CN103804412A - Preparation method of top-grade ultrafine particle diethyl aluminum phosphinate - Google Patents
Preparation method of top-grade ultrafine particle diethyl aluminum phosphinate Download PDFInfo
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Abstract
The invention relates to a preparation method of top-grade ultrafine particle diethyl aluminum phosphinate. The preparation method comprises the following steps: by taking acetic acid as a solvent, acetone as an initiator and organic alkyl phosphinic ionic liquid modified nano titanium dioxide as a photocatalyst, carrying out concerted catalysis on addition reaction of sodium hypophosphite and ethylene to synthesize high purity diethyl sodium phosphinate; then, acidifying the high purity diethyl sodium phosphinate to obtain diethyl phosphinic acid; and finally, neutralizing the diethyl phosphinic acid by aluminum hydroxide to generate the diethyl aluminum phosphinate. The preparation method provided by the invention has the advantages that the production process comprises two steps: S1, the light-catalyzed reaction is carried out at low temperature and low pressure, so that the safety is high and byproducts are effectively avoided; concerted catalysis is used, so that the reaction time is greatly shortened and the conversion rate is extremely high; filtering is performed for removing sodium salt after acidification, so that the influence on the quality of the product is avoided, and the photocatalyst is recovered; S2, the neutralization reaction is carried out close to a condition of room temperature, so that the neutralization reaction is simple to operate and low in energy consumption; finally, the obtained white solid product is ultrafine in particle, high in purity and good in heat stability.
Description
Technical field
The present invention relates to the preparation of environmental type diethyl phosphinates fire retardant, particularly a kind of preparation method of higher-grade ultra-fine grain diethyl phospho acid aluminium.
Background technology
Halogen flame is one of organic fire-retardant of current global output maximum.It is high that halogen flame has flame retarding efficiency, low cost and other advantages, but halogen containing flame-retardant material produces and contains that hydrogen halide etc. is poisonous, the smog of corrosive gases in when burning, easily makes the crowd of scene of fire that poisoning and death by suffocation occurs.Along with Macromolecular materials industry fast development and flame retardant regulation are constantly sound and perfect, at present further urgent to demand nontoxic, the agent of smoke-inhibiting type environment friendly halogen-free fireproof both at home and abroad.
Phosphorus flame retardant comprises organophosphorus and inorganic phosphorus system.Organic phosphorus flame retardant comprises phosphate compounds, phosphonic acid ester, organophosphorated salt, phosphorus-containing polyol and phosphorus compound etc., and the poison gas and the corrosive gases that when burning, produce are fewer than halogen flame.And alkyl phosphinate is the new generation of green environment-friendly type phosphorus flame retardant of in recent years developing, there is good consistency with macromolecule polymer material.Fire-retardant in high molecular polymer of alkyl phosphinate is to play a role at condensed phase, effectively to become charcoal promotor, can strengthen charcoal layer structure, can be used for the fire-retardant of thermoplastics, fiber and textiles, be specially adapted to thin-walled electronic devices and components, transparent products and film.Exolit OP1311 take diethyl phospho acid aluminium as main component and the Exolit OP1312 of the exploitation of especially German Clariant company, the former is mainly used in fire-retardant GRPA6, and the latter is for fire-retardant GRPA66.This class flame retardant products density is lower, and amount of flame-retardant agent is less, better mechanical property, and color and luster is better, and smoke density is lower, and relatively electric trace index is higher, in electric industry, has broad application prospects.But the particle diameter of its product is larger at present, be about 42 about μ m, can affect the consistency of itself and macromolecular material.
US6011172 and CN1280581 have reported that by yellow phosphorus and alkylogen be the method that raw material is prepared dialkylphosphinic salts.It is phosphorus source that the method is used yellow phosphorus, and obtaining product is the mixture systems such as dialkyl phosphinic acid, monoalkyl-phosphinous acid, Hypophosporous Acid, 50, and dialkyl phosphinic acid productive rate is low, is only 16%; US6300516 and US6329544 reported under peroxide radical initiator effect, and alkene reacts the method for preparing dialkylphosphinic salts with hypophosphite.In the method, the temperature of reaction of reaction system is determined by the decomposition temperature of thermal initiator (organic or inorganic superoxide), and the decomposition temperature of most peroxide initiator is all greater than 100 ℃.Therefore, reaction system is temperature required generally higher, and energy consumption is larger.Although the method is compared with US6011172 and CN1280581 report, dialkyl phosphinic acid or salt productive rate increase (molar percentage of dialkyl phosphinic acid or salt reaches 90% left and right) in product, but in product, also contain a large amount of other by products that affects product purity, for example, due to hypertonia polymerization reaction take place, easily produce the by products such as butyl phospho acid or salt take ethene as raw material.
