CN104817589A - Dialkyl phosphinic acid compound or salt thereof and preparation method thereof - Google Patents
Dialkyl phosphinic acid compound or salt thereof and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a dialkyl phosphinic acid compound or salt thereof. The method includes the following steps that a compound in a formula A and a compound in a formula B are reacted for 10-30h under conditions of existing of catalyst PdLn, alkali and inert solvent, nitrogen protection and 80-180 DEG C heating temperature and then PNMR detecting reaction is performed; then an organic layer is obtained through filtering, adding of defined amount of water, acidification and organic solvent extraction; then the obtained organic layer is subjected to steps of drying, filtering and pressure reducing to remove the solvent. The preparation method is simple, convenient and novel, a halogenate material directly serves as a raw material, meanwhile, side reaction and by-product are reduced, the product purity is high, the operability is high, and the method is worth popularizing.
Description
Technical field
The present invention relates to a kind of preparation method of compound, particularly relate to a kind of two alkyl phosphinic acid compounds or its salt and preparation method thereof.
Background technology
It is solvent extraction that the separation of rare earth should have at present the most widely, and the solvent be most widely used at present in rare-earth extractant is extraction agent di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507), it has excellent extraction ability and separation factor, the problems such as but P507 exists back extraction, and acidity is high, the waste pollution environment that extraction process also produces.
Two alkyl phosphinic acid due to its pKa higher, it has the lower advantage of back extraction acidity.The method of the two alkyl phosphinic acid of current synthesis mainly contains following several: 1) Grignard reagent method, is prepared that to carry out oxidation after Grignard reagent reacts with diethyl phosphite (or dibutyl phosphite) obtained by halogenated alkane; 2) free radical addition of alkene, general inferior sodium phosphate and the alkene of adopting, under the existence of initiator, carries out free radical addition and obtains.These two kinds of methods all directly can not directly prepare two alkyl phosphinic acid from halogenated alkane, and first the Grignard reagent method of method one must prepare Grignard reagent, and this method has certain danger, and amplify enforcement inconvenience; Free radical addition in method two, also needs to prepare alkene, and needs add more or add initiator in batches, such long reaction time, and cost is also higher.Two-(2,4,4-tri-methyl-amyl) phospho acid (Cyanex272) are the two alkyl phosphinic acid extraction agents of one that Qing Te company of the U.S. produces, obtained as Separation of nickel and cobalt and applied widely, the separation of centering heavy rare earth element has good separating factor.Its synthesis is with diisobutylene and PH
3, add initiator and issue raw Radical Addition in certain temperature and pressure, then pass through H
2o
2carry out oxydrolysis in acid condition, obtain the product of about 85%.The method step is many, raw material PH
3for violent in toxicity, reaction needed acidic conditions, therefore high to equipment requirements, and usually with other by product in product, affect the extraction ability of extraction agent.
Summary of the invention
In order to solve technical problem and the deficiency of above-mentioned existing existence, the invention provides that a kind of reactions steps is short, mild condition, side reaction are few, the method for reaction process environmental protection more prepares two alkyl phosphinic acid compounds or its salt, concrete invention technical scheme is as follows:
A kind of two alkyl phosphinic acid compounds or its salt, the general formula of its pair of alkyl phosphinic acid compounds or its salt is for such as formula described in I:
Wherein R
1for hydrogen, replacement or unsubstituted C
1-C
20alkyl, replacement or unsubstituted C
5-C
8cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted benzyl;
R
2for replacing or not being substituted C
1-C
20alkyl, replacement or unsubstituted C
5-C
8cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted benzyl;
M is H, alkalimetal ion, alkaline-earth metal ions or ammonium radical ion;
A preparation method for pair alkyl phosphinic acid compounds or its salt, comprises the steps one;
By the compound shown in the compound shown in following formula A and following formula B at catalyst P dL
n, alkali, under inert solvent existent condition, under the protection of nitrogen, Heating temperature is react 10-30 h under 80-180 DEG C of condition, carries out the step that intersection coupled reaction as follows obtains two alkyl phosphinic acid compounds or its salt;
Wherein R
1for hydrogen, replacement or unsubstituted C
1-C
20alkyl, replacement or unsubstituted C
5-C
8cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted benzyl;
R
2for replacing or unsubstituted C
1-C
20alkyl, replacement or unsubstituted C
5-C
8cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted benzyl;
M is H, alkalimetal ion, alkaline-earth metal ions or ammonium radical ion;
In B, X is halogen.
