CN103739624B - The synthetic method of aluminum diethylphosphinate - Google Patents
The synthetic method of aluminum diethylphosphinate Download PDFInfo
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- CN103739624B CN103739624B CN201410018804.4A CN201410018804A CN103739624B CN 103739624 B CN103739624 B CN 103739624B CN 201410018804 A CN201410018804 A CN 201410018804A CN 103739624 B CN103739624 B CN 103739624B
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Abstract
The present invention relates to organic synthesis field, provide a kind of synthetic method of aluminum diethylphosphinate, comprise the following steps: ammonium hypophosphite and organic solvent mixing, add catalyzer, then, under 80 ~ 130 DEG C of temperature condition, in solution, the obtained two trimethylsiloxy group phosphorus of hexamethyldisilazane is dripped; The two trimethylsiloxy group phosphorus produced are joined in pressure reaction still, passes into ethene and bromize hydrogen gas, and keep reaction pressure with nitrogen, obtain intermediate product, collect toluene through underpressure distillation, in solution, add dissolved water, separatory collects water layer, obtains diethyl phospho acid solution; Regulate diethyl phospho acid solution pH value to 3.0 ± 0.2 with sulfuric acid, then drip aluminum sulfate aqueous solution, generate aluminum diethylphosphinate.The synthetic method of aluminum diethylphosphinate of the present invention, its product purity is high, transformation efficiency is high, cost is low, technique is simple.
Description
Technical field
The present invention relates to organic synthesis field, be specially a kind of synthetic method of aluminum diethylphosphinate.
Background technology
The macromolecular materials such as plastics, rubber, synthon are applied very extensive in the industry, but macromolecular material is normally inflammable or flammable, burning can produce toxic gas fatal in a large number, fire retardant is added in macromolecular material, making synthetic materials have the characteristics such as flame retardancy, self-extinguishing and smoke elimination, is a kind of effective method.
Aluminum diethylphosphinate is a kind of good flame retardation effect and the phosphonium flame retardant of being used widely, phosphorus content is up to 23.85%, its fire-retardant principle is that P contained compound exists many oxidation state, its decomposes product has strong dehydration, make covered polymer surfaces charing, form carbon film, play fire retardation, in aluminum diethylphosphinate.What widely apply in industry is the aluminum diethylphosphinate that German Clariant is produced, and the trade mark is ExolitOP1230.
The aluminum diethylphosphinate preparation method of prior art mainly contains following two kinds: (1) free radical addition method: central principle is free radical addition, the molecule of Hypophosporous Acid, 50 or its an alkali metal salt and radical source and initiator molecule is mainly utilized to collide, and form the free radical of active stronger Hypophosporous Acid, 50 or its an alkali metal salt, then add on olefin hydrocarbon molecules, obtain target product.(2) alkylation of element phosphor: the method prepares an alkali metal salt of alkyl phosphorous acid and dialkyl phosphinic acid or the method for alkaline earth salt by element yellow phosphorus and alkylogen, this reaction is carried out under alkali metal hydroxide aqueous solution or the alkaline earth metal hydroxides aqueous solution or the existence of its mixture, and its important resultant is the salt of phostonic acid, phosphonic acids and Hypophosporous Acid, 50.Its product purity is generally 70% ~ 90%.
In US6300516 and US6248921 patent, describe a kind of preparation method of dialkylphosphinic salts, obtain dialkyl phosphinic acid by phospho acid and olefine reaction in the presence of a free-radical initiator, but the by product of butyl phospho acid can be obtained simultaneously, reduce the purity of product, affect the use of derived product.Chinese patent CN1280582A disclose a kind of with yellow phosphorus and haloalkane for raw material, there is reaction at alkali metal hydroxide or alkaline earth metal hydroxides, prepare the mixture of alkyl phosphorous acid, phosphoric acid and dialkylphosphinic salts.Then obtain dialkyl phosphinic acid and alkali metal compound in the presence of a free-radical initiator to react prepare dialkylphosphinic salts with olefine reaction, the method is that the product that phosphorus source obtains comprises the mixtures such as dialkylphosphinic salts, monoalkylphosphinic acid salt and phospho acid with yellow phosphorus, product purity is low, yield is low, be not suitable for the suitability for industrialized production of product, refined product produces a large amount of waste pollution environment.
