CN108558943A - A method of dissociation dichloromethylphosphine and aluminum chloride complex - Google Patents
A method of dissociation dichloromethylphosphine and aluminum chloride complex Download PDFInfo
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- CN108558943A CN108558943A CN201810443908.8A CN201810443908A CN108558943A CN 108558943 A CN108558943 A CN 108558943A CN 201810443908 A CN201810443908 A CN 201810443908A CN 108558943 A CN108558943 A CN 108558943A
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- dichloromethylphosphine
- dissociation
- aluminum chloride
- chloride complex
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
Abstract
The invention discloses a kind of methods of dissociation dichloromethylphosphine and aluminum chloride complex, belong to technical field of chemical separation.The present invention is low for aluminum chloride complex production capacity in dissociation dissociation dichloromethylphosphine in the prior art and aluminum chloride complex, high energy consumption, generates the problems such as waste residue amount is big and production cost is high, propose a kind of method of dissociation dichloromethylphosphine and aluminum chloride complex, this method reaction yield is up to 90~95%, low energy consumption, the waste residue generated simultaneously is easy to subsequent processing, dissociation agent is easily recycled, easy to operate.
Description
Technical field
The present invention relates to a kind of methods of dissociation dichloromethylphosphine and aluminum chloride complex, more particularly to use dissociation
The method that dichloromethylphosphine and tri-chlorination complex compound are dissociated in agent, belongs to technical field of chemical separation.
Background technology
State Intellectual Property Office disclosed application number CN201610095303.5, entitled one kind on 06 15th, 2016
The patent of invention of the synthetic method of methyl dichloro phosphorus discloses a kind of synthetic method of methyl dichloro phosphorus, the synthetic method
Using chloromethanes, alchlor and phosphorus trichloride as raw material, using petroleum ether as solvent, reaction generates ligand CH3PCl4·AlCl3, steam
After evaporating recycling petroleum ether, aluminium powder and sodium chloride is added, under the effect of the catalyst, reduction obtains product methyl dichloro phosphorus.This
Invent the methyl dichloro phosphorus synthetic method that is related to be it is a kind of can substitute the prior art, solve the row of organic exhaust gas in preparation process
Problem is put, the synthesis technology flow of the complete set of clean manufacturing principle is more met, in addition to this, which also cries existing
Technology has better production effect, that is, the yield of product methyl dichloro phosphorus can reach 90 ~ 95%.
It will produce dichloromethylphosphine and alchlor complexing when preparing dichloromethylphosphine as raw material using aluminium and chloromethanes
Object will obtain dichloromethylphosphine, need to dissociate in this complex compound, and dissociating complex compound at present, there are two types of methods：First, alkali metal
Halide mixing distillation dissociation；Second is that repefral, diethyl phthalate, benzene acetonitrile, phosphorus oxychloride etc.
Material mixing distillation dissociation, method and present invention difference.Alkali halide mixing distillation dissociation is at present using relatively broad
Method, the method is evaporated under reduced pressure, and required vacuum reaches 12KPa, and final vapo(u)rizing temperature needs to rise to 160 DEG C of left sides
The right side, energy consumption is high, and has part methyl dichloride phosphine and decompose and taken away by vacuum, and dichloromethylphosphine yield is caused to drop
It is low, while the waste residue generated needs have preferable mobility when temperature is more than 120 DEG C, is cooled to after 80 DEG C or less and is just solidified as admittedly
Body, it has not been convenient to carry out subsequent processing, the method dichloromethylphosphine yield 85% or so；Second method dichloromethylphosphine is received
Rate 80%~86%, the dissociation agent used is either at high price either to belong to extremely toxic substance or boiling point height, dissociates agent recovery set
Used time needs to steam solvent, and recycling is difficult, while energy consumption is higher, and cost is big, is not suitable for industrial production.
Invention content
Present invention seek to address that dissociating trichlorine from dichloromethylphosphine and aluminum chloride complex system in the prior art
Change that aluminium production capacity is low, high energy consumption, generates the problems such as waste residue amount is big and production cost is high, it is proposed that a kind of dissociation dichloromethylphosphine with
The method of aluminum chloride complex, this method reaction yield are up to 90~95%, and low energy consumption, while the waste residue generated is easy to follow-up
Processing, dissociation agent is easily recycled, easy to operate.