The problems such as, reaction system security high for energy consumption, patent CN101891762A has proposed one and has had low-temp low-pressure, the diethyl phosphinates synthetic method of processing safety high.But the effective constituent of its target product diethyl phospho acid aluminium is low, is only 90% left and right, in product, contain single ethyl phospho acid aluminium and other unidentified compound, these impurity will have a strong impact on the performance index such as product quality and temperature of initial decomposition.
Summary of the invention
The object of the invention is for above-mentioned existing problems, a kind of preparation method of higher-grade ultra-fine grain diethyl phospho acid aluminium is provided, this preparation method's reaction conditions gentleness, technique is simple, the reaction times is short, productive rate is high, energy consumption is low, and products obtained therefrom granular superfine, purity are high, Heat stability is good.
Technical scheme of the present invention:
A kind of preparation method of higher-grade ultra-fine grain diethyl phospho acid aluminium, Using Sodium Hypophosphite and ethene are reaction raw materials, acetic acid is solvent, acetone is initiator, and Organoalkyl phospho acid class Ionic Liquid Modified nano titanium oxide is photocatalyst, the addition reaction of concerted catalysis sodium hypophosphite and ethene, synthesis of high purity diethyl phospho acid sodium, then its acidifying is obtained to diethyl phospho acid, finally neutralize and generate diethyl hypo-aluminum orthophosphate with aluminium hydroxide, specifically comprise the steps:
1) acetic acid solution of sodium hypophosphite is placed in to reactor, add Organoalkyl phospho acid class Ionic Liquid Modified nano titanium oxide, pass into ethene, control the inner certain pressure that keeps of reactor, add at ambient temperature acetone, then under ultra violet lamp, react 4-7h, make diethyl phospho acid sodium solution system;
2) add sulfuric acid or hydrochloric acid soln above-mentioned in containing diethyl phospho acid sodium solution system, obtain diethyl phospho acid solution after crossing filter solid, and water is diluted to finite concentration;
3) use at a certain temperature in aluminium hydroxide solution and 2) in diethyl phospho acid solution to pH5.0, obtain diethyl phospho acid aluminium white precipitate;
4) gained diethyl phospho acid aluminium white precipitate is washed 3 times in 50 ℃ of hot water, then be 0.085 to 0.09MPa in vacuum tightness, drying temperature is 150 ℃ of vacuum drying oven inner dryings under condition, can obtain the Powdered diethyl phospho acid of superfine white aluminium.
Described reactor internal pressure is 0.2～0.3MPa.
Described Organoalkyl phospho acid class ionic liquid negatively charged ion is two (2,4,4-tri-methyl-amyl) phospho acid root, list (2,4,4-tri-methyl-amyl) phospho acid root, two (1-octyl group) phospho acid root or single (1-octyl group) phospho acid root.
Described Organoalkyl phospho acid class Ionic Liquid Modified nano titanium oxide add-on is 1%～10% of sodium hypophosphite quality.
The concentration of described sulphuric acid soln is 50%～98%, and the volume ratio of sulphuric acid soln and diethyl phospho acid sodium solution is 0.001: 1～0.1: 1.
The concentration of described hydrochloric acid soln is 15%～36%, and the volume ratio of hydrochloric acid soln and diethyl phospho acid sodium solution is 0.001: 1～0.1: 1.
Described neutralization reaction temperature is 20～50 ℃.
In described neutralization reaction, diethyl phospho acid strength of solution is 0.05～1.0mol/L.
Described aluminium hydroxide strength of solution is 0.05～1.0mol/L.
Advantage of the present invention is: this production technique is divided into two steps: the first step light concerted catalysis reaction is to carry out under low-temp low-pressure, safe, and the by product such as polymkeric substance alkyl produces while having avoided high pressure and peroxide initiator to use; Due to the concerted catalysis effect of Organoalkyl phospho acid class Ionic Liquid Modified nano titanium oxide, the reaction times shortens and gained diethyl phospho acid sodium very high purity greatly, approaches 100%; After acidifying, remove by filter sodium sulfate or sodium-chlor, avoid the negative impact to quality product of sodium sulfate or sodium-chlor, recycle photocatalyst simultaneously; Second step neutralization reaction is in room temperature or approaches under room temperature condition and carry out, mild condition, simple to operate, and energy consumption is low; Final gained white solid product particle is ultra-fine, purity is high, Heat stability is good.