Summary of the invention
Technical problem to be solved by this invention is: for the defect of existing dialkylphosphinic salts preparation method, provides that a kind of product purity is high, transformation efficiency is high, cost is low, the synthetic method of the simple aluminum diethylphosphinate of technique.
For solving the problems of the technologies described above, the invention provides following technical scheme:
The synthetic method of aluminum diethylphosphinate, comprises the following steps:
By ammonium hypophosphite and organic solvent mixing, add catalyzer, then under 80 ~ 130 DEG C of temperature condition, in solution, dripping hexamethyldisilazane, reaction backflow 8.5 ~ 9.5 hours, there is layering in reaction soln, by organic matter layer after filtration, obtained two trimethylsiloxy group phosphorus;
The two trimethylsiloxy group phosphorus produced are joined in pressure reaction still, pass into ethene and bromize hydrogen gas, and keep reaction pressure 0.5 ~ 0.8Mpa with nitrogen, 80 ± 5 DEG C of reactions 4.0 ~ 5.0 hours, obtain intermediate product, collect toluene through underpressure distillation, after having distilled, in solution, add dissolved water, separatory collects water layer, obtains diethyl phospho acid solution;
Regulate diethyl phospho acid solution pH value to 3.0 ± 0.2 with sulfuric acid, then drip aluminum sulfate aqueous solution, generate aluminum diethylphosphinate.
Preferably, described organic extractant is toluene, and described catalyzer is trifluoromethanesulfonic acid.
Preferably, toluene consumption is 3.0 ~ 5.5 times of ammonium hypophosphite quality, ammonium hypophosphite and trifluoromethanesulfonic acid mol ratio are 20:1 ~ 40:1, the mol ratio of ammonium hypophosphite and hexamethyldisilazane is 1:1.1 ~ 1:1.5, the mol ratio of ethene and hydrogen bromide is 1:1.1 ~ 1:1.5, and the mol ratio of diethyl phospho acid and Tai-Ace S 150 is 1:0.17 ~ 1:0.25.
Preferably, toluene consumption is 4.5 times of ammonium hypophosphite quality.
Preferably, the mol ratio 35:1 of ammonium hypophosphite and trifluoromethanesulfonic acid.
Preferably, the mol ratio of ammonium hypophosphite and hexamethyldisilazane is 1:1.2.
Preferably, the mol ratio of diethyl phospho acid and Tai-Ace S 150 is 1:0.22.
Preferably, the mol ratio of ethene and hydrogen bromide is 1:1.2.
Preferably, adopt washing, suction filtration, drying step to purify to the aluminum diethylphosphinate generated, and described washing process carry out in a crystallizer.
Preferably, described sulfuric acid is 30wt% dilute sulphuric acid.
After have employed technique scheme, the invention has the beneficial effects as follows:
First, two trimethylsiloxy group phosphorus that employing ammonium hypophosphite of the present invention and hexamethyldisilazane (HMDS) reaction produce and monobromethane coupling produce diethyl phospho acid trimethylsilyl group, overcome the quencher of free radical in reaction system cause ethene and the addition of phosphorus hydrogen bond suppressed, make the purity of product low, the aluminum diethylphosphinate purity that present method obtains is high;
Secondly, catalyzer of the present invention is trifluoromethanesulfonic acid (TfOH), trifluoromethanesulfonic acid is that organic acid is the strongest, the sulfuric acid of acidity more than 100%, so it belongs to super acids, it has strongly-acid and reductibility can be used as isomerization and alkylating catalyzer, with other conventional catalyzer as titanium system solid super-strong acid and aluminum trichloride (anhydrous) phase specific catalytic activity higher, efficiency is higher, better effects if;
Again, synthetic method product of the present invention and organic solvent easily separated, solvent does not remain, and the thermostability of product is high, and reaction effect is good, reduces the generation of waste, environmentally friendly, easy to operate, is easy to suitability for industrialized production.
