CN106975519A - The method for preparing the antigravity system for hydrocyanation and isomerization - Google Patents
The method for preparing the antigravity system for hydrocyanation and isomerization Download PDFInfo
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- CN106975519A CN106975519A CN201610842855.8A CN201610842855A CN106975519A CN 106975519 A CN106975519 A CN 106975519A CN 201610842855 A CN201610842855 A CN 201610842855A CN 106975519 A CN106975519 A CN 106975519A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
- C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/322—Hydrocyanation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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Abstract
The present invention discloses a kind of method for preparing the antigravity system for hydrocyanation butadiene or one or more monoolefine mononitriles, and methods described, which is included, makes metallic nickel, at least one double tooth organophosphor ligands and at least one formula P (XaRa)(XbRb)(XcRc) compound reaction in single step in the presence of liquid diluent；Wherein Xa、XbAnd XcRespectively it independently is oxygen or singly-bound；And wherein Ra、RbAnd RcRespectively it independently is the alkyl with 1 to 10 carbon atoms or the aryl with 1 to 20 carbon atoms.
Description
Technical field
The present invention relates to the method for the antigravity system for producing the hydrocyanation for butadiene or allyl acetonitrile.More properly
Say, the present invention also relates to be used for the hydrocyanation of butadiene or allyl acetonitrile using the antigravity system prepared in one-step reaction, and
Method for 2- methyl -3- butene nitriles to be isomerized into 3 pentene nitrile.
Background technology
The hydrocyanation catalyst system of the known hydrocyanation for being specifically used for butadiene or allyl acetonitrile in art.Definitely
Say, it is adaptable to which the hydrocyanation of 1,3-butadiene is to form system of the follow-up hydrocyanation of allyl acetonitrile and allyl acetonitrile to form adiponitrile
It is commercially known in important nylon synthesis field.
Such hydrocyanation reaction is complexed in the zero-valent nickel catalyst with single tooth or double tooth organophosphor ligands, such as phosphite ester
Carried out in the presence of thing.There are the various methods for becoming known for preparing the zero valent nickel complex with single tooth organophosphor ligand, including
It is described in those in US 3,903,120 and US 4,416,825.In US 3,903,120, Ni [P (OAr)3]4Type complex compound
By making elemental nickel and list tooth part P (OAr)3At a temperature in the range of 0 DEG C to 150 DEG C, containing list as catalyst
React and prepare in the presence of the halogen of the derivative of tooth part.US 4,416,825 is described by the amount control relative to single tooth part
Reaction temperature processed and reacted and prepared comprising having single tooth organophosphor in the presence of chlorion and organic nitrile (such as adiponitrile)
The continuation method of the hydrocyanation catalyst of the zero valent nickel complex of part.
There are some nickel catalysis that can be used for manufacture with single tooth and double tooth organophosphor ligands (exactly phosphite ester)
The method of agent complex compound.A kind of method is double (1,5- the cyclo-octadiene) [Ni (COD) of nickel2] anti-with organic phosphite part
Should.But, the method is due to Ni (COD)2High cost and be poorly efficient and uneconomic and therefore can not be in commercial size
Upper production.Another method is using Dehydrated nickel chloride and in-situ reducing of the zinc metal in the presence of organic phosphite part.This
Program is effective for single tooth and double tooth organic phosphite parts, but causes one mole of the nickel complex formation of every mole of formation
Zinc chloride.Method is also difficult to carry out in business method, because it needs accurate measurement to go out to enter two kinds of solids of reactor, and
Dehydrated nickel chloride is not easy to obtain on a commercial scale.
The another way for preparing the Raney nickel complex compound with organic phosphite part is using catalytic amount
Ar2PCl make the nickel by powder of fine crushing directly with organic phosphite ligand reaction, wherein Ar is aryloxy, such as cresols, such as
Disclosed in US 3,847,959.The method is effective for single tooth organic phosphite part using commercially available nickel by powder,
But it is not useable for preparing double tooth zero-valent nickel organic phosphite complex compounds due to lacking reactivity.
US 8,815,186 is open directly to prepare double tooth zeroth order organic phosphorous acid Raney nickel complex compounds from nickel metal powder.
But, nickel metal powder must be prepared by wherein disclosed ad hoc approach.One shortcoming of the method is anti-using height for it
Answering property spontaneous combustion nickel by powder, the powder must be disposed in the case of in the absence of oxygen.In addition, it is necessary to such as ZnCl2Louis
Acid is to be reacted, if catalyst is used subsequently to the hydrocyanation of butadiene or 2- methyl -3- butene nitriles is isomerized to 3- penta
Alkene nitrile, then the acid of trace is harmful.
The another method for preparing double tooth zeroth order organic phosphorous acid Raney nickel complex compounds is EP 1 414 567 theme, institute
State the two-stage process that patent description prepares the double teeth of mixing and single tooth zeroth order organic phosphorous acid Raney nickel complex compound.Method is comprising extremely
Few two steps.First, zero-valent nickel and P (OR)3(wherein " R " is organic group) reacts to form the first system.Then, in second step
In, the first system with double tooth organic phosphite ligand reactions with produce including single tooth material (i.e. comprising with single P (OR)3
The catalyst of the nickel of complexing) and double tooth material (i.e. comprising only with double tooth organic phosphite parts or P (OR)3It is organic with double teeth
Phosphite ester ligand mixture complexing nickel catalyst) zeroth order organic phosphorous acid Raney nickel complex compound.This two-step method
Having the shortcomings that can not be commercial, because catalyst complex can not possibly be reclaimed in single standard extraction procedures for further
Use.Recovery reuses most important in continuation method and is economically for reusing in business method for catalyst
It is required.In addition, it would be desirable to separated before catalyst synthesis step is repeated single tooth material (i.e. comprising with single P (OR)3Network
The catalyst of the nickel of conjunction) and double tooth material (i.e. comprising only with double tooth organic phosphite parts or P (OR)3With the organic Asia of double teeth
The catalyst of the nickel of the mixture complexing of phosphate part) to repeat two-stage process, it is by extremely difficult (even if not can not possibly).
EP 1 414 567 also discloses a kind of method, wherein Ni (COD)2, between phosphorous acid/toluene ester and double tooth organic phosphites are matched somebody with somebody
Body reacts in single step.One-step program is by Ni (COD)2Shortcoming described above too expensive is stranded for commercial mass production
Disturb.
An object of the invention is to solve one or more in these problems.
As used herein, the term " single tooth " used on organophosphor ligand means that having one can form with single nickle atom
Close with the part for the phosphorus atoms for forming nickel complex.
As used herein, the term " double teeth " used on organophosphor ligand means that there are two to be associated with single nickle atom
With the part for the phosphorus atoms for forming nickel complex.
As used herein, term " phosphite ester " means to include the organophosphor for the trivalent phosphorus atoms for being attached to three oxygen atoms
Compound.
As used herein, term " phosphonous acid diester " means comprising the trivalent for being attached to two oxygen atoms and a carbon atom
The organic phosphorus compound of phosphorus atoms.
As used herein, term " phosphonous acid diester " means comprising the trivalent for being attached to an oxygen atom and two carbon atoms
The organic phosphorus compound of phosphorus atoms.
As used herein, term " phosphine " means to include the organophosphor chemical combination for the trivalent phosphorus atoms for being attached to three carbon atoms
Thing.
As used herein, term " tolyl " means at ortho position, meta or para position through methyl substituted phenyl.
As used herein, term "comprising" cover " comprising " and " by ... constitute " and " mainly by ... group
Into ", such as composition "comprising" X can only be made up of or may include additional component, such as X+Y X.
The content of the invention
According to the present invention, there is provided a kind of catalyst system prepared for hydrocyanation butadiene or one or more monoolefine mononitriles
The method of system, methods described, which is included, makes metallic nickel, at least one double tooth organophosphor ligands and at least one formula P (XaRa)(XbRb)
(XcRc) compound reaction in single step in the presence of liquid diluent；Wherein
Xa、XbAnd XcRespectively it independently is oxygen or singly-bound；And
Wherein Ra、RbAnd RcRespectively it independently is the alkyl with 1 to 10 carbon atoms or the virtue with 1 to 20 carbon atoms
Base.
According to another aspect of the present invention there is provided a kind of method for hydrocyanation butadiene, it is included：
I) by making metallic nickel, at least one double tooth organophosphor ligands and at least one formula P (XaRa)(XbRb)(XcRc) change
Compound reaction in single step in the presence of liquid diluent prepares antigravity system, wherein Xa、XbAnd XcRespectively it independently is oxygen or list
Key, and wherein Ra、RbAnd RcRespectively it independently is the alkyl with 1 to 10 carbon atoms or the aryl with 1 to 20 carbon atoms；
And
Ii butadiene is reacted with HCN in step i) in the presence of the antigravity system of preparation and include 3- amylenes to be formed
The mixture of nitrile and the butene nitrile of 2- methyl -3.