In order to achieve the above-mentioned object of the invention, technical scheme is as follows：
A method of dissociation dichloromethylphosphine and aluminum chloride complex include the following steps：
A. petroleum ether is added into dichloromethylphosphine and aluminum chloride complex system；30~50 DEG C are warming up under stirring；
System including dichloromethylphosphine and aluminum chloride complex is warming up to 30~50 DEG C by the present invention, is to allow system
More disperse, complex compound viscosity when at temperature is less than 30 DEG C is larger, and being warming up to 30~50 DEG C can make complex compound mixed with petroleum ether
Conjunction is more uniform, and when the agent of dropwise addition dissociation later is dissociated, reaction is more abundant.
B. the dissociation agent that aluminum chloride complex can be dissociated is added in the system obtained to step A；Dissociate the dropwise addition of agent
Temperature is 40~55 DEG C, and 10~15min of stirring at 40~55 DEG C is added dropwise；
C. the direct split-phase of reaction solution step B obtained, for dichloromethylphosphine i.e. in the petroleum ether phase of upper layer, lower layer is to dissociate
The complex compound of agent and alchlor.Further, the present invention is separated material levels by phase splitting device, and is set using difference
It is standby to be collected；Condition of phase separation is：40~50℃.
Further, described in step B of the present invention dissociate agent be repefral, diethyl phthalate,
The C of dipropyl phthalate, linear chain or branched chain1~C4The C of carboxylate methyl ester, linear chain or branched chain1~C4Carboxylic acid, ethyl ester or straight chain or
The C of branch1~C4Propyl carboxylate.
Further, it is ethyl acetate, isoamyl acetate, butyl acetate or neighbour that agent is dissociated described in step B of the present invention
Diethyl phthalate.
Further, the petroleum ether solution of dichloromethylphosphine can pass through rectifying recycling design and purification methyl in the present invention
Dichloride phosphine.
The petroleum ether boiling range that the present invention uses is 30~60 DEG C, and rectifying recycling design is to be set using laboratory rectifying herein
It is standby, atmospheric distillation is carried out, by adjusting reflux ratio, collects petroleum ether of the boiling point at 30~60 DEG C, and then reach recycling design
Purpose；After solvent recovery, atmospheric distillation is equally used, by further adjusting reflux ratio, collects boiling range at 80~82 DEG C
Fraction, this fraction is dichloromethylphosphine, after this fraction collection, that is, reached recycling design and purification methyl two
The purpose of phosphonium chloride.
Further, the present invention dissociates the complex compound of agent and alchlor, is directly added into deionized water and is reacted, instead
Organic phase recycling dissociation agent is separated after answering, water phase carries out waste residue conversion.
The complex compound of dissociation agent and alchlor can be directly separated in deionized water.Dissociate the network of agent and alchlor
Closing object can react with deionized water, and with exothermic phenomenon, and reaction herein is actually alchlor and deionized water
Reaction, only unlike pure alchlor and deionized water reaction it is so violent；Dissociation agent is not involved in reaction, when reaction finishes
Afterwards, alchlor and deionized water, which are reacted, to form soluble matter and is dissolved in deionized water, and dissociates agent solubility in deionized water
It is smaller, to carry out recycling dissociation agent.
Further, petroleum ether of the present invention could alternatively be n-hexane, hexamethylene, and toluene is one such or more
Kind combination.
Further, the invention also provides ethyl acetate, n-butyl acetate or isoamyl acetates in dissociation methyl two
The application of aluminum chloride complex in phosphonium chloride and aluminum chloride complex system.
Beneficial effects of the present invention：
（One）When the key of the present invention is to carry out dissociation reaction using dissociation agent, dichloromethylphosphine and alchlor are complexed
Dichloromethylphosphine in objects system cements out, and using dissociation agent of the present invention, carries out the item of needs when dissociation reaction
Part is mild, and temperature is 40~55 DEG C.It is pervious using traditional sodium chloride to the complex compound of dichloromethylphosphine and alchlor
It is dissociated, since the complexing of sodium chloride and alchlor is weaker relative to the dissociation agent of the present invention, and sodium chloride is
Solid needs high temperature then the dissociation condition of sodium chloride is just harsher, and the novel complex formed is under the same conditions very
It is difficult, increase so as to cause cost.
The dissociation of sodium chloride needs to be gradually increased to 160 DEG C from 30 DEG C；Novel complex is the network of sodium chloride and alchlor
Close object：NaAlCl4；This novel complex fusing point formed in this reaction system reaches 150 DEG C or so, when less than 80 DEG C, i.e.,
Condense into monoblock solid；And this novel complex meets air and emerges a large amount of white cigarettes, to handle this complex compound need its is heavy
It newly breaks into pieces, or is handled at higher than 130 DEG C；Intractability is high, dangerous larger.
