CN101269341A - Catalyst for synthesizing fragrant carbamic acid ester, preparation method and application thereof - Google Patents
Catalyst for synthesizing fragrant carbamic acid ester, preparation method and application thereof Download PDFInfo
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- CN101269341A CN101269341A CNA2008100551102A CN200810055110A CN101269341A CN 101269341 A CN101269341 A CN 101269341A CN A2008100551102 A CNA2008100551102 A CN A2008100551102A CN 200810055110 A CN200810055110 A CN 200810055110A CN 101269341 A CN101269341 A CN 101269341A
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Abstract
The invention relates to a catalyst used for synthesizing aromatic carbamate, the mass percentage thereof is as follows: an SBA-15-COOH molecular sieve ranges from 80 to 95 percent; zinc ranges form 5 to 20 percent. The catalyst has simple technics, cheap raw materials, strong operability and easy separation of products; besides, the catalyst can be safely and repeatedly used and the synthetic aromatic carbamate has high yield, etc.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method and application that is used for synthesizing fragrant carbamic acid ester, relate in particular to a kind of method that is used for the Catalysts and its preparation method of synthesizing fragrant carbamic acid ester and is used for aromatic amine and the direct synthesizing fragrant carbamic acid ester of organic carbonate.
Background technology
Aromatic amine and organic carbonate reaction synthesizing fragrant carbamic acid ester, the catalyst of open report have acidic catalyst as zinc or Bivalent Tin, ferrous halide; Zinc or Bivalent Tin, ferrous monobasic organic salt compound comprise (U.S.Pat.4268684,4268683) such as zinc acetate, zinc naphthenate, zinc octoate, ferric acetate, iron naphthenates.Base catalyst is as the alcoholates of alkali metal or alkaline-earth metal, as (petrochemical industry, 28 (1999): 611-614) such as the methylate of sodium, potassium, calcium, barium, beryllium, alcoholate, tert-butyl alcohol things; Basic zinc carbonate or copper, hydration basic zinc carbonate or copper, basic ion exchanger resin (U.S.Pat.5688988) etc.Aresta (Tetrahedron, 54 (1998): 14145-14156) select for use Br φ nsted acid as Ph
2P (O) OH, (PHO)
2P (O) OH etc. is a catalyst, and (U.S.Pat.5002880) such as Robet W.Mason proposed with hydrolysis enzymatic amine and dimethyl carbonate synthesis of carbamates, and this reaction conversion ratio and productive rate are not high, and the required reaction time is longer.Wang Yanji etc. (J.Chem.Technol.Biotechnol.76 (2001): 857-861) investigated the influence of different carriers to zinc acetate solid-supported catalyst activity, 2, the highest yield of 4-toluene diamino-methyl formate can arrive 53.5%.In addition, Katada (Catal.Lett.80 (2002): 47-51) investigated H-ZSM-5, H β, MCM-41, the activity of catalyst aniline such as H-modenite and dimethyl carbonate synthesizing Amino-methye-formate, Esakki durai (J.Mol.Catal.A.218 (2004): 196-201) select for use y-type zeolite that above-mentioned reaction is studied, find that NaY or KY type still are that the HY type is not high to the synthesizing activity of carbamate.The productive rate of above-mentioned catalyst gained fragrant carbamic acid ester is lower, about 20-60%, and has the N-a large amount of accessory substances such as aromatic amine or urea that methylate.Because accessory substance is more, the separation and purification difficulty is not suitable for large-scale industrial production.Therefore demand filtering out the good catalyst that is fit to this reaction system urgently.Improve the conversion ratio and the selectivity of reaction.
Summary of the invention
The purpose of this invention is to provide a kind of conversion ratio and selectivity height, accessory substance is few, and post processing simply is used for the Catalysts and its preparation method of synthesizing fragrant carbamic acid ester and is used for the method for aromatic amine and the direct synthesizing fragrant carbamic acid ester of organic carbonate.
