CN103694141A - A method of synthesizing phenylcarbamate - Google Patents
A method of synthesizing phenylcarbamate Download PDFInfo
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- CN103694141A CN103694141A CN201210366090.7A CN201210366090A CN103694141A CN 103694141 A CN103694141 A CN 103694141A CN 201210366090 A CN201210366090 A CN 201210366090A CN 103694141 A CN103694141 A CN 103694141A
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- China
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- catalyst
- catalyzer
- carbamate
- phenyl carbamate
- aniline
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Abstract
The invention discloses a method of synthesizing phenylcarbamate. Aniline and micromolecule carbamate are used as reactants and a micromolecule alcohol is used as a reaction medium. The phenylcarbamate is synthesized under existence of a catalyst at 80-250 DEG C for 0.5-20 h under 0.1-3 MPa by utilization of a continuous ammonia discharging mode/or a closed reaction mode. The catalyst is a single metal oxide or a composition of two metal oxides, or comprises a catalytic active component and a catalyst carrier. The method is advantageous in that: the catalyst is liable to prepare, separate and recycle, and has high activity and stable performance, and the adopted continuous ammonia discharging mode further increases the yield and the selectivity of the phenylcarbamate by breaking the limit of ammonia to the reaction balance.
Description
Technical field
The present invention relates to a kind of method of synthesis of carbamates, specifically relate to a kind of method that is catalyzed and synthesized phenyl urethan by aniline and small molecules carbamate.
Background technology
Isocyanic ester is the important large Chemicals of a class, is mainly used as the raw material of synthesis of polyurethane, also for the synthesis of agricultural chemicals, dyestuff, leather etc.Wherein, '-diphenylmethane diisocyanate (MDI) is because toxicity is less than tolylene diisocyanate (TDI), derivative advantages such as urethane excellent performance, become most important aromatic isocyanate kind, also be the maximum kind of consumption simultaneously, global demand amount increases with 8%, within 2010, surpass 4,800,000 tons, the market requirement is huge.But in current MDI compound probability, mostly adopt phosgenation synthetic, first with aniline and formaldehyde, under an acidic catalyst effect, react and generate diphenylmethanediamiand (MDA), then MDA is reacted to generation MDI with phosgene.Phosgenation exists raw material phosgene severe toxicity, byproduct hcl corrosion equipment, product chlorine residue to be difficult to remove and affects the shortcomings such as quality product; face environment protection and safe dual-pressure; therefore in the urgent need to developing the non-phosgene of synthetic MDI, to substitute the phosgenation of traditional mode of production MDI.
Since the seventies in last century, non-phosgene synthesis MDI has become problem very important in chemical industry.In the non-phosgene of having reported, by phenyl urethan, become diphenyl methane diamino formic ether (MDC) with formaldehyde condensation, then by MDC pyrolysis, prepare the non-phosgene synthesis technique of MDI, get most of the attention.Wherein, phenyl urethan, as the important intermediate in non-phosgene synthesis MDI, adopts economically viable reaction scheme, develops its effective synthesis technique, significant to successfully realizing the industrialization of non-phosgene synthesis MDI.Using small molecules carbamate during as carbonylation agent, and small molecules carbamate cost is lower, by-product NH
3can be recycled in the production of urea, form a pollution-free industry chain simultaneously.Therefore, usining small molecules carbamate as carbonylation agent, by aniline and small molecules carbamate, catalyze and synthesize phenyl urethan, is the route of an important non-phosgene synthesis MDI with industrial prospect and practicality.
In the reaction of aniline and small molecules carbamate synthesizing phenyl carbamate, using under the reaction conditions of catalyzer, the catalyzer using comprises the Bi (NO that CN 101468960A is disclosed
3)
3, Sn (CH
3cOO)
2, ZnO, SnC1
2, Zn (CH
3cOO)
2or Pb (OAc)
2, can make aniline almost can transform completely, and phenyl urethan selectivity reach more than 98%, but its shortcoming is ZnO, can be dissolved in solvent methanol and runs off, other several catalyzer are homogeneous phase, not easily separated and reuse.