（Two）The ratio for dissociating agent and aluminum chloride complex is 1.1 ~ 1.5:1, it is an optimal proportion, if dissociation agent
Less than 1.1, then dissociation is incomplete, yield declines very much, and dissociates agent and be higher than 1.5, then dissociation agent is excessive, although receiving
Rate is equally higher, but dissociation agent has and is partly dissolved in petroleum ether phase, and bad recycling causes to waste.
Specific implementation mode
The present invention is described in further detail with reference to embodiment, embodiments of the present invention are not limited thereto.
Embodiment 1
By 1mol, 250.5g dichloromethylphosphines and aluminum chloride complex are added in 1000ml four-hole bottles, add 250.5g
Petroleum ether makees solvent, the petroleum ether and complex compound mass ratio 1:1；It is warming up to 40 DEG C under stirring, starts that 1.3mol is added dropwise i.e.
The ethyl acetate of 114.54g, control dropping temperature are added dropwise at 50 DEG C at 50 DEG C and are stirred to react 15min；By above-mentioned reaction solution
It is transferred to pears type separatory funnel at 50 DEG C, in 40~50 DEG C of split-phases while hot, obtains upper layer petroleum ether phase 341.5g, lower layer is faint yellow
Thick liquid 274.04g；Lower liquid 274.04g is transferred to 500ml four-hole bottles, then 125.25g petroleum ethers are added into bottle, is stirred
It mixes down and is warming up to 40 DEG C and stirs 10min, material is transferred to pears type separatory funnel immediately, is layered, obtains while hot after standing
Layer colourless transparent liquid 136.55g, lower layer light yellow viscous liquid 262.74g, this walks obtained upper layer petroleum ether phase and first
The upper layer that secondary clearing obtains merges total 478.05g, and dichloromethylphosphine is i.e. in the petroleum ether phase of upper layer, the total 262.74g of lower layer, i.e.,
For the complex compound and a small amount of petroleum ether of ethyl acetate and alchlor.
The upper materials 478.05g that split-phase obtains is added in rectifying device and carries out atmospheric distillation, in reflux ratio 1:2 item
Under part, the fraction of 30~60 DEG C of acquisition top temperature is collected into fraction 370.55g, in reflux ratio 1 altogether:Under conditions of 1, top temperature is collected
80~82 DEG C of the total 107g of fraction, GC purity 99.3%, dichloromethylphosphine yield 90.81%.Remaining bottom Liquid Residue 0.5g.
The lower layer material 262.74g that split-phase obtains is added dropwise in 300g deionization deionized waters, exothermic heat of reaction is apparent, drop
Temperature is less than 70 DEG C in being kept when adding reaction, and after completion of the reaction, system is supernatant liquid, and is layered, and system temperature is made to be down to 20
~30 DEG C, layering obtains upper layer colourless transparent liquid 96.5g（91.63g containing ethyl acetate）, lower layer's weak yellow liquid
466.24g can be obtained recycling ethyl acetate, the rate of recovery about 80% after the drying of upper layer；Lower layer's whereabouts waste residue conversion.
If above-mentioned reaction dissociation agent uses n-butyl acetate, the n-butyl acetate rate of recovery is up to 95%；If above-mentioned anti-
Agent, which should be dissociated, uses isoamyl acetate, the isoamyl acetate rate of recovery to can reach 98%.
The principle of the present invention is：There is the atom with lone pair electrons in dissociation agent, and outside alchlor compound aluminium atom
Layer has electronics unoccupied orbital, and complex compound can be formed by dissociating agent and alchlor, and three kinds of the present invention are dissociated agent and tri-chlorination
The complex compound of aluminium is more stablized than the complex compound of dichloromethylphosphine and alchlor, to displace dichloromethylphosphine, shape
At a kind of complex compound of new dissociation agent and alchlor, to reach dissociation purpose.Dropping temperature is controlled at 40~55 DEG C
Dissociation effect is more preferable.Dissociation agent has certain exothermic phenomenon in dissociation process, system temperature can be made to increase, therefore for technique
Security consideration, selection are added dropwise.It is to allow dissociation reaction to carry out more complete that 10~15min is stirred after being added dropwise.
