CN103467514A - Method for preparing dialkylphosphinate through oxidation reduction initiation system - Google Patents
Method for preparing dialkylphosphinate through oxidation reduction initiation system Download PDFInfo
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- CN103467514A CN103467514A CN2013103446289A CN201310344628A CN103467514A CN 103467514 A CN103467514 A CN 103467514A CN 2013103446289 A CN2013103446289 A CN 2013103446289A CN 201310344628 A CN201310344628 A CN 201310344628A CN 103467514 A CN103467514 A CN 103467514A
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Abstract
The present invention discloses a method for preparing dialkylphosphinate through an oxidation reduction initiation system. The method comprises that: 1) in the presence of a peroxide initiator and a reduction agent, hypophosphrous acid and/or an alkali metal salt thereof and olefin are subjected to a reaction in a solvent to obtain a mixture containing dialkyl hypophosphrous acid and/or an alkali metal salt thereof; and 2) the solvent in the obtained mixture is removed, water is added to obtain an aqueous solution containing the dialkyl hypophosphrous acid and/or the alkali metal salt thereof, a metal salt is added to carry out a reaction to obtain a slurry, and separation, purification and drying are sequentially performed to obtain the finished product. The production method has the following characteristics that: the process time is short, the temperature is not high, risk of the reaction at the high temperature is avoided, and the prepared product has characteristics of good performance and high yield.
Description
Technical field
The present invention relates to a kind of method that redox initiation system prepares dialkylphosphinic salts.
Background technology
Organic secondary phosphine acid salt belongs to novel organophosphorous fire retardant, and its prepared flame retardant products has the advantages such as product density is low, the fire retardant addition is few, good mechanical property, color and luster is good, smoke density is lower and widely paid close attention to.Be widely used in junctor and switch block, rigidity and flexible print circuit board, weld-proof membrane, scolding tin that PA, PBT make and shelter the fields such as coating, automobile and used in electronic industry parts, have broad application prospects in electric industry, and be specially adapted to thin-walled electronic devices and components, transparent film-making and film.
In prior art, the method for preparing dialkylphosphinic salts is utilized azo compound, and original position produces alkene, with Hypophosporous Acid, 50 and/or its an alkali metal salt generation addition reaction, makes dialkylphosphinic salts etc.
Yet, in prior art, the technique course that reaction prepares dialkylphosphinic salts is often very long, and, due to the reason of initiator system self, cause the temperature of reaction must be very high, thereby the easy explosion caused danger that waits, simultaneously, under high temperature, the probability that produces side reaction increases greatly, and productive rate is often not high yet.
Summary of the invention
The object of the present invention is to provide a kind of redox initiation system to prepare the method for dialkylphosphinic salts.
The technical solution used in the present invention is:
A kind of redox initiation system prepares the method for dialkylphosphinic salts, comprises step:
1) in the situation that peroxide initiator and reductive agent exist, Hypophosporous Acid, 50 and/or its an alkali metal salt are reacted in solvent with alkene, obtain the mixture that contains dialkyl phosphinic acid and/or its an alkali metal salt;
2) removal of solvents in the mixture upper step obtained, add the aqueous solution that water obtains dialkyl phosphinic acid and/or its an alkali metal salt, then add metal salt solution to react to obtain soup compound, separates purifying, dry getting final product.
Described peroxide initiator is at least one in benzoyl peroxide, di-t-butyl peroxide, cyclohexanone peroxide; Described reductive agent is DMA, N, N-Diethyl Aniline, N, at least one in the N-dibutyl aniline.
In step 1), during a kind of in an alkali metal salt that raw material used is Hypophosporous Acid, 50 or Hypophosporous Acid, 50, the mol ratio of a kind of and peroxide initiator in an alkali metal salt of Hypophosporous Acid, 50 or Hypophosporous Acid, 50 is 10-1000:1; During the mixture of an alkali metal salt that raw material used is Hypophosporous Acid, 50 and Hypophosporous Acid, 50, Hypophosporous Acid, 50 is 10-1000:1 with the total amount of the amount of substance of an alkali metal salt of Hypophosporous Acid, 50 with the ratio of the amount of substance of peroxide initiator; The mol ratio of described peroxide initiator and reductive agent is 1.8-2.2:1.
Described an alkali metal salt is sodium salt.