Catalyst quality percentage of the present invention consists of: SBA-15-COOH molecular sieve 80-95%, zinc element 5-20%.
Concrete preparation method of the present invention is:
By the SBA-15-COOH molecular sieve: zinc ion exchange reagent=0.5-1.5g:50mL adds the SBA-15-COOH molecular sieve in the zinc ion exchange reagent that concentration is 0.05-0.3mol/L, normal temperature stirs 2-6h down, filtration, washing, absolute ethanol washing make catalyst to there not being chlorion in 90-100 ℃ of dry 6-20h.
Concrete application process of the present invention is:
With organic carbonate and aromatic amine with mol ratio 5-50: 1 and the catalyst of aromatic amine quality 1-20% add in the reactor, stir and be warming up to 100-200 ℃ down and react 0.5-8h, make fragrant carbamic acid ester.
Organosilicon accounts for the 5-25% of total silicon molar fraction in the SBA-15-COOH molecular sieve as mentioned above.
Aforesaid zinc ion exchange reagent is: zinc nitrate, zinc acetate, zinc chloride or zinc propionate.
Aforesaid aromatic amine is 4-chloroaniline, 2-fluoroaniline, 3,4-dichloroaniline, diisopropyl aniline, 2,4-diphenylmethane diamine, 4,4 '-diphenylmethane diamine, 2,2 '-diphenylmethane diamine with and high polymer, 2,4-toluenediamine, 2,6-toluenediamine, o-phenylenediamine or p-phenylenediamine (PPD).Wherein preferred aromatic amine is diphenylmethane diamine, aniline or 2, the 4-toluenediamine.
Aforesaid organic carbonate comprises: ring family or cycloaliphatic carbonates such as ethylene carbonate, propene carbonate, styrene carbonic ester, diphenyl carbonate, methyl benzol carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, Methylethyl carbonic ester or methyl-propyl carbonic ester etc.Wherein preferably diethyl carbonate, diphenyl carbonate or dimethyl carbonate.
The present invention compared with prior art has following advantage:
1. simple to operate, easy to make, reaction condition is gentle.
2. product is easy to separate, and is reusable, the productive rate height of fragrant carbamic acid ester.
3. the specific surface of gained catalyst is 414-591m
2/ g, the aperture is 6.14-7.63nm, pore volume is 0.69-0.98cm
3/ g.
The specific embodiment
Embodiment 1
To 0.4g molecular sieve SBA-15-COOH (organosilicon account for total silicon molar fraction 5%)
In add 0.05mol/L acetic acid zinc solution 50mL normal temperature lower magnetic force stir 6h, then after filtration, washing, absolute ethanol washing, make catalyst S BA-15-COO (Zn) (zinc element mass fraction is 7%) in the dry 15h of 353K.The specific surface of catalyst, pore volume, aperture see Table 1.In the 20mL autoclave reactor, add aniline 1.0g, dimethyl carbonate 9.7g, catalyst S BA-15-COO (Zn) 0.2g is reflected under the 0.9MPa in 140 ℃ of reaction 4h, after reaction finishes, after filtration, washing, drying obtain product.Products therefrom and filtrate are used high pressure liquid chromatographic analysis, and the result is: the conversion ratio of aniline is 89%, and the productive rate of phenyl urethan is 85.6%.
Embodiment 2
The zinc nitrate solution 50mL that in 0.5g molecular sieve SBA-15-COOH (organosilicon account for total silicon molar fraction 10%), adds 0.3mol/L, the normal temperature lower magnetic force stirs 4h, then after filtration, washing, absolute ethanol washing, make catalyst S BA-15-COO (Zn) (zinc element mass fraction is 12.1%) in the dry 10h of 363K.The specific surface of catalyst, pore volume, aperture see Table 1.In the 100mL autoclave reactor, add diphenylmethane diamine 10g, diethyl carbonate 118g, catalyst S BA-15-COO (Zn) 0.5g, the disposable adding of reactant and catalyst, after using in the nitrogen replacement still air three times then, charging into nitrogen to still internal pressure is 2MPa, stirs to be warming up to 170 ℃ down and to react 3h, after reaction finishes, after filtration, washing, drying obtain product.Products therefrom and filtrate are analyzed with high pressure liquid chromatography, and the result is: the conversion ratio of diphenylmethane diamine is 100%, and the productive rate of diphenyl methane diamino Ethyl formate is 83.5%, and about 7% mono amino Ethyl formate generates.