There is provided a kind of method for one or more monoolefine mononitriles of hydrocyanation, institute according to another aspect of the present invention
The method of stating is included：
I) by making metallic nickel, at least one double tooth organophosphor ligands and at least one formula P (XaRa)(XbRb)(XcRc) change
Compound reaction in single step in the presence of liquid diluent prepares antigravity system, wherein Xa、XbAnd XcRespectively it independently is oxygen or list
Key, and wherein Ra、RbAnd RcRespectively it independently is the alkyl with 1 to 10 carbon atoms or the aryl with 1 to 20 carbon atoms；
And
Ii one or more monoolefine mononitriles) are made to be reacted with HCN in step i) in the presence of the antigravity system of preparation with shape
Into the mixture comprising one or more dintrile.
It is used to 2- methyl -3- butene nitriles is isomerized to 3 pentene nitrile there is provided one kind according to another aspect of the present invention
Method, methods described includes：
I) by making metallic nickel, at least one double tooth organophosphor ligands and at least one formula P (XaRa)(XbRb)(XcRc) change
Compound reaction in single step in the presence of liquid diluent prepares antigravity system, wherein Xa、XbAnd XcRespectively it independently is oxygen or list
Key, and wherein Ra、RbAnd RcRespectively it independently is the alkyl with 1 to 10 carbon atoms or the aryl with 1 to 20 carbon atoms；
And
Ii) 2- methyl -3- butene nitriles are made to be isomerized to 3 pentene nitrile using the antigravity system prepared in step i).
Advantageously, commercially available nickel powder can be used to show in without art in known hydrocyanation reaction for one-step reaction
The selection rate shown is reduced and carried out in the case of resetting.For example, as shown in example, realized in the hydrocyanation of allyl acetonitrile
90% and Geng Gao selection rate.The combination of high selectivity and the ability originated using the readily available business nickel of low cost for
Business management provides notable benefit and advantage.The specific advantages of method can be readily adapted to commercial operation for it, because nickel is catalyzed
Agent complexing material can be operated by standard extraction to be reclaimed and simply reuses.Therefore, inexpensive initial substance and high selectivity
Advantage can be easily achieved on a commercial scale.
Advantageously, lewis acid (Lewis Acid) need not be used by preparing the method for antigravity system, such as zinc chloride.Fourth
The hydrocyanation or 2- methyl -3- butene nitriles of diene are isomerized to exist in 3 pentene nitrile lewis acid and promote to be harmful formed methyl
Glutaronitrile (MGN).Therefore, the antigravity system being prepared by the method for the present invention can be directly used for the hydrocyanation or 2- first of butadiene
Base -3- butene nitriles are isomerized in 3 pentene nitrile.Disclosed antigravity system and method can also be used for by adding formoxyl
(CHO) and hydrogen to carbon-to-carbon double bond (hydroformylation) from alkene manufacture aldehyde.
Brief description of the drawings
Fig. 1 illustrates for the cis- and trans- 3 pentene nitrile of hydrocyanation and allyl acetonitrile to prepare the continuation method of adiponitrile.
Embodiment
Need to make metallic nickel, double tooth organophosphor ligands and formula P (X for preparing the inventive method of antigravity systemaRa)
(XbRb)(XcRc) compound reaction in single step in the presence of liquid diluent.In this context, " single step " means metal
Nickel, double tooth organophosphor ligands and formula P (XaRa)(XbRb)(XcRc) compound is same in single container in the presence of liquid diluent
Shi Fanying.In other words, in the absence of the different step for adding reactant and in the absence of the progress for the reaction for forming antigravity system
In the individualized stage.
Monoolefine mononitrile is preferably chosen from allyl acetonitrile.It is preferred that allyl acetonitrile be selected from cis- and trans- 3 pentene nitrile and 4- amylenes
Nitrile.Antigravity system is further being used (such as hydrocyanation butadiene, for hydrocyanation monoolefine mononitrile and for making
In the step of 2- methyl -3- butene nitriles are isomerized to the inventive method of 3 pentene nitrile (ii)) before, antigravity system is preferably
Through filtering to remove metallic nickel, and nickel is not in complex form.Then, based on the amount through filtering nickel remaining in antigravity system
Calculate amount of the reagent relative to nickel.
The inventive method uses metallic nickel, preferably claims powdery form.Metallic nickel is preferably commercially available metallic nickel,
The types of INCO 123 such as produced by Vale Canada Limited.Ability using commercially available metallic nickel means the present invention
Method has advantage that is relatively inexpensive and simply carrying out.Metallic nickel is alternatively the height prepared by initial substance of alkaline carbonic acid nickel
The reactive nickel by powder of degree.The preparation of highly reactive property nickel by powder is described in A1, the US 8,815,186 of US 2011/0196168
In the B1 of B2, US 8,969,606 and the B2 of US 9,0240,49, it is incorporated herein in entirety by reference.
For example, highly reactive property nickel by powder can be by the TIB Chemicals A.G. alkaline carbons containing about 0.5% sulphur
It is prepared by sour nickel.Nickelous carbonate is calcined in flowing nitrogen, is then reduced in flowing hydrogen.Gained nickel by powder is spontaneous combustion, and not
It must allow to contact with oxygen-containing gas (such as air).Or, nickel source (such as nickel sulfate) mixed with the precipitating reagent aqueous solution of sodium carbonate with
The nickelous carbonate containing about 0.5% or less sulphur is produced, it is then calcined in flowing nitrogen, is then reduced in flowing hydrogen.
Or, sulphur can be added to through calcined oxide nickel or nickelous carbonate to produce the highly reactive property nickel powder containing about 0.5% or less sulphur
End.
The inventive method for preparing the antigravity system is carried out in the presence of liquid diluent.Liquid diluent can be alkene
Hydrocarbon unsaturated nitrile, preferably allyl acetonitrile, such as cis- 2- allyl acetonitriles, trans- 2- allyl acetonitriles, cis- 3 pentene nitrile, trans- 3 pentene nitrile, 4-
Allyl acetonitrile, 2- methyl -3- butene nitriles, trans- 2- methyl-2-butenes nitrile, cis- 2- methyl-2-butenes nitrile.Liquid diluent is alternatively
Dintrile, such as adiponitrile or methyl cellosolve acetate glutaronitrile.Liquid diluent can also contain non-polar solven, such as aliphatic hydrocarbon, such as hexamethylene or
Aromatic hydrocarbon, such as benzene, toluene, ortho-xylene, meta-xylene, paraxylene.Liquid diluent can include chemical combination referred to above
The mixture of any one of thing.
In the method for preparing the antigravity system, using relative to metallic nickel preferably at least about 4 molar equivalents, excellent
Selection of land at least about 5 molar equivalents, preferably no more than about 30 molar equivalents, preferably no more than about 15 molar equivalents, preferably
P (the X of no more than about 10 molar equivalentsaRa)(XbRb)(XcRc)。
Preferably, using relative to metallic nickel at least about 1 molar equivalent, preferably at least about 2 molar equivalents, preferably extremely
Lack about 3 molar equivalents, preferably no more than about 13 molar equivalents, be preferably no more than about 8 molar equivalents, be preferably no more than about
Double tooth organophosphor ligands of 6 molar equivalents.
Suitably, the method for the antigravity system is prepared at least about 50 DEG C, at a temperature of preferably at least about 70 DEG C
Carry out.Suitably, temperature is no more than about 130 DEG C, preferably no more than about 110 DEG C.
Preferably, in the method for hydrocyanation butadiene of the present invention, butadiene and HCN reaction are at least about 50
DEG C, carried out at a temperature of preferably at least about 70 DEG C.Suitably, temperature is no more than about 180 DEG C, preferably no more than about 160 DEG C.
Suitably, using at least about 500 molar equivalents, preferably at least about 750 molar equivalents, and preferably no more than about 7000 moles
The butadiene Ni (0) of equivalent, preferably no more than about 3500 molar equivalents.Preferably, using relative to butadiene at least about 0.5
The HCN of molar equivalent, preferably at least about 0.85 molar equivalent, preferably no more than about 0.95 molar equivalent.Preferably, use
Relative to the HCN of the molar equivalent of butadiene about 0.90.
As described herein hydrocyanation and isomerization method suitably enter in conventional liquid diluent in the art
OK.
