CN103396340A - 2-methyl-3-butenenitrile isomerization method - Google Patents
2-methyl-3-butenenitrile isomerization method Download PDFInfo
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- CN103396340A CN103396340A CN2013103603167A CN201310360316A CN103396340A CN 103396340 A CN103396340 A CN 103396340A CN 2013103603167 A CN2013103603167 A CN 2013103603167A CN 201310360316 A CN201310360316 A CN 201310360316A CN 103396340 A CN103396340 A CN 103396340A
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- methyl
- crotononitrile
- isomerization method
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- isomerization
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Abstract
The present invention relates to an improved 2-methyl-3-butenenitrile isomerization method, wherein elementary metal powder and a trivalent phosphate ester ligand are adopted, and liquid phase and solid phase reactions are adopted to catalyze isomerization of 2-methyl-3-butenenitrile into linear pentenenitrile. According to the 2-methyl-3-butenenitrile isomerization method, the elementary metal powder and the phosphate ester ligand are adopted to catalyze isomerization of 2-methyl-3-butenenitrile into linear pentenenitrile so as to simplify the isomerization reaction method for isomerization of 2-methyl-3-butenenitrile into linear pentenenitrile.
Description
Technical field
The present invention relates to a kind of isomerization process of 2-methyl-3 crotononitrile, be specifically related to a kind of isomerization method of 2-methyl-3 crotononitrile.
Technical background
Pentenenitrile is the intermediate for preparing adiponitrile, and can continue hydrocyanation is adiponitrile, and adiponitrile is nylon 66 intermediates.United States Patent (USP) 3676481(1972) openly with three organic borons with nickel complex acting in conjunction liquid-phase catalysis 2-methyl-the 3-crotononitrile is linear pentenenitrile technique; US Patent No. 3853948(1974), US4298546(1981) the zero-valent nickel composition catalyst is disclosed in succession and excess ligand catalysis 2-methyl-3-crotononitrile isomery turns to linear alkene nitrile technique, put into reaction system and carry out catalyzed reaction but all need to prepare after the zero-valent nickel title complex.Chinese patent 03136857.3 discloses improved 2-methyl-3-crotononitrile isomery and turns to non-annularity alkene nitrile technique, and method is to select a kind of (mentioning multiple bitooth ligand in literary composition) bitooth ligand and cyclooctadiene nickel to mix, and first generates title complex; Or nickel salt, part and reductive agent are prepared composition catalyst, preferably coordinate again the Lewis acid auxiliary agent to come into operation, this technique shortcoming is that the bitooth ligand cost is high, operates more difficult and cost is high, and as this catalysts activity, there is no obvious advantage.
Summary of the invention
The objective of the invention is in order to overcome 2-methyl-3-crotononitrile isomerization process shortcoming, the isomerization process of a kind of 2-methyl of simplification-3-crotononitrile is provided, be convenient to industrialization.
The isomerization method of improved 2-methyl-3 crotononitrile of the present invention, step is as follows:
2-methyl-3-crotononitrile and three valent phosphors ester ligand are mixed, add the elemental metals powder, pass into nitrogen gas stirring, keep for some time after heating up, liquid phase, solid state reaction catalyzed reaction obtain 2-methyl-3-crotononitrile isomery and turn to linear pentenenitrile.
Add chloride element auxiliary agent in reaction.
Described chlorine auxiliary agent is ZnCl
2, NiCl
2, CaCl
2, SnCl
2, PCl
3, FeCl
3Or FeCl
2In one or more.
Chloride element promoter addition is 200～1000ppm.
Reaction Raw mol ratio is the elemental metals powder: 2-methyl-3-crotononitrile: the three valent phosphors ester ligand is 1:10～1000:1～20.
Reaction Raw mol ratio is the elemental metals powder: 2-methyl-3-crotononitrile: the three valent phosphors ester ligand is 1:50～200:1～8.
Described elemental metals powder is one or more in palladium, cobalt or nickel, and preferred nickel, if metal-powder partial oxidation or oxide film is arranged uses elemental metals powder good dispersity after the rupture of membranes drying.
Described three valent phosphors ester ligand is formula P(OR)
3, wherein, R is with aromatic yl group or alkyl group, preferably contains the group of aryl.
In formula, R is phenyl, tolyl and ethylbenzene, p-methoxy-phenyl, ethoxyl phenenyl, phenyl ring derivatives group, one or more in ethyl, propyl group, butyl or the tertiary butyl.Preferred phenyl or tolyl.
