CN103980160B - A kind of method of synthesis of isophorone diamino-methyl formate - Google Patents
A kind of method of synthesis of isophorone diamino-methyl formate Download PDFInfo
- Publication number
- CN103980160B CN103980160B CN201410193921.4A CN201410193921A CN103980160B CN 103980160 B CN103980160 B CN 103980160B CN 201410193921 A CN201410193921 A CN 201410193921A CN 103980160 B CN103980160 B CN 103980160B
- Authority
- CN
- China
- Prior art keywords
- isophorone
- methyl formate
- diamino
- synthetic method
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of method of synthesis of isophorone diamino-methyl formate, isophorone diamine and methylcarbonate under the katalysis of phenoxy compounds, synthesis of isophorone diamino-methyl formate under normal pressure.The method of synthesis of isophorone diamino-methyl formate of the present invention has reaction conditions gentleness, and the reaction times is short, the advantage that isophorone diamino-methyl formate productive rate is high.
Description
Technical field
The invention belongs to chemical industry synthesis field, relate to a kind of method of synthesis of isophorone diamino-methyl formate, refer to isophorone diamine (being called for short IPDA) especially with methylcarbonate (being called for short DMC) under the katalysis of phenoxy compounds, the method for generation isophorone diamino-methyl formate (being called for short IPDC).
Background technology
IPDC is the intermediate of synthesis of isophorone isocyanic ester (IPDI), because IPDI can be used for synthesizing not yellowing polyurethane coating, high-grade adhesive for polyurethane and elastomerics, performance is significantly better than the polyurethane material containing aromatic ring, thus the favor of extremely industry member.
The phosgenation that the technique of current IPDI suitability for industrialized production is mainly traditional, the shortcoming that this technique exists: raw material phosgene belongs to highly toxic product, large to environmental hazard; The HCl that a large amount of added value of reaction by-product is low, sell after making hydrochloric acid with water absorption, because by-product hydrochloric acid is containing organic impurities, market capacity is little, seriously constrains the development of isocyanic ester manufacturing enterprise.Therefore, the Technology of non-phosgene synthesis IPDI comes into one's own day by day.
Non-phosgene synthesis IPDI technique comprises synthesis and thermo-cracking two committed steps of IPDC.The synthesis of IPDC adopts isophorone diamine (being called for short IPDA) to be raw material with DMC, and be obtained by reacting under the effect of catalyzer, reaction formula is as follows:
Patent CN101747233 discloses a kind of method adopting fe-cr-ni alloy catalysis IPDA and DMC to synthesize IPDC, and this method temperature of reaction is 150 ~ 200 DEG C, needs to carry out under an increased pressure, high to the requirement of equipment; Have employed a large amount of polar solvents in simultaneous reactions, need to be separated and recycle from reaction mixture, process energy consumption is high.Patent CN103012210 adopts with silicon-dioxide or the aluminum oxide plumbous oxide that is carrier or zinc oxide for catalyzer, and catalysis IPDA and DMC reacts the yield preparing IPDC, IPDC and is up to 90%, but plumbous catalyzer easily causes heavy metal contamination.Patent CN103145586 take solid phosgene as raw material, in the organic solvents such as chloroform, ethylene dichloride or toluene, IPDA and solid phosgene carry out reaction and prepare IPDC, this process need strictly control reaction Wei ?20 ~ 5 DEG C, also need to carry out under the existence of the catalyzer such as triethylamine, DMF or urotropine simultaneously, reaction conditions is comparatively harsh, and process is wayward.Document [Bai Junjun etc., petrochemical technology and application, 2013,31 (2): 129 ?132] reports IPDA and DMC and synthesize IPDC under the catalysis of sodium ethylate, and under optimal conditions, the yield of product IPDC is only 83%.
There is the shortcomings such as catalyst preparing difficulty, easily contaminate environment, severe reaction conditions, product yield are low in existing IPDC synthetic technology, developing efficient catalyzer, under the reaction conditions of gentleness, obtain higher IPDC yield, is one of key of non-phosgene synthesis IPDI technical development.
Summary of the invention
The object of the invention is the above-mentioned deficiency for prior art, a kind of IPDC synthetic method obtaining higher yields under the reaction conditions of gentleness is provided.
A synthetic method for isophorone diamino-methyl formate, employing phenoxy compounds is catalyzer, with isophorone diamine and methylcarbonate for raw material, Reactive Synthesis isophorone diamino-methyl formate.
The preferred phenol of described phenoxy compounds, phenolate, described phenolate is the one in phenol lithium, sodium phenylate, potassium phenylate, phenol magnesium, calcium phenylate, phenol zinc or phenol zirconium.
Described method, the preferred 1:2 ~ 1:10 of mol ratio of IPDA and DMC, further preferred 1:3 ~ 1:8.
Described method, the mass ratio preferably 0.001 ~ 0.1:1 of catalyzer phenoxy compounds and HDA, further preferred 0.01 ~ 0.05:1.
Described method, temperature of reaction preferably 30 ~ 90 DEG C, preferably 50 ~ 80 DEG C further.