Embodiment
Following examples are for illustration of the present invention.It is to be understood however that, herein to describe in detail and the present invention stated in the claims not intended to be are limited to the details of following examples.
Aluminum diethylphosphinate chemical formula is as formula I:
Invention mechanism of the present invention is as follows:
The first step: the synthesis of two (trimethylsiloxy group) phosphorus: join in toluene by ammonium hypophosphite and trifluoromethanesulfonic acid, drips hexamethyldisilazane under nitrogen protection and is obtained by reacting two (trimethylsiloxy group) phosphorus.Reaction formula is as follows:
Second step: the synthesis of diethyl phospho acid: quantitative ethene and bromize hydrogen gas are passed in the organic solvent containing two (trimethylsiloxy group) phosphorus, utilize halogenated alkane to be coupled on P atom and form diethyl phospho acid trimethylsilyl group, toluene is collected in underpressure distillation, regulate about PH=6 to be hydrolyzed by water dissolution, separatory is collected water layer and is obtained diethyl phospho acid solution.Reaction formula is as follows:
, there is replacement(metathesis)reaction and obtain aluminum diethylphosphinate in the 3rd step: the synthesis of aluminum diethylphosphinate: diethyl phospho acid solution with water is diluted when adjusting PH=3 and alum liquor, solid is through cooling, and suction filtration, washing, drying obtains aluminum diethylphosphinate.Reaction formula is as follows:
。
Embodiment 1
In the four-hole boiling flask of 1L that agitator, constant pressure funnel and reflux exchanger are housed, add toluene 186.8 grams, 41.5 grams of ammonium hypophosphites are added after opening stirring, then 2.2 grams of trifluoromethanesulfonic acids are added, 96.8 grams of hexamethyldisilazanes are joined in constant pressure funnel, first air in nitrogen replacement four-hole bottle is used, temperature is raised to 90 DEG C, in 3 hours, evenly drip hexamethyldisilazane, collect by product, after being added dropwise to complete with alkali liquor absorption bottle simultaneously, 90 DEG C are incubated 9 hours, be incubated rear cooling, filtered, obtain organic layer product.Organic layer product is joined in the pressure reaction still of 1L, opens stirring, be warmed up to 80 DEG C, pass into ethene 28.1 grams, then pass into bromize hydrogen gas 97.1 grams, pass into nitrogen simultaneously and keep reaction pressure to be 0.6Mpa, 80 DEG C are reacted 4.5 hours, react rear cooling, emptying reaction gas reactor, joins distillation in distiller and collects toluene, add 146.0 grams of water dissolution after having distilled by solution, use separating funnel separatory, collect water layer product and treat next step crystallization.Solution is joined in crystallizer, add 150 grams of water dilutions, with the dilute sulphuric acid regulator solution PH=3.0 of 30%, 73.3 grams of Patent alums are made into the aqueous solution of 30% again, within room temperature 3 hours, are evenly added drop-wise in crystallizer, be then rapidly heated 90 DEG C of insulations 1 hour, cooling, suction filtration, oven dry obtain product 58.3 grams, yield 89.7%, carries out the detection of phosphorus nuclear-magnetism by product
31pNMR, aluminum diethylphosphinate: 98.3%, ethylphosphinic acid aluminium: 1.3%, unknown compound: 0.4%.