PbO, Pb that CN 1403442A is disclosed
3o
4, ZnCl
2, Zn (AC)
2, HZSM5 or CH
3oK, can make aniline transformation efficiency and phenyl urethan selectivity reach more than 90%, but its shortcoming is that plumbous class catalyzer is unfavorable to environment, and latter four kinds is homogeneous catalyst, inconvenience separation and recycling and Zn (AC)
2easy inactivation, ZnCl
2can corroding metal equipment.
Pb (the C that CN 101845001 A are disclosed
mh
no
x)
y, Zn (C
mh
no
x)
y(m=1 ~ 8, n=4 ~ 18, x=1 ~ 3, y=0.5 ~ 4), aniline transformation efficiency and MPC productive rate are all higher, and selectivity reaches more than 90%, and its shortcoming is that these two kinds of catalyzer are met the easy inactivation of the water capacity, and can gradually run off because being partially soluble in methyl alcohol; In addition, plumbous class catalyzer is also unfavorable to environment, does not meet the requirement of Green Chemistry.
Therefore, from industrial application value and practicality, be badly in need of a kind of new method that is applicable to aniline and small molecules carbamate synthesizing phenyl carbamate of development, catalyzer and the efficient reaction pattern by development with excellent catalytic performance, effectively synthesizing phenyl carbamate, promotes non-phosgene route to prepare the exploitation of the environmental friendliness route of MDI.
Summary of the invention
The technology of the present invention is dealt with problems: overcome the deficiencies in the prior art, a kind of method that is applicable to aniline and small molecules carbamate synthesizing phenyl carbamate is provided, improve yield and the selectivity of phenyl urethan.
The technology of the present invention solution: a kind of method of synthesizing phenyl carbamate, its feature is: take aniline and small molecules carbamate is reactant, take small molecular alcohol as reaction medium, under the existence of catalyzer, control 80 ℃ to 250 ℃ of range of reaction temperature, 0.5 hour to 20 hours reaction times, reaction pressure 0.1MPa to 3MPa, adopt continuous ammonia excretion pattern or confined reaction pattern, synthesizing phenyl carbamate; The mol ratio of described aniline and small molecules carbamate is 0.1:1 ~ 1:20; The mol ratio of described aniline and small molecular alcohol is 1:1 ~ 1:20; The weight ratio of described catalyzer and aniline is 0.002:1 ~ 0.5:1.
Described small molecules carbamate is a kind of in Urethylane, urethanum, carboxylamine propyl ester, butyl carbamate.
Described small molecules carbamate is preferably Urethylane.
Described small molecular alcohol is a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol.
Described catalyzer is single metal oxide, or is the mixture of two kinds of metal oxides, or is comprised of a kind of catalytic active component and a kind of support of the catalyst.
Described metal oxide has general formula AO
x, A represents a kind of metallic element;
The mixture of described metal oxide has general formula AO
x-BO
y, A, B represent a kind of metal independently of one another;
The described catalyzer being comprised of a kind of catalytic active component and a kind of support of the catalyst has general formula AO
x/ BO
y, A, B represent a kind of metal independently of one another;
The span of described x, y is 0.5-4;
Described metallic element is selected from: magnesium, titanium, iron, cobalt, nickel, zirconium, molybdenum, lanthanum, cerium, aluminium, tin, bismuth.
The solid support material of described catalyzer is aluminum oxide, titanium dioxide, silicon-dioxide, zirconium white, tricobalt tetroxide, tindioxide, ferric oxide.
When described catalyzer comprises a kind of catalyst activity composition and a kind of support of the catalyst, in the gross weight of catalyzer, by 100%, catalyst activity component content is 0.1-20wt.%.
When described catalyzer comprises a kind of catalyst activity composition and a kind of support of the catalyst, performing step is as follows:
A. heat described support of the catalyst, Heating temperature is 200 ℃ to 1000 ℃;
B. by described impregnation of catalyst carriers in a solution that contains described catalyst activity composition precursor to obtain catalyst precursor, described catalyst activity composition precursor comprises a kind of anhydrous salt or salt hydrate of metal;
C. calcined catalyst precursor is to obtain described catalyzer, and the temperature of described roasting process is 100 ℃ to 1500 ℃.
