0.05mol.After logical nitrogen vacuumized, autoclave under agitation with the heat-up rate of 6 ℃/min, was warming up to 170 ℃, reacts 3 hours.After 3 hours, the cooling autoclave, sampling is carried out GC and is analyzed.Result: transformation efficiency 22%, selectivity 68%.
Embodiment 6:
At volume is in the autoclave that has induction stirring and automatic temperature control system of 150ml, adds the aniline of 0.1mol, the urea of 0.07mol, the n-propyl alcohol of 0.6mol, the CH of 0.06mol
3OK.After logical nitrogen vacuumized, autoclave under agitation with the heat-up rate of 4 ℃/min, was warming up to 120 ℃, reacts 8 hours.After 8 hours, the cooling autoclave, sampling is carried out GC and is analyzed.Result: transformation efficiency 19%, selectivity 62%.
Embodiment 7:
At volume is in the autoclave that has induction stirring and automatic temperature control system of 150ml, adds the aniline of 0.1mol, the urea of 0.09mol, the methyl alcohol of 0.5mol, the HY of 0.05mol.After logical nitrogen vacuumized, autoclave under agitation with the heat-up rate of 8 ℃/min, was warming up to 140 ℃, reacts 6 hours.After 6 hours, the cooling autoclave, sampling is carried out GC and is analyzed.Result: transformation efficiency 18%, selectivity 70%.
Claims (6)
1, a kind of method by aniline, urea and alcohol reaction synthesizing phenyl carbamate is characterized in that comprising the steps:
In autoclave, add aniline, urea, pure and mild catalyzer, logical nitrogen vacuumizes, and with the temperature rise rate of 2～10 ℃/min, is warming up to 100～200 ℃, reacts 2～8 hours;
Wherein the mol ratio of each component is: aniline: urea=1: 0.3～3
Aniline: alcohol=1: 1～10
Catalyzer: aniline=1: 5～100.
2, a kind of method by aniline, urea and pure synthesizing phenyl carbamate as claimed in claim 1, the mol ratio that it is characterized in that described aniline and urea is 1: 0.6～1.5.
3, a kind of method by aniline, urea and pure synthesizing phenyl carbamate as claimed in claim 1 is characterized in that the described aniline and the mol ratio of alcohol are 1: 2～8.
4, a kind of method by aniline, urea and pure synthesizing phenyl carbamate as claimed in claim 1, the mol ratio that it is characterized in that described catalyzer and aniline is 1: 10～50.
5, a kind of method by aniline, urea and pure synthesizing phenyl carbamate as claimed in claim 1 is characterized in that described alcohol is methyl alcohol, ethanol or n-propyl alcohol.
6, a kind of method by aniline, urea and pure synthesizing phenyl carbamate as claimed in claim 1 is characterized in that described catalyzer is PbO, KOH, ZnCl
2, Pd/C, HZSM5, HY or CH
3OK.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109691 CN1231463C (en) | 2003-12-11 | 2003-12-11 | Method for synthesizing carbanilate by the reaction of aniline, urea and alcohol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109691 CN1231463C (en) | 2003-12-11 | 2003-12-11 | Method for synthesizing carbanilate by the reaction of aniline, urea and alcohol |
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| Publication Number | Publication Date |
|---|---|
| CN1546464A true CN1546464A (en) | 2004-11-17 |
| CN1231463C CN1231463C (en) | 2005-12-14 |
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| CN 200310109691 Expired - Fee Related CN1231463C (en) | 2003-12-11 | 2003-12-11 | Method for synthesizing carbanilate by the reaction of aniline, urea and alcohol |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130508B (en) * | 2006-08-22 | 2011-05-04 | 中国科学院过程工程研究所 | Process for synthesizing phenyl urethane in atmospheric condition |
| CN102190602A (en) * | 2010-03-10 | 2011-09-21 | 中国石油天然气股份有限公司 | Method of preparing benzene carbamate through continuous reactions and equipment thereof |
| CN102659635A (en) * | 2012-04-17 | 2012-09-12 | 河北工业大学 | Method for preparing toluene diamino butyl formate |
| CN102971287A (en) * | 2010-06-16 | 2013-03-13 | 三井化学株式会社 | Carbamate production method, isocyanate production method, carbamate production device and isocyanate production device |
| CN103172541A (en) * | 2011-12-23 | 2013-06-26 | 中国科学院兰州化学物理研究所 | Clean synthesis method of phenyl carbamate |
| CN104058995A (en) * | 2014-06-17 | 2014-09-24 | 青岛农业大学 | Method for synthesizing phenyl carbamate |
| CN106146353A (en) * | 2015-04-22 | 2016-11-23 | 中国科学院过程工程研究所 | A kind of preparation method of methyl phenyl carbamate |
-
2003
- 2003-12-11 CN CN 200310109691 patent/CN1231463C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130508B (en) * | 2006-08-22 | 2011-05-04 | 中国科学院过程工程研究所 | Process for synthesizing phenyl urethane in atmospheric condition |
| CN102190602A (en) * | 2010-03-10 | 2011-09-21 | 中国石油天然气股份有限公司 | Method of preparing benzene carbamate through continuous reactions and equipment thereof |
| CN102971287A (en) * | 2010-06-16 | 2013-03-13 | 三井化学株式会社 | Carbamate production method, isocyanate production method, carbamate production device and isocyanate production device |
| CN102971287B (en) * | 2010-06-16 | 2014-11-12 | 三井化学株式会社 | Carbamate production method, isocyanate production method, carbamate production device and isocyanate production device |
| US8940926B2 (en) | 2010-06-16 | 2015-01-27 | Mitsui Chemicals, Inc. | Method for producing carbamate, method for producing isocyanate, carbamate production system, and isocyanate production system |
| US9321024B2 (en) | 2010-06-16 | 2016-04-26 | Mitsui Chemicals, Inc. | Method for producing carbamate, method for producing isocyanate, carbamate production system, and isocyanate production system |
| CN103172541A (en) * | 2011-12-23 | 2013-06-26 | 中国科学院兰州化学物理研究所 | Clean synthesis method of phenyl carbamate |
| CN102659635A (en) * | 2012-04-17 | 2012-09-12 | 河北工业大学 | Method for preparing toluene diamino butyl formate |
| CN102659635B (en) * | 2012-04-17 | 2015-09-02 | 河北工业大学 | A kind of method preparing toluene diamino butyl formate |
| CN104058995A (en) * | 2014-06-17 | 2014-09-24 | 青岛农业大学 | Method for synthesizing phenyl carbamate |
| CN106146353A (en) * | 2015-04-22 | 2016-11-23 | 中国科学院过程工程研究所 | A kind of preparation method of methyl phenyl carbamate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1231463C (en) | 2005-12-14 |
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