Embodiment 2
1mol dichloromethylphosphines and aluminum chloride complex are added in four-hole bottle, a certain amount of petroleum ether is added and makees solvent,
The petroleum ether and complex compound mass ratio 1:1；30 DEG C are warming up under stirring, start be added dropwise with complex compound molar ratio 1.25~
1.35:1 n-butyl acetate, control dropping temperature are added dropwise at 40 DEG C at 40 DEG C and are stirred to react 12min；By above-mentioned reaction
The direct split-phase of liquid, for dichloromethylphosphine i.e. in the petroleum ether phase of upper layer, lower layer is the complexing of n-butyl acetate and alchlor
Object.
After the petroleum ether solution of dichloromethylphosphine is by rectifying recycling design and purification dichloromethylphosphine, methyl is obtained
Dichloride phosphine 108.4g, GC purity 99.2%, dichloromethylphosphine yield 91.91%.
Embodiment 3
1mol dichloromethylphosphines and aluminum chloride complex are added in four-hole bottle, a certain amount of petroleum ether is added and makees solvent,
The petroleum ether and complex compound mass ratio 1:1；40 DEG C are warming up under stirring, start be added dropwise with complex compound molar ratio 1.25~
1.35:1 ethyl acetate, control dropping temperature are added dropwise at 50 DEG C at 50 DEG C and are stirred to react 15min；By above-mentioned reaction solution
Direct split-phase, for dichloromethylphosphine i.e. in the petroleum ether phase of upper layer, lower layer is the complex compound of ethyl acetate and alchlor.
After the petroleum ether solution of dichloromethylphosphine is by rectifying recycling design and purification dichloromethylphosphine, methyl is obtained
Dichloride phosphine 107.8g, GC purity 99.4%, dichloromethylphosphine yield 91.51%.
Embodiment 4
The application of ethyl acetate aluminum chloride complex in dissociation dichloromethylphosphine and aluminum chloride complex system.
A method of dissociation dichloromethylphosphine and aluminum chloride complex include the following steps：
A. petroleum ether is added into dichloromethylphosphine and aluminum chloride complex system；30~50 DEG C are warming up under stirring；
System including dichloromethylphosphine and aluminum chloride complex is warming up to 30~50 DEG C by the present invention, is to allow system
More disperse, complex compound viscosity when at temperature is less than 30 DEG C is larger, and being warming up to 30~50 DEG C can make complex compound mixed with petroleum ether
Conjunction is more uniform, and when dropwise addition ethyl acetate is dissociated later, reaction is more abundant.
B. the ethyl acetate that aluminum chloride complex can be dissociated is added in the system obtained to step A；Ethyl acetate
Dropping temperature is 40~55 DEG C, and 10~15min of stirring at 40~55 DEG C is added dropwise；
C. the direct split-phase of reaction solution step B obtained, for dichloromethylphosphine i.e. in the petroleum ether phase of upper layer, lower layer is acetic acid
The mixture of ethyl ester and alchlor.
Embodiment 5
The application of n-butyl acetate aluminum chloride complex in dissociation dichloromethylphosphine and aluminum chloride complex system.
A method of dissociation dichloromethylphosphine and aluminum chloride complex include the following steps：
A. petroleum ether is added into dichloromethylphosphine and aluminum chloride complex system；30~50 DEG C are warming up under stirring；
System including dichloromethylphosphine and aluminum chloride complex is warming up to 30~50 DEG C by the present invention, is to allow system
More disperse, complex compound viscosity when at temperature is less than 30 DEG C is larger, and being warming up to 30~50 DEG C can make complex compound mixed with petroleum ether
Conjunction is more uniform, and when dropwise addition n-butyl acetate is dissociated later, reaction is more abundant.
B. the n-butyl acetate that aluminum chloride complex can be dissociated is added in the system obtained to step A；The positive fourth of acetic acid
The dropping temperature of ester is 40~55 DEG C, and 10~15min of stirring at 40~55 DEG C is added dropwise；
C. the direct split-phase of reaction solution step B obtained, for dichloromethylphosphine i.e. in the petroleum ether phase of upper layer, lower layer is acetic acid
The mixture of N-butyl and alchlor.
Embodiment 6
The application of isoamyl acetate aluminum chloride complex in dissociation dichloromethylphosphine and aluminum chloride complex system.
A method of dissociation dichloromethylphosphine and aluminum chloride complex include the following steps：
A. petroleum ether is added into dichloromethylphosphine and aluminum chloride complex system；30~50 DEG C are warming up under stirring；
System including dichloromethylphosphine and aluminum chloride complex is warming up to 30~50 DEG C by the present invention, is to allow system
More disperse, complex compound viscosity when at temperature is less than 30 DEG C is larger, and being warming up to 30~50 DEG C can make complex compound mixed with petroleum ether
Conjunction is more uniform, and when dropwise addition isoamyl acetate is dissociated later, reaction is more abundant.