The anhydrous salt of described metal or salt hydrate are elected halogenide, oxyhydroxide, nitrate, vitriol, acetate, molybdate, carbonate or the oxalate of described metal as.
The invention has the advantages that: used catalyst activity of the present invention is high, be easy to separation and reuse, be convenient to industrial application, practical; By adopting the reaction pattern of continuous ammonia excretion, break the restriction of ammonia to molecular balance, can further improve yield and the selectivity of phenyl urethan.
Embodiment
The quantitative analysis of described object product phenyl urethan, can utilize Agilent 1200series high performance liquid chromatograph.Its moving phase is methyl alcohol: water=60%:40%(volume ratio), chromatographic column is Zorbax Eclipse XDB-C18(150 * 4.6mm), flow velocity is 1mL/min, and detection wavelength is 245nm, and column temperature is 30 ℃.Phenyl urethan utilizes external standard method quantitative.
Specific embodiment disclosed in this invention and method, its description is exemplary and nonrestrictive.
the preparation of catalyzer
Embodiment 1
By 2.545gZn (NO
3)
26H
2o joins in the 100mL beaker that fills a certain amount of deionized water and mixes, then by solution and 10.294g 2CoCO after dissolving
33Co (OH)
2xH
2o stirs into a paste, and obtains catalyst precursor.The catalyst precursor obtaining is dried to 7 hours at 110 ℃, and then under 300 ℃ of conditions, calcines 4 hours in air atmosphere, obtain catalyst A.Described catalyst A is labeled as ZnO-Co
3o
4, the ZnO that comprises 8wt.%, 92wt.%Co
3o
4.
Embodiment 2
Under room temperature, 3.394g butyl (tetra) titanate is added drop-wise under vigorous stirring to 30mL dehydrated alcohol and (in this dehydrated alcohol, is dissolved with 4.343gCe (NO
3)
36H
2o), in, through the stirring of 15 to 20 minutes, obtain evenly faint yellow transparent solution (1); The solution that 5mL deionized water and 10mL dehydrated alcohol are made into slowly drips HNO under vigorous stirring
3, obtain pH and be 3 solution (2); Under vigorous stirring, by solution (1), the speed with approximately 1 drop/sec is slowly added drop-wise in solution (2) again, obtains the colloidal sol of homogeneous transparent, continues to be stirred to obtain translucent wet gel, i.e. catalyst precursor.By the catalyst precursor of gained at 80 ℃ dry 12.5 hours, and then roasting 2 hours under 450 ℃ of conditions in air atmosphere after dried powder is ground, catalyst B obtained.Described catalyst B is labeled as CeO
2-TiO
2, the CeO that comprises 50wt.%
2, 50wt.%TiO
2.
Embodiment 3
By Bi (NO
3)
35H
2o calcines at 500 ℃ 6 hours in air atmosphere, obtains catalyzer C.Described catalyzer C is labeled as Bi
2o
3.
Embodiment 4
By (NH
4)
6mo
7o
244H
2o calcines at 500 ℃ 5 hours in air atmosphere, obtains catalyzer D.Described catalyzer D is labeled as MoO
3.
Embodiment 5
By 0.545g (NH
4)
6mo
7o
244H
2o joins in the 10mL small beaker containing 2g deionized water, after ultra-sonic oscillation shake up, then 4.000g is heated to the γ-Al of 3 hours in 650 ℃ of air atmospheres
2o
3join in this solution, at room temperature flood 10 hours, obtain catalyst precursor.By the vacuum-drying 11 hours at 80 ℃ of gained catalyst precursor, and then under the condition of 500 ℃, calcine 3 hours in air atmosphere, obtain catalyzer E.Described catalyzer E is labeled as MoO
3/ γ-Al
2o
3, the MoO that comprises 10.0wt.%
3, the carrier of catalyzer E is γ-Al
2o
3.
