CN102286021A - Method for producing 2-carboxyethyl(phenyl)phosphinicacid - Google Patents
Method for producing 2-carboxyethyl(phenyl)phosphinicacid Download PDFInfo
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- CN102286021A CN102286021A CN201110162487XA CN201110162487A CN102286021A CN 102286021 A CN102286021 A CN 102286021A CN 201110162487X A CN201110162487X A CN 201110162487XA CN 201110162487 A CN201110162487 A CN 201110162487A CN 102286021 A CN102286021 A CN 102286021A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention provides a method for producing 2-carboxyethyl(phenyl)phosphinicacid, which comprises the following steps: synthesizing an ionic liquid catalyst by using aluminum trichloride and an organic amine salt; synthesizing dichlorophenylphosphine under the catalytic action of the ionic liquid catalyst by using phosphorus trichloride and benzene as a raw material; reacting dichlorophenylphosphine purified by distillation with acrylic acid; and finally, performing hydrolysis reaction to synthesize a 2-carboxyethyl(phenyl)phosphinicacid flame retardant. The method overcomes the drawback of serious pollution to the environment by lots of industrial waste residue and liquid produced in the prior art. In the technical process of the method, harmful waste residue is not generated, the used phosphorus trichloride, benzene solvent and ionic liquid catalyst can be reclaimed and reused after simple activation treatment; the consumption of the ionic liquid catalyst is small and the catalysis efficiency is high; the total yield is increased to over 50 percent, and the product purity is high; and the method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of synthesis technique of 2-carboxyethyl phenyl phosphinic acid.
Background technology
Fire retardant is in order to improving the material non-flame properties, promptly stops material to be ignited and suppresses the auxiliary agent of propagation of flame.The ideal fire retardant should be efficient, and low toxicity with good by the consistency of fire retardant material, is difficult for migration, has enough thermostabilitys, the unlikely too much substrate performance that influences.Press the ignition-proof element kind, fire retardant mainly can be divided into halogen system, organophosphorus system, expanded polystyrene veneer, inorganic combustion inhibitor.
In the present flame retardant products both domestic and external, mainly be based on the halogen fire retardant, but halogen flame is in stoping combustion processes, though can play the effect that delays polymer combustion, but it is in this pyroprocess, can emit obnoxious flavour, there are huge injury in the hydrogenchloride that is discharged and other hydrogen halides to the people of scene of fire.
Organic phosphorus flame retardant mostly has advantages such as low cigarette, nontoxic, low halogen, Halogen, meets the developing direction of fire retardant, has good development prospect.Japanese phosphorus flame retardant consumption in 1993 is 0.931 ten thousand t, and nineteen ninety-five then reaches 1.97 ten thousand t, has increased more than one times.U.S.'s consumption in 1993 is 0.7716 ten thousand t, then reaches 5.7685 ten thousand t in 1998, has increased nearly 6.5 times.
In the world, the copoly type phosphonium flame retardant is the main flow of current research, and the good reactive flame retardant that can be used for polyester at present is the derived product based on dichlorophenyl phosphine (DCPP) mostly.The 2-carboxyethyl phenyl phosphinic acid is that a class has higher thermostability, oxidative stability and hydrolytic resistance preferably, than the reactive flame retardant of the excellent property of high reaction activity.Companies such as existing Hoechst, Eastman are that fire retardant is produced flame retardant polyester with the 2-carboxyethyl phenyl phosphinic acid in the world, are the famous brand names that is used for polyester and reactive flame retardant in the world.Producing 2-carboxyethyl phenyl phosphinic acid traditional technology at present is: add aluminum chloride as catalyzer, after reaction is finished, add complexing agent again, product phenyl phosphorus dichloride is separated from catalyst system.The deficiency that exists is: industrial residue, waste liquid that association is a large amount of, cause serious pollution to environment.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of production method of 2-carboxyethyl phenyl phosphinic acid, can eliminate a large amount of waste residues, the waste liquid that produce in the production process, thereby realize the suitability for industrialized production of 2-carboxyethyl phenyl phosphinic acid.