Embodiment 3
The liquor zinci chloridi 50mL normal temperature lower magnetic force that adds 0.1mol/L in 0.8g molecular sieve SBA-15-COOH (organosilicon account for total silicon molar fraction 15%) stirs 3h, then after filtration, washing, absolute ethanol washing, make catalyst S BA-15-COO (Zn) (zinc element mass fraction is 14.7%) in the dry 18h of 343K.The specific surface of catalyst, pore volume, aperture see Table 1.In the 100mL autoclave reactor, add 2,4-toluenediamine 10g, diphenyl carbonate 90g, catalyst S BA-15-COO (Zn) 0.5g, the disposable adding of reactant and catalyst, use in the nitrogen replacement still air three times then after, charging into nitrogen to still internal pressure is 1MPa, stir and to be warming up to 170 ℃ of reaction 5h down, after the reaction end, after filtration, washing, drying obtain product.Products therefrom and filtrate are analyzed with high pressure liquid chromatography, and the result is: 2, and the conversion ratio of 4-toluenediamine is 100%, 2, the productive rate of 4-toluene diamino acid phenyl ester is 80.5%, and 8.1% single-amido acid ester generation is arranged approximately.
Embodiment 4
The zinc propionate solution 50mL normal temperature lower magnetic force that adds 0.2mol/L in 1g molecular sieve SBA-15-COOH (organosilicon account for total silicon molar fraction 20%) stirs 2h, then after filtration, washing, absolute ethanol washing, make catalyst S BA-15-COO (Zn) (zinc element mass fraction is 16.3%) in the dry 15h of 373K.The specific surface of catalyst, pore volume, aperture see Table 1.In the 100mL autoclave reactor, add o-phenylenediamine 9g, dibutyl carbonate 80g, catalyst S BA-15-COO (Zn) 0.8g, the disposable adding of reactant and catalyst, after using in the nitrogen replacement still air three times then, charging into nitrogen to still internal pressure is 1.5MPa, stirs to be warming up to 160 ℃ down and to react 3h, after reaction finishes, after filtration, washing, drying obtain product.Products therefrom and filtrate are analyzed with high pressure liquid chromatography, and the result is: the conversion ratio of o-phenylenediamine is 100%, and the productive rate of o-dihydroxy ammon base butyl formate is 77.5%, and 5.1% single-amido acid ester generation is arranged approximately.
The performance indications of table 1SBA-15-COO (Zn)
| Embodiment | Pore volume (cm 3/g) | Aperture (nm) | Specific surface (m 2/g) |
| Embodiment 1 | 0.98 | 7.63 | 591.23 |
| Embodiment 2 | 0.82 | 6.90 | 514.91 |
| Embodiment 3 | 0.78 | 7.12 | 424.03 |
| Embodiment 3 | 0.69 | 6.14 | 414.66 |
Claims (7)
1, a kind of catalyst that is used for synthesizing fragrant carbamic acid ester is characterized in that catalyst quality percentage consists of: SBA-15-COOH molecular sieve 80-95%, zinc element 5-20%.
2, a kind of catalyst that is used for synthesizing fragrant carbamic acid ester as claimed in claim 1 is characterized in that organosilicon in the described SBA-15-COOH molecular sieve accounts for the 5-25% of total silicon molar fraction.