Embodiment 6
By 170ml 0.33mol/L Ce (NO
3)
36H
2o and appropriate 1mol/L NaOH are added drop-wise in the beaker that a certain amount of deionized water is housed simultaneously, constantly stir.In this process, pH remains on 10 ± 1, and temperature remains on 60 ℃, and at this temperature aging 7 hours.The precipitate with deionized water washing forming, to neutral, obtains catalyst precursor.By the vacuum-drying 4 hours at 60 ℃ of gained catalyst precursor, then in 600 ℃ of air atmospheres, calcine 3 hours.The catalyzer F obtaining.Described catalyzer F is labeled as CeO
2.
synthesizing of phenyl urethan
Embodiment 7
0.133mol Urethylane (MC), 0.053mol aniline (AN), 0.624mol methyl alcohol, 1wt.%(is in the consumption of raw material aniline) described catalyst A or B or C or D or E or F, join in 100mL autoclave air in logical nitrogen replacement still, be warming up to 150 ℃, then confined reaction 1 hour under 150 ℃, agitation condition, after completion of the reaction, is cooled to room temperature by reactor.Reacted catalyzer in the instrument H1650 high speed tabletop centrifuge of Hunan, Changsha with the centrifugal rear filtration of rotating speed of 4000 ~ 6000r/min, then at 80 ℃ dry 6 hours, for reusing next time.
Embodiment 8
0.133mol Urethylane (MC), 0.053mol aniline (AN), 0.624mol methyl alcohol, 3wt.%Fe
2o
3(being designated as G) or ZrO
2(being designated as H) (in consumption of raw material aniline), joins in 100mL autoclave, and air in logical nitrogen replacement still, is warming up to 170 ℃, and then confined reaction 3 hours under 170 ℃, agitation condition, after completion of the reaction, is cooled to room temperature by reactor.Reacted catalyzer in the instrument H1650 high speed tabletop centrifuge of Hunan, Changsha with the centrifugal rear filtration of rotating speed of 4000 ~ 6000r/min, then at 80 ℃ dry 6 hours, for reusing next time.
Embodiment 9
1.332mol Urethylane (MC), 0.537mol aniline, 12.484mol methyl alcohol, 1wt.%TiO
2(consumption in raw material aniline, is designated as I) joins in 1L autoclave, is warming up to 180 ℃, keeps 3 hours at 180 ℃.In this process, control reaction pressure 0.1MPa to 3MPa, nitrogen buffer gas, ammonia excretion continuously.After completion of the reaction, reactor is cooled to room temperature.Reacted catalyzer in the instrument H1650 high speed tabletop centrifuge of Hunan, Changsha with the centrifugal rear filtration of rotating speed of 4000 ~ 6000r/min, then at 80 ℃ dry 6 hours, for reusing next time.
Table 1 continuously ammonia excretion pattern/or confined reaction pattern under, aniline and Urethylane catalyzed reaction synthesizing Amino-methye-formate
Note: a: catalyzer is reused four times.
It should be noted that, according to the various embodiments described above of the present invention, those skilled in the art are the four corners that can realize the claims in the present invention 1 and appurtenance completely, implementation procedure and method same the various embodiments described above; And non-elaborated part of the present invention belongs to techniques well known.`
The present invention discloses preferred embodiment as above, by Optimizing Technical, will reach more excellent result.These embodiment are not in order to limit the present invention, anyly have the knack of this skill person, and without departing from the spirit and scope of the present invention, when doing various changes and retouching, therefore the protection domain of invention should be as the criterion with the claim scope of applying for a patent.
Claims (9)
1. the method for a synthesizing phenyl carbamate, it is characterized in that: take aniline and small molecules carbamate is reactant, take small molecular alcohol as reaction medium, under the existence of catalyzer, control 80 ℃ to 250 ℃ of range of reaction temperature, 0.5 hour to 20 hours reaction times, reaction pressure 0.1MPa to 3MPa, adopt continuous ammonia excretion pattern or confined reaction pattern, synthesizing phenyl carbamate; The mol ratio of described aniline and small molecules carbamate is 0.1:1 ~ 1:20; The mol ratio of described aniline and small molecular alcohol is 1:1 ~ 1:20; The weight ratio of described catalyzer and aniline is 0.002:1 ~ 0.5:1.