Design philosophy of the present invention is: with aluminum chloride and the synthetic ionic-liquid catalyst of organic amine salt; With phosphorus trichloride and benzene is raw material, synthesis of phenyl phosphorus dichloride under the katalysis of ionic-liquid catalyst of the present invention; After the phenyl phosphorus dichloride rectification and purification, with the vinylformic acid reaction, the reaction that is hydrolyzed at last synthesizes the 2-carboxyethylphenylphacidinic acidinic flame-proof agent.Whole process does not have deleterious waste residue and produces, and ionic-liquid catalyst is reusable, and overall yield is brought up to more than 50%, is fit to suitability for industrialized production.
Chemical equation:
Technical scheme of the present invention is:
Production method of the present invention is specially:
Operation
: ionic-liquid catalyst synthetic
By the mol ratio of aluminum chloride and organic ammonium salt is that the amount of 0.2-50:0.1-10 joins in the reactor, stirs synthetic ionic-liquid catalyst under 20-100 ℃ of temperature;
This reaction process need not to carry out in organic solvent, and the productive rate of reaction is more than 95%, owing to do not introduce other chemical substance in the reaction process, ionic-liquid catalyst need not to handle and can be directly used in the next step.
Operation
: phenyl phosphorus dichloride synthetic
Press ionic-liquid catalyst: phosphorus trichloride: the mol ratio of benzene=0.01-0.5:1-30:1-10, with phosphorus trichloride and operation
The ionic-liquid catalyst that obtains mixes stirring, has been warming up to backflow simultaneously; Drip the benzene of aforementioned proportion, and be controlled within 2-8 hour and drip off, the maintenance system refluxes, and the HC1 gas recovery that reaction process is produced is handled simultaneously; After reacting completely, system temperature is reduced to room temperature, separatory is isolated ionic-liquid catalyst and reaction liquid respectively; Add phosphorus trichloride in the ionic-liquid catalyst and (add volume ratio: ionic-liquid catalyst: the extraction separatory of phosphorus trichloride=1:1-100), and be heated to 40-60 ℃, stirred 0.5～1 hour, left standstill 30 minutes, ionic-liquid catalyst separates storage, after extraction solution and reaction liquid merge, carry out underpressure distillation, distill out phosphorus trichloride, benzene, continue elevated temperature, gas clean-up rectifying, obtain the phenyl phosphorus dichloride.
Operation
: 2-carboxyethyl phenyl phosphinic acid synthetic
The reaction product in second step is joined in the vinylformic acid, generate target product; We select the phenyl phosphorus dichloride is dripped in liquid acrylic, initial reaction is carried out under 10 ℃ of 80 ℃ of scholars, avoided the self-crosslinking reaction of more lower boiling vinylformic acid under comparatively high temps, and guaranteed the complete reaction of phenyl phosphorus dichloride, made product purity satisfy technical requirement.
Vinylformic acid is added in the reactor, stir and be heated to 70-85 ℃, press the mol ratio of phenyl phosphorus dichloride: vinylformic acid=0.6-1.5, operation
The phenyl phosphorus dichloride that obtains is added drop-wise in the reaction system, maintains the temperature at 10 ℃ of 80 scholars, drips the phenyl phosphorus dichloride in 2-4 hour; Under 10 ℃ of temperature of 80 scholars, continue reaction 0. 5-2 hour, when being heated to 110-120 ℃ then isothermal reaction 2-4 hour, be cooled to room temperature afterwards, obtain the acyl chlorides intermediate; Press deionized water: acyl chlorides intermediate=1-20:0.1-20 mol ratio slowly is added drop-wise to deionized water in the acyl chlorides intermediate; After deionized water drips and finishes, the rising system temperature is to 60-75 ℃, press hydrogen peroxide: acyl chlorides intermediate=0.1-5:1-100 mol ratio, hydrogen peroxide is added drop-wise to reaction system, drips off in 4 hours, and make temperature of reaction constant, continued insulation reaction 2 hours, be cooled to room temperature afterwards, crystallization is filtered, is separated; With isolated product under 80-120 ℃ of condition dry 4 hours, promptly get the finished product 2-carboxyethyl phenyl phosphinic acid.
