CN112794867A - Synthesis method of aluminum diethylphosphinate - Google Patents
Synthesis method of aluminum diethylphosphinate Download PDFInfo
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- CN112794867A CN112794867A CN202011365313.9A CN202011365313A CN112794867A CN 112794867 A CN112794867 A CN 112794867A CN 202011365313 A CN202011365313 A CN 202011365313A CN 112794867 A CN112794867 A CN 112794867A
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- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
Abstract
The invention discloses a method for synthesizing aluminum diethylphosphinate, and particularly relates to a method for synthesizing aluminum diethylphosphinate by reacting sodium hypophosphite with ethylene in water-insoluble organic acid under the action of an initiator to generate a diethylphosphinate solution, and extracting the diethylphosphinate solution with water and then reacting the diethylphosphinate solution with aluminum sulfate. The process of the invention has the advantages of simple synthesis method, high product yield, high purity and low energy consumption in the process.
Description
Technical Field
The invention relates to a synthesis method of aluminum diethylphosphinate.
Background
Aluminum diethylphosphinate is used as an excellent halogen-free flame retardant for engineering plastics, such as polyamides, polyesters, thermosets and elastomers; the diethyl aluminum phosphinate can play a role in a condensed phase to promote the polymer to form carbon and can remove high-energy free radicals in a combustion zone; the diethyl aluminum phosphinate has the characteristics of environmental friendliness and health friendliness.
Chinese patent CN103073576B discloses a method for preparing dialkyl phosphinic acid and salts thereof, which takes an organic solvent as a solvent, and high-concentration hypophosphorous acid reacts with olefin under the action of an initiator to obtain dialkyl phosphinic acid-organic phase solution; extracting with water or distilling under reduced pressure to remove organic solvent, and diluting with water to obtain dialkyl phosphinic acid aqueous solution; neutralizing with the water solution of alkali compound to obtain the water solution of dialkyl phosphinic acid alkali metal salt; and (3) reacting the dialkyl phosphinic acid alkali metal salt aqueous solution with the metal compound aqueous solution to obtain the dialkyl phosphinic acid metal salt. However, the method disclosed in the patent requires the preparation of high-concentration hypophosphorous acid in advance before the reaction, and requires the removal of an organic solvent after the reaction is completed, which is complicated in operation steps.
Chinese patent CN102617638B discloses a normal pressure two-phase transfer catalytic synthesis process of dialkyl phosphinate, which comprises the steps of raw material preparation, phase transfer catalytic synthesis, neutralization and separation and the like, wherein the process takes a water-insoluble organic solvent and water as two phases, and one of phosphinate and monoalkyl phosphinate and a water-soluble initiator are transferred to an organic phase under the action of a phase transfer catalyst and react with olefin dissolved in the organic phase; after the reaction is finished, the separation of the organic solvent and the dialkyl phosphinate aqueous solution is realized through phase separation, and the organic solvent and part of the phase transfer catalyst dissolved in the organic solvent are directly recycled; the dialkyl phosphinate aqueous solution directly reacts with aluminum salt and the like to prepare the dialkyl phosphinate aluminum. It can be seen that the process of this patent also introduces an organic solvent during the reaction.
At present, the synthesis method of the dialkyl phosphinate is mainly a free radical addition method, i.e. under the action of an initiator, olefin and hypophosphorous acid react to generate dialkyl phosphinate, such as patents CN1280582, US6248921, etc. The methods all use a large amount of acetic acid, the acetic acid needs to be removed after the reaction is finished, and the recovered acetic acid can be recycled after being treated, so that the energy consumption is high, and the environmental protection pressure is high.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a method for synthesizing aluminum diethylphosphinate.
The synthesis method of the aluminum diethylphosphinate is characterized by comprising the following steps of:
1) adding sodium hypophosphite monohydrate, water-insoluble organic acid and an initiator into a reaction kettle, displacing and exhausting air in the reaction kettle by using nitrogen, and filling ethylene gas into the reaction kettle for reaction to obtain a diethylphosphinic acid solution;
2) extracting the diethyl phosphinic acid solution obtained in the step 1) with water for layering to obtain a water layer, namely the diethyl phosphinic acid aqueous solution;
3) reacting the diethyl phosphinic acid aqueous solution obtained in the step 2) with aluminum sulfate, and filtering after the reaction is finished to obtain a diethyl phosphinic acid aluminum crude product; and washing and drying the obtained crude product to obtain the finished product of the diethyl aluminum phosphinate.
