CN108314693B - Method for improving stability of alkyl phosphonic acid anhydride derivative - Google Patents
Method for improving stability of alkyl phosphonic acid anhydride derivative Download PDFInfo
- Publication number
- CN108314693B CN108314693B CN201810019642.4A CN201810019642A CN108314693B CN 108314693 B CN108314693 B CN 108314693B CN 201810019642 A CN201810019642 A CN 201810019642A CN 108314693 B CN108314693 B CN 108314693B
- Authority
- CN
- China
- Prior art keywords
- alkyl phosphonic
- stabilizer
- anhydride derivative
- phosphonic anhydride
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 alkyl phosphonic acid Chemical compound 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003381 stabilizer Substances 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims 1
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 11
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012445 acidic reagent Substances 0.000 description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- PAQZWJGSJMLPMG-UHFFFAOYSA-N propylphosphonic anhydride Substances CCCP1(=O)OP(=O)(CCC)OP(=O)(CCC)O1 PAQZWJGSJMLPMG-UHFFFAOYSA-N 0.000 description 3
- OLQJQHSAWMFDJE-UHFFFAOYSA-N 2-(hydroxymethyl)-2-nitropropane-1,3-diol Chemical compound OCC(CO)(CO)[N+]([O-])=O OLQJQHSAWMFDJE-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a method for improving the stability of alkyl phosphonic anhydride derivatives, which is a method for adding a stabilizer into the alkyl phosphonic anhydride derivatives for treatment and then obtaining alkyl phosphonic anhydride derivatives with higher stability; the stabilizer is treated silicon dioxide or aluminosilicate; the treated silicon dioxide or aluminosilicate is added into the alkyl phosphonic anhydride derivative to be treated as a stabilizer, so that the stability of the alkyl phosphonic anhydride derivative can be effectively improved, and the shelf life and the service life can be prolonged.
Description
Technical Field
The invention relates to a method for improving the stability of alkyl phosphonic anhydride derivatives, belonging to the technical field of compound processing.
Background
The alkylphosphonic acid anhydride can be applied to polypeptide condensing agents, has the characteristic of easy separation, can obtain alkylphosphonic acid products again by recycling the obtained alkylphosphonic acid aqueous solution and performing the conventional operation process, realizes the cyclic utilization of phosphorus elements, has zero emission to the environment and realizes the environmental friendliness of the products.
In recent years, the alkyl phosphonic acid anhydride derivatives added into the lithium battery electrolyte with a specific formula have the characteristics of obviously protecting electrodes, have the obvious effects of high-temperature stability and improvement of battery voltage, effectively improve the energy density of the battery, and can be used for manufacturing power lithium batteries.
The known synthesis technical means is to dehydrate alkyl phosphonic acid or alkyl phosphonate into polyalkyl phosphonic acid through solution reaction, and then obtain a crude product of phosphonic acid anhydride with a specific composition through high-temperature high-vacuum reactive distillation. The improvement in the quality of the crude product needs to be achieved by repeated distillation, giving a colorless to pale yellow product, even though the product obtained by such operation has a problem of storage stability. During storage, the colorless product also gradually turns yellow with the increase of storage time, and the change of color indirectly reflects the change of the product quality, so that the application is limited, particularly in the aspect of electronic materials with high stability and high purity.
The quality and the storage stability of the product severely restrict the later application of the product, in particular the use in lithium battery materials.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for improving the stability of alkyl phosphonic anhydride derivatives, wherein the alkyl phosphonic anhydride derivatives are added with treated silicon dioxide or aluminosilicate as a stabilizer for treatment, so that the stability of the alkyl phosphonic anhydride derivatives can be effectively improved, and the shelf life and the service life can be prolonged.
The purpose of the invention can be achieved by adopting the following technical scheme: a method for improving the stability of alkyl phosphonic anhydride derivatives is a method for adding a stabilizer into the alkyl phosphonic anhydride derivatives for treatment and then obtaining alkyl phosphonic anhydride derivatives with higher stability; the stabilizer is treated silica or aluminosilicate.