Embodiment
Below in conjunction with embodiment, the present invention is further described, but they are not that the present invention is imposed any restrictions.Here only point out, the reagent using in the present invention and testing apparatus, except indicating the source especially, are the commercially available universal product.
Embodiment 1:
A preparation method for higher-grade ultra-fine grain diethyl phospho acid aluminium, comprises the steps:
1) 106g (1mol) hydration sodium hypophosphite be dissolved in 600ml acetic acid and fully stir the acetic acid solution that obtains sodium hypophosphite, then moved to 2L jacketed and be equipped with in the withstand voltage reactor of ultraviolet lamp, add 2g Organoalkyl phospho acid class Ionic Liquid Modified nano titanium oxide fully to stir, under room temperature, pass into ethene, make its still internal pressure maintain 0.3MPa, and reach capacity, then open ultraviolet lamp, in 5h, evenly slowly add 1.5g acetone, gained reaction mixture carries out 31p nuclear magnetic resonance spectrum (CDCCl simultaneously
3) phenetic analysis, data presentation, diethyl phospho acid sodium content reaches 99% (molar percentage), and single ethyl phospho acid sodium is only 1%, without sodium hypophosphite;
2) in the above-mentioned reaction mixture system that contains 99% diethyl phospho acid sodium, add 50% sulphuric acid soln, the volume ratio of sulphuric acid soln and diethyl phospho acid sodium solution is 0.01: 1, after crossing filter solid, obtain diethyl phospho acid solution, and water is diluted to 0.5mol/L;
3) under room temperature with in 0.5mol/L aluminium hydroxide solution and 2) in diethyl phospho acid solution to pH5.0, obtain diethyl phospho acid aluminium white precipitate;
4) gained diethyl phospho acid aluminium white precipitate is washed 3 times in 50 ℃ of hot water, be then 0.085 to 0.09MPa in vacuum tightness, temperature is 150 ℃ of vacuum drying oven inner dryings under condition, obtains the Powdered diethyl phospho acid of superfine white aluminium.
Analyzed median size (D by particle size analyzer
50) be about 10nm; According to
31p nuclear magnetic resonance spectrum (CDCCl
3) characterize diethyl phospho acid aluminium content 100%, without other impurity; Temperature of initial decomposition reaches 392 ℃ (99%).
Embodiment 2:
A preparation method for higher-grade ultra-fine grain diethyl phospho acid aluminium, comprises the steps:
1) 212g (2mol) hydration sodium hypophosphite be dissolved in 1000ml acetic acid and fully stir the acetic acid solution that obtains sodium hypophosphite, then moved to 2L jacketed and be equipped with in the withstand voltage reactor of ultraviolet lamp, add 10g Organoalkyl phospho acid class Ionic Liquid Modified nano titanium oxide fully to stir, under room temperature, pass into ethene, make its still internal pressure maintain 0.2MPa, and reach capacity, then open ultraviolet lamp, in 5h, evenly slowly add 3.5g acetone, gained reaction mixture carries out simultaneously
31p nuclear magnetic resonance spectrum (CDCCl
3) phenetic analysis, data presentation, diethyl phospho acid sodium content reaches 98% (molar percentage), and single ethyl phospho acid sodium is only 2%, without sodium hypophosphite;
2) in the above-mentioned reaction mixture system that contains 98% diethyl phospho acid sodium, add 98% sulphuric acid soln, the volume ratio of sulphuric acid soln and diethyl phospho acid sodium solution is 0.005: 1, after crossing filter solid, obtain diethyl phospho acid solution, and water is diluted to 0.25mol/L;
3) at 50 ℃ with in 0.25mol/L aluminium hydroxide solution and 2) in diethyl phospho acid solution to pH5.0, obtain diethyl phospho acid aluminium white precipitate;
4) gained diethyl phospho acid aluminium white precipitate is washed 3 times in 50 ℃ of hot water, be then 0.085 to 0.09MPa in vacuum tightness, temperature is 150 ℃ of vacuum drying oven inner dryings under condition, obtains the Powdered diethyl phospho acid of superfine white aluminium.
Analyzed median size (D by particle size analyzer
50) be about 14nm; According to
31p nuclear magnetic resonance spectrum (CDCCl
3) characterize diethyl phospho acid aluminium content 100%, without other impurity; Temperature of initial decomposition reaches 390 ℃ (99%).