In step 1), described solvent is a kind of in formic acid, acetic acid; During a kind of in an alkali metal salt that raw material used is Hypophosporous Acid, 50 or Hypophosporous Acid, 50, the mass ratio of a kind of and solvent in an alkali metal salt of Hypophosporous Acid, 50 or Hypophosporous Acid, 50 is 1:(4-6); During alkali metal salt mixture that raw material used is Hypophosporous Acid, 50 and Hypophosporous Acid, 50, the total mass of an alkali metal salt of Hypophosporous Acid, 50 and Hypophosporous Acid, 50 and the mass ratio of solvent are 1:(4-6).
Described alkene is at least one in ethene, propylene, iso-butylene, tetrahydrobenzene.
In step 1), reaction pressure is 0.2-2.0MPa, and temperature of reaction is 60-80 ℃.
Step 2) in, described metal-salt is aluminum chloride, Tai-Ace S 150, aluminum nitrate, at least one in zinc chloride, zinc sulfate; The concentration of described metal salt solution is 1.5-2.5mol/L.
The mol ratio of the metal-salt during a kind of in an alkali metal salt that in step 1), raw material used is Hypophosporous Acid, 50 or Hypophosporous Acid, 50, a kind of and step 2 in an alkali metal salt of Hypophosporous Acid, 50 or Hypophosporous Acid, 50) is 1:(2.5-4.5); During alkali metal salt mixture that in step 1), raw material used is Hypophosporous Acid, 50 and Hypophosporous Acid, 50, total amount and the step 2 of the amount of substance of an alkali metal salt of Hypophosporous Acid, 50 and Hypophosporous Acid, 50) in the ratio of amount of substance of metal-salt be 1:(2.5-4.5).
Described separation, purifying, dry concrete grammar are: by soup compound suction filtration under 0.01-0.1MPa, and the washing filter cake, and dry.
The invention has the beneficial effects as follows: preparation method's flow time of the present invention is short, and temperature is not high, has avoided the danger of reacting under high temperature, and the performance of the product made is good, and productive rate is high.
The accompanying drawing explanation
The thermogravimetric analysis figure of the diethyl phospho acid aluminium that Fig. 1 is embodiment 1 preparation.
The IR figure of the diethyl phospho acid aluminium that Fig. 2 is embodiment 1 preparation.
Embodiment
A kind of redox initiation system prepares the method for dialkylphosphinic salts, comprises the steps:
1) a hydration sodium hypophosphite, peroxide initiator and acetic acid are added in the enamel pressure reaction still of 5L, open heating, stir, when temperature rises to 60-65 ℃, ethene is added in reactor by reducing valve, make pressure remain on 0.2-2.0MPa, reductive agent is dissolved in acetic acid and makes solution, this solution evenly is metered in 4-6h, control temperature at 60-80 ℃, reaction 1-3h, shed pressure;
2) by 1) the mixed solution underpressure distillation that obtains removes acetic acid, adds water until clarification adds the metal salt solution be dissolved in water in above-mentioned settled solution, and reaction obtains soup compound, by soup compound suction filtration under 0.01-0.1MPa, washing filter cake, drying.
In step 1), described peroxide initiator is at least one in benzoyl peroxide, di-t-butyl peroxide, cyclohexanone peroxide; Described reductive agent is DMA, N, N-Diethyl Aniline, N, at least one in the N-dibutyl aniline; The mass ratio of one hydration sodium hypophosphite and acetic acid is 1:(4-6); The mol ratio of one hydration sodium hypophosphite and peroxide initiator is 10-1000:1; The mol ratio of described peroxide initiator and reductive agent is 1.8-2.2:1.
Step 2) in, described metal-salt is at least one in aluminum chloride, Tai-Ace S 150, aluminum nitrate, zinc sulfate, zinc chloride, and the concentration of metal salt solution is 1.5-2.5mol/L.
The mol ratio of the metal-salt in the metal salt solution hydration sodium hypophosphite and the step 2 in step 1)) is 1:(2.5-4.5).
Below in conjunction with specific embodiment, the present invention is described further:
embodiment 1:
1) 530g mono-hydration sodium hypophosphite and 12.11g benzoyl peroxide are dissolved in 2500g acetic acid, then solution is moved in 5L enamel autoclave, open stirring heating, when temperature rises to 60 ℃, then pass into ethylene gas, make the still internal pressure reach 1.0MPa and maintain under this pressure, by the 7.46gN be dissolved in 250g acetic acid, N-diethylbenzene amine aqueous solution evenly adds in the still that pressure is 1.0MPa in 4h, keeps 60 ℃ of temperature in the kettle to continue reaction 1h, and pressure in still is shed.