In the inventive method for hydrocyanation monoolefine mononitrile, for making monoolefine mononitrile with HCN by this hair
Monoolefine mononitrile in the step of being reacted in the presence of antigravity system prepared by bright method can be suitably for preparing glutaronitrile
3- butene nitriles, and/or for preparing the allyl acetonitrile of adiponitrile, such as cis- and trans- 3 pentene nitrile and allyl acetonitrile.Liquid diluting
Agent can be advantageously and identical with the monoolefine mononitrile that HCN reacts.Suitably, monoolefine mononitrile and HCN reaction are at least about 20
DEG C, carried out at a temperature of preferably at least about 40 DEG C.Suitably, temperature is no more than about 100 DEG C, preferably no more than about 80 DEG C.
Suitably, in monoolefine mononitrile and HCN reaction, using relative to Ni (0) at least about 500 molar equivalents, preferably at least
The monoolefine list of about 750 molar equivalents, preferably more than about 7000 molar equivalents, preferably no more than about 3500 molar equivalents
Nitrile.Using relative to monoolefine mononitrile preferably at least about 0.5 molar equivalent, preferably at least about 0.85 molar equivalent, preferably
Ground is no more than about the HCN of 0.95 molar equivalent.Preferably, using the HCN relative to the molar equivalent of monoolefine mononitrile about 0.90.
In the method for hydrocyanation monoolefine mononitrile of the present invention, monoolefine mononitrile is set to be urged with HCN in of the invention
The step of being reacted in the presence of agent system is carried out advantageously in the presence of at least one lewis acid.It is adapted to lewis acidic example
For inorganic or organo-metallic compound, its cationic, which is selected from, includes following group：Scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper,
Zinc, boron, aluminium, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium, lanthanum, europium, ytterbium, tantalum, samarium and tin.Preferably, at least one lewis acid be selected from by with
The group of lower composition：The combination of zinc chloride, frerrous chloride or zinc chloride and frerrous chloride.At least one lewis acid is preferably
It is anhydrous.Mol ratio for the lewis acid in method and Ni (0) is preferably at least about 0.9: 1, preferably no more than 1.1
∶1。
For making 2- methyl -3- butene nitriles be isomerized to this hair of 3 pentene nitrile in the presence of the antigravity system of the present invention
Bright method is suitably carried out at a temperature of at least about 80 DEG C, preferably at least about 100 DEG C.Preferably, temperature is no more than about 160
DEG C, preferably no more than about 140 DEG C.Preferably, using relative to Ni (0) at least about 500 molar equivalents, preferably at least about
2- methyl-the 3- of 750 molar equivalents, preferably no more than about 7000 molar equivalents, preferably no more than about 3500 molar equivalents
Butene nitrile.
The inventive method can be conducted batch-wise, but preferably, it is carried out with semicontinuous or continuation mode.Continuously or semi-continuously
In the case of method, operated for hydrocyanation and the inventive method of isomerization under continuous recycling catalyst loop, wherein nickel
Catalyst material extracts from hydrocyanation or isomerization reaction together with ligand substance and is recycled to the step of preparing antigravity system
In.
Extraction is carried out using known program in art.A kind of such procedure publication in US 3,773,809, its
It is incorporated herein in entirety by reference.Being adapted to solvent includes the fat with the boiling point in the range of about 30 DEG C to about 135 DEG C
Race's hydrocarbon.Typical linear aliphatic hydrocarbon solvent include pentane, n-hexane, normal heptane and normal octane and with about 30 DEG C to about
The respective branches chain hydrocarbon of boiling point in the range of 135 DEG C.Typical cyclic hydrocarbon solvents include pentamethylene, hexamethylene and cycloheptane and had
The corresponding alkyl substituted cyclic hydrocarbon of boiling point in the range of about 30 DEG C to about 135 DEG C.The mixed of straight chain and/or cyclic hydrocarbon solvents can be used
Compound.It is preferred that solvent include hexamethylene and hexahydrotoluene or its mixture.Extraction suitably at least about 10 DEG C, preferably
Carried out at a temperature of at least about 20 DEG C.100 DEG C are suitably no more than about, preferably no more than about 70 DEG C, is preferably no more than about
60℃.Preferably, the composition of the products stream in control extraction is to cause the ratio of dintrile and mononitrile to be less than about 0.35, preferably
About 0.3.It is preferred that ratio can by controlling transforming degree (if such reaction betide in ad hoc approach) of the mononitrile to dintrile,
Or by be manually introduced a certain amount of dintrile needed for reach the ratio of dintrile and mononitrile and realize.
Can be double tooth phosphite esters, double tooth phosphonous acid diester, the sub- phosphine of double teeth for double tooth organophosphors in the inventive method
Acid diesters or double tooth phosphines.
When double tooth organophosphor ligands are double tooth phosphite esters, double tooth phosphite esters can be selected from by Formulas I a, Formulas I b, formula
The one or more for the group that Ic, Formula VII, Formula VIII, Formula IX or Formula X are constituted：
Wherein in Formulas I a, Ib and Ic：
O-Z-O and O-Z1- O is each independently selected from the group being made up of formula II, III, IV, V and VI：
Wherein in Formula II and III：
R2、R3、R4、R5、R6、R7、R8And R9Independently selected from by H, C1To C12Alkyl and C1To C12The group of alkoxy composition
Group；X is O, S or CH (R10)；
R10For H or C1To C12Alkyl；
Wherein in formula IV and V：
R20And R30Independently selected from by H, C1To C12Alkyl and C1To C12Alkoxy and CO2R13The group of composition；
R13For C1To C12Alkyl or C6To C10Aryl, it is unsubstituted or through C1To C4Alkyl replaces；
W is O, S or CH (R14)；
R14For H or C1To C12Alkyl；
Wherein in Formula IV：
R15Selected from by H, C1To C12Alkyl and C1To C12Alkoxy and CO2R16The group of composition；R16For C1To C12Alkyl
Or C6To C10Aryl, it is unsubstituted or through C1To C4Alkyl replaces；
Wherein in Formulas I a, Ib and Ic：
R1To be unsubstituted or through one or more C1To C12Alkyl, C1To C12The benzene of alkoxy or formula A and B substituent group
Base, or-(CH2)nOY2, wherein n=1 to 4 and Y2Independently selected from cycloalkyl, aryl or C1To C18The group of alkyl；
Or R1To be unsubstituted or through one or more C1To C12Alkyl or C1To C12The naphthyl of alkoxy substitution, or-(CH2)nOY2, wherein n=1 to 4 and Y2Independently selected from cycloalkyl, aryl or C1To C18The group of alkyl；Or 5,6,7,8- tetrahydrochysene -1-
Naphthyl；Or formula A and B group
Wherein in formula A and B,
Y1Independently selected from H, cycloalkyl or aryl or C1To C18The group of alkyl；
Y3Independently selected from O or CH2Group,
Formula VII and VIII double tooth phosphite esters are：
Wherein,
R41And R45Independently selected from by C1To C5The group of alkyl composition, and R42、R43、R44、R46、R47、R48And R49In
Each is independently selected from by H and C1To C4The group of alkyl composition；
Or wherein
R41For methyl, ethyl, isopropyl or cyclopenta；
R42For H or methyl；
R43For H or C1To C4Alkyl；
R44For H or methyl；
R45For methyl, ethyl or isopropyl；And
R46、R47、R48And R49Independently selected from by H and C1To C4The group of alkyl composition；
Or wherein
R41、R44And R45For methyl；
R42、R46、R47、R48And R49For H；And
R43For C1To C4Alkyl；
Or wherein
R41For isopropyl；
R42For H；
R43For C1To C4Alkyl；
R44For H or methyl；
R45For methyl or ethyl；
R46、R48And R49For H or methyl；And
R47For H, methyl or the tert-butyl group；
Or wherein
R41For isopropyl or cyclopenta；
R45For methyl or isopropyl；And
R46、R47、R48And R49For H；
Or wherein R41For isopropyl；R42、R46、R48And R49For H；And R43、R44、R45And R47For methyl.
Formula IX and X double tooth phosphite esters are：
Wherein R17For isopropyl, R18For hydrogen, and R19For methyl；
Wherein R50For methyl, R51For methyl, and R52For hydrogen.
It is available for specific pair of tooth phosphite ester ligand in the inventive method：
Formula P (X in for the inventive methodaRa)(XbRb)(XcRc) in compound, Xa、XbAnd XcRespectively it independently is oxygen
Or singly-bound and Ra、RbAnd RcRespectively it independently is the alkyl with 1 to 10 carbon atoms or the aryl with 1 to 20 carbon atoms.No
With formula P (XaRa)(XbRb)(XcRc) compound mixture or single formula P (XaRa)(XbRb)(XcRc) compound can be used for this
In inventive method.