B. the isoamyl acetate that aluminum chloride complex can be dissociated is added in the system obtained to step A；Acetic acid isoamyl
The dropping temperature of ester is 40~55 DEG C, and 10~15min of stirring at 40~55 DEG C is added dropwise；
C. the direct split-phase of reaction solution step B obtained, for dichloromethylphosphine i.e. in the petroleum ether phase of upper layer, lower layer is acetic acid
The mixture of isopentyl ester and alchlor.
The above is only presently preferred embodiments of the present invention, not does limitation in any form to the present invention, it is every according to
According to the technical spirit of the present invention to any simple modification, equivalent variations made by above example, the protection of the present invention is each fallen within
Within the scope of.
Claims (10)
1. a kind of method of dissociation dichloromethylphosphine and aluminum chloride complex, it is characterised in that：Include the following steps：
A. solvent is added into dichloromethylphosphine and aluminum chloride complex system；It is stirred simultaneously according to the rate of 300 r/min
It is warming up to 30~50 DEG C；
B. the dissociation agent that aluminum chloride complex can be dissociated is added in the system obtained to step A；Dissociate the dropping temperature of agent
It is 40~55 DEG C, 10~15min of stirring at 40~55 DEG C is added dropwise；
C. reaction solution step B obtained split-phase at 40 ~ 50 DEG C, dichloromethylphosphine is i.e. in the petroleum ether phase of upper layer, lower layer
As dissociate the complex compound of agent and alchlor.
2. the method for dissociation dichloromethylphosphine and aluminum chloride complex as described in claim 1, it is characterised in that：It is described
Petroleum ether and the mass ratio of aluminum chloride complex are 1~2:1~3.
3. the method for dissociation dichloromethylphosphine and aluminum chloride complex as described in claim 1, it is characterised in that：In step
In rapid C, material levels are separated by phase splitting device；Condition of phase separation is：40~50℃.
4. the method for dissociation dichloromethylphosphine and aluminum chloride complex as described in claim 1, it is characterised in that：Step
It is repefral, diethyl phthalate, dipropyl phthalate, linear chain or branched chain that agent is dissociated described in B
C1~C4The C of carboxylate methyl ester, linear chain or branched chain1~C4The C of carboxylic acid, ethyl ester or linear chain or branched chain1~C4Propyl carboxylate.
5. the method for dissociation dichloromethylphosphine and aluminum chloride complex as described in claim 1 or 4, it is characterised in that：
The dissociation agent is SILVER REAGENT, and content is more than 99%.
6. the method for dissociation dichloromethylphosphine and aluminum chloride complex as described in claim 1, it is characterised in that：Step
The petroleum ether solution of dichloromethylphosphine in C detaches solvent and dichloromethylphosphine by rectifying.
7. the method for dissociation dichloromethylphosphine and aluminum chloride complex as claimed in claim 4, it is characterised in that：It is described
Distillation operation is：The petroleum ether solution of dichloromethylphosphine is added in rectifying device and carries out rectifying；The rectifying device is reason
The rectifying column that length by glass spring and filler that the number of plates is 15~20 pieces/meter is 1~2 meter；Rectifying pressure is
100.6KPa~101Kpa.
8. the method for dissociation dichloromethylphosphine and aluminum chloride complex as claimed in claim 7, it is characterised in that：It adjusts
Reflux ratio is 1 ~ 5:1 ~ 10, it is petroleum ether to collect the fraction that boiling range is 30~60 DEG C；It is 1 ~ 5 to adjust reflux ratio:1 ~ 10, it collects
Boiling range is dichloromethylphosphine in 80~82 DEG C of fraction.
9. the method for dissociation dichloromethylphosphine and aluminum chloride complex as described in claim 1, it is characterised in that：Step
The complex compound addition deionized water for dissociating agent and alchlor in C in lower layer is reacted, and is separated organic phase after completion of the reaction and is returned
Dissociation agent is received, water phase carries out waste residue conversion.
10. the method for dissociation methyl titanium dioxide phosphine and aluminum chloride complex as claimed in claim 1, it is characterised in that：
Solvent described in step A is aliphatic saturated hydrocarbon, aromatic hydrocarbon, chloralkane or chlorination aromatic hydrocarbon.
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| CN112456462A (en) * | 2019-09-09 | 2021-03-09 | 江苏优士化学有限公司 | Recovery processing method of sodium tetrachloroaluminate catalyst composition |
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