Embodiment 2
In the four-hole boiling flask of 1L that agitator, constant pressure funnel and reflux exchanger are housed, add toluene 228.3 grams, 41.5 grams of ammonium hypophosphites are added after opening stirring, then 3.8 grams of trifluoromethanesulfonic acids are added, 121 grams of hexamethyldisilazanes are joined in constant pressure funnel, first air in nitrogen replacement four-hole bottle is used, again temperature is raised to 80 DEG C, in 3 hours, evenly drip hexamethyldisilazane, collect by product, after being added dropwise to complete with alkali liquor absorption bottle simultaneously, 80 DEG C are incubated 9 hours, be incubated rear cooling, filtered, obtain organic layer product.Organic layer product is joined in the pressure reaction still of 1L, opens stirring, be warmed up to 80 DEG C, pass into ethene 28.1 grams, then pass into bromize hydrogen gas 121.4 grams, pass into nitrogen simultaneously and keep reaction pressure to be 0.8Mpa, 80 DEG C are reacted 4.5 hours, react rear cooling, emptying reaction gas reactor, joins distillation in distiller and collects toluene, add 146.0 grams of water dissolution after having distilled by solution, use separating funnel separatory, collect water layer product and treat next step crystallization.Solution is joined in crystallizer, add 150 grams of water dilutions, with the dilute sulphuric acid regulator solution PH=3.0 of 30%, 83.3 grams of Patent alums are made into the aqueous solution of 30% again, within room temperature 3 hours, are evenly added drop-wise in crystallizer, be then rapidly heated 90 DEG C of insulations 1 hour, cooling, suction filtration, oven dry obtain product 54.3 grams, yield 83.5%, carries out the detection of phosphorus nuclear-magnetism by product
31pNMR, aluminum diethylphosphinate: 94.2%, ethylphosphinic acid aluminium: 2.0%, unknown compound: 3.8%.
Embodiment 3
In the four-hole boiling flask of 1L that agitator, constant pressure funnel and reflux exchanger are housed, add toluene 124.5 grams, 41.5 grams of ammonium hypophosphites are added after opening stirring, then 1.9 grams of trifluoromethanesulfonic acids are added, 88.8 grams of hexamethyldisilazanes are joined in constant pressure funnel, first air in nitrogen replacement four-hole bottle is used, again temperature is raised to 130 DEG C, in 3 hours, evenly drip hexamethyldisilazane, collect by product, after being added dropwise to complete with alkali liquor absorption bottle simultaneously, 130 DEG C are incubated 9 hours, be incubated rear cooling, filtered, obtain organic layer product.Organic layer product is joined in the pressure reaction still of 1L, opens stirring, be warmed up to 80 DEG C, pass into ethene 28.1 grams, then pass into bromize hydrogen gas 81.0 grams, pass into nitrogen simultaneously and keep reaction pressure to be 0.5Mpa, 80 DEG C are reacted 4.5 hours, react rear cooling, emptying reaction gas reactor, joins distillation in distiller and collects toluene, add 146.0 grams of water dissolution after having distilled by solution, use separating funnel separatory, collect water layer product and treat next step crystallization.Solution is joined in crystallizer, add 150 grams of water dilutions, with the dilute sulphuric acid regulator solution PH=3.0 of 30%, 56.6 grams of Patent alums are made into the aqueous solution of 30% again, within room temperature 3 hours, are evenly added drop-wise in crystallizer, be then rapidly heated 90 DEG C of insulations 1 hour, cooling, suction filtration, oven dry obtain product 52.7 grams, yield 81.1%, carries out the detection of phosphorus nuclear-magnetism by product
31pNMR, aluminum diethylphosphinate: 85.6%, ethylphosphinic acid aluminium: 7.7%, unknown compound: 6.7%.
Comparative example 1
In the four-hole boiling flask of 1L that agitator, constant pressure funnel and reflux exchanger are housed, add toluene 186.8 grams, 41.5 grams of ammonium hypophosphites are added after opening stirring, then 2.0 grams of titanium system solid super-strong acids are added, 96.8 grams of hexamethyldisilazanes are joined in constant pressure funnel, first air in nitrogen replacement four-hole bottle is used, again temperature is raised to 90 DEG C, in 3 hours, evenly drip hexamethyldisilazane, collect by product, after being added dropwise to complete with alkali liquor absorption bottle simultaneously, 90 DEG C are incubated 9 hours, be incubated rear cooling, filtered, obtain organic layer product.Organic layer product is joined in the pressure reaction still of 1L, opens stirring, be warmed up to 80 DEG C, pass into ethene 28.1 grams, then pass into bromize hydrogen gas 97.1 grams, pass into nitrogen simultaneously and keep reaction pressure to be 0.6Mpa, 80 DEG C are reacted 4.5 hours, react rear cooling, emptying reaction gas reactor, joins distillation in distiller and collects toluene, add 146.0 grams of water after having distilled by solution, use separating funnel separatory, collect water layer product and treat next step crystallization.Solution is joined in crystallizer, add 150 grams of water dilutions, with the dilute sulphuric acid regulator solution PH=3.0 of 30%, after 73.3 grams of Patent alums are made into 30% the aqueous solution, within room temperature 3 hours, be evenly added drop-wise in crystallizer, be then rapidly heated 90 DEG C of insulations 1 hour, cooling, suction filtration, oven dry obtain product 46.5 grams, yield 71.6%, carries out the detection of phosphorus nuclear-magnetism by product
31pNMR, aluminum diethylphosphinate: 77.3%, ethylphosphinic acid aluminium: 13.2%, unknown compound: 9.5%.