2. the method for synthesizing phenyl carbamate according to claim 1, is characterized in that: described small molecules carbamate is a kind of in Urethylane, urethanum, carboxylamine propyl ester, butyl carbamate.
3. the method for synthesizing phenyl carbamate according to claim 2, is characterized in that: the preferred Urethylane of described small molecules carbamate.
4. the method for synthesizing phenyl carbamate according to claim 1, is characterized in that: described small molecular alcohol is a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol.
5. the method for synthesizing phenyl carbamate according to claim 1, is characterized in that: described catalyzer is single metal oxide, or is the mixture of two kinds of metal oxides, or be comprised of a kind of catalytic active component and a kind of support of the catalyst;
Described metal oxide has general formula AO
x, A represents a kind of metallic element;
The mixture of described metal oxide has general formula AO
x-BO
y, A, B represent a kind of metal independently of one another;
The described catalyzer being comprised of a kind of catalytic active component and a kind of support of the catalyst has general formula AO
x/ BO
y, A, B represent a kind of metal independently of one another;
The span of described x, y is 0.5-4;
Described metallic element is selected from: magnesium, titanium, iron, cobalt, nickel, zirconium, molybdenum, lanthanum, cerium, aluminium, tin, bismuth.
6. the method for synthesizing phenyl carbamate according to claim 5, is characterized in that, the solid support material of described catalyzer is aluminum oxide, titanium dioxide, silicon-dioxide, zirconium white, tricobalt tetroxide, tindioxide, ferric oxide.
7. the method for synthesizing phenyl carbamate according to claim 5, it is characterized in that: when described catalyzer comprises a kind of catalyst activity composition and a kind of support of the catalyst, in the gross weight of catalyzer, by 100%, catalyst activity component content is 0.1-20wt.%.
8. the method for synthesizing phenyl carbamate according to claim 5, is characterized in that: when described catalyzer is comprised of a kind of catalyst activity composition and a kind of support of the catalyst, performing step is as follows:
A. heat described support of the catalyst, Heating temperature is 200 ℃ to 1000 ℃;
B. by described impregnation of catalyst carriers in a solution that contains described catalyst activity composition precursor to obtain catalyst precursor, described catalyst activity composition precursor comprises a kind of anhydrous salt or salt hydrate of metal;
C. calcined catalyst precursor is to obtain described catalyzer, and the temperature of described roasting process is 100 ℃ to 1500 ℃.
9. the method for synthesizing phenyl carbamate according to claim 8, is characterized in that: the anhydrous salt of described metal or salt hydrate are elected halogenide, oxyhydroxide, nitrate, vitriol, acetate, molybdate, carbonate or the oxalate of described metal as.
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|---|---|---|---|
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Cited By (4)
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|---|---|---|---|---|
| WO2019185608A1 (en) | 2018-03-28 | 2019-10-03 | Covestro Deutschland Ag | Heterogeneous catalysts for the synthesis of carbamates |
| CN113731398A (en) * | 2020-05-27 | 2021-12-03 | 中国科学院过程工程研究所 | Catalyst for preparing dicarbamate and application thereof |
| CN114989044A (en) * | 2022-07-21 | 2022-09-02 | 中国科学院过程工程研究所 | Catalytic synthesis method of dicarbamate |
| CN115364843A (en) * | 2022-07-13 | 2022-11-22 | 河南科技学院 | Sm-Ti-MMT catalyst for synthesizing methyl phenyl carbonate and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019185608A1 (en) | 2018-03-28 | 2019-10-03 | Covestro Deutschland Ag | Heterogeneous catalysts for the synthesis of carbamates |
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| CN115364843B (en) * | 2022-07-13 | 2023-05-23 | 河南科技学院 | Sm-Ti-MMT catalyst for synthesizing methyl phenyl carbonate, and preparation method and application thereof |
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Application publication date: 20140402 |