Operation
: with operation
In isolated ionic-liquid catalyst join in the exsiccant reactor, stir, be heated to 40-50 ℃, press ionic-liquid catalyst then: the mol ratio of metal aluminium flake=1-10:0.1-1, add the metal aluminium flake, after treating to dissolve fully, continue to stir 0.5-2 hour, filtration residue, the ionic-liquid catalyst that obtains reactivating.
The present invention is in operation
After reaction is finished, product is simple and easy to do with separating of ionic-liquid catalyst, adopt the method (separate mode of reaction liquid and ionic-liquid catalyst is a separatory) of separatory, do not need decomplexing, only need in isolating ionic-liquid catalyst, add phosphorus trichloride and make the solvent extraction reaction product, 40-60 ℃ of reaction 1～3 hour, reduce to room temperature, standing demix.Get twice stratified upper strata product solution and merge, underpressure distillation obtains phosphorus trichloride and benzene liquid earlier, and rectifying obtains the phenyl phosphorus dichloride again, the cut under vacuumizing down, collecting 85-120 ℃.Lower floor's ionic-liquid catalyst separates the back for secondary response use down.
Operation of the present invention
In isolated ionic-liquid catalyst or/and the isolated ionic-liquid catalyst in extraction back after using 3-5 time, needs to activate, the present invention also comprises operation
: with operation
In isolated ionic-liquid catalyst or/and the isolated ionic-liquid catalyst in extraction back join in the exsiccant reactor, stir, be heated to 40-50 ℃, press ionic-liquid catalyst then: the mol ratio of metal aluminium flake 1-10:0.1-1 adds the metal aluminium flake, after treating to dissolve fully, continue to stir 0.5-2 hour, the hydrogen chloride gas that produces imports in the water, and filtration residue obtains activating the ionic-liquid catalyst of living again.
Operation of the present invention
In, said organic ammonium salt is specially the alkylamine hydrochlorate, comprising: 1. the substituting group on the amido is various alkyl groups such as methyl, cyclopropyl, sec.-propyl; 2. the substituting group on the amido is one-level, secondary, three grades of replacements; 3. the sour kind with above-mentioned amino-complex complexing is various inorganic or organic acids, and said mineral acid is hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and said organic acid is formic acid, acetate, vinylformic acid, methylsulfonic acid, phenylformic acid, Phenylsulfonic acid.
Operation of the present invention
In, said organic ammonium salt is methylamine hydrochloride, triethylamine hydrochloride, pyridine hydrochloride, Trimethylamine 99 vitriol, triethylamine mesylate etc.
Operation of the present invention
In the consumption of the ionic-liquid catalyst that added few, separatory after reaction is finished does not need to add complexing agent, and is simple to operate, is easy to industrial production.The ionic liquid of separating is told after adding the phosphorus trichloride extraction, can be directly used in operation
In catalyzed reaction, access times are 3-10 time.
The solvent that technological process of the present invention is used can be recycled after distillation is reclaimed, and does not have waste liquid and waste gas to produce substantially, can not produce environmental pollution; The ionic-liquid catalyst that uses in the reaction process is recyclable, reuses after simple activation treatment, and the phosphorus trichloride of use and benzene solvent need not to handle after distillation is reclaimed can be recycled; Last handling process is avoided network the live adding of agent and extraction repeatedly, filter operation.Compare with prior art, building-up process environmental protection of the present invention, the ionic-liquid catalyst recirculation is used, and has eliminated the generation of three industrial wastes; It is few that ionic-liquid catalyst of the present invention has usage quantity, the catalytic efficiency height; Technological reaction condition of the present invention realizes that easily post-processing operation is easy, the productive rate height, and overall yield is brought up to more than 50%; The product purity height is easy to realize the industry amplification.