The synthesis method of aluminum diethylphosphinate is characterized in that the water-insoluble organic acid is at least one of caproic acid, heptanoic acid, octanoic acid and nonanoic acid.
The synthesis method of aluminum diethylphosphinate is characterized in that the feeding mass of the water-insoluble organic acid is 1-3 times of the mass of sodium hypophosphite monohydrate.
The synthesis method of aluminum diethylphosphinate is characterized in that the initiator is di-tert-butyl peroxide, and the mass of the initiator is 1.5-4% of that of sodium hypophosphite monohydrate, preferably 2.5-3%.
The synthesis method of aluminum diethylphosphinate is characterized in that in the step 1), the reaction temperature is 90-140 ℃, the reaction time is 6-12h, and the ethylene pressure during the reaction is 0.2-1.0 MPa.
The synthesis method of aluminum diethylphosphinate is characterized in that in the step 3), the reaction temperature is 85-95 ℃ and the reaction time is 2-4 h.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention designs a method for synthesizing aluminum diethylphosphinate, namely, sodium hypophosphite reacts with ethylene in organic acid which is insoluble in water under the action of an initiator to generate a diethylphosphinate solution, and the diethylphosphinate solution is extracted by water and then reacts with aluminum sulfate to obtain the aluminum diethylphosphinate.
2. In the process method, the diethyl phosphinic acid is extracted from the organic acid which is not dissolved in water by water, and the recovered organic acid can be recycled, so that compared with other methods, the process method greatly saves the cost, simplifies the process, reduces the environmental protection pressure and reduces the energy consumption.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
A synthesis method of aluminum diethylphosphinate comprises the following steps:
1) adding 1000g of sodium hypophosphite monohydrate, 1642g of n-hexanoic acid and 27.6g of di-tert-butyl peroxide into a 5L stainless steel sealed reaction kettle with a tetrafluoro lining, displacing air in the reaction kettle with nitrogen, heating to 110 ℃, introducing ethylene gas, and keeping the ethylene pressure at 0.4Mpa for 8 hours;
2) after the reaction in the step 1) is finished, naturally cooling to room temperature, and discharging reaction liquid in the stainless steel sealed reaction kettle; extracting the reaction liquid by using 1000g of deionized water, putting a water layer into a normal-pressure kettle, heating to 90 ℃, dropwise adding 1540g of aluminum sulfate solution with the mass concentration of 41%, separating out a large amount of white solid during dropwise adding, and preserving heat for 3 hours after dropwise adding;
3) after the heat preservation is finished, cooling to room temperature, filtering the white solid, washing with deionized water for 2 times, and drying to obtain a diethyl aluminum hypophosphite finished product; the yield is 94.7%, and the purity of diethyl aluminum hypophosphite is 95.3% by nuclear magnetic resonance phosphorus spectrum analysis.
Example 2
A synthesis method of aluminum diethylphosphinate comprises the following steps:
1) adding 1000g of sodium hypophosphite monohydrate, 1843g of n-heptanoic acid and 27.6g of di-tert-butyl peroxide into a 5L stainless steel sealed reaction kettle with a tetrafluoro lining, displacing and exhausting air in the reaction kettle by nitrogen, heating to 110 ℃, introducing ethylene gas, and keeping the ethylene pressure at 0.4Mpa for 8 h;
2) after the reaction in the step 1) is finished, naturally cooling to room temperature, and discharging reaction liquid in the stainless steel sealed reaction kettle; extracting the reaction liquid by using 1000g of deionized water, putting a water layer into a normal-pressure kettle, heating to 90 ℃, dropwise adding 1540g of aluminum sulfate solution with the mass concentration of 41%, separating out a large amount of white solid during dropwise adding, and preserving heat for 3 hours after dropwise adding;
3) after the heat preservation is finished, cooling to room temperature, filtering the white solid, washing with deionized water for 2 times, and drying to obtain a diethyl aluminum hypophosphite finished product; the yield is 93.8%, and the purity of diethyl aluminum hypophosphite is 95.2% by nuclear magnetic resonance phosphorus spectrum analysis.