Further: described R
1and R
2in, described replacement refers to and to be replaced by following one or more substituting group: C
1-C
4alkyl, C
3-C
10cycloalkyl, halogen, ester group, alkoxyl group.
Further, also comprise the steps in described preparation method;
Step 2: the product obtained above-mentioned steps one carries out the step of PNMR detection reaction;
Step 3: by above-mentioned steps two gained reaction solution through filtering, adding suitable quantity of water, acidifying, organic solvent extraction obtains the step of organic layer;
Step 4: step 3 is obtained the step that organic layer carries out drying, filtration, decompression removal solvent.
Further, described used catalyst P dL
n,wherein L is 1,1
,-bis-(diphenylphosphine) ferrocene (dppf), 4,5-two diphenylphosphine-9,9-dimethyl xanthene (xantphos), polymkeric substance (polymer), 4,6-bis-(diphenylphosphine) azophenlyene (nixantphos), acetate (AcO
-), the halogen X shown in described formula B is chlorine or bromine or iodine, and described alkali is organic bases or mineral alkali, and described alkali is diisopropyl ethyl amine (DIPA), triethylamine (Et
3n) wherein a kind of, in pyridine, quadrol, piperidines, salt of wormwood, sodium carbonate, cesium carbonate, sodium-acetate, described inert solvent is C
5-C
20alkane solvents, C
5-C
20cycloalkane solvent, C
2-C
10esters solvent, C
2-C
10ether solvent, C
6-C
20aryl kind solvent, C
2-C
10alcoholic solvent and C
2-C
10one or more in amide solvent, the temperature of reaction is 100-130 DEG C; The time of described reaction is 18-24 h, described such as formula the compound shown in B with the mol ratio such as formula the compound shown in A for being more than or equal to 1.0, described catalyst P dL
nconsumption be 0.01-0.1 such as formula the mol ratio of the compound shown in A, the consumption of described alkali with the mol ratio such as formula the compound shown in A for being more than or equal to 1.
Further, described C
4-C
10alkyl be 3,3-dimethylbutyl, 2,4,4-tri-methyl-amyls, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl one wherein.
Further, described step 3 for by step 2 gained reacting liquid filtering, add water, acidifying, extraction into ethyl acetate aqueous phase repeatedly, the step of organic layer, the sulfuric acid that the acid solution of described use is 10%-30% for massfraction, massfraction are 10%-30% hydrochloric acid, acetic acid, citric acid wherein one or more.
Further, described in obtain organic layer after, organic layer is washed to neutrality, salt washing, dry, decompression removes solvent.
Further, the hydrochloric acid of acid solution for massfraction 10%-20%, the sulfuric acid of 10%-30% of described use.
Further, two alkyl phosphinic acid compounds step 4 obtained or the thick product of its salt are through recrystallization, underpressure distillation, column chromatography.
It is provided by the invention a kind of such as formula the compound shown in I,
Described such as formula the compound shown in I, best, it is following arbitrary compound:
。
Present invention also offers a kind of foregoing such as formula the application of the compound shown in I in the separation of metallic mixture.
In the present invention, the molecular volume concentration of described extraction agent I in thinner is 0.1 mol/L-2.0 mol/L, described extraction agent I is one or more in Compound I optimizing compound, and described molecular volume concentration refers to the mole number of extractant composition and the ratio of diluent volume.One or more in the preferred sulfonated kerosene of described thinner, kerosene, aviation kerosene, normal heptane, n-dodecane, normal hexane, octane, Benzene and Toluene.
Present invention also offers a kind of described application of extractant composition in the metallic mixture of extracting and separating; Wherein, described metallic mixture is the mixture containing rare earth element.
Described rare earth element is preferably the rare earth element described in the routine of this area, and described rare earth element is preferably La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
Present invention also offers a kind of extracting process, described extracting process preferably comprises the following steps: in thinner, mixes foregoing such as formula the compound shown in I or extractant composition with the aqueous phase of containing metal mixture, forms extraction system, concussion; The pH value of described extraction system is 2.5-3.5.