For example, formula P (XaRa)(XbRb)(XcRc) compound can be formula P (Ra)(Rb)(Rc) phosphine；Formula P (ORa)(Rb)
(Rc)、P(Ra)(ORb)(Rc) or P (Ra)(Rb)(ORc) phosphonous acid diester；Formula P (Ra)(ORb)(ORc)、P(ORa)(Rb)(ORc)
Or P (ORa)(ORb)(Rc) phosphonous acid diester；Or formula P (ORa)(ORb)(ORc) phosphite ester.Preferably, formula P (XaRa)
(XbRb)(XcRc) compound be formula P (ORa)(ORb)(ORc) phosphite ester.
It is suitable for Ra、RbAnd RcAlkyl for methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl and
The tert-butyl group.
It is suitable for Ra、RbAnd RcAryl for phenyl, o-tolyl, a tolyl, p-methylphenyl, 1- naphthyls, 2- naphthyls,
1,1 '-xenol, 1,1 '-bis--beta naphthal.
Preferably, every Ra、RbAnd RcSelect the group of free phenyl, o-tolyl, a tolyl and p-methylphenyl composition.
It is highly preferred that every Ra、RbAnd RcSelect the group of free phenyl, a tolyl and p-methylphenyl composition.In a preferred method, P
(XaRa)(XbRb)(XcRc) it is formula P (ORa)(ORb)(ORc) phosphite ester and every Ra、RbAnd RcSelect free phenyl, a toluene
The group of base and p-methylphenyl composition.Accordingly, it is preferred that P (XaRa)(XbRb)(XcRc) it is following formula: compound：
P (O- o-tolyls)w(tolyl between O-)x(O- p-methylphenyls)y(O- phenyl)z
Wherein w, x, y and z are 0 or 1 to 3 integer, and w+x+y+z=3.Preferably, w=0.In single x, y or z
One is preferably 3, and the other two in x, y or z is 0.Therefore, especially preferred formula P (XaRa)(XbRb)(XcRc) chemical combination
Thing is P (tolyl between O-)3P (O- p-methylphenyls)3With P (O- phenyl)3。
Suitably, for the formula P (X in the inventive methodaRa)(XbRb)(XcRc) compound can be selected from consisting of
Group one or more：P (O- o-tolyls) (O- phenyl)2, P (tolyl between O-) (O- phenyl)2, P (O- p-methylphenyls)
(O- phenyl)2, P (O- o-tolyls) (tolyl between O-) (O- phenyl), P (O- o-tolyls) (O- p-methylphenyls) (O- benzene
Base), P (tolyl between O-) (O- p-methylphenyls) (O- phenyl), P (O- o-tolyls)2(tolyl between O-), P (O- neighbour's toluene
Base)2(O- p-methylphenyls), P (O- o-tolyls)2(O- phenyl), P (O- p-methylphenyls)2(tolyl between O-), (O- is to toluene by P
Base)2(O- o-tolyls), P (O- p-methylphenyls)2(O- phenyl), P (tolyl between O-)2(O- o-tolyls), P (toluene between O-
Base)2(O- p-methylphenyls), P (tolyl between O-)2(O- phenyl), P (tolyl between O-)3, P (O- p-methylphenyls)3With P (O- benzene
Base)3, P (O- o-tolyls)3.Preferably, formula P (XaRa)(XbRb)(XcRc) compound can be selected from the group consisted of
- or many persons：P (tolyl between O-) (O- phenyl)2, P (O- p-methylphenyls) (O- phenyl)2, (O- is to toluene by P (tolyl between O-)
Base) (O- phenyl), P (O- p-methylphenyls)2(tolyl between O-), P (O- p-methylphenyls)2(O- phenyl), P (tolyl between O-)2
(O- p-methylphenyls), P (tolyl between O-)2(O- phenyl), P (tolyl between O-)3, P (O- p-methylphenyls)3With P (O- phenyl)3。
For example, two kinds of formula P (X can be used with least about 1: 4, preferably at least about 1: 2 ratioaRa)(XbRb)
(XcRc) compound.Preferably no more than about 4: 1, preferably no more than about 2: 1.Suitably, using P (tolyl between O-)3And P
(O- p-methylphenyls)3Mixture.Preferably, mixture is used with least about 1: 4, preferably at least about 1: 2 this rate.It is preferred that
Ground is no more than about 4: 1, and preferably no more than about 2: 1.
For preparing the inventive method of antigravity system preferably in catalytic amount selected from the group consisted of
Carried out in the presence of compound：P(XaRa)2Cl、P(XaRa)Cl2Or its mixture, wherein XaAnd RaAs hereinbefore defined.Formula P
(XaRa)2Cl and P (XaRa)Cl2Compound serve as P (XaRa)(XbRb)(XcRc) catalyst with the reaction of metallic nickel.It is suitable
Locality, (ppm based on the weight of whole antigravity system is measured as using at least about 50ppm, about preferably at least 200ppm
Chlorine) P (XaRa)2Cl、P(XaRa)Cl2Or its mixture.Suitably, about 500ppm is used no more than, preferably no more than about
300ppm。
The antigravity system being prepared by the method for the present invention includes active nickel catalyst material, and it includes Ni, and (double teeth are organic
Phosphorus part)2With mixed-ligand complex Ni (P (XaRa)(XbRb)(XcRc))x(double tooth organophosphor ligands), wherein x=1 or 2.This
A little active nickel materials dissolve in in the liquid diluent in the inventive method and therefore its exist can be by measurement from urging
The measurement of the dissolving Ni (0) in system after the unreacted metallic nickel powder of agent system filtering is determined.
Fig. 1 illustrates for the cis- and trans- 3 pentene nitrile of hydrocyanation and allyl acetonitrile to prepare the continuation method of adiponitrile.Urge
Agent system is following to be prepared in single step：By adding the type nickel metals of INCO 123 produced by Vale Canada Limited
Stirring 3 pentene nitrile of the powder (1) into reactor A at 90 DEG C, together with ligand 1, with front three phenyl ester between 2.0 phosphorous acid：It is sub-
Phosphoric acid is front three phenyl ester the phosphorous acid of front three phenyl ester mol ratio and phosphorous acid to the mixture of front three phenyl ester and the bag of catalytic amount
Chloride phosphorous acid two (tolyl) ester, (p-methylphenyl) ester of torak acid two and torak are sour (tolyl) (p-methylphenyl)
(TPP) of ester2PCl mixture.
Antigravity system is subsequently passed through filter B, wherein unreacted nickel metal powder is filtered off antigravity system and company
With fresh nickel metal powder (1) reactor A is returned in continuous catalyst system preparation process via stream (2).
Through after filter B, antigravity system is transferred to reactor C via stream 3, and cis- and trans- 3- is carried out wherein
The hydrocyanation of allyl acetonitrile and allyl acetonitrile.Mixture containing cis- and trans- 3 pentene nitrile and allyl acetonitrile is via stream (4) addition
And HCN is added via stream (5).Reactor content is stirred under atmospheric pressure at a temperature of 100 DEG C.
Product stream (6) is transferred to the extraction column D containing hexahydrotoluene.Raney nickel and free ligand extracting substances are to first
In butylcyclohexane phase, it is transferred to distillation column E via stream (9).In distillation column E, hexahydrotoluene is removed and passed through from column top
It is transferred back to by flowing (8) in extraction column D.Raney nickel and free ligand material are removed from post E bottoms and are transferred to via stream (10)
It is used to antigravity system in reactor A regenerate.
Flow (7) and contain adiponitrile product.
The isomerization of the hydrocyanation of butadiene and 2- methyl -3- butene nitriles almost consistent mode can be carried out.Butadiene
Or 2- methyl -3- butene nitriles are added to reactor (C) via stream (4), do not add in the case of 2- methyl -3- butene nitrile isomerization
Plus HCN, but add cis- and trans- 3 pentene nitrile and allyl acetonitrile.
The present invention is further illustrated by following non-limitative illustration example.The scope of the present invention is by appended claims
Book is defined.
For the Raney nickel source in experiment
The nickel metal powder in two kinds of sources is used to prepare nickel (0) catalyst complex described in example below.
First nickel is the nickel by powder of INCO 123 produced by Vale Canada Limited.This is by Vale
The commercially available level nickel by powder of CanadaLimited productions.This nickel will be referred to as nickel 1 in example below.
