CN109293694B - One-pot preparation of aluminum methylphosphinate - Google Patents
One-pot preparation of aluminum methylphosphinate Download PDFInfo
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- CN109293694B CN109293694B CN201811456096.7A CN201811456096A CN109293694B CN 109293694 B CN109293694 B CN 109293694B CN 201811456096 A CN201811456096 A CN 201811456096A CN 109293694 B CN109293694 B CN 109293694B
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- JQXGYQOIODSVCH-UHFFFAOYSA-K CP([O-])=O.CP([O-])=O.CP([O-])=O.[Al+3] Chemical compound CP([O-])=O.CP([O-])=O.CP([O-])=O.[Al+3] JQXGYQOIODSVCH-UHFFFAOYSA-K 0.000 title claims abstract description 55
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 37
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- BCDIWLCKOCHCIH-UHFFFAOYSA-N methylphosphinic acid Chemical compound CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 15
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 150000007529 inorganic bases Chemical class 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- -1 methyl aluminum phosphinate Chemical compound 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- BCDIWLCKOCHCIH-UHFFFAOYSA-M methylphosphinate Chemical compound CP([O-])=O BCDIWLCKOCHCIH-UHFFFAOYSA-M 0.000 abstract description 2
- XKCQASMZNPBLKI-UHFFFAOYSA-N phosphorosooxymethane Chemical compound COP=O XKCQASMZNPBLKI-UHFFFAOYSA-N 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 19
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 19
- 239000007787 solid Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LOAHJABDATVOQU-UHFFFAOYSA-N ethyl(methyl)alumane Chemical compound C[AlH]CC LOAHJABDATVOQU-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002602 strong irritant Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a method for preparing methyl aluminum phosphinate by a one-pot method, belonging to the technical field of chemical synthesis. The invention provides a one-pot method for preparing aluminum methylphosphinate, which comprises the following steps: taking dichloromethylphosphine as a raw material, and reacting with water to prepare a methylphosphinic acid aqueous solution; and (3) adjusting the pH value of the methyl hypophosphite aqueous solution to be less than or equal to 3 and less than 7, adding aluminum sulfate, and reacting to obtain the methyl hypophosphite aluminum salt. The method takes dichloromethylphosphine as an initial raw material to prepare the aluminum methylphosphinate by a one-pot method, and the methylphosphinate does not need to be separated; by controlling the water consumption, the side reaction of the dichloro methyl phosphine can be avoided, and the yield of the methyl phosphinic acid is improved; optimizing the pH value of salification, and improving the yield of the aluminum methylphosphinate; the method has the advantages of cheap and easily obtained raw materials, simple operation and convenient post-treatment, and is favorable for realizing the industrial production of the aluminum methylphosphinate.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and relates to a one-pot method for preparing aluminum methylphosphinate.
Background
The alkyl hypophosphorous acid metal salt is a new generation of green environmental protection phosphorus flame retardant developed in recent years. In the research and development aspect of the flame retardant, at present, China is still in the initial stage, and alkyl hypophosphite series flame retardants mainly depend on import. Although a few research units have been conducting the synthesis research of alkyl hypophosphorous acid or its salt in China, the research is far behind abroad, not to mention the large-scale application in industrial production.
The aluminum methylphosphinate is a good flame retardant with condensed phase and gas phase flame retardance in the metal alkyl phosphinate. Quan Hu et al (Journal of Thermal Analysis and calibration, 2017, vol.128, #1, p.201-210) disclose a process for preparing aluminum methylphosphinate by reacting methylphosphinic acid as a starting material with sodium hydroxide, in turn, aluminum sulfate; however, the starting material methylphosphinic acid for this process is relatively expensive.
CN107021981A discloses a method for preparing methyl ethyl aluminum hypophosphite, wherein a hydrochloric acid aqueous solution is adopted to prepare methyl phosphinic acid, the reaction is violent, the requirement on equipment is high, a large amount of hydrogen chloride gas can be generated, the corrosion to reaction equipment is serious, in addition, in order to remove the hydrogen chloride as far as possible, HCl in a system needs to be removed under negative pressure, the reaction environment is complex, and the industrial application is not facilitated.
Therefore, a method for producing aluminum methylphosphinate with low cost and simple operation is urgently needed.