Example 3
A synthesis method of aluminum diethylphosphinate comprises the following steps:
1) adding 1000g of sodium hypophosphite monohydrate, 2041g of n-octanoic acid and 27.6g of di-tert-butyl peroxide into a 5L stainless steel sealed reaction kettle with a tetrafluoro lining, displacing and exhausting air in the reaction kettle by using nitrogen, heating to 110 ℃, introducing ethylene gas, and keeping the ethylene pressure at 0.4Mpa for 8 hours;
2) after the reaction in the step 1) is finished, naturally cooling to room temperature, and discharging reaction liquid in the stainless steel sealed reaction kettle; extracting the reaction liquid by using 1000g of deionized water, putting a water layer into a normal-pressure kettle, heating to 90 ℃, dropwise adding 1540g of aluminum sulfate solution with the mass concentration of 41%, separating out a large amount of white solid during dropwise adding, and preserving heat for 3 hours after dropwise adding;
3) after the heat preservation is finished, cooling to room temperature, filtering the white solid, washing with deionized water for 2 times, and drying to obtain a diethyl aluminum hypophosphite finished product; the yield is 90.5%, and the purity of diethyl aluminum hypophosphite is 93.47% by nuclear magnetic resonance phosphorus spectrum analysis.
Comparative example 1
A synthesis method of aluminum diethylphosphinate comprises the following steps:
1) adding 1000g of sodium hypophosphite monohydrate, 1700g of acetic acid and 27.6g of di-tert-butyl peroxide into a 5L stainless steel sealed reaction kettle with a tetrafluoro lining, displacing and exhausting air in the reaction kettle by using nitrogen, heating to 110 ℃, introducing ethylene gas, and keeping the ethylene pressure at 0.4Mpa for 8 hours;
2) after the reaction in the step 1) is finished, naturally cooling to room temperature, and discharging reaction liquid in the stainless steel sealed reaction kettle; removing glacial acetic acid from the reaction liquid through rotary evaporation, adding 1000g of water, heating to 90 ℃, dropwise adding 1540g of an aluminum sulfate solution with the mass concentration of 41%, separating out a large amount of white solid during dropwise adding, and preserving heat for 3 hours after dropwise adding;
3) after the heat preservation is finished, cooling to room temperature, filtering the white solid, washing with deionized water for 2 times, and drying to obtain a diethyl aluminum hypophosphite finished product; the yield is 93.6%, and the purity of diethyl aluminum hypophosphite is 93.8% by nuclear magnetic resonance phosphorus spectrum analysis.
Comparative example 2
A synthesis method of aluminum diethylphosphinate comprises the following steps:
1) adding 1000g of sodium hypophosphite monohydrate, 1247g of n-butyric acid and 27.6g of di-tert-butyl peroxide into a 5L stainless steel sealed reaction kettle with a tetrafluoro lining, displacing and exhausting air in the reaction kettle by nitrogen, heating to 110 ℃, introducing ethylene gas, and keeping the ethylene pressure at 0.4Mpa for 8 hours;
2) after the reaction in the step 1) is finished, naturally cooling to room temperature, and discharging reaction liquid in the stainless steel sealed reaction kettle; extracting the reaction liquid by using 1000g of deionized water, putting a water layer into a normal-pressure kettle, heating to 90 ℃, dropwise adding 1540g of aluminum sulfate solution with the mass concentration of 41%, separating out a large amount of white solid during dropwise adding, and preserving heat for 3 hours after dropwise adding;
3) after the heat preservation is finished, cooling to room temperature, filtering the white solid, washing with deionized water for 2 times, and drying to obtain a diethyl aluminum hypophosphite finished product; the yield is 72.6%, and the purity of diethyl aluminum hypophosphite is 83.2% by nuclear magnetic resonance phosphorus spectrum analysis.