Wherein, the described volumetric molar concentration in thinner such as formula the compound shown in I or described extractant composition is preferably 0.1mol/L-2.0mol/L, is more preferably 0.2mol/L-0.5mol/L.Described thinner can be the thinner of ability routine, is preferably one or more in sulfonated kerosene, aero oil, kerosene, benzene, toluene, heptane and n-dodecane.In the aqueous phase of described metal mixture, preferably, also salting-out agent are comprised.Described salting-out agent can be the salting-out agent in the extraction system of this area described in routine, are preferably sodium-chlor and/or sodium perchlorate.Described salting-out agent preferably exist in form of an aqueous solutions, and the volumetric molar concentration of the described salting-out agent aqueous solution can be described in the routine of this area, is preferably 0.1mol/L ~ 4mol/L.
Organic phase in described extraction system and the volume ratio of aqueous phase are be preferably 10:1-1:10, are more preferably 5:1-1:5.The concentration of the rare earth ion in described aqueous phase can be described in the routine of this area, is preferably 0.01-0.5mol/L.The time of described vibration can be described in the routine of this area, is preferably 5min-30min.
After described concussion terminates, above-mentioned extraction system is left standstill phase-splitting, water intaking phase or organic phase are carried out reextraction and are analyzed rare earth ion concentration.
The present invention compared with prior art has following technique effect: the easy novelty of preparation method of the present invention, direct is raw material with halides, decrease the generation of side reaction and the generation of by product simultaneously, the purity of product is high, major advantage is that in preparation method, reaction conditions is simple, reaction conditions is gentle, raw material environmental protection rate, simple to operate, safe and reliable, one-step synthesis target compound, make product purity higher, reduce the possibility that by product produces, simultaneously, in preparation method of the present invention, post-processing operation step is easy, product yield is high, preparation method is simple, workable, be worthy to be popularized.
Accompanying drawing explanation
fig. 1 is the reaction equation of preparation method of the present invention.
Embodiment
Below by specific embodiment and accompanying drawing 1, technical scheme of the present invention is described in further detail.
Embodiment 1: the synthesis of cyclohexyl phenyl phospho acid:
By phenyl phosphinic acid 14.2 g(0.1mol), bromocyclohexane 19.6g(0.12 mol), toluene 80mL, diisopropyl ethyl amine 15.5g(0.12mol) and, Pd (OAc)
20.9g(0.004mol), 1,1
,-bis-(diphenylphosphine) ferrocene 2.2g(0.004mol) under nitrogen protection 120 DEG C reaction 18h.PNMR detection reaction, after reaction terminates, cooling, adds suitable quantity of water, adds 20%(wt) sulphuric acid soln acidifying, be extracted with ethyl acetate 2 times, merge organic phase, after brine It, anhydrous sodium sulfate drying, suction filtration, removal of solvent under reduced pressure, obtains product 17.9g, yield 80.1%.
31p NMR(CDCl
3): cyclohexyl phenyl phospho acid: δ: 47.2ppm, 98.3%(purity, by peak meter)
The synthesis of embodiment 2:2,2-dimethylbutyl phenyl phosphinic acid
By phenyl phosphinic acid 14.2 g(0.1mol), 3,3-dimethyl n-butyl bromide 16.4g(0.1 mol), DMF (DMF) 80mL, triethylamine 10.1g(0.1mol) and, Pd (OAc)
20.9g(0.004mol), two diphenylphosphine-9, the 9-dimethyl xanthene 2.3g(0.004mol of 4,5-) 130 DEG C of reaction 24h under nitrogen protection.
31pNMR detection reaction, after reaction terminates, cooling, add suitable quantity of water, add 10%(wt) hydrochloric acid soln acidifying, be extracted with ethyl acetate 2 times, merge organic phase, after brine It, anhydrous sodium sulfate drying, suction filtration, removal of solvent under reduced pressure, obtain obtaining product 16.9 g, yield 75% after white solid methylene dichloride carries out recrystallization.
31p NMR(CDCl
3): 2,2-dimethylbutyl phenyl phosphinic acid: δ: 46.4ppm, 99 %(purity, by peak meter).
Embodiment 3: the synthesis of n-octyl phenyl phosphinic acid
By phenyl phosphinic acid 14.2 g(0.1mol), n-octane bromide 29 g(0.15 mol), ethanol 80mL, salt of wormwood 20.7g(0.15mol) and, Pd (OAc)
20.45g(0.002mol), under nitrogen protection 100 DEG C reaction 30h.