2) by 1) in the mixture underpressure distillation that obtains remove acetic acid, then add water to clarification, in 1h, add reaction to obtain soup compound the 403.31g Aluminium chloride hexahydrate solution be dissolved in 1000g water.By the soup compound suction filtration, washing leaching cake, dry under 120 ℃, obtain diethyl phospho acid aluminium 624.65g, productive rate is 96.1%.
The thermogravimetric analysis figure of the diethyl phospho acid aluminium that Fig. 1 is embodiment 1 preparation.
The IR figure of the diethyl phospho acid aluminium that Fig. 2 is embodiment 1 preparation.
embodiment 2:
1) 530g mono-hydration sodium hypophosphite and 12.32g cyclohexanone peroxide are dissolved in 2500g acetic acid, then solution is moved in 5L enamel autoclave, open stirring heating, when temperature rises to 60 ℃, then pass into ethylene gas, make the still internal pressure reach 1.0MPa and maintain under this pressure, by the 6.09gN be dissolved in 250g acetic acid, accelerine solution evenly adds in the still that pressure is 1.0MPa in 4h, keeps 60 ℃ of temperature in the kettle to continue reaction 1h, and pressure in still is shed.
2) by 1) in the mixture underpressure distillation that obtains remove acetic acid, then add water to clarification, the 559.6g 18 water Tai-Ace S 150 be dissolved in 1000g water is added in 1h.By the soup compound suction filtration, washing leaching cake, dry under 120 ℃, obtain diethyl phospho acid aluminium 622.31g, productive rate is 95.7%.
embodiment 3:
1) 530g mono-hydration sodium hypophosphite and 7.31g di-t-butyl peroxide are dissolved in 2500g acetic acid, then solution is moved in 5L enamel autoclave, open stirring heating, when temperature rises to 70 ℃, then pass into ethylene gas, make the still internal pressure reach 1.0MPa and maintain under this pressure, by the 10.20gN be dissolved in 250g acetic acid, N-dibutyl aniline solution evenly adds in the still that pressure is 1.0MPa in 4h, keeps 70 ℃ of temperature in the kettle to continue reaction 1h, and pressure in still is shed.
2) by 1) in the mixture underpressure distillation that obtains remove acetic acid, then add water to clarification, in 1h, add reaction to obtain soup compound the 626.5g nine water aluminum nitrate solutions that are dissolved in 1000g water.By the soup compound suction filtration, washing leaching cake, dry under 120 ℃, obtain diethyl phospho acid aluminium 627.34g, productive rate is 96.5%.
embodiment 4:
1) 530g mono-hydration sodium hypophosphite and 12.11g benzoyl peroxide are dissolved in 2500g acetic acid, then solution is moved in 5L enamel autoclave, open stirring heating, when temperature rises to 60 ℃, then pass into ethylene gas, make the still internal pressure reach 1.5MPa and maintain under this pressure, by the 5.96gN be dissolved in 250g acetic acid, accelerine solution evenly adds in the still that pressure is 1.5MPa in 4h, keeps 60 ℃ of temperature in the kettle to continue reaction 1h, and pressure in still is shed.
2) by 1) in the mixture underpressure distillation that obtains remove acetic acid, then add water to clarification, in 1h, add reaction to obtain soup compound the 718.9g Zinc Sulphate Heptahydrate solution be dissolved in 1000g water.By the soup compound suction filtration, washing leaching cake, dry under 120 ℃, obtain diethyl phospho acid zinc 750.7g, productive rate is 97.8%.
Can find out, the product yield that the present invention makes is higher, and temperature is lower, and the reaction times is shorter, saves cost.
Claims (10)
1. a redox initiation system prepares the method for dialkylphosphinic salts, it is characterized in that: comprise step:
1) in the situation that peroxide initiator and reductive agent exist, Hypophosporous Acid, 50 and/or its an alkali metal salt are reacted in solvent with alkene, obtain the mixture that contains dialkyl phosphinic acid and/or its an alkali metal salt;
2) removal of solvents in the mixture upper step obtained, add the aqueous solution that water obtains dialkyl phosphinic acid and/or its an alkali metal salt, then add metal salt solution to react to obtain soup compound, separates purifying, dry getting final product.
2. a kind of redox initiation system according to claim 1 prepares the method for dialkylphosphinic salts, it is characterized in that: described peroxide initiator is at least one in benzoyl peroxide, di-t-butyl peroxide, cyclohexanone peroxide; Described reductive agent is DMA, N, N-Diethyl Aniline, N, at least one in the N-dibutyl aniline.
