CN108395384A - The green synthesis method of isocyanates - Google Patents
The green synthesis method of isocyanates Download PDFInfo
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- CN108395384A CN108395384A CN201810311193.0A CN201810311193A CN108395384A CN 108395384 A CN108395384 A CN 108395384A CN 201810311193 A CN201810311193 A CN 201810311193A CN 108395384 A CN108395384 A CN 108395384A
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- isocyanates
- synthesis method
- green synthesis
- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of green synthesis methods of isocyanates, include the following steps：Nano metal hydride is initiator, and amine compound and dimethyl carbonate carry out necleophilic reaction and generate amido formate in organic solvent, and amido formate is pyrolyzed up to isocyanates；The temperature of the necleophilic reaction is 0~30 DEG C, and pressure is normal pressure.The present invention uses amine compound and dimethyl carbonate for reactant, nano metal hydride is initiator synthesizing isocyanate, since nano metal hydride has the surface-active of height, chemical property work wave, it is reacted with amine compound, attack dimethyl carbonate again enhances necleophilic reaction performance so that the conversion ratio and selectivity of isocyanates are far above traditional phosgene reaction.In addition, the advantages that synthesising method reacting condition provided by the invention is mild, easily operated and industrialization, and cost is relatively low, entirely simple at production. art, nontoxic, environment friendly and pollution-free, recyclable byproduct methanol, great popularization.
Description
Technical field
The present invention relates to isocyanates field, especially a kind of green synthesis method of isocyanates.
Background technology
Isocyanates is common a kind of organic intermediate, and chemical property wave very living is easy to and having with wave H living
Machine compound reacts, and has highly important status in chemical pharmacy and pesticide synthesis, and purposes is wide, yield is country greatly
Modernize the mark of organic synthesis level.Isocyanates includes the isocyanates of monoisocyanates and two functional groups or more, single
Isocyanates is the important intermediate of organic synthesis, can be made into a series of carbamate insecticides, fungicide, herbicide,
It is also used for improving the water proofing property of plastics, fabric, leather etc..The isocyanates of two functional groups or more can be used for synthesizing a series of property
Polyurethane foam plastics, rubber, elastic fibers, coating, adhesive, synthetic leather, imitation wood etc. that can be excellent, purposes be very
Extensively.Isocyanates comes out for 1848, since people do not go deep into its structure and repercussion study, does not cause the weight of scientific circles
Depending on.To nineteen twenty-one, Staudinger et al. reports isocyanates to ketenes with after similar structure, and people just start weight
Point research.After nineteen thirty, Germany has carried out the scientific research that plastics, fiber, viscose and coating are prepared with polyurethane, makes different
The commercial Application of cyanate has gone on fast traffic lane.The production of the isocyanates of mainstream all uses phosgenation, production to have high poison
The characteristics of property and highly corrosive, safety accident happens occasionally, but its is with a long history, and the production line built up is more, considerably long
Still it is the method generally used in a period of time.People's environmental consciousness constantly enhances, requirement of the country to newly-built chemical enterprise
It is higher and higher, it finds nontoxic, free of contamination green synthesis process and prepares isocyanates as our main task.
Invention content
In view of this, the object of the present invention is to provide a kind of green synthesis method of isocyanates, isocyanic acid can be improved
The conversion ratio and selectivity of ester, and it is entirely simple at production. art, it is nontoxic, it is environment friendly and pollution-free.
To achieve the goals above, the present invention provides the following technical solutions：
A kind of green synthesis method of isocyanates, includes the following steps：
Nano metal hydride is initiator, and amine compound and dimethyl carbonate carry out necleophilic reaction in organic solvent
Amido formate is generated, amido formate is pyrolyzed up to isocyanates；
The temperature of the necleophilic reaction is 0~30 DEG C, and pressure is normal pressure.
Preferably, the nano metal hydride is alkali metal, alkaline-earth metal or transition metal.
Preferably, the nano metal hydride is nanometer magnesium hydride, nanometer hydrogenation lanthanum or nanometer cesium hydride.