Further, the chemical formula of the alkyl phosphonic anhydride derivative is shown as formula I or formula II;
wherein R is1、R2And R3Is a linear or branched C1-C5 alkyl group, n is 1-10, A1Is alkoxy or hydroxy; a. the2Is alkyl or hydrogen.
Further, said R1、R2And R3Are all n-propyl.
Further, the silica or aluminosilicate is treated by: adding silicon dioxide or aluminosilicate into water with pH more than 7, and adding 10-60 wt% to obtain suspension; adjusting the temperature of the suspension to 10-80 ℃, the pH to 7-8, stirring for at least 0.5h under the conditions of a stirring speed of 200 and 400rpm, and then filtering to obtain filter residue.
Further, before treatment, the purity of the silicon dioxide is more than 95 percent, and the particle size is less than or equal to 30 percent0 μm; the structural general formula of the aluminosilicate is as follows: m2/a·Al2O3·bSiO2·cH2O, where M is an alkali metal, an alkaline earth metal, H and NH3Wherein a is the valence of the M element, b is 1.8-12, and c is 0-8.
Further, the alkaline agent for adjusting pH is at least one of an organic amine compound, an alkaline earth metal hydroxide, and a main group metal oxide; the acidic reagent for adjusting the pH is at least one of inorganic acids.
Further, the organic amine compound is at least one of methylamine, diethylamine, triethylamine and trihydroxymethyl nitromethane.
Further, the alkaline earth metal hydroxide is at least one of potassium hydroxide, sodium hydroxide, and barium hydroxide.
Further, the main group metal oxide is at least one of calcium oxide and magnesium oxide.
Further, the inorganic acid is at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
Further, comprising:
a dissolving step: preparing the alkyl phosphonic anhydride derivative into a solution with the weight percent of 10-70, wherein the used solvent is an organic solvent;
mixing: contacting the solution of the alkyl phosphonic anhydride derivative with a stabilizer, wherein the mass ratio of the stabilizer to the alkyl phosphonic anhydride derivative is (0.1-10): 100;
the extraction step comprises: filtering to obtain filtrate.
Further, in the mixing step, the stabilizer is added to the solution of the alkylphosphonic anhydride derivative and stirred.
Further, in the mixing step, the stabilizer is loaded on the filter unit, and then the alkylphosphonic anhydride derivative solution is passed through the stabilizer.
Further, in the mixing step, the mass ratio of the stabilizer to the alkylphosphonic acid anhydride derivative is (0.5-3): 100.
Further, in the extraction step, filtration is performed with neutral or weakly alkaline activated carbon.
Compared with the prior art, the invention has the beneficial effects that:
the invention adds the treated silicon dioxide or aluminosilicate as the stabilizer into the alkyl phosphonic anhydride derivative for treatment, can effectively delay the color change or change the structure of the alkyl phosphonic anhydride derivative, improve the stability and prolong the retention period and the service life.
Detailed Description
The invention will be further described with reference to specific embodiments:
a method for improving the stability of alkyl phosphonic anhydride derivatives, wherein the chemical formula of the alkyl phosphonic anhydride derivatives is formula I or formula II;
wherein R is1、R2And R3Is a linear or branched C1-C5 alkyl group, n is 1-10, A1Is alkoxy or hydroxy; a. the2Is alkyl or hydrogen.
1. Preparation of reagents:
1) a stabilizer:
the silica or aluminosilicate in the stabilizer is treated by the following method: adding silicon dioxide or aluminosilicate into water with pH more than 7, and adding 10-60 wt% to obtain suspension; adjusting the temperature of the suspension to 10-80 ℃, the pH to 7-8, stirring for at least 0.5h under the conditions of a stirring speed of 200-400rpm, wherein the pH of the suspension needs to be kept at 7-8, and the pH can be increased by continuously adding an alkaline reagent or reduced by an acidic reagent; filtering to obtain filter residue, washing with water, drying the filter residue at above 200 deg.C, and keeping air circulation during drying.