Second nickel is the special nickel powder prepared by initial substance of alkaline carbonic acid nickel.The preparation of nickel by powder is with it as anti-
Answer thing and be described in US 2011/0196168 A1, US 8,815,186 B2, US to prepare the purposes of phosphorous acid nickel (0) catalyst
In 8,969,606 B1 and the B2 of US 9,0240,49, it is incorporated herein in entirety by reference.This nickel metal powder has shown
Show with this much higher reaction rate with double tooth phosphite ester ligands of nickel of INCO 123.Make for preparing in present example
The nickel of special nickel powder is TIB Chemicals A.G. alkaline carbonic acid nickel, and it contains about 0.5% sulphur.Nickelous carbonate is in flowing
Calcine 1 hour, then reduced two hours at a temperature of 325 DEG C in flowing hydrogen at a temperature of 350 DEG C in nitrogen.Gained
Nickel by powder is spontaneous combustion, and must not allow to contact with oxygen-containing gas (such as air).This nickel will be referred to as nickel 2 in example below.
For the phosphite ester ligand in experiment
Single tooth phosphite ester (i.e. formula P (X in exampleaRa)(XbRb)(XcRc) compound) it is tricresyl phosphite
(TPP).It is with front three phenyl ester between 2.0 phosphorous acid for the specific T PP reagents in following instance: phosphorous acid is to front three phenyl ester
The mixture of front three phenyl ester and phosphorous acid to front three phenyl ester between the phosphorous acid of mol ratio.Reagent is also containing on a small quantity comprising torak acid
Two (tolyl) esters, (TPP) of torak acid two (p-methylphenyl) ester2PCl mixture, it is served as between phosphorous acid three
The catalyst of toluene ester and phosphorous acid to the reaction of front three phenyl ester and nickel metal powder.
Two kinds of double tooth phosphite ester ligands are used in example.First pair of tooth part is referred to as ligand 1：
Second pair of tooth part is referred to as part 2：
For the abbreviation in example：
The trans- 2- methyl-2-butenes nitriles of T2M2BN
2M3BN 2- methyl -3- butene nitriles
3PN 3 pentene nitriles
The cis- 2- allyl acetonitriles of C2PN
The cis- 2- methyl-2-butenes nitriles of C2M2BN
The trans- 2- allyl acetonitriles of T2PN
The trans- 3 pentene nitriles of T3PN
4PN allyl acetonitriles
The cis- 3 pentene nitriles of C3PN
MGN methyl cellosolve acetate glutaronitriles
ADN adiponitriles
Analysis method
Scope and application
Method is applied to determine dintrile (DN) and allyl acetonitrile (PN).
Principle
Component is separated by capillary gas chromatography.Use two kinds of internal standards：Cyclohexanone for PN and pungent two for DN
Nitrile is to realize preferable group method accuracy and precision.(FID) is detected using flame ionization to detect the component of separation.Use
EZChrom Elite data systems are integrated.
Sensitivity, precision and accuracy
Sensitivity：
Now not yet determine the detectable limit (LOD) or quantitation limit (LOQ) of all components.The calibrated scope of application exists
Listed in calibrated section.
Accuracy：
Accuracy by multiple injection QC (QC is Quality control samples, wherein the concentration of main constituent is known) and
ADN adjusts sample and determined.
| C2PN | VN* | T3PN | MGN | ADN | |
| QC-1 | 10.60 | 3.67 | 17.14 | 5.04 | 31.54 |
| QC-2 | 10.58 | 3.67 | 17.14 | 5.048 | 31.53 |
| QC-3 | 10.60 | 3.67 | 17.15 | 5.048 | 31.54 |
| Average value | 10.59 | 3.67 | 17.14 | 5.04 | 31.54 |
| Theoretical value | 10.61 | 3.68 | 16.57 | 4.94 | 30.90 |
| Error % | -0.16 | -0.21 | 3.44 | 2.00 | 2.06 |
* VN=valeronitriles
| ADN is adjusted | |
| ADN adjusts sample #1 | 100.44 |
| ADN adjusts sample #2 | 100.51 |
| ADN adjusts sample #3 | 100.32 |
| Average value | 100.42 |
| Theoretical value | 99.99 |
| Error % | 0.44 |
Precision：
Precision is adjusted sample by multiple injection QC and ADN and determined.
| C2PN | VN | T3PN | MGN | ADN | |
| QC-1 | 10.60 | 3.67 | 17.14 | 5.04 | 31.54 |
| QC-2 | 10.58 | 3.67 | 17.14 | 5.04 | 31.53 |
| QC-3 | 10.60 | 3.67 | 17.15 | 5.04 | 31.54 |
| Average value | 10.59 | 3.67 | 17.14 | 5.04 | 31.54 |
| %RSD | 0.07 | 0.06 | 0.02 | 0.03 | 0.02 |
Equipment
Gas-chromatography：The II of HP 7890 series (or equivalent), be equipped with flame ionisation detector, capillary shunting/
Not split entry and automatic liquid sampler.
Capillary column：J＆W Scientific DB-23 (30m × 0.25mm I.D. × 0.25 μm), Agilent P/N
122-2332 (or equivalent).
2.0mL Autosampler screw cap vial Agilent P/N 5182-0864
0.2 μm of polypropylene syringe filter.
Metrohm 756KF coulometric titrations device (Coulometric Titrator) or equivalent-be directly injected into, without every
Membrane electrode.
AQUASTAR AQC34 KF coulometric titrations devices or equivalent-be directly injected into, burning infiltration electrode, for aldehyde and ketone.
Operating condition HP7890
EZChrom Elite data system methods：
NIR0004_PNDN_front_2012-10-07.met
Temperature
Inlet temperature： 250℃
Detector temperature： 300℃
50 DEG C of oven temperature
Baking oven program：
| Temperature program(me) | Speed (DEG C/Min) | Temperature (DEG C) | Hold time (min.) | Total time (min.) |
| 1 | 50 | 3 | 3 | |
| 2 | 5 | 80 | 0 | 9 |
| 3 | 40 | 210 | 6 | 18.25 |
| 4 | 50 | 240 | 9.15 | 28 |
Examples general
Example 1 (this compared with) display uses the manufacture Ni of nickel 2 [TTP]4The program of catalyst.
Example 2 shows the program that catalyst of the present invention is manufactured using nickel 2.
Example 3 (comparison) display makes 2M3BN be isomerized to T3PN program using the catalyst from example 1, and obtains
Result.
The display of example 4 makes 2M3BN be isomerized to T3PN program using the catalyst of the present invention from example 2, and obtains
Result.
The comparison of example 3 and 4 is shown provides much higher 2M3BN to T3PN's using catalyst of the present invention made from nickel 2
Conversion ratio.
Example 5 (comparison) display is used to be ADN program by T3PN hydrocyanations using the catalyst from example 1, and obtains
The result obtained.
The display of example 6 is used to be ADN program by T3PN hydrocyanations using the catalyst of the present invention from example 2, and obtains
The result obtained.
The comparison of example 5 and 6 is shown provides the much higher selection rate to ADN using catalyst of the present invention made from nickel 2
(92.5% relative to 75.3%).
Example 7 (comparison) display uses the manufacture Ni of nickel 1 [TTP]4The program of catalyst.
Example 8 shows the program that catalyst of the present invention is manufactured using nickel 1.
Example 9 (this compared with) display makes 2M3BN be isomerized to T3PN program using the catalyst from example 7, and obtains
Result.
The display of example 10 makes 2M3BN be isomerized to T3PN program using the catalyst of the present invention from example 8, and obtains
Result.
The comparison of example 9 and 10 is shown provides conversions of the much higher 2M3BN to T3PN using the catalyst of the present invention of nickel 1
Rate.
Example 11 (comparison) display is used to be ADN program by T3PN hydrocyanations using the catalyst from example 7, and obtains
The result obtained.
The display of example 12 is used to be ADN program by T3PN hydrocyanations using the catalyst of the present invention from example 8, and obtains
The result obtained.
The comparison of example 11 and 12 is shown provides the much higher selection rate to ADN using the catalyst of the present invention of nickel 1
(92.1% relative to 72.1%).
Example 13 is shown for manufacturing double tooth ligand catalysts using ligand 1 in the case of in the absence of TTP using nickel 2
Program.
Example 14 is shown for manufacturing double tooth ligand catalysts using ligand 1 in the case of in the absence of TTP using nickel 1
Program.
Example 13 and 14 shows the Ni (0) much lower compared to the concentration of example 1 and 2 carried out in the presence of TTP.
Example 15 shows the program that catalyst of the present invention is manufactured using part 2 and nickel 2.
Example 16 shows the program that catalyst of the present invention is manufactured using part 2 and nickel 1.
The display of example 17 uses the program that the catalyst from example 15 makes 2M3BN be isomerized to T3PN, and the knot obtained
Really.