Embodiment 3:
A preparation method for higher-grade ultra-fine grain diethyl phospho acid aluminium, comprises the steps:
1) 212g (2mol) hydration sodium hypophosphite be dissolved in 1000ml acetic acid and fully stir the acetic acid solution that obtains sodium hypophosphite, then moved to 2L jacketed and be equipped with in the withstand voltage reactor of ultraviolet lamp, add 12g Organoalkyl phospho acid class Ionic Liquid Modified nano titanium oxide fully to stir, under room temperature, pass into ethene, make its still internal pressure maintain 0.3MPa, and reach capacity, then open ultraviolet lamp, in 5h, evenly slowly add 3.5g acetone, gained reaction mixture carries out simultaneously
31p nuclear magnetic resonance spectrum (CDCCl
3) phenetic analysis, data presentation, diethyl phospho acid sodium content reaches 99% (molar percentage), and single ethyl phospho acid sodium is 1%, without sodium hypophosphite;
2) in the above-mentioned reaction mixture system that contains 99% diethyl phospho acid sodium, add 20% hydrochloric acid soln, the volume ratio of hydrochloric acid soln and diethyl phospho acid sodium solution is 0.05: 1, after crossing filter solid, obtain diethyl phospho acid solution, and water is diluted to 0.15mol/L;
3) at 50 ℃ with in 0.15mol/L aluminium hydroxide solution and 2) in diethyl phospho acid solution to pH5.0, obtain diethyl phospho acid aluminium white precipitate;
4) gained diethyl phospho acid aluminium white precipitate is washed 3 times in 50 ℃ of hot water, be then 0.085 to 0.09MPa in vacuum tightness, temperature is 150 ℃ of vacuum drying oven inner dryings under condition, obtains the Powdered diethyl phospho acid of superfine white aluminium.
Analyzed median size (D by particle size analyzer
50) be about 7nm; According to
31p nuclear magnetic resonance spectrum (CDCCl
3) characterize diethyl phospho acid aluminium content 100%, without other impurity; Temperature of initial decomposition reaches 395 ℃ (99%).
The present invention discloses a kind of preparation method of higher-grade ultra-fine grain diethyl phospho acid aluminium, those skilled in the art can be by using for reference content herein, the links such as appropriate change operational path realize, although method of the present invention is described by preferred embodiment, person skilled obviously can change or reconfigure method as herein described not departing from content of the present invention and scope, realizes net result.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the artly, they are all deemed to be included in content of the present invention and scope.
Claims (9)
1. the preparation method of a higher-grade ultra-fine grain diethyl phospho acid aluminium, it is characterized in that: Using Sodium Hypophosphite and ethene are reaction raw materials, acetic acid is solvent, acetone is initiator, Organoalkyl phospho acid class Ionic Liquid Modified nano titanium oxide is photocatalyst, the addition reaction of concerted catalysis sodium hypophosphite and ethene, synthesis of high purity diethyl phospho acid sodium, then its acidifying is obtained to diethyl phospho acid, finally neutralize and generate diethyl hypo-aluminum orthophosphate with aluminium hydroxide, specifically comprise the steps:
1) acetic acid solution of sodium hypophosphite is placed in to reactor, add Organoalkyl phospho acid class Ionic Liquid Modified nano titanium oxide, pass into ethene, control the inner certain pressure that keeps of reactor, add at ambient temperature acetone, then under ultra violet lamp, react 4-7h, make diethyl phospho acid sodium solution system;
2) add sulfuric acid or hydrochloric acid soln above-mentioned in containing diethyl phospho acid sodium solution system, obtain diethyl phospho acid solution after crossing filter solid, and water is diluted to finite concentration;
3) use at a certain temperature in aluminium hydroxide solution and 2) in diethyl phospho acid solution to pH5.0, obtain diethyl phospho acid aluminium white precipitate;
4) gained diethyl phospho acid aluminium white precipitate is washed 3 times in 50 ℃ of hot water, then be 0.085 to 0.09MPa in vacuum tightness, drying temperature is 150 ℃ of vacuum drying oven inner dryings under condition, can obtain the Powdered diethyl phospho acid of superfine white aluminium.
2. a kind of preparation method of higher-grade ultra-fine grain diethyl phospho acid aluminium according to claim 1, is characterized in that: described light-catalyzed reaction still internal pressure is 0.2～0.3MPa.
3. a kind of preparation method of higher-grade ultra-fine grain diethyl phospho acid aluminium according to claim 1, it is characterized in that: described Organoalkyl phospho acid class ionic liquid negatively charged ion is two (2,4,4-tri-methyl-amyl) phospho acid root, list (2,4,4-tri-methyl-amyl) phospho acid root, two (1-octyl group) phospho acid root or single (1-octyl group) phospho acid root.