Embodiment
Embodiment 1
(1) synthetic ionic liquid
By the mol ratio of aluminum chloride and methylamine hydrochloride is that the amount of 0.2:0.1 joins in the reactor, stirs synthetic under 100 ℃ of temperature.
(2) synthesis of phenyl phosphorus dichloride
Press ionic liquid: phosphorus trichloride: the mol ratio of benzene=0.01:1:1, phosphorus trichloride and ionic-liquid catalyst are mixed stirring, be warming up to backflow simultaneously; Drip the benzene of aforementioned proportion, and be controlled within 2 hours and drip off, the maintenance system refluxes, and the HC1 gas recovery that reaction process is produced is handled simultaneously.After reacting completely, system temperature is reduced to room temperature, separatory is isolated ionic-liquid catalyst and reaction liquid respectively.Adding phosphorus trichloride extraction separatory in the ionic-liquid catalyst (adding volume ratio: ionic-liquid catalyst: phosphorus trichloride=1:1), and be heated to 40 ℃, stirred 40 minutes, left standstill 30 minutes, ionic liquid separates storage, after extraction solution and reaction liquid merge, carry out underpressure distillation, distill out phosphorus trichloride, benzene, continue elevated temperature, gas clean-up rectifying, obtain purified phenyl phosphorus dichloride.
(3) Synthetic 2-carboxyethyl phenyl phosphinic acid
Vinylformic acid is added in the dry reaction still, stir and be heated to 70 ℃, press the mol ratio of phenyl phosphorus dichloride: vinylformic acid=0.6:1, purified phenyl phosphorus dichloride is added drop-wise in the reaction system, maintain the temperature at 80 ℃, in 2 hours, drip the phenyl phosphorus dichloride.Continue reaction 0. 5 hours under 80 ℃ of temperature, isothermal reaction is 2 hours when being heated to 110 ℃ then, is cooled to room temperature afterwards, obtains the acyl chlorides intermediate.Press deionized water: acyl chlorides intermediate=1:0.1 mol ratio slowly is added drop-wise to deionized water in the acyl chlorides intermediate.
After deionized water drips and finishes, rising system temperature to 60 ℃ is pressed hydrogen peroxide: acyl chlorides intermediate=0.1:1 mol ratio, hydrogen peroxide is added drop-wise to reaction system, drips off in 4 hours, and make temperature of reaction constant, continued insulation reaction 2 hours, be cooled to room temperature afterwards, crystallization is filtered, is separated, with isolated product under 80 ℃ of conditions dry 4 hours, promptly get the finished product 2-carboxyethyl phenyl phosphinic acid.
(4) ionic liquid activation
Isolated ionic liquid is after using 3-5 time, need activation, be about to ionic liquid and join in the exsiccant reactor, stir, be heated to 40 ℃, press the mol ratio of ionic-liquid catalyst: aluminium=1:0.1 then, add aluminium flake, after treating to dissolve fully, continue to stir 0.5 hour, filtration residue, the ionic-liquid catalyst that obtains reactivating.
Embodiment 2
(1) synthetic ionic liquid
By the mol ratio of aluminum chloride and triethylamine hydrochloride is that the amount of 2.5:1 joins in the reactor, stirs synthetic under 40 ℃ of temperature.
(2) synthesis of phenyl phosphorus dichloride
Press ionic liquid: phosphorus trichloride: the mol ratio of benzene=0.5:30:10, phosphorus trichloride and ionic liquid are mixed stirring, be warming up to backflow simultaneously; Drip the benzene of aforementioned proportion, and be controlled within 4 hours and drip off, the maintenance system refluxes, and the HC1 gas recovery that reaction process is produced is handled simultaneously.After reacting completely, system temperature is reduced to room temperature, separatory is isolated ionic-liquid catalyst and reaction liquid respectively.Adding phosphorus trichloride extraction separatory in the ionic-liquid catalyst (adding volume ratio: ionic-liquid catalyst: phosphorus trichloride=1:10), and be heated to 50 ℃, stirred 40 minutes, left standstill 30 minutes, ionic liquid separates storage, after extraction solution and reaction liquid merge, carry out underpressure distillation, distill out phosphorus trichloride, benzene, continue elevated temperature, gas clean-up rectifying, obtain purified phenyl phosphorus dichloride.