Preferably, the amount ratio for stating initiator and amine compound substance is 3:1、2:1 or 1:1；The amine compound with
The amount ratio of the substance of the dimethyl carbonate is 1:1.05~1:1.1.
Preferably, the organic solvent is THF, toluene, benzene or ethyl methyl ether.
Preferably, the amine compound be aniline, diaminotoluene, 3,4-DCA, trifluoro-methoxyaniline or
4- isobutoxy benzylamines.
Preferably, further include evaporating the organic solvent removed in amido formate before the pyrolysis.
Preferably, the pyrolytic process be specially to amido formate be added solvent, adjust solution a concentration of 20~
40g/L, then metallic catalyst is added into solution, increases the temperature to 180~220 DEG C, carries out pyrolytic reaction under normal pressure, when reaction
Between be 3~5h, obtain pyrogen.
Preferably, the metallic catalyst is iron, cobalt, nickel, zinc or copper；The solvent is DOA and DBP.
Preferably, the addition of the metallic catalyst is the 3~8% of the pyrogen, the DOA and DBP's
Amount ratio is 1:5.
The present invention provides a kind of green synthesis method of isocyanates, amine compound and dimethyl carbonate are reaction
Object uses nano metal hydride for initiator synthesizing isocyanate, and nano metal hydride has the surface-active of height, changes
Property work wave is learned, is reacted with amine compound, then attack dimethyl carbonate, enhances necleophilic reaction performance so that isocyanates
Conversion ratio and selectivity be far above traditional phosgene reaction.In addition, synthesising method reacting condition provided by the invention it is mild,
Easily operated and industrialization, cost is relatively low, entirely simple at production. art, nontoxic, environment friendly and pollution-free, recyclable byproduct methanol etc.
Advantage, great popularization.
Specific implementation mode
A kind of green synthesis method of isocyanates provided by the invention, includes the following steps：
Nano metal hydride is initiator, and amine compound and dimethyl carbonate carry out necleophilic reaction in organic solvent
Amido formate is generated, amido formate is pyrolyzed up to isocyanates；
The temperature of necleophilic reaction is 0~30 DEG C, and pressure is normal pressure.
In above-mentioned technical proposal, amine compound and dimethyl carbonate are reactant, use nano metal hydride to draw
Agent synthesizing isocyanate is sent out, nano metal hydride has the surface-active of height, chemical property work wave anti-with amine compound
It answers, then attack dimethyl carbonate, enhances necleophilic reaction performance so that the conversion ratio and selectivity of isocyanates, which are far above, to be passed
The phosgene reaction of system.In addition, synthesising method reacting condition provided by the invention is mild, easily operated and industrialization, cost is relatively low,
It is entirely simple at production. art, it is nontoxic, it is environment friendly and pollution-free, the advantages that recyclable byproduct methanol, great popularization.
In the present invention, nano metal hydride is initiator, and amine compound and dimethyl carbonate are in organic solvent
It carries out necleophilic reaction and generates amido formate.According to the present invention, initiator is first reacted with amine compound, then attack carbonic acid diformazan
Ester can improve necleophilic reaction performance.Among the above, nano metal hydride is preferably alkali metal, alkaline-earth metal or transition metal,
Nano metal hydride is more preferably nanometer magnesium hydride, nanometer hydrogenation lanthanum or nanometer cesium hydride；Amine compound be preferably aniline,
Diaminotoluene, 3,4- dichloroanilines, trifluoro-methoxyaniline or 4- isobutoxy benzylamines；Organic solvent is preferably THF, first
Benzene, benzene or ethyl methyl ether, organic solvent are more preferably THF or toluene.
It should be noted that in order to enable the conversion ratio of isocyanates and selective highest, initiator and amine compound
The amount ratio of substance is 3:1、2:1 or 1:1；The amount ratio of the substance of amine compound and dimethyl carbonate is 1:1.05~1:1.1.