4. a kind of preparation method of higher-grade ultra-fine grain diethyl phospho acid aluminium according to claim 1, is characterized in that: described Organoalkyl phospho acid class Ionic Liquid Modified nano titanium oxide add-on is 1%～10% of sodium hypophosphite quality.
5. a kind of preparation method of higher-grade ultra-fine grain diethyl phospho acid aluminium according to claim 1, is characterized in that: in light concerted catalysis reaction, the transformation efficiency of diethyl phospho acid sodium is more than or equal to 98%.
6. a kind of preparation method of higher-grade ultra-fine grain diethyl phospho acid aluminium according to claim 1, is characterized in that: the concentration of described sulphuric acid soln is 50%～98%; The volume ratio of described sulphuric acid soln and diethyl phospho acid sodium solution is 0.001: 1～0.1: 1.
7. a kind of preparation method of higher-grade ultra-fine grain diethyl phospho acid aluminium according to claim 1, is characterized in that: the concentration of described hydrochloric acid soln is 15%～36%; The volume ratio of described hydrochloric acid soln and diethyl phospho acid sodium solution is 0.001: 1～0.1: 1.
8. a kind of preparation method of higher-grade ultra-fine grain diethyl phospho acid aluminium according to claim 1, is characterized in that: in described neutralization reaction, temperature of reaction is 20～50 ℃; In described neutralization reaction, diethyl phospho acid strength of solution is 0.05～1.0mol/L; In described neutralization reaction, aluminium hydroxide strength of solution is 0.05～1.0mol/L.
9. a kind of preparation method of higher-grade ultra-fine grain diethyl phospho acid aluminium according to claim 1, is characterized in that: the median size (D of described synthetic diethyl phospho acid aluminium
50) be less than 15nm; Described synthetic diethyl phospho acid aluminium content 100%; More than described synthetic diethyl phospho acid aluminium temperature of initial decomposition reaches 390 ℃ (99%); Described synthetic diethyl phospho acid aluminium is for flame retardant area.
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Cited By (6)
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| CN104072537A (en) * | 2014-06-19 | 2014-10-01 | 中国科学院宁波材料技术与工程研究所 | High-impurity diethyl phosphinates and preparation process thereof |
| CN104230986A (en) * | 2014-09-17 | 2014-12-24 | 中国科学院宁波材料技术与工程研究所 | Technology for preparing dialkyl phosphinate |
| CN107652321A (en) * | 2017-09-30 | 2018-02-02 | 济南泰星精细化工有限公司 | A kind of preparation method and applications of graininess alkyl phosphinic acid aluminium |
| CN109608491A (en) * | 2018-12-14 | 2019-04-12 | 湖北宏嘉化工股份有限公司 | A kind of preparation method of diethyl hypophosphites |
| CN110903642A (en) * | 2018-09-18 | 2020-03-24 | 上海凯赛生物技术股份有限公司 | Halogen-free flame-retardant resin and preparation method thereof |
| CN116925132A (en) * | 2023-07-03 | 2023-10-24 | 太仓维龙化工有限公司 | Preparation method of fine-particle-size dialkyl phosphinate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104072537A (en) * | 2014-06-19 | 2014-10-01 | 中国科学院宁波材料技术与工程研究所 | High-impurity diethyl phosphinates and preparation process thereof |
| CN104230986A (en) * | 2014-09-17 | 2014-12-24 | 中国科学院宁波材料技术与工程研究所 | Technology for preparing dialkyl phosphinate |
| CN107652321A (en) * | 2017-09-30 | 2018-02-02 | 济南泰星精细化工有限公司 | A kind of preparation method and applications of graininess alkyl phosphinic acid aluminium |
| CN110903642A (en) * | 2018-09-18 | 2020-03-24 | 上海凯赛生物技术股份有限公司 | Halogen-free flame-retardant resin and preparation method thereof |
| CN110903642B (en) * | 2018-09-18 | 2022-03-18 | 上海凯赛生物技术股份有限公司 | Halogen-free flame-retardant resin and preparation method thereof |
| CN109608491A (en) * | 2018-12-14 | 2019-04-12 | 湖北宏嘉化工股份有限公司 | A kind of preparation method of diethyl hypophosphites |
| CN109608491B (en) * | 2018-12-14 | 2023-12-05 | 湖北宏嘉化工股份有限公司 | Preparation method of diethyl phosphinate |
| CN116925132A (en) * | 2023-07-03 | 2023-10-24 | 太仓维龙化工有限公司 | Preparation method of fine-particle-size dialkyl phosphinate |
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