The display of example 18 makes 2M3BN be isomerized to T3PN program using the catalyst of the present invention from example 16, and obtains
The result obtained.
The display of example 17 and 18 provides high conversions of the 2M3BN to T3PN using catalyst of the present invention made from part 2.
The display of example 19 is used for the program that T3PN hydrocyanations are ADN using the catalyst from example 15, and obtain
As a result.
The display of example 20 is used for the program that T3PN hydrocyanations are ADN using the catalyst of the present invention from example 16, and
The result of acquisition.
Example 19 and 20 shows the high selectivity to ADN using part 2.
Example 21 is shown for manufacturing double tooth phosphite ester ligands using part 2 in the case of in the absence of TTP using nickel 2
The program of catalyst.
Example 22 is shown for manufacturing double tooth phosphite ester ligands using part 2 in the case of in the absence of TTP using nickel 1
The program of catalyst.
Example 21 and 22 shows the Ni (0) much lower compared to the concentration of example 15 and 16 carried out in the presence of TTP.
Program and result
Example 1. prepares nickel (0) complex compound using nickel 2 and TTP
Following reactant is loaded to and is equipped with the 10mL of magnetic stirring bar bottles：4.0g TTP, 1.0g 3PN and 0.12g
Nickel 2.TTP mixtures contain [TTP] on a small quantity2PCl is to be catalyzed the reaction.Mixture is heated to 90 DEG C, and with continuous stirring
It is held in the temperature 24 hours.Sample then filters to remove unreacted nickel by powder under nitrogen atmosphere.Catalyst is complexed
The resulting solution of thing contains 78.6%TTP, 19.6%3PN and 1.94% solvable nickel (0), and with 6.7 TTP: Ni (0) mole
This.
Example 2：Nickel (0) complex compound is prepared using nickel 2, ligand 1 and TTP
Following reactant is loaded to and is equipped with the 10mL of magnetic stirring bar bottles：0.94g TTP、0.5g 3PN、1.06g
Ligand 1 mixture (it contains 61.8% ligand 1) and 0.027g nickel 2.Mixture is heated to 90 DEG C, and protects with continuous stirring
It is held in the temperature 24 hours.Sample then filters to remove unreacted nickel by powder under nitrogen atmosphere.Catalyst complex
Resulting solution contain 79.5% mixing phosphite ester ligand, the solvable nickel of 19.9%3PN and 0.64% (0), and have
10.2TTP/3.2 ligand 1s/1.0Ni (0) mol ratio.
Example 3：Catalyst using example 1 makes 2M3BN be isomerized to 3PN
Catalyst from example 1 is used to make 2M3BN be isomerized to 3PN.Raney nickel (the 0.036mmol of-molar equivalent
Ni (0)) mixed with the 2M3BN of 852 molar equivalents, and mixture is heated to 115 DEG C.In 0min, 60min and 150min autoreaction
Device obtains sample (0.2g) and analyzed.As a result directly display under：
| T2M2BN | 2M3BN | C2PN | C2M2BN | T2PN | T3PN | 4PN | C3PN | 3PN/2M3BN | |
| 0min | 6.47 | 61.64 | 14.96 | 1.25 | 0.13 | 15.08 | 0.13 | 0.33 | 0.25 |
| 60min | 6.55 | 59.88 | 14.99 | 1.28 | 0.14 | 16.68 | 0.15 | 0.34 | 0.28 |
| 150min | 6.59 | 57.76 | 14.99 | 1.31 | 0.17 | 18.68 | 0.15 | 0.36 | 0.33 |
These results show minimum increase (15.08% to 18.68%) of the 3PN concentration after 150min reactions.
Example 4：Catalyst using example 2 makes 2M3BN be isomerized to 3PN
Catalyst from example 2 is used to make 2M3BN be isomerized to 3PN.The Raney nickel of one molar equivalent
(0.037mmol Ni (0)) is mixed with the 2M3BN of 822 molar equivalents, and mixture is heated to 115 DEG C.In 0min, 60min and
150min autoreactors obtain sample (0.2g) and analyzed.As a result directly display under：
| T2M2BN | 2M3BN | C2PN | C2M2BN | T2PN | T3PN | 4PN | C3PN | 3PN/2M3BN | |
| 0min | 6.39 | 60.91 | 14.79 | 1.24 | 0.13 | 15.97 | 0.13 | 0.40 | 0.27 |
| 60min | 6.43 | 43.41 | 14.82 | 1.27 | 0.14 | 33.32 | 0.16 | 0.46 | 0.78 |
| 150min | 6.46 | 26.16 | 14.81 | 1.31 | 0.15 | 50.43 | 0.17 | 0.53 | 1.95 |
These results show the increase much bigger compared to example 1 after 150min reactions of 3PN concentration, and (15.97% arrives
50.43%) much higher catalyst activity, is indicated.
Example 5：Using example 1 catalyst by 3PN hydrocyanations be ADN
It is ADN that catalyst from example 1, which is used for 3PN hydrocyanations,.Raney nickel (the 0.0182mmol of-molar equivalent
Ni (0)) contain 1.05 molar equivalent ZnCl with 1291 molar equivalents23PN mixing.Mixture is heated to 55 DEG C, then adds
Ni in the 64 * valeronitrile solvents of molar equivalent HCN/ hours.After 20.4 hours, analytical reactions mixture, and obtain following tie
Really
| MGN | ADN | ADN selection rates |
| 5.9% | 17.9% | 75.3% |
MGN is the byproducts of 3PN hydrocyanations.
Example 6：Using example 2 catalyst by 3PN hydrocyanations be ADN
It is ADN that catalyst from example 2, which is used for 3PN hydrocyanations,.Raney nickel (the 0.0219mmol of-molar equivalent
Ni (0)) contain 0.99 molar equivalent ZnCl with 1342 molar equivalents23PN mixing.Mixture is heated to 55 DEG C, then adds
Ni in the 52 * valeronitrile solvents of molar equivalent HCN/ hours.After 25.9 hours, analytical reactions mixture, and obtain following tie
Really
| MGN | ADN | ADN selection rates |
| 3.3% | 40.6% | 92.5% |
These results show the selection rate (92.5%) to ADN much higher compared to (75.3%) obtained in example 5.
Example 7：Nickel (0) complex compound is prepared using nickel 1 and TTP
Following reactant is loaded to and is equipped with the 10mL of magnetic stirring bar bottles：1.97g TTP, 0.5g 3PN and
0.088g nickel 1.TTP contains [TTP] on a small quantity2PCl is to be catalyzed the reaction.Mixture is heated to 90 DEG C, and with continuous stirring
It is held in the temperature 24 hours.Sample then filters to remove unreacted nickel by powder under nitrogen atmosphere.Catalyst is complexed
The resulting solution of thing contains 78.23%TTP, 19.86%3PN and 1.91% solvable nickel (0), and is rubbed with 6.8 TTP: Ni (0)
You compare.
Example 8：Nickel (0) complex compound is prepared using nickel 1, ligand 1 and TTP
Following reactant is loaded to and is equipped with the 10mL of magnetic stirring bar bottles：1.02g TTP、0.51g 3PN、
1.00g ligand 1s mixture (it contains 61.8% ligand 1) and 0.058g nickel 1.Mixture is heated to 90 DEG C, and is continuously stirring
Mix down and be held in the temperature 24 hours.Sample then filters to remove unreacted nickel by powder under nitrogen atmosphere.Catalyst
The resulting solution of complex compound contains 79.24% mixing phosphite ester ligand, the solvable nickel of 20.01%3PN and 0.75% (0), and tool
There is 8.9TTP/2.6 ligand 1s/1.0Ni (0) mol ratio.
Example 9：Catalyst using example 7 makes 2M3BN be isomerized to 3PN
Catalyst from example 7 is used to make 2M3BN be isomerized to 3PN.Raney nickel (the 0.032mmol of-molar equivalent
Ni (0)) mixed with the 2M3BN of 905 molar equivalents, and mixture is heated to 115 DEG C.In 0min, 60min and 150min autoreaction
Device obtains sample (0.2g) and analyzed.As a result directly display under：
| T2M2BN | 2M3BN | C2PN | C2M2BN | T2PN | T3PN | 4PN | C3PN | 3PN/2M3BN | |
| 0min | 6.47 | 61.53 | 14.97 | 1.27 | 0.14 | 15.15 | 0.15 | 0.33 | 0.25 |
| 60min | 6.53 | 59.81 | 15.00 | 1.36 | 0.14 | 16.68 | 0.14 | 0.33 | 0.28 |
| 150min | 6.60 | 57.75 | 15.00 | 1.39 | 0.15 | 18.61 | 0.14 | 0.35 | 0.33 |
These results show minimum increase (15.15% to 18.61%) of the 3PN concentration after 150min reactions.It should note
Meaning, the result of this experiment is almost identical with example 3.Unique difference is that example 3 uses the catalyst prepared by nickel 2, and example 9 makes
With the catalyst prepared by nickel 1.
