CN103396340B - 2-methyl-3-butenenitrile isomerization method - Google Patents
2-methyl-3-butenenitrile isomerization method Download PDFInfo
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- CN103396340B CN103396340B CN201310360316.7A CN201310360316A CN103396340B CN 103396340 B CN103396340 B CN 103396340B CN 201310360316 A CN201310360316 A CN 201310360316A CN 103396340 B CN103396340 B CN 103396340B
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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 preparing adiponitrile, and can continue hydrocyanation is adiponitrile, and adiponitrile is nylon66 fiber intermediate.United States Patent (USP) 3676481(1972) be openly linear pentenenitrile technique with three organic borons and nickel complex acting in conjunction liquid-phase catalysis 2-methyl-3-crotononitrile; US Patent No. 3853948(1974), US4298546(1981) in succession disclose zero-valent nickel complexes catalyzer and excess ligand catalysis 2-methyl-3-crotononitrile isomery turns to linear alkene nitrile technique, but put into reaction system after all needing to prepare zero-valent nickel complexes and carry out catalyzed reaction.The open 2-methyl-3-crotononitrile isomery improved of Chinese patent 03136857.3 turns to non-annularity alkene nitrile technique, and method is a kind of (mentioning multiple bitooth ligand in literary composition) bitooth ligand of choosing and the mixing of cyclooctadiene nickel, first generates title complex; Or composition catalyst prepared by nickel salt, part and reductive agent, Lewis acid auxiliary agent is preferably coordinated to come into operation again, this processing disadvantages is that bitooth ligand cost is high, operates more difficult and cost is high, and does not have obvious advantage as this catalysts activity.
Summary of the invention
The object of the invention is, in order to overcome 2-methyl-3-crotononitrile isomerization process shortcoming, a kind of isomerization process of 2-methyl-3-crotononitrile of simplification to be provided, to be convenient to industrialization.
The isomerization method of 2-methyl-3 crotononitrile of improvement of the present invention, step is as follows:
By 2-methyl-3-crotononitrile and the mixing of three valent phosphors ester ligand, add elemental metals powder, pass into nitrogen gas stirring, keep for some time after intensification, liquid phase, solid state reaction catalyzed reaction obtain 2-methyl-3-crotononitrile isomery and turn to linear pentenenitrile.
Add chloride element auxiliary agent in the 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 elemental metals powder: 2-methyl-3-crotononitrile: three valent phosphors ester ligand is 1:10 ~ 1000:1 ~ 20.
Reaction Raw mol ratio is elemental metals powder: 2-methyl-3-crotononitrile: three valent phosphors ester ligand is 1:50 ~ 200:1 ~ 8.
Described elemental metals powder is one or more in palladium, cobalt or nickel, preferred nickel, if metal-powder partial oxidation or have oxide film, use after rupture of membranes drying, elemental metals powder dispersibility is good.
Described three valent phosphors ester ligand is formula P(OR)
3, wherein, R is with aromatic yl group or alkyl group, preferably containing 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 DEG C, preferably 100 ~ 170 DEG C, more selects 120 ~ 150 DEG C.
The time that described intensification keeps is 2-9 hour.
Pressure required for reaction is the air pressure of system self generation or adds 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 flask mixing, deoxidation, elemental metals powder is added under oxygen free condition, with injecting chloride element auxiliary agent under liquid level, shake 1-3 minute, covers two plugs, nitrogen is kept to pass into the speed of 1 ~ 5ml/min, jog moves two-mouth bottle, adding reaction vessel stirring, keeping for some time namely to obtain product after heating up configuring reaction solution.
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 for subsequent use.
Compared with prior art, the present invention has following beneficial effect:
The isomerization method of 2-methyl-3 crotononitrile of the present invention, adopts the isomery of metal simple-substance powder and phosphorus ligand catalysis 2-methyl-3 crotononitrile to turn to linear 3 pentene nitrile, simplifies 2-methyl-3 crotononitrile isomery and turn to linear molecule isomerization reaction method.The method, without the need to another solubilizing agent, decreases Catalyst Preparation Procedures, reduces facility investment, reduces process costs, increase technology stability, have certain industrial value.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.But range of application is not limited only to embodiment below.
In the following example, 2-methyl-3-crotononitrile material purity is 70%, and all the other impurity are linear pentenenitrile and trace 2-methyl-2-butene nitrile.
Three valent phosphors ester ligand is homemade, adopts PCl
3be with aromatic yl group or alkyl group reaction with R, underpressure distillation collects out the cut of 180 DEG C ~ 240 DEG C.The PCl used
3for Tianjin recovery SILVER REAGENT.
Transformation efficiency and selectivity adopt gas-chromatography (Shimadzu-GC2014C) method, analyze all nitriles, and because raw material and product are isomerss, therefore transformation efficiency calculates gained according to chromatogram Raw, product area change.