Described method, the reaction times is 0.5 ~ 3h preferably, further preferred 1 ~ 2h.
Beneficial effect: compared with the prior art, method of the present invention adopts phenoxy compounds to be catalyzer, and have reaction conditions gentleness, the reaction times is short, the advantage that IPDC productive rate is high.
Embodiment
In following examples, reaction product adopts efficient liquid phase chromatographic analysis, Analytical equipment and condition are: Agilent1100Series type high performance liquid chromatograph, CZORBAXSB ?C18 post, UV-detector, moving phase is acetonitrile: water=55:45 (volume ratio), column temperature is room temperature, determined wavelength 200nm, flow velocity 0.8mLmin
?1, sample size 20 μ L.
Embodiment 1
In normal pressure reactor, add IPDA170g, DMC630g, catalyst phenol 8.5g, temperature of reaction is stirring reaction 2h at 85 DEG C, and reaction product is through efficient liquid phase chromatographic analysis, and the productive rate of IPDC is 99.0%.
Embodiment 2
In normal pressure reactor, add IPDA170g, DMC720g, catalyst phenol calcium 17g, temperature of reaction is stirring reaction 1h at 90 DEG C, and reaction product is through efficient liquid phase chromatographic analysis, and the productive rate of IPDC is 99.2%.
Embodiment 3
In normal pressure reactor, add IPDA170g, DMC270g, catalyst phenol potassium 17g, temperature of reaction is stirring reaction 2.5h at 80 DEG C, and reaction product is through efficient liquid phase chromatographic analysis, and the productive rate of IPDC is 99.6%.
Embodiment 4
In normal pressure reactor, add IPDA170g, DMC180g, catalyst phenol magnesium 1.7g, temperature of reaction is stirring reaction 3h at 90 DEG C, and reaction product is through efficient liquid phase chromatographic analysis, and the productive rate of IPDC is 98.6%.
Embodiment 5
In normal pressure reactor, add IPDA170g, DMC630g, catalyst phenol sodium 5.1g, temperature of reaction is stirring reaction 3h at 90 DEG C, and reaction product is through efficient liquid phase chromatographic analysis, and the productive rate of IPDC is 99.8%.
Embodiment 6
In normal pressure reactor, add IPDA170g, DMC450g, catalyst phenol 0.17g, temperature of reaction is stirring reaction 3h at 90 DEG C, and reaction product is through efficient liquid phase chromatographic analysis, and the productive rate of IPDC is 98.2%.
Embodiment 7
In normal pressure reactor, add IPDA170g, DMC360g, catalyst phenol zinc 5.1g, temperature of reaction is stirring reaction 3h at 50 DEG C, and reaction product is through efficient liquid phase chromatographic analysis, and the productive rate of IPDC is 99.1%.
Embodiment 8
In normal pressure reactor, add IPDA170g, DMC720g, catalyst phenol sodium 17g, temperature of reaction is stirring reaction 3h at 30 DEG C, and reaction product is through efficient liquid phase chromatographic analysis, and the productive rate of IPDC is 99.7%.
Embodiment 9
In normal pressure reactor, add IPDA170g, DMC900g, catalyst phenol magnesium 5.1g, temperature of reaction is stirring reaction 1.5h at 90 DEG C, and reaction product is through efficient liquid phase chromatographic analysis, and the productive rate of IPDC is 99.4%.
Embodiment 10
In normal pressure reactor, add IPDA170g, DMC720g, catalyst phenol zirconium 5.1g, temperature of reaction is stirring reaction 1.5h at 90 DEG C, and reaction product is through efficient liquid phase chromatographic analysis, and the productive rate of IPDC is 99.3%.
Embodiment 11
In normal pressure reactor, add IPDA170g, DMC720g, catalyst phenol magnesium 5.1g, temperature of reaction is stirring reaction 1.5h at 90 DEG C, and reaction product is through efficient liquid phase chromatographic analysis, and the productive rate of IPDC is 99.1%.
Claims (12)
1. a synthetic method for isophorone diamino-methyl formate, is characterized in that adopting phenoxy compounds to be catalyzer, with isophorone diamine and methylcarbonate for raw material, and Reactive Synthesis isophorone diamino-methyl formate.
2. the synthetic method of isophorone diamino-methyl formate according to claim 1, is characterized in that phenoxy compounds is the one of phenol or phenolate.
3. the synthetic method of isophorone diamino-methyl formate according to claim 2, is characterized in that phenolate is the one in phenol lithium, sodium phenylate, potassium phenylate, phenol magnesium, calcium phenylate, phenol zinc or phenol zirconium.
4. the synthetic method of isophorone diamino-methyl formate according to claim 1, is characterized in that the mol ratio of isophorone diamine and methylcarbonate is 1:2 ~ 1:10.
5. the synthetic method of isophorone diamino-methyl formate according to claim 4, is characterized in that the mol ratio of isophorone diamine and methylcarbonate is 1:3 ~ 1:8.
6. the synthetic method of isophorone diamino-methyl formate according to claim 1, is characterized in that the mass ratio of phenoxy compounds and isophorone diamine is 0.001 ~ 0.1:1.