31pNMR detection reaction, after reaction terminates, cooling, adds suitable quantity of water, adds 10%(wt) hydrochloric acid soln acidifying, be extracted with ethyl acetate 2 times, merge organic phase, after brine It, anhydrous sodium sulfate drying, suction filtration, removal of solvent under reduced pressure, obtains product 19.8g, yield 78%.
31p NMR(CDCl
3): n-octyl phenyl phosphinic acid: δ: 44.9 ppm, 91 %(purity, by peak meter).
The synthesis of embodiment 4: two (2-ethylhexyl) phospho acid
By 2-ethylhexyl phosphonous acid sodium 20 g(0.1mol), bromo-iso-octane 11.2(0.1mol), dioxane 70mL, pyridine 7.9g(0.1mol) and, Pd (OAc)
21.1g(0.005mol), 80 DEG C of reaction 24h under nitrogen protection.
31pNMR detection reaction, after reaction terminates, cooling, adds suitable quantity of water, adds formic acid acidifying, be extracted with ethyl acetate 2 times, and merge organic phase, after brine It, anhydrous sodium sulfate drying, suction filtration, removal of solvent under reduced pressure, obtains product 18.9g, yield 65%.
31p NMR(CDCl
3): two (2-ethylhexyl) phospho acid: δ: 61 ppm, 95 %(purity, by peak meter).
Embodiment 5:2-ethylhexyl-2', the synthesis of 4', 4'-tri-methyl-amyl phospho acid
By 2,4,4-tri-methyl-amyl phosphonous acid sodium 20 g(0.1mol), bromo-iso-octane 11.2g(0.1mol), DMF 50mL and octane 20mL, triethylamine 12 g(0.12mol) and, Pd (OAc)
21.1g(0.005mol), 4,6-bis-(diphenylphosphine) azophenlyene 3.3g(0.006mol), 90 DEG C of reaction 24 h under nitrogen protection.PNMR detection reaction, after reaction terminates, cooling, adds suitable quantity of water, adds formic acid acidifying, be extracted with ethyl acetate 2 times, and merge organic phase, after brine It, anhydrous sodium sulfate drying, suction filtration, removal of solvent under reduced pressure, obtains product 20.7 g, yield 71.2%.
31p NMR(CDCl
3): 2-ethylhexyl-2', 4', 4'-tri-methyl-amyl phospho acid: δ: 61.3ppm, 92.0%(purity, by peak meter)
The synthesis of embodiment 6 1-methylheptyl-cyclohexyl phospho acid
by cyclohexyl phosphonous acid sodium 17g(0.1mol), sec-Octyl Bromide 23.2g(0.13mol), toluene 65mL and ethanol 5mL, sodium carbonate 13.8g(0.13mol) and, Pd/xantphos 2.4 g(0.003mol), 110 DEG C of reaction 24h under nitrogen protection.PNMR detection reaction, after reaction terminates, cooling, adds suitable quantity of water, adds acidifying with acetic acid, be extracted with ethyl acetate 2 times, and merge organic phase, after brine It, anhydrous sodium sulfate drying, suction filtration, removal of solvent under reduced pressure, obtains product 22 g, yield 85%.
31p NMR(CDCl
3): 1-methylheptyl-cyclohexyl phospho acid: δ: 60.3 ppm, 94 %(purity, by peak meter)
The synthesis of embodiment 7: two (NSC 62789 base) phospho acid:
By Octadecane base phosphonous acid sodium 34g(0.1mol), bromo Octadecane 63.9 g(0.2mol), suberane 80 mL, diisopropyl ethyl amine 25.8g(0.2mol) and, Pd/dppf 7.8g(0.01mol), 80 DEG C of reaction 30 h.P composes detection reaction, and after reaction terminates, cooling, adds suitable quantity of water, add acidifying with acetic acid, be extracted with ethyl acetate 2 times, and merge organic phase, after brine It, anhydrous sodium sulfate drying, suction filtration, removal of solvent under reduced pressure, obtains product 34.2 g, yield 60%.