(3) Synthetic 2-carboxyethyl phenyl phosphinic acid
Vinylformic acid is added in the dry reaction still, stir and be heated to 80 ℃, press the mol ratio of phenyl phosphorus dichloride: vinylformic acid=2.5:1, purified phenyl phosphorus dichloride is added drop-wise in the reaction system, maintain the temperature at 85 ℃, in 3 hours, drip the phenyl phosphorus dichloride.Continue reaction 1.5 hours under 85 ℃ of temperature, isothermal reaction is 3 hours when being heated to 115 ℃ then, is cooled to room temperature afterwards, obtains the acyl chlorides intermediate.Press deionized water: acyl chlorides intermediate=10:1 mol ratio slowly is added drop-wise to deionized water in the acyl chlorides intermediate.
After deionized water drips and finishes, rising system temperature to 70 ℃ is pressed hydrogen peroxide: acyl chlorides intermediate=1:20 mol ratio, hydrogen peroxide is added drop-wise to reaction system, drips off in 4 hours, and make temperature of reaction constant, continued insulation reaction 2 hours, be cooled to room temperature afterwards, crystallization is filtered, is separated, with isolated product under 100 ℃ of conditions dry 4 hours, promptly get the finished product 2-carboxyethyl phenyl phosphinic acid.
(4) ionic liquid activation
In operation
In, isolated ionic liquid needs activation after using 3-5 time, be about to ionic liquid and join in the exsiccant reactor, stir, be heated to 45 ℃, the mol ratio of pressing ionic liquid: aluminium=10:0.5 then adds aluminium flake, after treating to dissolve fully, continue to stir filtration residue, the ionic-liquid catalyst that obtains reactivating 1 hour.
Embodiment 3
(1) synthetic ionic liquid
By the mol ratio of aluminum chloride and pyridine hydrochloride is that the amount of 3:1 joins in the reactor, stirs synthetic under 100 ℃ of temperature.
(2) synthesis of phenyl phosphorus dichloride
Press ionic liquid: phosphorus trichloride: the mol ratio of benzene=0.5:20:10, phosphorus trichloride and ionic liquid are mixed stirring, be warming up to backflow simultaneously; Drip the benzene of aforementioned proportion, and be controlled within 8 hours and drip off, the maintenance system refluxes, and the HC1 gas recovery that reaction process is produced is handled simultaneously.After reacting completely, system temperature is reduced to room temperature, separatory is isolated ionic-liquid catalyst and reaction liquid respectively.Adding phosphorus trichloride extraction separatory in the ionic-liquid catalyst (adding volume ratio: ionic-liquid catalyst: phosphorus trichloride=1:100), and be heated to 60 ℃, stirred 40 minutes, left standstill 30 minutes, ionic liquid separates storage, after extraction solution and reaction liquid merge, carry out underpressure distillation, distill out phosphorus trichloride, benzene, continue elevated temperature, gas clean-up rectifying, obtain purified phenyl phosphorus dichloride.
(3) Synthetic 2-carboxyethyl phenyl phosphinic acid
Vinylformic acid is added in the dry reaction still, stir and be heated to 85 ℃, press the mol ratio of phenyl phosphorus dichloride: vinylformic acid=1.5:1, purified phenyl phosphorus dichloride is added drop-wise in the reaction system, maintain the temperature at 90 ℃, in 4 hours, drip the phenyl phosphorus dichloride.Continue reaction 2 hours under 90 ℃ of temperature, isothermal reaction is 4 hours when being heated to 120 ℃ then, is cooled to room temperature afterwards, obtains the acyl chlorides intermediate.Press deionized water: acyl chlorides intermediate=5:1 mol ratio slowly is added drop-wise to deionized water in the acyl chlorides intermediate.