Before treatment, the purity of the used silicon dioxide is more than 95 percent, and the particle size is less than or equal to 300 mu m; the structural general formula of aluminosilicate is: m2/a·Al2O3·bSiO2·cH2O, where M is an alkali metal, an alkaline earth metal, H and NH3Wherein a is the valence of the M element, b is 1.8-12, and c is 0-8.
The alkaline reagent used for adjusting the pH is at least one of methylamine, diethylamine, triethylamine and trihydroxymethyl nitromethane in the organic amine compound, or at least one of potassium hydroxide, sodium hydroxide and barium hydroxide in the alkaline earth metal hydroxide, or at least one of calcium oxide and magnesium oxide in the main group metal oxide; the acidic reagent for adjusting pH is at least one of hydrochloric acid, sulfuric acid and phosphoric acid in inorganic acid.
2) Alkyl phosphonic anhydride derivative solution: preparing 40-60 wt% alkyl phosphonic anhydride derivative solution with ethyl acetate, diethyl carbonate or toluene as solvent;
2. mixing:
the solution of alkylphosphonic anhydride derivative may be contacted with the stabilizer by one of the following means, the mass ratio of stabilizer to alkylphosphonic anhydride derivative being (0.5-3) to 100:
1) adding the stabilizer into the alkyl phosphonic anhydride derivative solution, and stirring for 5-120 min;
2) loading a stabilizer on the filter device, and then passing the alkyl phosphonic anhydride derivative solution through the stabilizer;
3. extraction:
filtering with neutral or weakly alkaline active carbon to obtain filtrate, and storing the alkyl phosphonic anhydride derivative directly in solution or after removing solvent.
Example 1:
a method for improving the stability of alkyl phosphonic anhydride derivatives, R1、R2And R31-propylphosphonic anhydride compounds which are each n-propyl.
1. Preparation of reagents:
1) a stabilizer: untreated silica about 300 mesh, 10 g;
and (3) treatment: adding silicon dioxide into 27g of water to obtain a suspension; adjusting the temperature of the suspension to 50 ℃, adjusting the pH to 7-8 by using trihydroxymethyl aminomethane, stirring for 2.5h at a stirring speed of 300rpm, wherein the pH of the suspension needs to be kept at 7-8, and the pH can be increased by continuously adding the trihydroxymethyl aminomethane or reduced by using dilute hydrochloric acid; then filtering and taking filter residue, washing the filter residue with water for three times, drying the filter residue at 300 ℃ for 3h, and introducing 100mL/min of air during drying to obtain the stabilizer.
2) 1-propylphosphonic anhydride solution: adding 400g of 1-propyl phosphonic anhydride into 400g of ethyl acetate to obtain a 1-propyl phosphonic anhydride solution; 200g of this solution was taken and retained as a control sample (AP-1), and another 200g of the solution (AP-1') was taken for subsequent experiments.
2. Mixing:
loading a stabilizing agent on a silica gel chromatography glass column, then enabling AP-1 'to pass through the stabilizing agent, reserving 50g (AP-2) of sample solution, and taking 150g (AP-2') of the sample solution for a subsequent test;
3. extraction:
the filtrate was collected by neutral activated carbon filtration of AP-2' and stored (AP-3).
AP-1, AP-2 and AP-3 were compared after 6 and 12 weeks under the same storage conditions: after 6 weeks, the color of AP-1 is darkest, and the color of AP-2 and AP-3 are basically the same; after 12 weeks AP-1 was the darkest and AP-2 was slightly darker than AP-3.
Example 2:
a method for improving the stability of alkyl phosphonic anhydride derivatives, R1、R2And R3Methylphosphonic acid anhydride compounds all being methyl.