3, a kind of Preparation of catalysts method that is used for synthesizing fragrant carbamic acid ester as claimed in claim 1 or 2 is characterized in that comprising the steps:
By the SBA-15-COOH molecular sieve: zinc ion exchange reagent=0.5-1.5g:50mL adds the SBA-15-COOH molecular sieve in the zinc ion exchange reagent that concentration is 0.05-0.3mol/L, normal temperature stirs 2-6h down, filtration, washing, absolute ethanol washing make catalyst to there not being chlorion in 90-100 ℃ of dry 6-20h.
4, a kind of Preparation of catalysts method that is used for synthesizing fragrant carbamic acid ester as claimed in claim 3 is characterized in that aforesaid zinc ion exchange reagent is: zinc nitrate, zinc acetate, zinc chloride or zinc propionate.
5, a kind of Application of Catalyst that is used for synthesizing fragrant carbamic acid ester as claimed in claim 1 or 2, it is characterized in that organic carbonate and aromatic amine with mol ratio 5-50: 1 and the catalyst of aromatic amine quality 1-20% add in the reactor, be warming up to 100-200 ℃ of reaction 0.5-8h under stirring, make fragrant carbamic acid ester.
6, a kind of Application of Catalyst that is used for synthesizing fragrant carbamic acid ester as claimed in claim 5, it is characterized in that described aromatic amine is 4-chloroaniline, 2-fluoroaniline, 3,4-dichloroaniline, diisopropyl aniline, 2,4-diphenylmethane diamine, 4,4 '-diphenylmethane diamine, 2,2 '-diphenylmethane diamine with and high polymer, 2,4-toluenediamine, 2,6-toluenediamine, o-phenylenediamine or p-phenylenediamine (PPD).Wherein preferred aromatic amine is diphenylmethane diamine, aniline or 2, the 4-toluenediamine.
7, a kind of Application of Catalyst that is used for synthesizing fragrant carbamic acid ester as claimed in claim 5 is characterized in that described organic carbonate is ring family or cycloaliphatic carbonates such as ethylene carbonate, propene carbonate, styrene carbonic ester, diphenyl carbonate, methyl benzol carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, Methylethyl carbonic ester or methyl-propyl carbonic ester etc.Wherein preferably diethyl carbonate, diphenyl carbonate or dimethyl carbonate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872912A (en) * | 2012-09-18 | 2013-01-16 | 哈尔滨理工大学 | Catalyst for synthesizing methyl phenyl carbamate and preparation and application methods thereof |
| WO2018210711A1 (en) | 2017-05-15 | 2018-11-22 | Covestro Deutschland Ag | Silica-based zinc catalysts. their preparation and use in the alkoxycarbonylation of amines |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1229144B (en) * | 1989-04-07 | 1991-07-22 | Enichem Sintesi | PROCEDURE FOR THE PRODUCTION OF CARBAMATES. |
| AU8018298A (en) * | 1997-06-05 | 1998-12-21 | Imperial Chemical Industries | Method for the preparation of carbamates |
| IT1317756B1 (en) * | 2000-02-03 | 2003-07-15 | Eni Spa | INTEGRATED PROCEDURE FOR THE PREPARATION OF AROMATIC ISOCYANATES AND PROCESSES FOR THE REALIZATION OF THE RELATIVE INTERMEDIATE PHASES. |
| CN1715267A (en) * | 2004-06-14 | 2006-01-04 | 中国科学院成都有机化学有限公司 | New process for preparing carbaniloyl ester |
| CN101157454B (en) * | 2007-09-15 | 2010-08-18 | 太原理工大学 | Spherical heteroatom mesopore molecular sieve and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872912A (en) * | 2012-09-18 | 2013-01-16 | 哈尔滨理工大学 | Catalyst for synthesizing methyl phenyl carbamate and preparation and application methods thereof |
| WO2018210711A1 (en) | 2017-05-15 | 2018-11-22 | Covestro Deutschland Ag | Silica-based zinc catalysts. their preparation and use in the alkoxycarbonylation of amines |
| US10807084B2 (en) | 2017-05-15 | 2020-10-20 | Covestro Deutschland Ag | Silica-based zinc catalysts, their preparation and use in the alkoxycarbonylation of amines |
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