Described temperature of reaction is 80～200 ℃, preferred 100～170 ℃, more selects 120～150 ℃.
The time that described intensification keeps is 2-9 hour.
React needed pressure and be the air pressure that system self produces or add rare gas element.
Described stirring is mechanical stirring or magnetic agitation, and preferred mechanical stirs.
Concrete steps of the present invention are:
Three valent phosphors ester ligand and 2-methyl-3-crotononitrile are put into two mouthfuls of reaction flasks mixing, deoxidation, add the elemental metals powder under oxygen free condition, with inject chloride element auxiliary agent under liquid level, shake 1-3 minute, cover two plugs, keep nitrogen to pass into the speed of 1～5ml/min, jog moves two-mouth bottle, configuring reaction solution, adds reaction vessel to stir, and keeps for some time namely to obtain product after heating up.
Reaction vessel preferred reaction still, reaction system contains liquid phase, solid phase.
Two plugs all punch and install the Glass tubing that internal diameter is 3～4mm, and the outer end of Glass tubing connects soft emulsion tube, and emulsion tube the other end clip is clamped standby.
Compared with prior art, the present invention has following beneficial effect:
The isomerization method of 2-methyl-3 crotononitrile of the present invention, adopt the isomery of metal simple-substance powder and phosphorus ligand catalysis 2-methyl-3 crotononitrile to turn to linear 3 pentene nitrile, simplified 2-methyl-3 crotononitrile isomery and turned to linear molecule isomerization reaction method.The method need not another solubilizing agent, has reduced the catalyzer preparation procedure, reduces facility investment, reduces process costs, increases technology stability, has certain industrial value.
Embodiment
The present invention will be further described below in conjunction with embodiment.But range of application is not limited only to following embodiment.
2-methyl in the following example-3-crotononitrile material purity is 70%, and all the other impurity are linear pentenenitrile and trace 2-methyl-2-butene nitrile.
The three valent phosphors ester ligand is homemade, adopts PCl
3With R band aromatic yl group or alkyl group reaction, underpressure distillation collects out the cut of 180 ℃～240 ℃.The PCl that uses
3For Tianjin recovery SILVER REAGENT.
Transformation efficiency and selectivity adopt gas-chromatography, and (method of Shimadzu-GC2014C), analyze all nitriles, because raw material and product are isomerss, therefore transformation efficiency is to calculate gained according to chromatogram Raw, product area change.
Embodiment 1
With ready room temperature three valent phosphors ester ligand P(OC
6H
4CH
3)
354.91g, with 41.5g room temperature 2-methyl-3-crotononitrile, mixing deoxidation with two mouthfuls of 200ml reaction flasks.Put into an anaerobic glove box operation and add the 2g nickel powder, with entry needle, inject 200ppmPCl under liquid level
3, shook 1 minute, cover two plugs.Two plugs all punch and install the Glass tubing that internal diameter is the long 10cm of 4mm, and the outer end of Glass tubing connects soft emulsion tube, and emulsion tube the other end clip is clamped standby.Reactor connects nitrogen tube, after nitrogen replacement, open still upper flange charging opening, keep nitrogen to pass into the speed of 1ml/min, this moment, two bottle of one end connected the nitrogen of pressure-fired, the other end connects charging opening and opens clip, jog moves two-mouth bottle, configuring reaction solution, adds still to stir, and reduces nickel powder as far as possible and sticks to a bottle wall.Reactor rises to 100 ℃ from room temperature, and keeps 3h.Reaction result such as table 1.
Embodiment 2
With ready room temperature three valent phosphors ester ligand P(OC
6H
5)
3105g and 290.5g room temperature 2-methyl-3-crotononitrile, mixing deoxidation with two mouthfuls of 200ml reaction flasks.Put into an anaerobic glove box operation and add the 2g cobalt powder, with entry needle, inject 500ppmNiCl under liquid level
2, shook 2 minutes, cover two plugs.Two plugs all punch and install the Glass tubing that internal diameter is the long 10cm of 3mm, and the outer end of Glass tubing connects soft emulsion tube, and emulsion tube the other end clip is clamped standby.Reactor connects nitrogen tube, after nitrogen replacement, open still upper flange charging opening, keep nitrogen to pass into the speed of 3ml/min, this moment, two bottle of one end connected the nitrogen of pressure-fired, the other end connects charging opening and opens clip, jog moves two-mouth bottle, configuring reaction solution, adds still to stir, and reduces nickel powder as far as possible and sticks to a bottle wall.Reactor rises to 130 ℃ from room temperature, and keeps 7h.Reaction result such as table 1.