The procedure for stability improvement was the same as in example 1.
AP-1, AP-2 and AP-3 were compared after 6 and 12 weeks under the same storage conditions: after 6 weeks, the color of AP-1 is darkest, and the color of AP-2 and AP-3 are basically the same; after 12 weeks AP-1 was the darkest and AP-2 was slightly darker than AP-3.
Various other changes and modifications to the above-described embodiments and concepts will become apparent to those skilled in the art from the above description, and all such changes and modifications are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (7)
1. A method for improving the stability of alkyl phosphonic anhydride derivatives is characterized in that a stabilizer is added into the alkyl phosphonic anhydride derivatives for treatment, and then the alkyl phosphonic anhydride derivatives with higher stability are obtained; the stabilizer is treated silicon dioxide; the silica is treated by the following method: adding silicon dioxide into water with pH value more than 7, wherein the adding amount is 10-60 wt%, and obtaining suspension; adjusting the temperature of the suspension to 10-80 ℃, the pH to 7-8, stirring for at least 0.5h under the conditions of a stirring speed of 200 and 400rpm, and then filtering to obtain filter residues; the chemical formula of the alkyl phosphonic anhydride derivative is shown as formula I;
wherein R is1、R2And R3Is straight chain or branched chain C1-C5 alkyl, and n is 1-10.
2. The method of claim 1, wherein R is selected from the group consisting of1、R2And R3Are all n-propyl.
3. The method of claim 1 for enhancing the stability of an alkylphosphonic acid anhydride derivative comprising:
a dissolving step: preparing the alkyl phosphonic anhydride derivative into a solution with the weight percent of 10-70, wherein the used solvent is an organic solvent;
mixing: contacting the solution of the alkyl phosphonic anhydride derivative with a stabilizer, wherein the mass ratio of the stabilizer to the alkyl phosphonic anhydride derivative is (0.1-10): 100;
the extraction step comprises: filtering to obtain filtrate.
4. The method of claim 3, wherein the stabilizer is added to the solution of the alkylphosphonic anhydride derivative and stirred during the mixing step.
5. The method of claim 3, wherein the mixing step comprises loading the stabilizing agent on a filter device and then passing the solution of the alkylphosphonic anhydride derivative through the stabilizing agent.
6. The method of claim 3, wherein the mass ratio of the stabilizer to the alkylphosphonic anhydride derivative in the mixing step is (0.5-3): 100.
7. The method of claim 3, wherein the step of extracting comprises filtration with neutral or weakly basic activated carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810019642.4A CN108314693B (en) | 2018-01-09 | 2018-01-09 | Method for improving stability of alkyl phosphonic acid anhydride derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810019642.4A CN108314693B (en) | 2018-01-09 | 2018-01-09 | Method for improving stability of alkyl phosphonic acid anhydride derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108314693A CN108314693A (en) | 2018-07-24 |
| CN108314693B true CN108314693B (en) | 2020-06-09 |
Family
ID=62894175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810019642.4A Active CN108314693B (en) | 2018-01-09 | 2018-01-09 | Method for improving stability of alkyl phosphonic acid anhydride derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108314693B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1823079A (en) * | 2003-07-21 | 2006-08-23 | 科莱恩产品（德国）有限公司 | The preparation method of cyclic phosphonic anhydride |
| CN103483386A (en) * | 2013-08-30 | 2014-01-01 | 山东汇海医药化工有限公司 | Improved preparation method of 1-propylphosphoric cyclic anhydride |