After deionized water drips and finishes, rising system temperature to 75 ℃ is pressed hydrogen peroxide: acyl chlorides intermediate=1:10 mol ratio, hydrogen peroxide is added drop-wise to reaction system, drips off in 4 hours, and make temperature of reaction constant, continued insulation reaction 2 hours, be cooled to room temperature afterwards, crystallization is filtered, is separated, with isolated product under 120 ℃ of conditions dry 4 hours, promptly get the finished product 2-carboxyethyl phenyl phosphinic acid.
(4) ionic liquid activation
In operation
In, isolated ionic liquid needs activation after using 3-5 time, be about to ionic liquid and join in the exsiccant reactor, stir, be heated to 50 ℃, the mol ratio of pressing ionic liquid: aluminium=5:1 then adds aluminium flake, after treating to dissolve fully, continue to stir filtration residue, the ionic-liquid catalyst that obtains reactivating 2 hours.
Claims (7)
1. the production method of a 2-carboxyethyl phenyl phosphinic acid is characterized in that: comprise following operation:
2. the production method of a 2-carboxyethyl phenyl phosphinic acid is characterized in that:
Operation
: ionic-liquid catalyst synthetic
By the mol ratio of aluminum chloride and organic ammonium salt is that the amount of 0.2-50:0.1-10 joins in the reactor, stirs synthetic ionic-liquid catalyst under 20-100 ℃ of temperature;
Operation
: phenyl phosphorus dichloride synthetic
Press ionic-liquid catalyst: phosphorus trichloride: the mol ratio of benzene=0.01-0.5:1-30:1-10, with phosphorus trichloride and operation
The ionic-liquid catalyst that obtains mixes stirring, has been warming up to backflow simultaneously; Drip the benzene of aforementioned proportion, and be controlled within 2-8 hour and drip off, the maintenance system refluxes; After reacting completely, system temperature is reduced to room temperature, separatory is isolated ionic-liquid catalyst and reaction liquid respectively; Add phosphorus trichloride solution extraction separatory in the ionic-liquid catalyst, and be heated to 40-60 ℃, stirred 0.5～1 hour, left standstill 30 minutes, ionic-liquid catalyst separates storage, after extraction solution and reaction liquid merge, carry out underpressure distillation, distill out phosphorus trichloride, benzene, continue elevated temperature, gas clean-up rectifying, obtain the phenyl phosphorus dichloride;
Operation
: 2-carboxyethyl phenyl phosphinic acid synthetic
Vinylformic acid is added in the reactor, stir and be heated to 70-85 ℃, press the phenyl phosphorus dichloride: vinylformic acid
The mol ratio of=0.6-25:1-10 is with operation
The phenyl phosphorus dichloride that obtains is added drop-wise in the reaction system, maintains the temperature at 10 ℃ of 80 scholars, drips the phenyl phosphorus dichloride in 2-4 hour; Under 10 ℃ of temperature of 80 scholars, continue reaction 0.5-2 hour, when being heated to 110-120 ℃ then isothermal reaction 2-4 hour, be cooled to room temperature afterwards, obtain the acyl chlorides intermediate; Press water: acyl chlorides intermediate=1-200:0.1-20 mol ratio slowly is added drop-wise to water in the acyl chlorides intermediate; Water droplet add finish after, the rising system temperature is pressed hydrogen peroxide to 60-75 ℃: acyl chlorides intermediate=0.1-5:1-100 mol ratio is added drop-wise to reaction system with hydrogen peroxide, drip off in 4 hours, and make temperature of reaction constant, continued insulation reaction 2 hours, be cooled to room temperature afterwards, crystallization is filtered, is separated; With isolated product under 80-120 ℃ of condition dry 4 hours, promptly get the 2-carboxyethyl phenyl phosphinic acid.
3. according to the production method of the said 2-carboxyethyl phenyl phosphinic acid of claim 2, it is characterized in that: operation
In, said organic ammonium salt is the alkylate that is connected with amino group, is the alkylamine hydrochlorate, comprising: 1. the substituting group on the amido is methyl, cyclopropyl, sec.-propyl; 2. the substituting group on the amido is one-level, secondary, three grades of replacements; 3. the sour kind with above-mentioned amino-complex complexing is mineral acid or organic acid.