Embodiment 3
With ready room temperature three valent phosphors ester ligand P(OC
4H
9)
3117g and 539g room temperature 2-methyl-3-crotononitrile, mixing deoxidation with two mouthfuls of 200ml reaction flasks.Put into an anaerobic glove box operation and add 4g palladium powder, with entry needle, inject 1000ppmFeCl under liquid level
3, shook 2 minutes, cover two plugs.Two plugs all punch and install the Glass tubing that internal diameter is the long 10cm of 4mm, and the outer end of Glass tubing connects soft emulsion tube, and emulsion tube the other end clip is clamped standby.Reactor connects nitrogen tube, after nitrogen replacement, open still upper flange charging opening, keep nitrogen to pass into the speed of 4ml/min, this moment, two bottle of one end connected the nitrogen of pressure-fired, the other end connects charging opening and opens clip, jog moves two-mouth bottle, configuring reaction solution, adds still to stir, and reduces nickel powder as far as possible and sticks to a bottle wall.Reactor rises to 80 ℃ from room temperature, and keeps 9h.Reaction result such as table 1.
Embodiment 4
With ready room temperature three valent phosphors ester ligand P(OC
6H
5CH
3)
3240g and 1400g room temperature 2-methyl-3-crotononitrile, mixing deoxidation with two mouthfuls of 200ml reaction flasks.Put into an anaerobic glove box operation and add the 2g nickel powder, with entry needle, inject 500ppmZnCl under liquid level
2, shook 3 minutes, cover two plugs.Two plugs all punch and install the Glass tubing that internal diameter is the long 10cm of 3mm, and the outer end of Glass tubing connects soft emulsion tube, and emulsion tube the other end clip is clamped standby.Reactor connects nitrogen tube, after nitrogen replacement, open still upper flange charging opening, keep nitrogen to pass into the speed of 5ml/min, this moment, two bottle of one end connected the nitrogen of pressure-fired, the other end connects charging opening and opens clip, jog moves two-mouth bottle, configuring reaction solution, adds still to stir, and reduces nickel powder as far as possible and sticks to a bottle wall.Reactor rises to 200 ℃ from room temperature, and keeps 2h.Reaction result such as table 1.
The reaction result of table 1 embodiment 1-4
| ? | Transformation efficiency | Selectivity |
| Embodiment 1 | 77.4% | 97.9% |
| Embodiment 2 | 44.8% | 98.1% |
| Embodiment 3 | 16.5% | 98.3% |
| Embodiment 4 | 71.0% | 98.0% |
Claims (10)
1. the isomerization method of 2-methyl-3 crotononitrile, is characterized in that, step is as follows:
2-methyl-3-crotononitrile and three valent phosphors ester ligand are mixed, add the elemental metals powder, pass into nitrogen gas stirring, keep for some time after heating up, liquid phase, solid state reaction catalyzed reaction obtain linear pentenenitrile.
2. the isomerization method of 2-methyl-3 crotononitrile according to claim 1, is characterized in that, adds chloride element auxiliary agent in reaction.
3. the isomerization method of 2-methyl-3 crotononitrile according to claim 2, is characterized in that, the chlorine auxiliary agent is ZnCl
2, NiCl
2, CaCl
2, SnCl
2, PCl
3, FeCl
3Or FeCl
2In one or more.
4. the isomerization method of according to claim 2 or 3 described 2-methyl-3 crotononitriles, is characterized in that, the chlorine promoter addition is 200～1000ppm.
5. the isomerization method of 2-methyl-3 crotononitrile according to claim 1, is characterized in that, elemental metals powder in reaction: 2-methyl-3-crotononitrile: three valent phosphors ester ligand mol ratio is 1:10～1000:1～20.
6. the isomerization method of 2-methyl-3 crotononitrile according to claim 1, is characterized in that, the elemental metals powder be in palladium powder, cobalt powder or nickel powder one or more.
7. the isomerization method of 2-methyl-3 crotononitrile according to claim 1, is characterized in that, the three valent phosphors ester ligand is formula P(OR)
3, wherein, R band aromatic yl group or alkyl group.