31p NMR(CDCl
3): two (NSC 62789 base) phospho acid: δ: 59 ppm, 90 %(purity, by peak meter)
Embodiment 8: the synthesis of methyl-cyclohexyl base-phospho acid
By methyl-phosphinic acid 8.0g(0.1mol), bromocyclohexane 24.5 g(0.15 mol), toluene 80mL, salt of wormwood 20.7g(0.15mol) and, Pd (OAc)
20.45g(0.002mol), under nitrogen protection 100 DEG C reaction 24h.PNMR detection reaction, after reaction terminates, cooling, adds suitable quantity of water, adds 10%(wt) hydrochloric acid soln acidifying, be extracted with ethyl acetate 2 times, merge organic phase, after brine It, anhydrous sodium sulfate drying, suction filtration, removal of solvent under reduced pressure, obtains product 12.6g, yield 78%.
31p NMR(CDCl
3): methylcyclohexyl phospho acid: δ: 59.8 ppm, 92 %(purity, by peak meter)
Embodiment 9:(benzyl) synthesis of (4-phenylcyclohexyl) phospho acid
by benzyl phospho acid 15.6g(0.1mol), dioxane 65mL, N; dinethylformamide DMF 5 mL; 4-phenyl-1-bromine hexanaphthene 23.9g(0.1mol), triethylamine 10.1g(0.1mol) Pd/xantphos 2.4 g(0.003mol), 110 DEG C of reaction 18h under nitrogen protection.PNMR detection reaction, after reaction terminates, cooling, adds suitable quantity of water, adds acidifying with acetic acid, be extracted with ethyl acetate 2 times, and merge organic phase, after brine It, anhydrous sodium sulfate drying, suction filtration, removal of solvent under reduced pressure, obtains product 24.5 g, yield 78%.
31p NMR:(benzyl) (4-phenylcyclohexyl) phospho acid: δ: 60.5ppm, 91%(purity, by peak meter).
Effect example: the performance test organic phase of two alkyl phosphinic acid extracting rare-earths of different structure: two alkyl phosphinic acid is mixed with 0.2M n-dodecane solution aqueous phase: [Ln]=0.01M, [(H, Na) Cl]=1.0M
Two alkyl phosphinic acid compounds obtained in above-described embodiment 1-6 are dissolved in n-dodecane respectively as extraction agent, the concentration of extraction agent in n-dodecane is 0.2mol/L, aqueous phase rare earth ion concentration is 0.01mol/L, sodium chloride concentration is 1mol/L, and pH value is 3, this aqueous phase and organic phase is respectively got 10mL and jointly adds in separating funnel, aqueous phase and organic phase ratio are 1:1, after concussion 30min, leave standstill phase-splitting, water intaking phase or organic phase are carried out reextraction and are analyzed rare earth ion concentration.
Dialkyl phosphinic acid extractant prepared by Application Example 1-6, the performance of extracting rare-earth is as shown in the table:
The extraction agent preparing synthesis as can be seen from the present invention carries out the result of rare earths separation, and this series of dialkyl phosphinic acid extractant Performance comparision is excellent.
Preparation method of the present invention, can synthesize a series of pair of alkyl phosphinic acid extraction agent quickly and efficiently, comprises symmetrical and asymmetric extraction agent, reaction process composes tracking by nuclear-magnetism P can determine the reaction times more accurately, reaction conversion ratio is high, and raw material is environmental protection more, simultaneously easy and simple to handle, safety.
The above, be only the present invention's preferably embodiment, but scope is not limited thereto, and is equal to and replaces or change, all should be encompassed within protection scope of the present invention according to technical scheme of the present invention and inventive concept thereof.
Claims (10)
1. two alkyl phosphinic acid compounds or its salt, the general formula of its pair of alkyl phosphinic acid compounds or its salt is for such as formula described in I:
Wherein R
1for hydrogen, replacement or unsubstituted C
1-C
20alkyl, replacement or unsubstituted C
5-C
8cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted benzyl;
R
2for replacing or not being substituted C
1-C
20alkyl, replacement or unsubstituted C
5-C
8cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted benzyl;
M is H, alkalimetal ion, alkaline-earth metal ions or ammonium radical ion.
2. according to claim 1 pair of alkyl phosphinic acid compounds or its salt, is characterized in that: described R
1and R
2in, described replacement refers to and to be replaced by following one or more substituting group: C
1-C
4alkyl, C
3-C
10cycloalkyl, halogen, ester group, alkoxyl group.