Embodiment 1
By ready room temperature three valent phosphors ester ligand P(OC
6h
4cH
3)
354.91g and 41.5g room temperature 2-methyl-3-crotononitrile, is mixing with two mouthfuls of 200ml reaction flasks, deoxidation.Put into an anaerobic glove box operation and add 2g nickel powder, under liquid level, inject 200ppmPCl with entry needle
3, shake 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 for subsequent use.Reactor connects nitrogen tube, after nitrogen replacement, open still upper flange charging opening, keep nitrogen to pass into the speed of 1ml/min, the now nitrogen of two bottles of one end connection pressure-fireds, the other end connects charging opening and opens clip, jog moves two-mouth bottle, adding still stirring, reducing nickel powder as far as possible and sticking to a bottle wall configuring reaction solution.Reactor rises to 100 DEG C from room temperature, and keeps 3h.Reaction result is as table 1.
Embodiment 2
By ready room temperature three valent phosphors ester ligand P(OC
6h
5)
3105g and 290.5g room temperature 2-methyl-3-crotononitrile, is mixing with two mouthfuls of 200ml reaction flasks, deoxidation.Put into an anaerobic glove box operation and add 2g cobalt powder, under liquid level, inject 500ppmNiCl with entry needle
2, shake 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 for subsequent use.Reactor connects nitrogen tube, after nitrogen replacement, open still upper flange charging opening, keep nitrogen to pass into the speed of 3ml/min, the now nitrogen of two bottles of one end connection pressure-fireds, the other end connects charging opening and opens clip, jog moves two-mouth bottle, adding still stirring, reducing nickel powder as far as possible and sticking to a bottle wall configuring reaction solution.Reactor rises to 130 DEG C from room temperature, and keeps 7h.Reaction result is as table 1.
Embodiment 3
By ready room temperature three valent phosphors ester ligand P(OC
4h
9)
3117g and 539g room temperature 2-methyl-3-crotononitrile, is mixing with two mouthfuls of 200ml reaction flasks, deoxidation.Put into an anaerobic glove box operation and add 4g palladium powder, under liquid level, inject 1000ppmFeCl with entry needle
3, shake 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 for subsequent use.Reactor connects nitrogen tube, after nitrogen replacement, open still upper flange charging opening, keep nitrogen to pass into the speed of 4ml/min, the now nitrogen of two bottles of one end connection pressure-fireds, the other end connects charging opening and opens clip, jog moves two-mouth bottle, adding still stirring, reducing nickel powder as far as possible and sticking to a bottle wall configuring reaction solution.Reactor rises to 80 DEG C from room temperature, and keeps 9h.Reaction result is as table 1.
Embodiment 4
By ready room temperature three valent phosphors ester ligand P(OC
6h
5cH
3)
3240g and 1400g room temperature 2-methyl-3-crotononitrile, is mixing with two mouthfuls of 200ml reaction flasks, deoxidation.Put into an anaerobic glove box operation and add 2g nickel powder, under liquid level, inject 500ppmZnCl with entry needle
2, shake 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 for subsequent use.Reactor connects nitrogen tube, after nitrogen replacement, open still upper flange charging opening, keep nitrogen to pass into the speed of 5ml/min, the now nitrogen of two bottles of one end connection pressure-fireds, the other end connects charging opening and opens clip, jog moves two-mouth bottle, adding still stirring, reducing nickel powder as far as possible and sticking to a bottle wall configuring reaction solution.Reactor rises to 200 DEG C from room temperature, and keeps 2h.Reaction result is 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 (1)
1. an isomerization method for 2-methyl-3 crotononitrile, it is characterized in that, step is as follows:
By ready room temperature three valent phosphors ester ligand P(OC
6h
5)
3105g and 290.5g room temperature 2-methyl-3-crotononitrile, is mixing with two mouthfuls of 200ml reaction flasks, deoxidation, puts into an anaerobic glove box operation and adds 2g cobalt powder, inject 500ppmNiCl with entry needle under liquid level
2, shake 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 for subsequent use; Reactor connects nitrogen tube, after nitrogen replacement, open still upper flange charging opening, keep nitrogen to pass into the speed of 3ml/min, the now nitrogen of two bottles of one end connection pressure-fireds, the other end connects charging opening and opens clip, and jog moves two-mouth bottle, still stirring is added configuring reaction solution, reduce nickel powder as far as possible and stick to a bottle wall, reactor rises to 130 DEG C from room temperature, and keeps 7h;
Three valent phosphors ester ligand is homemade, adopts PCl
3and phenol, underpressure distillation collects out the cut of 180 DEG C ~ 240 DEG C, the PCl of use
3for Tianjin recovery SILVER REAGENT.
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| 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 |
| 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 |
| 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 |
| CN113372209B (en) * | 2021-06-30 | 2022-09-13 | 上海烟草集团有限责任公司 | Synthesis method of megastigmatrienone |
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 |
-
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 |
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