In the present invention, amido formate is pyrolyzed up to isocyanates；According to the present invention, in order to will be in amido formate
Organic solvent is recycled, and the wasting of resources is avoided, and preferably further includes organic molten in evaporation removing amido formate before pyrolysis
Agent；Pyrolytic reaction preferably includes following steps, and solvent is added to amido formate, adjusts a concentration of 20~40g/L of solution,
Metallic catalyst is added into solution again, increases the temperature to 180~220 DEG C, pyrolytic reaction, reaction time 3 is carried out under normal pressure
~5h.
It should be noted that metallic catalyst is preferably iron, cobalt, nickel, zinc or copper, it is easily isolated back using different-phase catalyst
It receives；The addition of metallic catalyst is preferably the 3~8% of pyrogen, and solvent is preferably dioctyl adipate (DOA) and adjacent benzene two
The volume ratio of formic acid dibutyl ester (DBP), DOA and DBP are preferably 1:5.
In the present invention, nano metal hydride has prodigious specific surface area and surface energy, instead since its particle radii is small
Answer activity very high, the chemistry that the higher non-incident reaction of some activation energy can be catalyzed or accelerate some reaction rates slower
Reaction.It is that initiator prepares isocyanates using nano metal hydride, conversion ratio and selectivity are all far above using hypertoxic light
The reaction result of gas, also above nitro compound carbonylation method, electrochemical catalysis carbonylation method, the dehydration of carbamate anion
Method in the reports such as method.Raw material addition sequence is controlled in reaction makes nitrogen-atoms using nano metal hydride and primary amine reaction
Necleophilic reaction can occur to carbonyl attack, enhance necleophilic reaction performance, improve the conversion ratio and selectivity of isocyanates.
The experimental results showed that the present invention use the conversion ratio of isocyanates made from above-mentioned technical proposal 90.3% with
On, selectivity is 92.1% or more.
In order to further illustrate the present invention, with reference to embodiment to a kind of green conjunction of isocyanates provided by the invention
It is described in detail at method, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
3mmol nanometers of magnesium hydrides of precise, are placed in a reaction flask, and 20mL THF are added, and open magnetic stirring apparatus, normal pressure
Under the conditions of, the reflux temperature that oil bath controls THF is 30 DEG C, and 1mmol4- isobutoxy benzylamines are added after 10min, fully after reaction,
1.1mmol dimethyl carbonates are added, back flow reaction 3h obtains 4- isobutoxy benzamido group methyl formates；Evaporation removes 4- isobutyls
After THF and methanol in oxygroup benzamido group methyl formate, pyrogen is obtained, it is 1 that volume ratio is added into pyrogen:5 DOA and
DBP, adjustment solution concentration are 30g/L, add metallic zinc, and the addition of metallic zinc is the 6% of pyrogen quality, increase temperature
To 200 DEG C, pyrolysis time 4h is to get 4- isobutoxy benzyl mustard oils under normal pressure.
The conversion ratio of 4- isobutoxies benzyl mustard oil is up to 90.3% in embodiment 1, and high selectivity is up to 92.1%
Embodiment 2
2mmol nanometers of hydrogenation lanthanums of precise, are placed in a reaction flask, 10mlTHF are added, open magnetic stirring apparatus, normal pressure
Under the conditions of, the reflux temperature that oil bath controls THF is 0 DEG C, and 1mmol 4- isobutoxy benzylamines are added after 10min, fully after reaction,
1.05mmol dimethyl carbonates are added, back flow reaction 3h obtains 4- isobutoxy benzamido group methyl formates；Evaporation removes 4- isobutyls
After THF and methanol in oxygroup benzamido group methyl formate, pyrogen is obtained, it is 1 that volume ratio is added into pyrogen:5 DOA and
DBP, adjustment solution concentration are 30g/L, add metallic zinc, and the addition of metallic zinc is the 5% of pyrogen quality, increase temperature
To 200 DEG C, pyrolysis time 4h is to get 4- isobutoxy benzyl mustard oils under normal pressure.
The conversion ratio of 4- isobutoxies benzyl mustard oil is 93.5% in embodiment 2, and selectivity is 95%.