3. a preparation method for two alkyl phosphinic acid compounds or its salt, is characterized in that: comprise the steps one;
By the compound shown in the compound shown in following formula A and following formula B at catalyst P dL
n, alkali, under inert solvent existent condition, under the protection of nitrogen, Heating temperature is react 10-30 h under 80-180 DEG C of condition, carries out the step that intersection coupled reaction as follows obtains two alkyl phosphinic acid compounds or its salt;
Wherein R
1for hydrogen, replacement or unsubstituted C
1-C
20alkyl, replacement or unsubstituted C
5-C
8cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted benzyl;
R
2for replacing or unsubstituted C
1-C
20alkyl, replacement or unsubstituted C
5-C
8cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted benzyl;
M is H, alkalimetal ion, alkaline-earth metal ions or ammonium radical ion;
In B, X is halogen.
4. preparation method according to claim 3, is characterized in that: also comprise the steps;
Step 2: the product obtained above-mentioned steps one carries out the step of PNMR detection reaction;
Step 3: by above-mentioned steps two gained reaction solution through filtering, adding suitable quantity of water, acidifying, organic solvent extraction obtains the step of organic layer;
Step 4: step 3 is obtained the step that organic layer carries out drying, filtration, decompression removal solvent.
5. preparation method as claimed in claim 3, is characterized in that, described used catalyst P dL
n,wherein L is 1,1
,-bis-(diphenylphosphine) ferrocene (dppf), 4,5-two diphenylphosphine-9,9-dimethyl xanthene (xantphos), polymkeric substance (polymer), 4,6-bis-(diphenylphosphine) azophenlyene (nixantphos), acetate (AcO
-), the halogen X shown in described formula B is chlorine or bromine or iodine, and described alkali is organic bases or mineral alkali, and described alkali is diisopropyl ethyl amine (DIPA), triethylamine (Et
3n) wherein a kind of, in pyridine, quadrol, piperidines, salt of wormwood, sodium carbonate, cesium carbonate, sodium-acetate, described inert solvent is C
5-C
20alkane solvents, C
5-C
20cycloalkane solvent, C
2-C
10esters solvent, C
2-C
10ether solvent, C
6-C
20aryl kind solvent, C
2-C
10alcoholic solvent and C
2-C
10one or more in amide solvent, the temperature of reaction is 100-130 DEG C; The time of described reaction is 18-24 h, described such as formula the compound shown in B with the mol ratio such as formula the compound shown in A for being more than or equal to 1.0, described catalyst P dL
nconsumption be 0.01-0.1 such as formula the mol ratio of the compound shown in A, the consumption of described alkali with the mol ratio such as formula the compound shown in A for being more than or equal to 1.
6. as right wants the preparation method as described in 3, it is characterized in that, described C
4-C
10alkyl be 3,3-dimethylbutyl, 2,4,4-tri-methyl-amyls, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl one wherein.
7. preparation method as claimed in claim 4, it is characterized in that: described step 3 for by step 2 gained reacting liquid filtering, add water, acidifying, extraction into ethyl acetate aqueous phase repeatedly, the step of organic layer, the sulfuric acid that the acid solution of described use is 10%-30% for massfraction, massfraction are 10%-30% hydrochloric acid, acetic acid, citric acid wherein one or more.
8. preparation method as claimed in claim 7, is characterized in that: described in obtain organic layer after, organic layer is washed to neutrality, salt washing, dry, decompression removes solvent.
9. preparation method as claimed in claim 4, is characterized in that: the hydrochloric acid of acid solution for massfraction 10%-20% of described use, the sulfuric acid of 10%-30%.
10. preparation method as claimed in claim 4, is characterized in that: two alkyl phosphinic acid compounds step 4 obtained or the thick product of its salt are through recrystallization, underpressure distillation, column chromatography.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632465A (en) * | 2016-12-05 | 2017-05-10 | 北京科技大学 | Synthetic method for (2-ethylhexyl)(2,4,4'-trimehtyl amyl) phosphinic acid |
| CN110511242A (en) * | 2019-08-21 | 2019-11-29 | 贵州省材料产业技术研究院 | A kind of preparation method of high-purity monoalkylphosphinic acids |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632465A (en) * | 2016-12-05 | 2017-05-10 | 北京科技大学 | Synthetic method for (2-ethylhexyl)(2,4,4'-trimehtyl amyl) phosphinic acid |
| CN110511242A (en) * | 2019-08-21 | 2019-11-29 | 贵州省材料产业技术研究院 | A kind of preparation method of high-purity monoalkylphosphinic acids |
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