Disclosure of Invention
The invention provides a one-pot method for preparing aluminum methylphosphinate, aiming at solving the problems in the prior art, and the method comprises the following steps:
A. taking dichloromethylphosphine as a raw material, and reacting with water to prepare a methylphosphinic acid aqueous solution;
B. and C, adjusting the pH value of the aqueous solution of the methylphosphinic acid obtained in the step A to be less than or equal to 3 and less than 7, adding aluminum sulfate, and reacting to obtain the aluminum methylphosphinate.
Wherein, in the one-pot method for preparing the aluminum methylphosphinate, the step A is carried out under the protection of inert gas.
In the one-pot method for preparing the aluminum methylphosphinate, in the step A, the molar ratio of the water to the dichloromethylphosphine is more than 2.2: 1.
preferably, in the one-pot method for preparing the aluminum methylphosphinate, in the step a, the molar ratio of the water to the dichloromethylphosphine is 2.4-3: 1.
wherein, in the one-pot method for preparing the aluminum methylphosphinate, the specific operation of the step A is as follows: dropwise adding dichloromethylphosphine into water at-10-80 ℃ for reaction.
Preferably, in the above one-pot method for preparing the aluminum methylphosphinate, the specific operation of step a is as follows: dropwise adding dichloromethylphosphine into water at-10 ℃ to perform reaction.
In the one-pot method for preparing the aluminum methylphosphinate, in the step A, after the reaction is completed, the method also comprises the step of heating to remove HCl.
In the one-pot method for preparing the aluminum methylphosphinate, in the step A, the temperature for raising the temperature to remove HCl is not less than 80 ℃.
Preferably, in the one-pot method for preparing the aluminum methylphosphinate, in the step A, the temperature for raising the temperature to remove HCl is 120-130 ℃.
Preferably, in the one-pot method for preparing the aluminum methylphosphinate, in the step B, the pH of the aqueous solution of methylphosphinic acid obtained in the step A is adjusted to be less than or equal to 5 and less than or equal to 7.
In the step B, inorganic base is adopted to adjust the pH, wherein the inorganic base is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate.
Preferably, in the one-pot method for preparing the aluminum methylphosphinate, in the step B, the inorganic base is sodium hydroxide or sodium carbonate.
In the one-pot method for preparing the aluminum methylphosphinate, in the step B, the molar ratio of the aluminum sulfate to the dichloromethylphosphine is 1: 5.4 to 6.2.
Wherein, in the step B, the reaction temperature is 70-110 ℃ in the one-pot method for preparing the aluminum methylphosphinate.
In the step B, the reaction time is 4-48 h in the one-pot method for preparing the aluminum methylphosphinate.
The invention has the beneficial effects that:
the method takes dichloromethylphosphine as an initial raw material to prepare the aluminum methylphosphinate by a one-pot method, and the methylphosphinate does not need to be separated; by controlling the water consumption, the side reaction of the dichloromethylphosphine can be avoided, and the yield of the methylphosphinic acid is improved by optimizing the reaction conditions, so that HCl in the methylphosphinic acid aqueous solution is removed as much as possible; then optimizing the pH value of salification, and improving the yield of the aluminum methylphosphinate; the method has the advantages of cheap and easily obtained raw materials, simple operation and convenient post-treatment, and is favorable for realizing the industrial production of the aluminum methylphosphinate.
Detailed Description
Specifically, the one-pot method for preparing the aluminum methylphosphinate comprises the following steps:
A. taking dichloromethylphosphine as a raw material, and reacting with water to prepare a methylphosphinic acid aqueous solution;
B. and C, adjusting the pH value of the aqueous solution of the methylphosphinic acid obtained in the step A to be less than or equal to 3 and less than 7, adding aluminum sulfate, and reacting to obtain the aluminum methylphosphinate.
The inventors have surprisingly found that an excess of more than 10% of water is advantageous in suppressing the occurrence of side reactions when preparing methylphosphinic acid: when the mol of the water and the dichloromethylphosphine is not more than 2.2 (such as 2.2: 1, 2: 1, 1.8: 1 and 1.6: 1), a white solid with strong irritation and odor is found to be generated in the process of heating after ice bath; therefore, the amount of water to be used is at least 2.2 times (molar ratio) greater than that of dichloromethylphosphine; however, the difficulty of HCl removal by subsequent heating is increased and the yield of aluminum salt is influenced due to excessive water, and the molar ratio of water to dichloromethylphosphine is preferably 2.4-3: 1.
in the step A of the method, dichloromethylphosphine reacts violently with water, preferably under the temperature of minus 10-10 ℃ (such as ice bath), dichloromethylphosphine is dropwise added into water (if water is dropwise added into dichloromethylphosphine, the reaction effect is poor), the reaction is carried out (the reaction rate is high, the reaction time is determined according to the reaction scale, the temperature is generally kept for 10-20 min after the dropwise addition is finished, and the temperature is raised to remove HCl, so that the methylphosphinic acid aqueous solution is obtained.
Usually, dichloromethylphosphine is added into water dropwise, and a byproduct, namely hydrogen chloride can be generated in the reaction and can be absorbed by alkali liquor; after the dropwise addition is finished, the temperature can be increased to not less than 80 ℃, the temperature has little influence on the conversion rate, the residual quantity of HCl in the methylphosphinic acid solution is mainly influenced, the higher the temperature is, the better the removal effect is, and the shorter the time is; therefore, the temperature for heating to remove HCl is preferably 120-130 ℃; in order to ensure that HCl is sufficiently removed, the temperature is generally kept for 4-8 h (taking the stable content of chloride ions as a reference), the residual amount of HCl is reduced as much as possible, and the influence of HCl on the subsequent reaction is avoided.
In the present invention, HCl removal is carried out under normal pressure, usually without using negative pressure, which is easy to pump out methylphosphinic acid, for example: the methylphosphinic acid component was detected in the fractions at 80 ℃ and-0.08 MP.
In the method of the invention, the pH of the system has a great influence on the salifying effect of the methylphosphinic acid: when the pH is too small (pH)<3) When the aluminum salt is used, no aluminum methylphosphinate is separated out; the pH value of the system is increased, and the yield of the aluminum methylphosphinate is gradually increased; when the system is alkaline (pH 7. gtoreq., due to a portion of Al (OH)3A precipitate, which is difficult to separate from the aluminum methylphosphinate salt, affecting the product purity; therefore, in step B of the invention, the pH of the aqueous solution of the methylphosphinic acid is required to be adjusted to 3 ≦ pH < 7; when the pH value of the system is adjusted to be less than or equal to 5 and less than 7, the product yield is higher; the pH is adjusted by adopting inorganic base, and the inorganic base can be sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate; preferably sodium hydroxide or sodium carbonate.
In the step B, after the pH value is adjusted, aluminum sulfate is added; since the reaction conditions in step a of the present invention are optimized to convert dichloromethylphosphine to methylphosphinic acid with a conversion rate close to 100%, the molar ratio of aluminum sulfate to dichloromethylphosphine is 1: 5.4-6.2, the yield of the aluminum methylphosphinate is improved as much as possible, and the influence of too much excessive aluminum sulfate on the product is avoided.
As the aluminum sulfate in the present invention, Al can be used2(SO4)3·18H2O, anhydrous Al may also be used2(SO4)3。
In the step B of the method, in order to ensure the yield of the aluminum methylphosphinate, the reaction temperature is 70-110 ℃, and the reaction time is 4-48 h.
Preferably, the one-pot method for preparing the aluminum methylphosphinate comprises the following steps:
A. under the protection of inert gas and at the temperature of-10 ℃, dropwise adding dichloromethylphosphine into water, preserving heat for 10-20 min after dropwise adding, and then heating to 120-130 ℃ to remove HCl to obtain a methylphosphinic acid aqueous solution; the molar ratio of the water to the dichloromethylphosphine is 2.4-3: 1;
B. b, adjusting the pH value of the aqueous solution of the methylphosphinic acid obtained in the step A to be more than or equal to 5 and less than or equal to 7 by using sodium hydroxide or sodium carbonate, then adding aluminum sulfate, and reacting at 70-110 ℃ for 4-48 h to obtain aluminum methylphosphinate; the molar ratio of the aluminum sulfate to the dichloromethylphosphine is 1: 5.4 to 6.2.
The present invention is further illustrated by the following test examples and examples, but the scope of the present invention is not limited thereto.
Test example 1: water dosage screening
Replacing the four-mouth flask with nitrogen for three times, adding water into the four-mouth flask, weighing 10g of dichloromethylphosphine (0.085mol) in a constant-pressure titration funnel, replacing with nitrogen again, preparing a low-temperature condensation reflux device (the temperature is set to be-5 ℃), and connecting 30% NaOH alkali liquor at the tail for tail gas absorption; placing the four-mouth bottle in an ice bath, slowly dropwise adding dichloromethylphosphine when the internal temperature is reduced to about 0-10 ℃, preserving the temperature for 10-20 min after dropwise adding, then changing the oil bath, gradually raising the external temperature to 120-130 ℃, condensing and refluxing, and recording the reaction phenomenon and the reaction result, wherein the results are shown in table 1.
Table 1 screening results of water usage
| Test group | Amount of water used | Reaction phenomenon | Conversion rate |
| 1 | 0.136mol | Produce a highly irritating, off-flavoured white solid | — |
| 2 | 0.153mol | Produce a highly irritating, off-flavoured white solid | — |
| 3 | 0.170mol | Produce a highly irritating, off-flavoured white solid | — |
| 4 | 0.187mol | Produce a highly irritating, off-flavoured white solid | — |
| 5 | 0.256mol | No generation of strong irritant and stink white solid | 97％ |
As can be seen from the analysis of Table 1, when the molar ratio of water to dichloromethylphosphine is not more than 2.2 (e.g., 2.2: 1, 2: 1, 1.8: 1, 1.6: 1), a highly irritating, odorous white solid is found to be generated during the temperature rise after the ice bath; therefore, the amount of water used is at least 2.2 times (mol ratio) that of dichloromethylphosphine, but too much water increases the difficulty of removing HCl by subsequent temperature rise and affects the subsequent yield of aluminum methylphosphinate, and the mol ratio of water to dichloromethylphosphine is preferably 2.4-3: 1.
test example 2: effect of pH on salt formation yield
Slowly dropwise adding a 50 wt% NaOH aqueous solution into the methylphosphinic acid aqueous solution obtained in test example 5, and adjusting the pH value of the system; after the pH value is adjusted, the temperature is raised to 85 to 90 ℃, and 0.14mol mass is slowly dripped46% Al concentration2(SO4)3·18H2O aqueous solution, then refluxing and keeping the temperature for 5h, and recording the reaction phenomenon and the reaction result, the results are shown in Table 2.
TABLE 2 influence of pH on salt formation
Analysis table 1 shows that the pH of the system has a large influence on the reaction effect: when the pH value is too low (such as 1 < pH value < 3), no aluminum methylphosphinate salt is separated out; the pH value of the system is increased, and the yield of the aluminum methylphosphinate is gradually increased; when the system is alkaline, due to partial Al (OH)3A precipitate which is difficult to separate from the aluminum methylphosphinate salt; therefore, the dosage of the inorganic base is based on that the pH value of the system is adjusted to be less than or equal to 3 and less than or equal to 7; preferably, the pH of the system is adjusted to be less than or equal to 5 and less than 7.
On the basis of the above test, the inventor continuously performs reflux reaction on the mother liquor obtained from the test groups 6-12 for 5 hours, no solid is precipitated, and the fact that the reaction is complete after 5 hours is proved.
Test example 3: effect of different bases and Water contents on the reaction
With Na2CO3The solid replaces 50 wt% NaOH aqueous solution, the pH value is adjusted to be more than or equal to 3 and less than 4 or more than or equal to 6 and less than 7, the reaction result has no obvious difference, and the key influencing the reaction effect is the pH value.
Example 1
The four-necked flask was replaced with nitrogen three times, 46.15g of water (2.56mol) was charged into the four-necked flask, 100g of dichloromethylphosphine (0.85mol) was weighed in a constant pressure titration funnel, replaced with nitrogen again, and equipped with a low temperature condensation reflux apparatus (temperature set-5 ℃ C.), and 30% NaOH solution was added to the tail to absorb the off-gas.
Placing the four-mouth bottle in an ice bath, slowly dropwise adding dichloromethylphosphine when the internal temperature is reduced to about 0-10 ℃, preserving the temperature for 20min after dropwise adding, then changing the oil bath, gradually raising the external temperature to 120-130 ℃, condensing and refluxing for 4h, removing most HCl, and obtaining a methylphosphinic acid aqueous solution, wherein the conversion rate is 97%;
slowly dripping 50 wt% NaOH aqueous solution into the methylphosphinic acid aqueous solution in the four-neck flask, and adjusting the pH value to 6-7;
after the pH value is adjusted, the temperature is raised to 85 to 90 ℃, and 0.14mol Al is slowly dripped2(SO4)3Al of 46 mass%2(SO4)3·18H2And (3) refluxing and insulating the O aqueous solution for 5 hours, filtering the solution while the solution is hot after solids are gradually separated out, and finally putting the sample into a vacuum drying chamber at 110 ℃ to constant weight to obtain the aluminum methylphosphinate with the yield of 92%.
Claims (12)
1. The one-pot method for preparing the aluminum methylphosphinate is characterized in that: the method comprises the following steps:
A. taking dichloromethylphosphine as a raw material, and reacting with water to prepare a methylphosphinic acid aqueous solution;
B. adjusting the pH value of the aqueous solution of the methylphosphinic acid obtained in the step A to be less than or equal to 6 and less than 7, adding aluminum sulfate, and reacting to obtain aluminum methylphosphinate;
in the step A, the molar ratio of water to dichloromethylphosphine is 2.4-3: 1.
2. the one-pot process of claim 1 for preparing aluminum methylphosphinate, wherein: and step A is carried out under the protection of inert gas.
3. The one-pot process for preparing aluminum methylphosphinate according to claim 1 or 2, wherein: the specific operation of the step A is as follows: dropwise adding dichloromethylphosphine into water at-10-80 ℃ for reaction.
4. The one-pot process of claim 3 for preparing aluminum methylphosphinate, wherein: in the step A, the dichloromethylphosphine is dropwise added into water at-10 ℃ to react.
5. The one-pot process of claim 4 for preparing aluminum methylphosphinate, wherein: in the step A, after the reaction is completed, the method also comprises the step of heating to remove HCl.
6. The one-pot process of claim 5 for preparing aluminum methylphosphinate, wherein: in the step A, the temperature for raising the temperature to remove HCl is not less than 80 ℃.
7. The one-pot process of claim 6 for preparing aluminum methylphosphinate, wherein: in the step A, the temperature for heating and HCl removal is 120-130 ℃.
8. The one-pot process of claim 1 for preparing aluminum methylphosphinate, wherein: and in the step B, inorganic base is adopted to adjust the pH, and the inorganic base is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate.
9. The one-pot process of claim 8 for preparing aluminum methylphosphinate, wherein: in the step B, the inorganic base is sodium hydroxide or sodium carbonate.
10. The one-pot process of claim 1 for preparing aluminum methylphosphinate, wherein: in the step B, the molar ratio of the aluminum sulfate to the dichloromethylphosphine is 1: 5.4 to 6.2.
11. The one-pot process for preparing aluminum methylphosphinate according to any one of claims 1 to 2 or 4 to 10, wherein: in the step B, the reaction temperature is 70-110 ℃; in the step B, the reaction time is 4-48 h.
12. The one-pot process of claim 3 for preparing aluminum methylphosphinate, wherein: in the step B, the reaction temperature is 70-110 ℃; in the step B, the reaction time is 4-48 h.
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| CN110229184B (en) * | 2019-07-25 | 2021-12-03 | 利尔化学股份有限公司 | Preparation method of methyl ethyl phosphinic acid and aluminum salt thereof |
| CN111393473B (en) * | 2020-04-29 | 2023-08-01 | 利尔化学股份有限公司 | Preparation method of ethyl methyl ethyl phosphinate |
| CN112499587A (en) * | 2020-11-30 | 2021-03-16 | 洪湖市一泰科技有限公司 | Synergistic treatment method for by-products generated in production process of methyldichlorophosphine and diethyl methylphosphonite |
| CN112794868B (en) * | 2020-12-15 | 2023-04-07 | 洪湖市一泰科技有限公司 | Method for treating sodium tetrachloroaluminate generated in methyl dichlorophosphine production process |
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