Embodiment 3
2mmol nanometers of cesium hydrides of precise, are placed in a reaction flask, and 10mL ethyl methyl ethers are added, and open magnetic stirring apparatus, often
Under the conditions of pressure, the reflux temperature that oil bath controls ethyl methyl ether is 10 DEG C, and 2mmol aniline is added after 10min and is added fully after reaction
2.1mmol dimethyl carbonates, back flow reaction 3h obtain anilino- methyl formate；Evaporation removes the first in anilino- methyl formate
After ether and methanol, pyrogen is obtained, it is 1 that volume ratio is added into pyrogen:5 DOA and DBP, adjustment solution concentration are
20g/L adds metallic iron, and the addition of metallic iron is the 6% of pyrogen quality, increases the temperature to 180 DEG C, is pyrolyzed under normal pressure
Time, 5h was to get phenyl isocyanate.
The conversion ratio of phenyl isocyanate is 92.3% in embodiment 3, and selectivity is 93.3%.
Embodiment 4
3mmol nanometers of magnesium hydrides of precise, are placed in a reaction flask, and 10ml toluene is added, and open magnetic stirring apparatus, normal pressure
Under the conditions of, the reflux temperature that oil bath controls toluene is 20 DEG C, and 1mmol aniline is added after 10min and is added fully after reaction
1.05mmol dimethyl carbonates, back flow reaction 3h obtain anilino- methyl formate；Evaporation removes the first in anilino- methyl formate
After benzene and methanol, pyrogen is obtained, it is 1 that volume ratio is added into pyrogen:5 DOA and DBP, adjustment solution concentration are 40g/
L adds metallic cobalt, and the addition of metallic cobalt is the 5% of pyrogen quality, increases the temperature to 220 DEG C, pyrolysis time under normal pressure
3h is to get phenyl isocyanate.
The conversion ratio of phenyl isocyanate is 90.7% in embodiment 4, and selectivity is 98.1%.
Embodiment 5
3mmol nanometers of hydrogenation lanthanums of precise, are placed in a reaction flask, 10ml benzene are added, open magnetic stirring apparatus, normal pressure item
Under part, the reflux temperature that oil bath controls benzene is 20 DEG C, and 3mmol diaminotoluenes are added after 10min and are added fully after reaction
3.3mmol dimethyl carbonates, back flow reaction 3h, obtain tolylene dicarbamate；Evaporation removes in anilino- methyl formate
Benzene and methanol after, obtain pyrogen, into pyrogen be added volume ratio be 1:5 DOA and DBP, adjustment solution concentration are
20g/L adds metallic cobalt, and the addition of metallic cobalt is the 4% of pyrogen quality, increases the temperature to 180 DEG C, is pyrolyzed under normal pressure
Time, 3h was to get toluene di-isocyanate(TDI).
The conversion ratio of toluene di-isocyanate(TDI) is 90.2% in embodiment 5, and selectivity is 91.5%.
Embodiment 6
2mmol nanometers of cesium hydrides of precise, are placed in a reaction flask, and 10ml toluene is added, and open magnetic stirring apparatus, normal pressure
Under the conditions of, the reflux temperature that oil bath controls toluene is 30 DEG C, and 1mmol diaminotoluenes are added after 10min and add fully after reaction
Enter 1.1mmol dimethyl carbonates, back flow reaction 3h obtains tolylene dicarbamate；Evaporation removes anilino- methyl formate
In toluene and methanol after, obtain pyrogen, into pyrogen be added volume ratio be 1:5 DOA and DBP adjusts solution concentration
For 30g/L, metallic iron is added, the addition of metallic iron is the 6% of pyrogen quality, increases the temperature to 200 DEG C, hot under normal pressure
Time 4h is solved to get toluene di-isocyanate(TDI).
The conversion ratio of toluene di-isocyanate(TDI) is 91.7% in embodiment 6, and selectivity is 93.6%.