| CN107011384A (en) * | 2017-04-24 | 2017-08-04 | 中节能万润股份有限公司 | A kind of preparation method of ring-type propyl phosphonous acid acid anhydride |
-
2018
- 2018-01-09 CN CN201810019642.4A patent/CN108314693B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1823079A (en) * | 2003-07-21 | 2006-08-23 | 科莱恩产品（德国）有限公司 | The preparation method of cyclic phosphonic anhydride |
| CN103483386A (en) * | 2013-08-30 | 2014-01-01 | 山东汇海医药化工有限公司 | Improved preparation method of 1-propylphosphoric cyclic anhydride |
| CN107011384A (en) * | 2017-04-24 | 2017-08-04 | 中节能万润股份有限公司 | A kind of preparation method of ring-type propyl phosphonous acid acid anhydride |
Non-Patent Citations (3)
| Title |
|---|
| "An optimized and scalable synthesis of propylphosphonic anhydride for general use";H. Pizova et al.;《Tetrahedron Letters》;20150305;第56卷(第15期);第2014-2017页 * |
| "一种新的环状膦酸酐的合成与X射线晶体结构";安德烈等;《化学学报》;20040630;第62卷(第12期);第1166-1170页 * |
| "正丙级膦酸酐的合成及其在胸腺五肽合成上的应用";耿斌等;《精细与专用化学品》;20130921;第21卷(第9期);第28-31页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108314693A (en) | 2018-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109193063B (en) | Method for reprocessing positive active material of waste lithium ion battery | |
| CN104817059B (en) | A kind of method that battery-grade iron phosphate is prepared by iron powder and phosphatase reaction | |
| US9084980B2 (en) | Zeolite for treatment of nonaqueous electrolytic solution and treatment method of nonaqueous electrolytic solution | |
| US12162774B2 (en) | Method of preparing lithium compound | |
| JP5406386B2 (en) | Method for producing manganese sulfate monohydrate | |
| CN109535191B (en) | A kind of preparation method of lithium bis-oxalate borate | |
| JP7442617B2 (en) | Method for producing lithium hydroxide | |
| CN108314693B (en) | Method for improving stability of alkyl phosphonic acid anhydride derivative | |
| JP2024538354A (en) | Method for purifying lithium bis(fluorosulfonyl)imide | |
| CN109231180B (en) | Method for preparing high-purity barium dihydrogen phosphate | |
| CN116375020B (en) | Method for improving dispersibility of alkali purified graphite | |
| CN107732209A (en) | A method for preparing lithium-ion carbon negative electrode materials from mixed bacterial residue waste | |
| CN104627974B (en) | A kind of production method of battery-grade iron phosphate | |
| CN104752755B (en) | The preparation method of sulfide solid electrolyte | |
| CN108586263A (en) | A kind of simple and convenient process for preparing of tetraethyl ammonium tetrafluoroborate | |
| JP2005298375A (en) | Purification method of room temperature molten salt | |
| KR102744969B1 (en) | Method of preparing for cyanoethylpolyvinylalcohol | |
| AU2019336612B2 (en) | Method for controlling the properties of biogenic silica | |
| CN104445327A (en) | Method for treating potassium element in aluminum electrolyte by using acid process | |
| CN115386878A (en) | Copper metal etching liquid composition and use method thereof | |
| JP6180718B2 (en) | Method for producing lithium iodide aqueous solution and use thereof | |
| CN115849387B (en) | Method for preparing silica gel by utilizing steel slag powder | |
| CN101397126B (en) | Method for preparing primary standard reagent potash iodate | |
| JP2012067017A (en) | Method for producing fluorine-containing cyclic carbonate | |
| JP2006169134A (en) | Method for producing lignin from which organic acid is removed and lead storage battery obtained by adding lignin from which organic acid is removed to negative electrode active substance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: 215000 No. 388 Shui Shui Road, Suzhou Industrial Park, Jiangsu Patentee after: SUZHOU YACOO SCIENCE Co.,Ltd. Address before: 215000 No. 415, Changyang street, Suzhou Industrial Park, Jiangsu Patentee before: SUZHOU YACOO SCIENCE Co.,Ltd. |
|
| CP02 | Change in the address of a patent holder |