7. the synthetic method of isophorone diamino-methyl formate according to claim 6, is characterized in that the mass ratio of phenoxy compounds and isophorone diamine is 0.01 ~ 0.05:1.
8. the synthetic method of isophorone diamino-methyl formate according to claim 1, is characterized in that temperature of reaction is 30 ~ 90 DEG C.
9. the synthetic method of isophorone diamino-methyl formate according to claim 8, is characterized in that the mass ratio of phenoxy compounds and isophorone diamine is 50 ~ 80 DEG C.
10. the synthetic method of isophorone diamino-methyl formate according to claim 1, is characterized in that the reaction times is 0.5 ~ 3h.
The synthetic method of 11. isophorone diamino-methyl formates according to claim 10, is characterized in that the reaction times is 1 ~ 2h.
The synthetic method of 12. isophorone diamino-methyl formates according to claim 1, is characterized in that reaction pressure is normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410193921.4A CN103980160B (en) | 2014-05-08 | 2014-05-08 | A kind of method of synthesis of isophorone diamino-methyl formate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410193921.4A CN103980160B (en) | 2014-05-08 | 2014-05-08 | A kind of method of synthesis of isophorone diamino-methyl formate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103980160A CN103980160A (en) | 2014-08-13 |
| CN103980160B true CN103980160B (en) | 2016-02-24 |
Family
ID=51272359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410193921.4A Active CN103980160B (en) | 2014-05-08 | 2014-05-08 | A kind of method of synthesis of isophorone diamino-methyl formate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103980160B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114507161A (en) * | 2020-11-17 | 2022-05-17 | 中国科学院过程工程研究所 | Method for synthesizing isophorone diisocyanate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102356062A (en) * | 2009-03-16 | 2012-02-15 | 拜尔材料科学股份公司 | Process for preparing aromatic carbamates |
| CN102498087A (en) * | 2009-07-31 | 2012-06-13 | 国际壳牌研究有限公司 | Process for producing diphenyl carbonate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999047493A1 (en) * | 1998-03-17 | 1999-09-23 | Huntsman Ici Chemicals Llc | Method for the preparation of organic carbamates |
-
2014
- 2014-05-08 CN CN201410193921.4A patent/CN103980160B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102356062A (en) * | 2009-03-16 | 2012-02-15 | 拜尔材料科学股份公司 | Process for preparing aromatic carbamates |
| CN102498087A (en) * | 2009-07-31 | 2012-06-13 | 国际壳牌研究有限公司 | Process for producing diphenyl carbonate |
Non-Patent Citations (1)
| Title |
|---|
| 碳酸二甲酯氨解法合成异佛尔酮二氨基甲酸酯的工艺研究;白君君 等;《石化技术与应用》;20130331;第31卷(第2期);第129-132页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103980160A (en) | 2014-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102336654A (en) | Chloration method for phenoxyacetic acid and derivatives thereof | |
| CN103641722B (en) | A kind of production method of adjacent nitro bromobenzyl | |
| CN102516072A (en) | Preparation method of benzoic acid herbicide dicamba | |
| US10428012B2 (en) | Method of preparation of 4-isopropylamino-1-butanol | |
| CN105967986A (en) | 3-hydroxyacetophenone synthesis method | |
| CN103980160B (en) | A kind of method of synthesis of isophorone diamino-methyl formate | |
| CN105198707B (en) | The synthetic method of 4 biphenylmethanols | |
| CN105753643B (en) | A kind of synthetic method of 2,5 2 bromo-iodobenzene | |
| CN103936625B (en) | Method for synthesizing methyl hexamethylene-1,6-dicarbamate | |
| CN103717580A (en) | Method for preparing amino-triazolinone | |
| CN103819345B (en) | A kind of preparation method of 2-aminobiphenyl derivate | |
| CN109970793A (en) | A kind of process synthesizing 15 triphenylphosphine salt of carbon | |
| CN102675148B (en) | Preparation method of hydroxybenzyl cyanide | |
| CN103772240B (en) | Method for preparation of methylene diphenyl diisocyanate (MDI) | |
| CN104892371A (en) | Method for producing glycol dimethyl ether | |
| CN106336340B (en) | Synthesis method of o-bromobenzotrifluoride | |
| EP3196183B1 (en) | Method for producing 2'-trifluoromethyl group-substituted aromatic ketone | |
| CN104311456B (en) | A kind of preparation method of sulfogaiacol | |
| CN112573992A (en) | Synthesis method and process of halogenated cyclopropane | |
| CN112778161B (en) | Preparation method of dimethylcarbamoyl chloride | |
| CN103483186B (en) | Synthesis method for 4,4'-biphenyldicarboxylic acid | |
| CN114933527B (en) | Method for continuously synthesizing o-methylbenzoyl chloride in micro-channel | |
| CN115594617B (en) | Synthesis method of difluoromethyl sulfonyl chloride | |
| CN101265201B (en) | Method for synthesizing tramadol hydrochloride | |
| CN104693012B (en) | 9,9 2（4 hydroxy phenyls）The green synthesis method of fluorenes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |