CN110229184B - Preparation method of methyl ethyl phosphinic acid and aluminum salt thereof - Google Patents
Preparation method of methyl ethyl phosphinic acid and aluminum salt thereof Download PDFInfo
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- NXHKQBCTZHECQF-UHFFFAOYSA-N ethyl(methyl)phosphinic acid Chemical compound CCP(C)(O)=O NXHKQBCTZHECQF-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 49
- BCDIWLCKOCHCIH-UHFFFAOYSA-N methylphosphinic acid Chemical compound CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims abstract description 10
- GTOWTBKGCUDSNY-UHFFFAOYSA-K tris[[ethyl(methyl)phosphoryl]oxy]alumane Chemical compound [Al+3].CCP(C)([O-])=O.CCP(C)([O-])=O.CCP(C)([O-])=O GTOWTBKGCUDSNY-UHFFFAOYSA-K 0.000 claims abstract description 8
- -1 ethyl phosphinate aluminum salt Chemical compound 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 9
- 150000007529 inorganic bases Chemical class 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 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 description 3
- 238000010438 heat treatment Methods 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
- 238000011403 purification operation Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 21
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- JMJWMGLCPXGAFU-UHFFFAOYSA-M [PH2]([O-])=O.C[Al+]CC Chemical compound [PH2]([O-])=O.C[Al+]CC JMJWMGLCPXGAFU-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- CORRWSLEWBGTFG-UHFFFAOYSA-N butyl(methyl)phosphinic acid Chemical compound CCCCP(C)(O)=O CORRWSLEWBGTFG-UHFFFAOYSA-N 0.000 description 2
- AWYDVYYDVPFOMZ-UHFFFAOYSA-N dichloromethylphosphane Chemical compound PC(Cl)Cl AWYDVYYDVPFOMZ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- XKCQASMZNPBLKI-UHFFFAOYSA-N phosphorosooxymethane Chemical compound COP=O XKCQASMZNPBLKI-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HNIUKPPQZMVBHX-UHFFFAOYSA-N dichloromethylphosphinic acid Chemical compound OP(=O)C(Cl)Cl HNIUKPPQZMVBHX-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FOHFIPJIUNFWCI-UHFFFAOYSA-N ethyl(methyl)phosphinic acid;sodium Chemical compound [Na].CCP(C)(O)=O FOHFIPJIUNFWCI-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001291 vacuum drying 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
本发明公开了一种甲基乙基次膦酸及其铝盐的制备方法，属于有机合成技术领域。本发明为降低甲基乙基次膦酸的生产成本，并提高其纯度，提供了一种甲基乙基次膦酸及其铝盐的制备方法，包括：将二氯甲基膦与水反应，得甲基次膦酸水溶液；以过氧化二叔丁基为引发剂，使甲基次膦酸水溶液与乙烯反应，得甲基乙基次膦酸；将甲基乙基次膦酸水溶液与Al2(SO4)3·18H2O水溶液反应，得甲基乙基次膦酸铝盐。本发明将甲基次膦酸水溶液直接用于制备甲基乙基次膦酸，并对反应条件进行筛选，以高产率获得高纯度的甲基乙基次膦酸，再直接用于制备甲基乙基次膦酸铝盐，省去了各中间体的提纯操作，显著提高了生产效率和降低了生产成本。The invention discloses a preparation method of methyl ethyl phosphinic acid and its aluminum salt, and belongs to the technical field of organic synthesis. In order to reduce the production cost of methyl ethyl phosphinic acid and improve its purity, the present invention provides a preparation method of methyl ethyl phosphinic acid and its aluminum salt, comprising: reacting dichloromethyl phosphine with water , to obtain an aqueous solution of methyl phosphinic acid; using di-tert-butyl peroxide as an initiator, the aqueous solution of methyl phosphinic acid is reacted with ethylene to obtain methyl ethyl phosphinic acid; the aqueous solution of methyl ethyl phosphinic acid is reacted with ethylene Al 2 (SO 4 ) 3 ·18H 2 O aqueous solution reacts to obtain aluminum methyl ethyl phosphinate. In the present invention, the methyl phosphinic acid aqueous solution is directly used to prepare methyl ethyl phosphinic acid, and the reaction conditions are screened to obtain high-purity methyl ethyl phosphinic acid with high yield, which is then directly used to prepare methyl ethyl phosphinic acid. The ethyl phosphinate aluminum salt saves the purification operation of each intermediate, significantly improves the production efficiency and reduces the production cost.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of methyl ethyl phosphinic acid and aluminum salt thereof.
Background
Compared with inorganic phosphinates, alkyl phosphinate flame retardants have better hydrophobicity, higher decomposition temperature, better compatibility with a substrate, high leakage resistance constant index (CTI), and good mechanical properties of materials, and are widely applied to the field of engineering plastics, in particular to the fields of high-performance nylon, polyester, high-performance epoxy resin and the like, because alkyl is introduced into molecules, compared with the inorganic phosphinates.
CN1280583A discloses a method for preparing methyl ethyl phosphinic acid by reacting methyl phosphinic acid with ethylene, but the method for preparing methyl ethyl phosphinic acid has low purity, contains more methyl butyl phosphinic acid impurities, is difficult to remove, is carried into the next aluminum salt and influences the quality of the final aluminum salt product.
Therefore, it is necessary to find a method for preparing methylethylphosphinic acid with higher purity.
Disclosure of Invention
The invention provides a preparation method of methyl ethyl phosphinic acid for reducing the production cost of the methyl ethyl phosphinic acid and improving the purity of the methyl ethyl phosphinic acid, which comprises the following steps:
A. reacting dichloromethylphosphine with water, heating to remove HCl after the reaction is finished, and obtaining methylphosphinic acid aqueous solution;
B. and D, reacting the aqueous solution of the methylphosphinic acid obtained in the step A with ethylene by using di-tert-butyl peroxide as an initiator to obtain the methylethylphosphinic acid.
In the preparation method of methyl ethyl phosphinic acid, in the step A, the molar ratio of water to dichloromethyl phosphine is more than 2.2: 1.
preferably, in the method for preparing methylethylphosphinic acid, in step a, the molar ratio of water to dichloromethylphosphine is 2.4-3: 1.
in the preparation method of methyl ethyl phosphinic acid, in the step A, the reaction temperature is 0-10 ℃.
In the preparation method of methyl ethyl phosphinic acid, in the step A, the temperature for refluxing and removing HCl is 120-130 ℃.
Wherein, the preparation method of the methyl ethyl phosphinic acid is that in the step A, H in the methyl phosphinic acid aqueous solution2The content of O is 12-14 wt%, and the content of HCl is 12-15 wt%.
In the preparation method of methyl ethyl phosphinic acid, in the step B, the amount of the initiator is 3-5 mol%.
In the preparation method of methyl ethyl phosphinic acid, in the step B, the reaction temperature is 150-160 ℃.
In the preparation method of the methyl ethyl phosphinic acid, in the step B, the reaction time is 10-15 h, and the pressure is 0.8-1.5 MPa.
In the preparation method of methyl ethyl phosphinic acid, after the reaction of the methyl phosphinic acid aqueous solution and ethylene in the step B is finished, the methyl ethyl phosphinic acid aqueous solution is obtained.
On the basis of the preparation method of the methyl ethyl phosphinic acid, the preparation method of the aluminum salt of the methyl ethyl phosphinic acid also comprises the following steps:
C. and C, adjusting the pH value of the methyl ethyl hypophosphite aqueous solution obtained in the step B to be 6-7, adding aluminum sulfate, and reacting to obtain the methyl hypophosphite aluminum salt.
In the step C, 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.
Preferably, in the preparation method of the methyl ethyl aluminum phosphinate, in the step C, the inorganic base is preferably sodium hydroxide or sodium carbonate.
In the preparation method of the methyl ethyl phosphinic acid aluminum salt, in the step C, the reaction temperature is 85-90 ℃.
The invention has the beneficial effects that:
firstly, dichloromethylphosphine reacts with water to prepare a methylphosphinic acid aqueous solution, and the methylphosphinic acid aqueous solution is directly used for preparing methylethylphosphinic acid, so that the production cost is reduced; then, aiming at the characteristics of the methylphosphinic acid aqueous solution, the reaction conditions are screened to obtain the reaction conditions with high tolerance to the purity of the raw material methylphosphinic acid aqueous solution, so that the high-purity methylethylphosphinic acid can be obtained with high yield; so that the methyl ethyl phosphinic acid aqueous solution can be directly used for preparing the methyl ethyl phosphinic acid aluminum salt; the method of the invention omits the purification operation of each intermediate, obviously improves the production efficiency and reduces the production cost.
Detailed Description
Specifically, the preparation method of the methyl ethyl phosphinic acid comprises the following steps:
A. reacting dichloromethylphosphine with water, heating to remove HCl after the reaction is finished, and obtaining methylphosphinic acid aqueous solution;
B. and D, reacting the aqueous solution of the methylphosphinic acid obtained in the step A with ethylene by using di-tert-butyl peroxide as an initiator to obtain the methylethylphosphinic acid.
In the step A of the method, dichlormethylphosphinic acid is prepared by reacting dichlormethylphosphine with water, in order to avoid over violent reaction, the dichlormethylphosphine is generally dropwise added into water, the reaction temperature is controlled to be 0-10 ℃, and side reaction caused in an oxidation environment is avoided under the protection of nitrogen; the reaction rate is high, and in order to ensure complete reaction as much as possible, the temperature is generally kept for 10-20 min after the dripping is finished. The extraction of methylphosphinic acid from methylphosphinic acid aqueous solution generally adopts rectification purification, however, the operation is costly, partial methylphosphinic acid is lost, and the production efficiency and the cost are obviously influenced, so that the inventor considers that the methylphosphinic acid aqueous solution is directly used for the subsequent reaction, but the unpurified methylphosphinic acid contains water and hydrogen chloride, and needs to explore reaction conditions which are adaptive to the methylphosphinic acid aqueous solution and have high tolerance to the raw material purity.
After the reaction of the dichloromethylphosphine is finished, a large amount of HCl is generated in the system, the system is refluxed at 120-130 ℃, most of HCl can be removed through simple operation (tail NaOH alkali liquor is connected for tail gas absorption), in order to avoid the influence of HCl residual quantity on subsequent reaction, the refluxing time is too long, the production efficiency is reduced, and the loss of the methylphosphinic acid is caused, the refluxing is generally carried out for 4-8H, so that the methylphosphinic acid aqueous solution is obtained, usually H of the methylphosphinic acid aqueous solution is obtained2The content of O is 12-14 wt%, and the content of HCl is 12-15 wt%.
While CN1280583A discloses a method for preparing methylethylphosphinic acid by reacting methylphosphinic acid with ethylene, it has a serious impact on product purity since it produces more methylbutylphosphinic acid impurities which are difficult to remove; in addition, the invention adopts an unpurified methylphosphinic acid aqueous solution, so that a great amount of impurities are avoided from being generated, and the yield of the methylethylphosphinic acid is ensured, and the inventor conducts a great number of experiments.
The invention adopts di-tert-butyl peroxide as an initiator, the effect is obviously better than that of other initiators, and the using amount of the initiator is 3-5 mol%; meanwhile, in the step B, when the reaction temperature is lower, more raw materials are left, and tests show that the reaction temperature is preferably 150-160 ℃.
According to the comprehensive test result, in the step B, di-tert-butyl peroxide is used as an initiator, the dosage of the di-tert-butyl peroxide is controlled to be 3-5 mol%, the reaction temperature is 150-160 ℃, the time is 10-15 hours, the pressure is 0.8-1.5 MPa, the raw material methyl phosphinic acid basically has no residue, the yield of methyl ethyl phosphinic acid is more than 95%, the generation amount of impurities is very small, and the subsequent reaction is not influenced.
In the preparation method of methyl ethyl phosphinic acid, after the reaction of the methyl phosphinic acid aqueous solution and ethylene in the step B is finished, the methyl ethyl phosphinic acid aqueous solution is obtained.
On the basis of the preparation method of the methyl ethyl phosphinic acid, the preparation method of the aluminum salt of the methyl ethyl phosphinic acid also comprises the following steps:
C. and C, adjusting the pH value of the methyl ethyl hypophosphite aqueous solution obtained in the step B to be 6-7, adding aluminum sulfate, and reacting to obtain the methyl hypophosphite aluminum salt.
Methyl ethyl phosphinic acid and Al2(SO4)3.18H2The pH of the O (the concentration is generally 30-50 wt%) reaction is generally 6-7, so in the step C, before the reaction, inorganic alkali such as sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate is adopted to adjust the pH of the methyl ethyl phosphinic acid aqueous solution to 6-7; preferably, the inorganic base is preferably sodium hydroxide or sodium carbonate.
In order to accelerate the reaction efficiency, in the step C, the reaction temperature is 85-90 ℃, the reaction end point is determined by no residue of methylphosphinic acid, and the reaction time is generally 4-48 h.
The preparation of methylethylphosphinic acid and aluminum salts thereof according to the present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and that all techniques realized based on the above-described contents of the present invention are within the scope of the present invention.
Test examples
100g of an aqueous solution of methylphosphinic acid (wherein H is2O content of 12.5 wt%, HCl content of 12.5 wt%, methylphosphinic acid content of 75g, 0.94mol) is added into a high-temperature autoclave, replaced by ethylene gas for three times, 3-5 mol% of initiator is uniformly dripped in the reaction, the pressure of the reaction kettle is controlled to be 0.8-1.0 MPa, the temperature is 80-170 ℃, after 10-14 h of reaction, the methyl ethyl phosphinic acid aqueous solution is taken out after pressure relief, and the liquid and the solution are used31P-NMR nuclear magnetic phosphorus spectrum analysis showed that the results are shown in Table 1 (in Table 1, the units of the starting material, the product and the unknown component are in mol%).
Table 1 process screening test conditions and results
The half-life period of the initiator is related to the temperature, and the influence of the half-life period is considered for the initiation temperature of a specific initiator, so that when ammonium persulfate, potassium persulfate, sodium persulfate or 2,2' -azo (2-methylpropylamidine) dihydrochloride is used as the initiator in a test, the reaction temperature of 80-100 ℃ is designed, but the reaction effect is poor, the raw materials are more in residue, and the impurities are more.
The effect is obviously better than that of other initiators by adopting di-tert-butyl peroxide as the initiator; the effect is better than 3mol% when 5 mol%; when the temperature is lower (80-130 ℃), more raw materials are left, and the effect is better at 150-160 ℃; the reaction pressure is 0.8 MPa-1.5 MPa; the reaction time is 10-15 h, and 10h is preferred in comprehensive consideration.
Using the process conditions of test group 9, p-methylphosphinic acid waterThe application range of the solution is expanded, and different H is selected2The reaction results of the methylphosphinic acid aqueous solution with O and HCl contents have no significant difference, such as H212 wt% of O and 12 wt% of HCl; h2O content 13.5 wt%, HCl content 13 wt%; h2O content 14 wt.% and HCl content 15 wt.%.
Example 1
1.1 preparation of an aqueous solution of methylphosphinic acid
The four-neck flask is replaced by nitrogen for three times, 46.15g of water (2.56mol) is added into the four-neck flask, 100g of dichloromethylphosphine (0.85mol) is weighed in a constant pressure titration funnel and replaced by nitrogen again, a low temperature condensation reflux device is arranged (the temperature is set to be-5 ℃), and 30% NaOH alkali liquor is connected at the tail end 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 20min after dropwise adding, then changing the oil bath, gradually raising the external temperature to 120-130 ℃, carrying out condensation reflux for 4H, removing most HCl, and obtaining the methylphosphinic acid aqueous solution (wherein H is H)2O content 12.5 wt.%, HCl content 12.5 wt.%), conversion 97%.
The aqueous solution of methylphosphinic acid obtained in this way, H2The contents of O and HCl fluctuate within a small range, H2The content of O is 12-14 wt%, and the content of HCl is 12-15 wt%.
1.2 preparation of methylethylphosphinic acid
100g of the above methylphosphinic acid aqueous solution (wherein H is2O content of 12.5 wt%, HCl content of 12.5 wt%, methylphosphinic acid content of 75g, 0.94mol) was added into a high-temperature autoclave, three times replaced with ethylene gas, 5mol% of di-tert-butyl peroxide was uniformly dropped into the reaction as an initiator, the pressure of the autoclave was controlled to 1.0MPa, the temperature was controlled to 0.0 MPaReacting at 150 deg.C for 10 hr, removing pressure, mixing with aqueous solution of methyl ethyl phosphinic acid31P-NMR nuclear magnetic phosphorus spectrum analysis shows that the content of methyl ethyl phosphinic acid is 96 mol%, the content of methyl phosphinic acid is 3mol%, and the content of unknown components is 1 mol%.
Example 2
1.1 preparation of an aqueous solution of methylphosphinic acid
The four-necked flask was replaced with nitrogen three times, 36.72g of water (2.04mol) 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 the methylphosphinic acid aqueous solution (containing H therein)2O content 12.5% by weight, HCl content 12.5% by weight) and conversion 97%.
1.2 preparation of methylethylphosphinic acid
Adding 100g of the methyl phosphinic acid aqueous solution (wherein the methyl phosphinic acid accounts for 75g and 0.94mol) into a high-temperature high-pressure kettle, replacing the mixture with ethylene gas for three times, uniformly dropwise adding 5mol% of di-tert-butyl peroxide as an initiator in the reaction, controlling the pressure of the reaction kettle to be 1.0MPa and the temperature to be 160 ℃, relieving the pressure after reacting for 10 hours, taking out the methyl ethyl phosphinic acid aqueous solution, reacting with liquid and31P-NMR nuclear magnetic phosphorus spectrum analysis shows that the content of methyl ethyl phosphinic acid is 97 mol%, the content of methyl phosphinic acid is 2 mol%, and the content of unknown components is 1 mol%.
1.3 preparation of aluminum methyl ethyl phosphinate
Slowly dripping 50 wt% of NaOH aqueous solution into the methyl ethyl phosphinic acid aqueous solution, carrying out acid-base neutralization, and adjusting the pH value to be 6-7 to obtain a methyl ethyl phosphinic acid sodium solution; then raising the temperature of the system to 85-90 ℃, and slowly dropwise adding Al with the mass concentration of 46%2(SO4)3·18H2And (3) carrying out reflux heat preservation reaction on the O aqueous solution for 4 hours, filtering while the O aqueous solution is hot after solids are gradually separated out to obtain white solid powder, and finally putting the sample into a vacuum drying device at 110 ℃ to constant weight to obtain the methyl ethyl aluminum phosphinate with the yield of 91%.
Claims (11)
1. The preparation method of methyl ethyl phosphinic acid is characterized by comprising the following steps: the method comprises the following steps:
A. reacting dichloromethylphosphine with water, heating to remove HCl after the reaction is finished, and obtaining methylphosphinic acid aqueous solution;
B. b, reacting the aqueous solution of the methylphosphinic acid obtained in the step A with ethylene by using di-tert-butyl peroxide as an initiator to obtain methylethylphosphinic acid;
in the step B, the reaction temperature is 150-160 ℃;
in the step B, the using amount of the initiator is 3-5 mol%.
2. The process for preparing methylethylphosphinic acid, according to claim 1, wherein: in step A, the molar ratio of water to dichloromethylphosphine is greater than 2.2: 1.
3. the process for preparing methylethylphosphinic acid, according to claim 1, wherein: in the step A, the molar ratio of water to dichloromethylphosphine is 2.4-3: 1.
4. the process for preparing methylethylphosphinic acid, according to claim 1, wherein: in the step A, the reaction temperature is 0-10 ℃.
5. The process for preparing methylethylphosphinic acid, according to claim 1, wherein: in the step A, the temperature for raising the temperature and removing HCl is 120-130 ℃.
6. The process for preparing methylethylphosphinic acid, according to claim 1, wherein: in the step A, the content of H2O in the methylphosphinic acid aqueous solution is 12-14 wt%, and the content of HCl in the methylphosphinic acid aqueous solution is 12-15 wt%.
7. Process for the preparation of methylethylphosphinic acid according to any one of claims 1 to 6, wherein: in the step B, the reaction time is 10-15 h, and the pressure is 0.8 MPa-1.5 MPa.
8. The preparation method of the methyl ethyl phosphinic acid aluminum salt is characterized in that: the method as claimed in claim 1 to 7, further comprising the following steps:
C. and C, adjusting the pH of the aqueous solution of the methyl ethyl hypophosphite obtained in the step B to be 6-7, adding aluminum sulfate, and reacting to obtain the methyl ethyl hypophosphite.
9. The process according to claim 8 for the preparation of aluminum methyl ethyl phosphinate, characterized in that: and in the step C, adjusting the pH value by adopting inorganic base, wherein the inorganic base is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate.
10. Process for the preparation of aluminium methylethylphosphinate salt according to claim 9, characterized in that: in the step C, the inorganic alkali is sodium hydroxide or sodium carbonate.
11. The method for producing an aluminum methylethylphosphinate salt according to any one of claims 8 to 10, characterized by: in the step C, the reaction temperature is 85-90 ℃.
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| CN112552338B (en) * | 2020-12-10 | 2021-07-27 | 洪湖市一泰科技有限公司 | Comprehensive recycling method of phosphorus-containing composite salt as byproduct in organic phosphine production |
| CN116903657A (en) * | 2023-07-21 | 2023-10-20 | 永农生物科学有限公司 | A kind of synthesis method of disubstituted phosphinic acid and its salt |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280584A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing dialkylphosphinic acids |
| CN1280583A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing salts of dialkylphosphinic acids |
| EP1308451A1 (en) * | 2001-11-02 | 2003-05-07 | Clariant GmbH | Process for the preparation of carboxyethylmethyl phosphinic acid glycol ester |
| CN101830926A (en) * | 2010-05-04 | 2010-09-15 | 云梦县江山新材料有限公司 | Dialkyl metal phosphinate and synthesis process of fire retardant thereof |
| CN103102367A (en) * | 2013-02-27 | 2013-05-15 | 广州金凯新材料有限公司 | Preparation method and application of dialkyl phosphinate with high density and large diameter |
| CN104163831A (en) * | 2014-08-12 | 2014-11-26 | 江苏利思德新材料有限公司 | Methylethyl hypophosphite, and preparation method and application thereof |
| CN104262392A (en) * | 2014-10-08 | 2015-01-07 | 云南大学 | Synthetic method of vinyl methylphosphonate |
| CN108484664A (en) * | 2018-03-15 | 2018-09-04 | 浙江工业大学 | A kind of preparation method of rodlike dialkylphosphinic salts crystal |
| CN109293694A (en) * | 2018-11-30 | 2019-02-01 | 利尔化学股份有限公司 | One-pot preparation of aluminum methylphosphinate |
| CN109400643A (en) * | 2019-01-02 | 2019-03-01 | 利尔化学股份有限公司 | Methylethyl phosphinicacid ethyl ester and Methylethyl phosphinic acids aluminium salt preparation process |
-
2019
- 2019-07-25 CN CN201910678095.5A patent/CN110229184B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280584A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing dialkylphosphinic acids |
| CN1280583A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing salts of dialkylphosphinic acids |
| EP1308451A1 (en) * | 2001-11-02 | 2003-05-07 | Clariant GmbH | Process for the preparation of carboxyethylmethyl phosphinic acid glycol ester |
| CN101830926A (en) * | 2010-05-04 | 2010-09-15 | 云梦县江山新材料有限公司 | Dialkyl metal phosphinate and synthesis process of fire retardant thereof |
| CN103102367A (en) * | 2013-02-27 | 2013-05-15 | 广州金凯新材料有限公司 | Preparation method and application of dialkyl phosphinate with high density and large diameter |
| CN104163831A (en) * | 2014-08-12 | 2014-11-26 | 江苏利思德新材料有限公司 | Methylethyl hypophosphite, and preparation method and application thereof |
| CN104262392A (en) * | 2014-10-08 | 2015-01-07 | 云南大学 | Synthetic method of vinyl methylphosphonate |
| CN108484664A (en) * | 2018-03-15 | 2018-09-04 | 浙江工业大学 | A kind of preparation method of rodlike dialkylphosphinic salts crystal |
| CN109293694A (en) * | 2018-11-30 | 2019-02-01 | 利尔化学股份有限公司 | One-pot preparation of aluminum methylphosphinate |
| CN109400643A (en) * | 2019-01-02 | 2019-03-01 | 利尔化学股份有限公司 | Methylethyl phosphinicacid ethyl ester and Methylethyl phosphinic acids aluminium salt preparation process |
Non-Patent Citations (1)
| Title |
|---|
| "烷基次膦酸铝阻燃剂的研究进展";曹琴等;《黄冈师范学院学报》;20190630;第39卷(第3期);第65-69页 * |
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