Embodiment 7
3mmol nanometers of magnesium hydrides of precise, are placed in a reaction flask, and 10mlTHF is added, and open magnetic stirring apparatus, normal pressure
Under the conditions of, the reflux temperature that oil bath controls THF is 10 DEG C, and 1.5mmol 3,4-DCAs are added after 10min, fully react
Afterwards, 1.65mmol dimethyl carbonates are added, back flow reaction 3h obtains 3,4-DCA base methyl formate；Evaporation removes 3,4-
After THF and methanol in dichloroanilino methyl formate, pyrogen is obtained, it is 1 that volume ratio is added into pyrogen:5 DOA and
DBP, adjustment solution concentration are 20g/L, add metallic copper, and the addition of metallic copper is the 5% of pyrogen quality, increase temperature
To 200 DEG C, pyrolysis time 4h is to get 3,4- dichlorophenyl isocyanates under normal pressure.
The conversion ratio of 3,4- dichlorophenyl isocyanates is 94.2% in embodiment 7, and selectivity is 95.6%.
Embodiment 8
2mmol nanometers of hydrogenation lanthanums of precise, are placed in a reaction flask, 10ml benzene are added, open magnetic stirring apparatus, normal pressure item
Under part, the reflux temperature that oil bath controls benzene is 0 DEG C, and 2mmol 3,4-DCAs are added after 10min and are added fully after reaction
2.1mmol dimethyl carbonates, back flow reaction 3h obtain 3,4-DCA base methyl formate；Evaporation removes 3,4- dichloroanilines
After benzene and methanol in base methyl formate, pyrogen is obtained, it is 1 that volume ratio is added into pyrogen:5 DOA and DBP, adjustment
Solution concentration is 30g/L, adds metallic nickel, and the addition of metallic nickel is the 8% of pyrogen quality, increases the temperature to 180 DEG C,
Pyrolysis time 5h is to get 3,4- dichlorophenyl isocyanates under normal pressure.
The conversion ratio of 3,4- dichlorophenyl isocyanates is 93.7% in embodiment 4, and selectivity is 96.5%.
Embodiment 9
3mmol nanometers of magnesium hydrides of precise, are placed in a reaction flask, and 10ml toluene is added, and open magnetic stirring apparatus, normal pressure
Under the conditions of, the reflux temperature that oil bath controls toluene is 20 DEG C, and 1mmol trifluoro-methoxyanilines are added after 10min, fully react
Afterwards, 1.1mmol dimethyl carbonates are added, back flow reaction 3h obtains trifluoro-methoxyaniline base methyl formate；Evaporation removes trifluoro
After toluene and methanol in methoxybenzene amido methyl formate, pyrogen is obtained, it is 1 that volume ratio is added into pyrogen:5
DOA and DBP, adjustment solution concentration are 30g/L, add metallic cobalt, and the addition of metallic cobalt is the 5% of pyrogen quality, are risen
High-temperature is to 220 DEG C, and pyrolysis time 4h is to get Trifluoromethoxyphen-l isocyanates under normal pressure.
The conversion ratio of Trifluoromethoxyphen-l isocyanates is 93.4% in embodiment 9, and selectivity is 92.6%.
Embodiment 10
3mmol nanometers of cesium hydrides of precise, are placed in a reaction flask, and 10ml ethyl methyl ethers are added, and open magnetic stirring apparatus, often
Under the conditions of pressure, the reflux temperature that oil bath controls ethyl methyl ether is 10 DEG C, and 1mmol trifluoro-methoxyanilines are added after 10min, fully anti-
Ying Hou, is added 1.05mmol dimethyl carbonates, and back flow reaction 3h obtains trifluoro-methoxyaniline base methyl formate；Evaporation removes
After ethyl methyl ether and methanol in trifluoro-methoxyaniline base methyl formate, pyrogen is obtained, volume ratio is added into pyrogen is
1:5 DOA and DBP, adjustment solution concentration are 40g/L, add metallic zinc, the addition of metallic zinc is pyrogen quality
3%, 200 DEG C are increased the temperature to, pyrolysis time 4h is to get Trifluoromethoxyphen-l isocyanates under normal pressure.