Example 10：Catalyst using example 8 makes 2M3BN be isomerized to 3PN
Catalyst from example 8 is used to make 2M3BN be isomerized to 3PN.The Raney nickel of one molar equivalent
(0.031mmol Ni (0)) is mixed with the 2M3BN of 884 molar equivalents, and mixture is heated to 115 DEG C.In 0min, 60min and
150min autoreactors obtain sample (0.2g) and analyzed.As a result directly display under：
| T2M2BN | 2M3BN | C2PN | C2M2BN | T2PN | T3PN | 4PN | C3PN | 3PN/2M3BN | |
| 0min | 6.43 | 61.13 | 14.84 | 1.26 | 0.14 | 15.97 | 0.15 | 0.39 | 0.26 |
| 60min | 6.44 | 45.54 | 14.86 | 1.29 | 0.14 | 31.15 | 0.15 | 0.43 | 0.69 |
| 150min | 6.46 | 27.87 | 14.86 | 1.32 | 0.15 | 48.69 | 0.16 | 0.50 | 1.77 |
These results show 3PN concentration 150min reaction after mutually this in the much bigger increase of example 9, (15.97% arrives
48.69%) much higher catalyst activity, is indicated.Result shown here is extremely similar with the result of example 4.Unique difference is
Example 4 is using the catalyst prepared by nickel 2, and example 10 uses the catalyst prepared by nickel 1.
Example 11：Using example 7 catalyst by 3PN hydrocyanations be ADN
It is ADN that catalyst from example 7, which is used for 3PN hydrocyanations,.Raney nickel (the 0.0252mmol of-molar equivalent
Ni (0)) contain 1.03 molar equivalent ZnCl with 1347 molar equivalents23PN mixing.Mixture is heated to 55 DEG C, then adds
Ni in the 79.2 * valeronitrile solvents of molar equivalent HCN/ hours.After 17 hours, analytical reactions mixture, and obtain following tie
Really
| MGN | ADN | ADN selection rates |
| 1.86% | 4.80% | 72.1% |
Example 12：Using example 8 catalyst by 3PN hydrocyanations be ADN
It is ADN that catalyst from example 8, which is used for 3PN hydrocyanations,.Raney nickel (the 0.0210mmol of-molar equivalent
Ni (0)) contain 0.97 molar equivalent ZnCl with 1399 molar equivalents23PN mixing.Mixture is heated to 55 DEG C, then adds
Ni in the 82.3 * valeronitrile solvents of molar equivalent HCN/ hours.After 17 hours, analytical reactions mixture, and obtain following tie
Really
| MGN | ADN | ADN selection rates |
| 2.88% | 33.5% | 92.1% |
This (72.1%) much higher selection rate to ADN obtained in example 11 of these results display phase
(92.1%).Result shown here is extremely similar with the result of example 6.Unique difference is that example 6 uses the catalysis prepared by nickel 2
Agent, and example 12 uses the catalyst prepared by nickel 1.
Example 13：Nickel (0) complex compound is prepared using single nickel 2 and ligand 1
Following reactant is loaded to and is equipped with the 10mL of magnetic stirring bar bottles：(it contains 0.95g ligand 1s mixture
61.8% ligand 1), 0.95g 3PN and 0.024g nickel 2.Mixture is heated to 90 DEG C, and is held in continuous stirring described
Temperature 24 hours.Sample then filters to remove unreacted nickel by powder under nitrogen atmosphere.The gained of catalyst complex is molten
Liquid contains 50.0% mixing phosphite ester ligand, the solvable nickel of 50.0%3PN and 0.016%.It is solvable compared to what is formed in example 2
The amount (0.64%) of nickel, forms few solvable nickel (0) complex compound (0.016%) in the case of in the absence of TTP in example 14.
Example 14：Nickel (0) complex compound is prepared using single nickel 1 and ligand 1
Following reactant is loaded to and is equipped with the 10mL of magnetic stirring bar bottles：(it contains 0.95g ligand 1s mixture
61.8% ligand 1), 0.95g 3PN and 0.024g nickel 1.Mixture is heated to 90 DEG C, and is held in continuous stirring described
Temperature 24 hours.Sample then filters to remove unreacted nickel by powder under nitrogen atmosphere.The gained of catalyst complex is molten
Liquid contains 50.0% mixing phosphite ester ligand, the solvable nickel of 50.0% 3PN and 0.0047%.What mutually this was formed in example 8 can
The amount (0.75%) of molten nickel, forms few solvable nickel (0) complex compound in the case of in the absence of TTP in example 14
(0.0047%).
Example 15：Nickel (0) complex compound is prepared using nickel 2, part 2 and TTP
Following reactant is loaded to and is equipped with the 10mL of magnetic stirring bar bottles：1.01g TTP、0.52g 3PN、
The mixture of 1.07g parts 2 and 0.026g nickel 2.Mixture is heated to 90 DEG C, and it is small to be held in the temperature 24 with continuous stirring
When.Sample then filters to remove unreacted nickel by powder under nitrogen atmosphere.The resulting solution of catalyst complex contains
79.6% mixing phosphite ester ligand, the solvable nickel of 19.9%3PN and 0.50%, and with 12.8TTP/5.5 parts 2/1.0Ni
(0) mol ratio.
Example 16：Nickel (0) complex compound is prepared using nickel 1, part 2 and TTP
Following reactant is loaded to and is equipped with the 10mL of magnetic stirring bar bottles：1.03gTTP、0.50g 3PN、1.06g
The mixture of part 2 and 0.049g nickel 1.Mixture is heated to 90 DEG C, and is held in the temperature with continuous stirring 24 hours.Sample
Product then filter to remove unreacted nickel by powder under nitrogen atmosphere.The resulting solution of catalyst complex contains 79.9% and mixed
Close phosphite ester ligand, the solvable nickel of 19.1% 3PN and 0.93%, and mole with 7.0TTP/2.9 parts 2/1.0Ni (0)
Than.
Example 17：Catalyst using example 15 makes 2M3BN be isomerized to 3PN
Catalyst from example 15 is used to make 2M3BN be isomerized to 3PN.The Raney nickel of one molar equivalent
(0.010mmol Ni (0)) is mixed with the 2M3BN of 788 molar equivalents, and mixture is heated to 115 DEG C.In 0min, 60min and
150min autoreactors obtain sample (0.2g) and analyzed.As a result directly display under：
| T2M2BN | 2M3BN | C2PN | C2M2BN | T2PN | T3PN | 4PN | C3PN | 3PN/2M3BN | |
| 0min | 6.38 | 60.64 | 14.73 | 1.26 | 0.15 | 15.92 | 0.29 | 0.63 | 0.28 |
| 60min | 6.45 | 35.43 | 14.72 | 1.41 | 0.16 | 40.71 | 0.32 | 0.80 | 1.18 |
| 150min | 6.51 | 16.86 | 14.68 | 1.53 | 0.19 | 58.86 | 0.34 | 1.03 | 3.57 |
These results, which are shown, provides the result similar with ligand 1 (example 4) using part 2.
Example 18：Catalyst using example 16 makes 2M3BN be isomerized to 3PN
Catalyst from example 16 is used to make 2M3BN be isomerized to 3PN.The Raney nickel of-molar equivalent
(0.018mmol Ni (0)) is mixed with the 2M3BN of 808 molar equivalents, and mixture is heated to 115 DEG C.In 0min, 60min and
150min autoreactors obtain sample (0.2g) and analyzed.As a result directly display under：
| T2M2BN | 2M3BN | C2PN | C2M2BN | T2PN | T3PN | 4PN | C3PN | 3PN/2M3BN | |
| 0min | 6.44 | 61.19 | 14.86 | 1.27 | 0.15 | 15.41 | 0.22 | 0.47 | 0.26 |
| 60min | 6.48 | 35.72 | 14.69 | 1.44 | 0.15 | 40.66 | 0.22 | 0.64 | 1.16 |
| 150min | 6.50 | 16.05 | 14.85 | 1.47 | 0.16 | 59.89 | 0.24 | 0.81 | 3.80 |
These results, which are shown, provides the result similar with ligand 1 (example 10) using part 2.