The reaction results of examples 1 to 3 and comparative examples 1 to 2 are summarized in Table 1.
TABLE 1
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (6)
1. The synthesis method of aluminum diethylphosphinate is characterized by comprising the following steps of:
1) adding sodium hypophosphite monohydrate, water-insoluble organic acid and an initiator into a reaction kettle, displacing and exhausting air in the reaction kettle by using nitrogen, and filling ethylene gas into the reaction kettle for reaction to obtain a diethylphosphinic acid solution;
2) extracting the diethyl phosphinic acid solution obtained in the step 1) with water for layering to obtain a water layer, namely the diethyl phosphinic acid aqueous solution;
3) reacting the diethyl phosphinic acid aqueous solution obtained in the step 2) with aluminum sulfate, and filtering after the reaction is finished to obtain a diethyl phosphinic acid aluminum crude product; and washing and drying the obtained crude product to obtain the finished product of the diethyl aluminum phosphinate.
2. The method for synthesizing aluminum diethylphosphinate according to claim 1, wherein the water-insoluble organic acid is at least one of hexanoic acid, heptanoic acid, octanoic acid, and nonanoic acid.
3. The method for synthesizing aluminum diethylphosphinate according to claim 1, wherein the mass of the water-insoluble organic acid fed is 1 to 3 times the mass of sodium hypophosphite monohydrate.
4. The method for synthesizing aluminum diethylphosphinate according to claim 1, wherein the initiator is di-tert-butyl peroxide, and the mass of the initiator is 1.5-4%, preferably 2.5-3%, of the mass of sodium hypophosphite monohydrate.
5. The method for synthesizing aluminum diethylphosphinate according to claim 1, wherein in the step 1), the reaction temperature is 90-140 ℃, the reaction time is 6-12h, and the ethylene pressure during the reaction is 0.2-1.0 MPa.
6. The method for synthesizing aluminum diethylphosphinate according to claim 1, wherein in the step 3), the reaction temperature is 85-95 ℃ and the reaction time is 2-4 h.
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Citations (5)
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| WO2011007687A1 (en) * | 2009-07-17 | 2011-01-20 | 東レ株式会社 | Flame-retardant thermoplastic resin composition and molded article |
| CN103073577A (en) * | 2012-09-19 | 2013-05-01 | 广州金凯新材料有限公司 | Dialkyl phosphinic acid salt and preparation method thereof |
| CN103087098A (en) * | 2012-09-19 | 2013-05-08 | 广州金凯新材料有限公司 | Dialkylhypophosphite and preparation method thereof |
| CN103172669A (en) * | 2013-03-04 | 2013-06-26 | 广州金凯新材料有限公司 | Monoalkyl/dialkyl phosphinate and preparation method thereof |
| CN104119377A (en) * | 2014-04-01 | 2014-10-29 | 中国科学院宁波材料技术与工程研究所 | Preparation process and product of dialkyl phosphinate |
-
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- 2020-11-28 CN CN202011365313.9A patent/CN112794867A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011007687A1 (en) * | 2009-07-17 | 2011-01-20 | 東レ株式会社 | Flame-retardant thermoplastic resin composition and molded article |
| CN103073577A (en) * | 2012-09-19 | 2013-05-01 | 广州金凯新材料有限公司 | Dialkyl phosphinic acid salt and preparation method thereof |
| CN103087098A (en) * | 2012-09-19 | 2013-05-08 | 广州金凯新材料有限公司 | Dialkylhypophosphite and preparation method thereof |
| CN103172669A (en) * | 2013-03-04 | 2013-06-26 | 广州金凯新材料有限公司 | Monoalkyl/dialkyl phosphinate and preparation method thereof |
| CN104119377A (en) * | 2014-04-01 | 2014-10-29 | 中国科学院宁波材料技术与工程研究所 | Preparation process and product of dialkyl phosphinate |
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| 王世泽等: ""二烷基次膦酸盐阻燃剂研究进展"", 《精细石油化工进展》 * |
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