3. a kind of redox initiation system according to claim 1 prepares the method for dialkylphosphinic salts, it is characterized in that: in step 1), during a kind of in an alkali metal salt that raw material used is Hypophosporous Acid, 50 or Hypophosporous Acid, 50, the mol ratio of a kind of and peroxide initiator in an alkali metal salt of Hypophosporous Acid, 50 or Hypophosporous Acid, 50 is 10-1000:1; During the mixture of an alkali metal salt that raw material used is Hypophosporous Acid, 50 and Hypophosporous Acid, 50, Hypophosporous Acid, 50 is 10-1000:1 with the total amount of the amount of substance of an alkali metal salt of Hypophosporous Acid, 50 with the ratio of the amount of substance of peroxide initiator; The mol ratio of described peroxide initiator and reductive agent is 1.8-2.2:1.
4. a kind of redox initiation system according to claim 1 prepares the method for dialkylphosphinic salts, it is characterized in that: described an alkali metal salt is sodium salt.
5. a kind of redox initiation system according to claim 1 prepares the method for dialkylphosphinic salts, it is characterized in that: in step 1), described solvent is a kind of in formic acid, acetic acid; During a kind of in an alkali metal salt that raw material used is Hypophosporous Acid, 50 or Hypophosporous Acid, 50, the mass ratio of a kind of and solvent in an alkali metal salt of Hypophosporous Acid, 50 or Hypophosporous Acid, 50 is 1:(4-6); During alkali metal salt mixture that raw material used is Hypophosporous Acid, 50 and Hypophosporous Acid, 50, the total mass of an alkali metal salt of Hypophosporous Acid, 50 and Hypophosporous Acid, 50 and the mass ratio of solvent are 1:(4-6).
6. a kind of redox initiation system according to claim 1 prepares the method for dialkylphosphinic salts, it is characterized in that: described alkene is at least one in ethene, propylene, iso-butylene, tetrahydrobenzene.
7. a kind of redox initiation system according to claim 1 prepares the method for dialkylphosphinic salts, it is characterized in that: in step 1), reaction pressure is 0.2-2.0MPa, and temperature of reaction is 60-80 ℃.
8. a kind of redox initiation system according to claim 1 prepares the method for dialkylphosphinic salts, it is characterized in that: step 2) in, described metal-salt is at least one in aluminum chloride, Tai-Ace S 150, aluminum nitrate, zinc chloride, zinc sulfate; The concentration of described metal salt solution is 1.5-2.5mol/L.
9. a kind of redox initiation system according to claim 1 prepares the method for dialkylphosphinic salts, it is characterized in that: during a kind of in an alkali metal salt that in step 1), raw material used is Hypophosporous Acid, 50 or Hypophosporous Acid, 50, a kind of and step 2 in an alkali metal salt of Hypophosporous Acid, 50 or Hypophosporous Acid, 50) in the mol ratio of metal-salt be 1:(2.5-4.5); During alkali metal salt mixture that in step 1), raw material used is Hypophosporous Acid, 50 and Hypophosporous Acid, 50, total amount and the step 2 of the amount of substance of an alkali metal salt of Hypophosporous Acid, 50 and Hypophosporous Acid, 50) in the ratio of amount of substance of metal-salt be 1:(2.5-4.5).
10. a kind of redox initiation system according to claim 1 prepares the method for dialkylphosphinic salts, it is characterized in that: described separation, purifying, dry concrete grammar are: by soup compound suction filtration under 0.01-0.1MPa, the washing filter cake, and dry.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015192487A1 (en) * | 2014-06-19 | 2015-12-23 | 中国科学院宁波材料技术与工程研究所 | High-purity diethyl phosphinate and preparation method thereof |
| CN110003268A (en) * | 2019-03-07 | 2019-07-12 | 清远市普塞呋磷化学有限公司 | A kind of preparation method of dialkylphosphinic salts |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660858A (en) * | 2003-12-19 | 2005-08-31 | 科莱恩有限公司 | Process for preparation of dialkylphosphinic salts |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660858A (en) * | 2003-12-19 | 2005-08-31 | 科莱恩有限公司 | Process for preparation of dialkylphosphinic salts |
Non-Patent Citations (2)
| Title |
|---|
| 张其锦: "《高分子化学教程》", 31 August 2012, article "氧化还原引发体系" * |
| 李青山: "《高分子化学教程》", 31 August 2012, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015192487A1 (en) * | 2014-06-19 | 2015-12-23 | 中国科学院宁波材料技术与工程研究所 | High-purity diethyl phosphinate and preparation method thereof |
| CN110003268A (en) * | 2019-03-07 | 2019-07-12 | 清远市普塞呋磷化学有限公司 | A kind of preparation method of dialkylphosphinic salts |
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Application publication date: 20131225 |