Example 19：Using example 15 catalyst by 3PN hydrocyanations be ADN
It is ADN that catalyst from example 15, which is used for 3PN hydrocyanations,.Raney nickel (the 0.0261mmol of-molar equivalent
Ni (0)) contain 0.99 molar equivalent ZnCl with 1309 molar equivalents23PN mixing.Mixture is heated to 55 DEG C, then adds
Ni in the 77.0 * valeronitrile solvents of molar equivalent HCN/ hours.After 17 hours, analytical reactions mixture, and obtain following tie
Really：
| MGN | ADN | ADN selection rates |
| 4.49% | 49.77% | 91.7% |
The result obtained in example 19 is extremely similar with the result in example 6 using ligand 1 acquisition.
Example 20：Using example 16 catalyst by 3PN hydrocyanations be ADN
It is ADN that catalyst from example 16, which is used for 3PN hydrocyanations,.Raney nickel (the 0.0322mmol of-molar equivalent
Ni (0)) contain 1.01 molar equivalent ZnCl with 1365 molar equivalents23PN mixing.Mixture is heated to 55 DEG C, then adds
Ni in the 80.3 * valeronitrile solvents of molar equivalent HCN/ hours.After 17 hours, analytical reactions mixture, and obtain following tie
Really
| MGN | ADN | ADN selection rates |
| 4.51% | 63.95% | 93.41% |
The result obtained in example 20 is extremely similar with the result in example 12 using ligand 1 acquisition.
Example 21：Nickel (0) complex compound is prepared using single nickel 2 and part 2
Following reactant is loaded to and is equipped with the 10mL of magnetic stirring bar bottles：2.0g parts 2,1.0g 3PN and
0.140g nickel 2.Mixture is heated to 90 DEG C, and is held in the temperature with continuous stirring 24 hours.Sample is then in nitrogen
Filter to remove unreacted nickel by powder under atmosphere.The resulting solution of catalyst complex, which contains 66.7% mixing phosphite ester, matches somebody with somebody
Body, the solvable nickel of 33.3%3PN and 0.0211% (0).Compared to the amount (0.50%) of the solvable nickel formed in example 15, do not depositing
Few solvable nickel (0) complex compound (0.0211%) is formed in example 21 in the case of TTP.
Example 22：Nickel (0) complex compound is prepared using single nickel 1 and part 2
Following reactant is loaded to and is equipped with the 10mL of magnetic stirring bar bottles：2.0g parts 2,1.0g 3PN and
0.142g nickel 1.Mixture is heated to 90 DEG C, and is held in the temperature with continuous stirring 24 hours.Sample is then in nitrogen
Filter to remove unreacted nickel by powder under atmosphere.The resulting solution of catalyst complex, which contains 66.7% mixing phosphite ester, matches somebody with somebody
Body, the solvable nickel of 33.3%3PN and 0.000%.Compared to the amount (0.90%) of the solvable nickel formed in example 16, in the absence of
Solvable nickel (0) complex compound (0.000%) is not formed in the case of TTP in example 22.
Claims (15)
1. a kind of method for preparing the antigravity system for hydrocyanation butadiene or one or more monoolefine mononitriles, methods described
Comprising making metallic nickel, at least one double tooth organophosphor ligands and at least one formula P (XaRa)(XbRb)(XcRc) compound is in liquid
Reacted in the presence of diluent in single step；Wherein
Xa、XbAnd XcRespectively it independently is oxygen or singly-bound；And
Wherein Ra、RbAnd RcRespectively it independently is the alkyl with 1 to 10 carbon atoms or the aryl with 1 to 20 carbon atoms.
2. according to the method described in claim 1, wherein the monoolefine mononitrile is or comprising one or more allyl acetonitriles.
3. a kind of method for hydrocyanation butadiene, it is included：
I) by making metallic nickel, at least one double tooth organophosphor ligands and at least one formula P (XaRa)(XbRb)(XcRc) compound
Reaction prepares antigravity system, wherein X in single step in the presence of liquid diluenta、XbAnd XcOxygen or singly-bound independently respectively are,
And wherein Ra、RbAnd RcRespectively it independently is the alkyl with 1 to 10 carbon atoms or the aryl with 1 to 20 carbon atoms；And
Ii) make to react in the presence of the antigravity system that butadiene and HCN prepared in step i) to be formed comprising 3 pentene nitrile and
The mixture of the butene nitrile of 2- methyl -3.
4. a kind of method for one or more monoolefine mononitriles of hydrocyanation, methods described is included：
I) by making metallic nickel, at least one double tooth organophosphor ligands and at least one formula P (XaRa)(XbRb)(XcRc) compound
Reaction prepares antigravity system, wherein X in single step in the presence of liquid diluenta、XbAnd XcOxygen or singly-bound independently respectively are,
And wherein Ra、RbAnd RcRespectively it independently is the alkyl with 1 to 10 carbon atoms or the aryl with 1 to 20 carbon atoms；And
Ii one or more described monoolefine mononitriles) are made to be reacted with HCN in step i) in the presence of the antigravity system of preparation with shape
Into the mixture comprising one or more dintrile.
5. method according to claim 4, wherein one or more described monoolefine mononitriles are or comprising one or more amylenes
Nitrile.
6. the method according to claim 2 or 5, wherein one or more described allyl acetonitriles are selected from cis- 3 pentene nitrile, trans- 3-
Allyl acetonitrile and allyl acetonitrile and one or more described dintrile are or comprising adiponitrile.
7. a kind of method for making 2- methyl -3- butene nitriles be isomerized to 3 pentene nitrile, methods described is included：
I) by making metallic nickel, at least one double tooth organophosphor ligands and at least one formula P (XaRa)(XbRb)(XcRc) compound
Reaction prepares antigravity system, wherein X in single step in the presence of liquid diluenta、XbAnd XcOxygen or singly-bound independently respectively are,
And wherein Ra、RbAnd RcRespectively it independently is the alkyl with 1 to 10 carbon atoms or the aryl with 1 to 20 carbon atoms；And
Ii) 2- methyl -3- butene nitriles are made to be isomerized to 3 pentene nitrile using the antigravity system prepared in step i).
8. the method according to any one of claim 1 to 7, wherein selected from by P (XaRa)2Cl、P(XaRa)Cl2It is mixed with it
The catalyst for being used for nickel complex formation of the group of compound composition is added to the step of preparing the antigravity system, wherein Xa
And RaAs defined in claim 1 to 4.
9. the wherein described catalyst for nickel complex formation of method according to claim 8 with least about 50ppm and
Amount addition no more than 500ppm, it is measured as the ppm chlorine based on the weight of whole antigravity system.
10. the method according to any one of claim 1 to 9, wherein the liquid diluent includes 3 pentene nitrile.
11. wherein described pair tooth organophosphor ligand of method according to any one of claim 1 to 10 is double tooth phosphorous acid
Ester part.
12. wherein described pair tooth phosphite ester ligand of method according to claim 11 is selected from and is made up of Formula VII and VIII
Group：
Wherein
R41And R45Independently selected from by C1To C5The group of alkyl composition, and R42、R43、R44、R46、R47、R48And R49In it is each
Person is independently selected from by H and C1To C4The group of alkyl composition.
13. according to any method of the preceding claims, wherein the formula P (XaRa)(XbRb)(XcRc) compound is
One or more formulas P (O- o-tolyls)w(tolyl between O-)x(O- p-methylphenyls)y(O- phenyl)zCompound, wherein w, x, y and z
It independently is 0 or 1 to 3 integer, and w+x+y+z=3.
14. method according to claim 13, wherein the formula P (XaRa)(XbRb)(XcRc) compound be one or more choosing
From the compound of the group consisted of：P (tolyl between O-) (O- phenyl)2, P (O- p-methylphenyls) (O- phenyl)2、P(O-
Between tolyl) (O- p-methylphenyls) (O- phenyl), P (O- p-methylphenyls)2(tolyl between O-), P (O- p-methylphenyls)2(O- benzene
Base), P (tolyl between O-)2(O- p-methylphenyls), P (tolyl between O-)2(O- phenyl), P (tolyl between O-)3, (O- is to first by P
Phenyl)3With P (O- phenyl)3。
15. the method according to any one of claim 1 to 14, wherein methods described are continuation method.
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| CN115433103A (en) * | 2022-10-09 | 2022-12-06 | 山东新和成维生素有限公司 | Synthesis method of isophorone nitrile |
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| CN115433103A (en) * | 2022-10-09 | 2022-12-06 | 山东新和成维生素有限公司 | Synthesis method of isophorone nitrile |
| CN115433103B (en) * | 2022-10-09 | 2023-08-18 | 山东新和成维生素有限公司 | Synthesis method of isophorone nitrile |
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