8. the isomerization method of 2-methyl-3 crotononitrile according to claim 7, it is characterized in that, in formula, R is phenyl, one or more in tolyl and ethylbenzene, p-methoxy-phenyl, ethoxyl phenenyl, phenyl ring derivatives group, ethyl, propyl group, butyl or the tertiary butyl.
9. the isomerization method of 2-methyl-3 crotononitrile according to claim 1, is characterized in that, temperature of reaction is 80～200 ℃; The time that intensification keeps is 2-9 hour.
10. the isomerization method of 2-methyl-3 crotononitrile according to claim 1, is characterized in that, reacts needed pressure and be the air pressure that system self produces or add rare gas element.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739516A (en) * | 2014-01-06 | 2014-04-23 | 重庆中平紫光科技发展有限公司 | Method for synthesizing adiponitrile by isomerization liquid of 2-methyl-3-crotononitrile |
| CN103804227A (en) * | 2014-02-17 | 2014-05-21 | 重庆中平紫光科技发展有限公司 | Method for synthesizing 2-methyl-2-butenenitrile through direct isomerization of alkene-nitrile mixed liquid |
| CN103804228A (en) * | 2014-02-17 | 2014-05-21 | 重庆中平紫光科技发展有限公司 | Method for synthesizing 3-pentenenitrile by direct isomerization of alkene-nitrile mixed liquid |
| CN113372209A (en) * | 2021-06-30 | 2021-09-10 | 上海烟草集团有限责任公司 | Synthesis method of megastigmatrienone |
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|---|---|---|---|---|
| US3536748A (en) * | 1965-11-23 | 1970-10-27 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles |
| US3676481A (en) * | 1970-06-29 | 1972-07-11 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles in the presence of certain metal salt and/or tri(hydrocarbyl)boron promoters |
| US3903120A (en) * | 1973-06-19 | 1975-09-02 | Du Pont | Preparation of zerovalent nickel complexes from elemental nickel |
-
2013
- 2013-08-16 CN CN201310360316.7A patent/CN103396340B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3536748A (en) * | 1965-11-23 | 1970-10-27 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles |
| US3676481A (en) * | 1970-06-29 | 1972-07-11 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles in the presence of certain metal salt and/or tri(hydrocarbyl)boron promoters |
| US3903120A (en) * | 1973-06-19 | 1975-09-02 | Du Pont | Preparation of zerovalent nickel complexes from elemental nickel |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739516A (en) * | 2014-01-06 | 2014-04-23 | 重庆中平紫光科技发展有限公司 | Method for synthesizing adiponitrile by isomerization liquid of 2-methyl-3-crotononitrile |
| CN103739516B (en) * | 2014-01-06 | 2016-04-27 | 重庆中平紫光科技发展有限公司 | A kind of method utilizing the isomerization liquid Adiponitrile of 2-methyl-3-crotononitrile |
| CN103804227A (en) * | 2014-02-17 | 2014-05-21 | 重庆中平紫光科技发展有限公司 | Method for synthesizing 2-methyl-2-butenenitrile through direct isomerization of alkene-nitrile mixed liquid |
| CN103804228A (en) * | 2014-02-17 | 2014-05-21 | 重庆中平紫光科技发展有限公司 | Method for synthesizing 3-pentenenitrile by direct isomerization of alkene-nitrile mixed liquid |
| CN103804227B (en) * | 2014-02-17 | 2016-02-10 | 重庆中平紫光科技发展有限公司 | A kind of method of alkene nitrile mixed solution By Direct Isomerization synthesis 2-methyl-2-butene nitrile |
| CN103804228B (en) * | 2014-02-17 | 2016-04-27 | 重庆中平紫光科技发展有限公司 | A kind of method of alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile |
| CN113372209A (en) * | 2021-06-30 | 2021-09-10 | 上海烟草集团有限责任公司 | Synthesis method of megastigmatrienone |
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Effective date of registration: 20210521 Address after: No.8 Huabei Road, chemical industrial park, Huantai Economic Development Zone, Zibo City, Shandong Province Patentee after: Shandong Haijiang Chemical Co.,Ltd. Address before: 256400 Maqiao industrial concentration area, Huantai County, Zibo City, Shandong Province Patentee before: SHANDONG HAILI CHEMICAL INDUSTRY Co.,Ltd. |