4. according to the production method of the said 2-carboxyethyl phenyl phosphinic acid of claim 3, it is characterized in that: said mineral acid is hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and said organic acid is formic acid, acetate, vinylformic acid, methylsulfonic acid, phenylformic acid, Phenylsulfonic acid.
5. according to the production method of claim 2 or 3 said 2-carboxyethyl phenyl phosphinic acids, it is characterized in that: operation
In, said organic ammonium salt is methylamine hydrochloride, triethylamine hydrochloride, pyridine hydrochloride, Trimethylamine 99 vitriol, triethylamine mesylate.
6. according to the production method of the said 2-carboxyethyl phenyl phosphinic acid of claim 2, it is characterized in that: also comprise operation
: with operation
In isolated ionic-liquid catalyst join in the exsiccant reactor, stir, be heated to 40-50 ℃, press ionic-liquid catalyst then: the mol ratio of metal aluminium flake=1-10:0.1-1, add the metal aluminium flake, after treating to dissolve fully, continue to stir 0.5-2 hour, filtration residue obtains the activatory ionic-liquid catalyst.
7. according to the production method of the said 2-carboxyethyl phenyl phosphinic acid of claim 2, it is characterized in that: to operation
The amount that adds phosphorus trichloride solution in the isolating ionic-liquid catalyst is: operation
Isolating ionic-liquid catalyst: the volume ratio=1-10:1-100 of phosphorus trichloride solution.
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| CN104926865A (en) * | 2015-06-24 | 2015-09-23 | 南通泰通化学科技有限公司 | Production process of 2-carboxyethyl phosphinic acid |
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| CN107793449A (en) * | 2017-10-28 | 2018-03-13 | 南通江山农药化工股份有限公司 | A kind of method of synthesizing methyl dimethyl phosphate |
| CN109970790A (en) * | 2019-04-29 | 2019-07-05 | 利尔化学股份有限公司 | The extraction separating method and rectifier unit of dichloromethylphosphine |
| CN110003268A (en) * | 2019-03-07 | 2019-07-12 | 清远市普塞呋磷化学有限公司 | A kind of preparation method of dialkylphosphinic salts |
| CN110003269A (en) * | 2019-04-29 | 2019-07-12 | 利尔化学股份有限公司 | The method of low energy consumption production glufosinate-ammonium |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926865A (en) * | 2015-06-24 | 2015-09-23 | 南通泰通化学科技有限公司 | Production process of 2-carboxyethyl phosphinic acid |
| CN105541908A (en) * | 2016-02-01 | 2016-05-04 | 东营美利达新型材料科技有限公司 | Method for producing 2-carboxethyl phenylphosphinic acid without wastewater |
| CN107793449A (en) * | 2017-10-28 | 2018-03-13 | 南通江山农药化工股份有限公司 | A kind of method of synthesizing methyl dimethyl phosphate |
| CN107793449B (en) * | 2017-10-28 | 2021-01-05 | 南通江山农药化工股份有限公司 | Method for synthesizing dimethyl methyl phosphate |
| CN110003268A (en) * | 2019-03-07 | 2019-07-12 | 清远市普塞呋磷化学有限公司 | A kind of preparation method of dialkylphosphinic salts |
| CN109970790A (en) * | 2019-04-29 | 2019-07-05 | 利尔化学股份有限公司 | The extraction separating method and rectifier unit of dichloromethylphosphine |
| CN110003269A (en) * | 2019-04-29 | 2019-07-12 | 利尔化学股份有限公司 | The method of low energy consumption production glufosinate-ammonium |
| CN109970790B (en) * | 2019-04-29 | 2021-12-03 | 利尔化学股份有限公司 | Extraction separation method and rectification device of methyl phosphine dichloride |
| CN110003269B (en) * | 2019-04-29 | 2022-04-05 | 利尔化学股份有限公司 | Method for producing glufosinate-ammonium with low energy consumption |
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Application publication date: 20111221 |