The conversion ratio of Trifluoromethoxyphen-l isocyanates is 90.3% in embodiment 10, and selectivity is 93.4%.More than
Described is only the preferred embodiment of the present invention, it is noted that for those skilled in the art, is not being taken off
Under the premise of from the principle of the invention, several improvements and modifications can also be made, these improvements and modifications also should be regarded as the present invention's
Protection domain.
Claims (10)
1. a kind of green synthesis method of isocyanates, which is characterized in that include the following steps：
Nano metal hydride is initiator, and amine compound and dimethyl carbonate carry out necleophilic reaction generation in organic solvent
Amido formate, amido formate are pyrolyzed up to isocyanates；
The temperature of the necleophilic reaction is 0~30 DEG C, and pressure is normal pressure.
2. the green synthesis method of isocyanates as described in claim 1, which is characterized in that the nano metal hydride is
Alkali metal, alkaline-earth metal or transition metal.
3. the green synthesis method of isocyanates as claimed in claim 2, which is characterized in that the nano metal hydride is
Nanometer magnesium hydride, nanometer hydrogenation lanthanum or nanometer cesium hydride.
4. the green synthesis method of isocyanates as described in claim 1, which is characterized in that the initiator and amido chemical combination
The amount ratio of object substance is 3:1、2:1 or 1:1；The amount ratio of the amine compound and the substance of the dimethyl carbonate is 1:1.05
~1:1.1.
5. the green synthesis method of isocyanates as described in claim 1, which is characterized in that the organic solvent is THF, first
Benzene, benzene or ethyl methyl ether.
6. the green synthesis method of isocyanates as described in claim 1, which is characterized in that the amine compound is benzene
Amine, diaminotoluene, 3,4- dichloroanilines, trifluoro-methoxyaniline or 4- isobutoxy benzylamines.
7. the green synthesis method of isocyanates as described in claim 1, which is characterized in that further include evaporation before the pyrolysis
Remove the organic solvent in amido formate.
8. the green synthesis method of isocyanates as claimed in claim 7, which is characterized in that the pyrolytic process be specially to
Solvent is added in amido formate, adjusts a concentration of 20~40g/L of solution, then metallic catalyst is added into solution, increases temperature
It spends to 180~220 DEG C, pyrolytic reaction is carried out under normal pressure, the reaction time is 3~5h, obtains pyrogen.
9. the green synthesis method of isocyanates as claimed in claim 8, which is characterized in that the metallic catalyst be iron,
Cobalt, nickel, zinc or copper；The solvent is DOA and DBP.
10. the green synthesis method of isocyanates as claimed in claim 9, which is characterized in that the metallic catalyst adds
Enter 3~8% that amount is the pyrogen, the dosage volume ratio of the DOA and DBP is 1:5.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998056758A1 (en) * | 1997-06-09 | 1998-12-17 | Huntsman Ici Chemicals Llc | Process for the production of organic isocyanates |
| CN1419538A (en) * | 2000-02-03 | 2003-05-21 | 恩尼化学有限公司 | Integrated process for the preparation of aromatic isocyanates and procedures for effecting the relative intermediate phases |
| CN102369183A (en) * | 2009-03-10 | 2012-03-07 | 康斯乔最高科学研究公司 | One-pot production of carbamates using solid catalysts |
-
2018
- 2018-04-09 CN CN201810311193.0A patent/CN108395384A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998056758A1 (en) * | 1997-06-09 | 1998-12-17 | Huntsman Ici Chemicals Llc | Process for the production of organic isocyanates |
| CN1419538A (en) * | 2000-02-03 | 2003-05-21 | 恩尼化学有限公司 | Integrated process for the preparation of aromatic isocyanates and procedures for effecting the relative intermediate phases |
| CN102369183A (en) * | 2009-03-10 | 2012-03-07 | 康斯乔最高科学研究公司 | One-pot production of carbamates using solid catalysts |
Non-Patent Citations (1)
| Title |
|---|
| 孙彦林等: "氨基甲酸酯热分解制备异氰酸酯的研究进展", 《精细石油化工》 * |
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Application publication date: 20180814 |