Comparative example 2
In the four-hole boiling flask of 1L that agitator, constant pressure funnel and reflux exchanger are housed, add toluene 186.8 grams, 41.5 grams of ammonium hypophosphites are added after opening stirring, then 3.0 grams of aluminum trichloride (anhydrous)s are added, 96.8 grams of hexamethyldisilazanes are joined in constant pressure funnel, first air in nitrogen replacement four-hole bottle is used, again temperature is raised to 90 DEG C, in 3 hours, evenly drip hexamethyldisilazane, collect by product, after being added dropwise to complete with alkali liquor absorption bottle simultaneously, 90 DEG C are incubated 9 hours, be incubated rear cooling, filtered, obtain organic layer product.Organic layer product is joined in the pressure reaction still of 1L, opens stirring, be warmed up to 80 DEG C, pass into ethene 28.1 grams, then pass into bromize hydrogen gas 97.1 grams, pass into nitrogen simultaneously and keep reaction pressure to be 0.6Mpa, 80 DEG C are reacted 4.5 hours, react rear cooling, emptying reaction gas reactor, joins distillation in distiller and collects toluene, add 146.0 grams of water dissolution after having distilled by solution, use separating funnel separatory, collect water layer product and treat next step crystallization.Solution is joined in crystallizer, add 150 grams of water dilutions, with the dilute sulphuric acid regulator solution PH=3.0 of 30%, 73.3 grams of Patent alums are made into the aqueous solution of 30% again, within room temperature 3 hours, are evenly added drop-wise in crystallizer, be then rapidly heated 90 DEG C of insulations 1 hour, cooling, suction filtration, oven dry obtain product 44.3 grams, yield 68.1%, carries out the detection of phosphorus nuclear-magnetism by product
31pNMR, aluminum diethylphosphinate: 72.0%, ethylphosphinic acid aluminium: 16.6%, unknown compound: 11.4%.
The synthetic method of aluminum diethylphosphinate of the present invention, its product purity is high, transformation efficiency is high, cost is low, technique is simple.
The present invention is not limited to above-mentioned concrete embodiment, and those of ordinary skill in the art is from above-mentioned design, and without performing creative labour, done all conversion, all drop within protection scope of the present invention.
Claims (3)
1. the synthetic method of aluminum diethylphosphinate, is characterized in that, comprises the following steps:
By ammonium hypophosphite and organic solvent mixing, add catalyzer, then under 80 ~ 90 DEG C of temperature condition, hexamethyldisilazane is dripped in solution, after being added dropwise to complete, 80 ~ 90 DEG C are reacted backflow 8.5 ~ 9.5 hours, and layering appears in reaction soln, by organic matter layer after filtration, obtained two trimethylsiloxy group phosphorus;
The two trimethylsiloxy group phosphorus produced are joined in pressure reaction still, pass into ethene and bromize hydrogen gas, and keep reaction pressure 0.6 ~ 0.8MPa with nitrogen, at 80 ± 5 DEG C of reaction 4-5 hour, obtain intermediate product, collect toluene through underpressure distillation, after having distilled, in solution, add dissolved water, separatory collects water layer, obtains diethyl phospho acid solution;
Regulate diethyl phospho acid solution ph to 3.0 ± 0.2 with sulfuric acid, then drip aluminum sulfate aqueous solution, generate aluminum diethylphosphinate;
Described organic solvent is toluene, and described catalyzer is trifluoromethanesulfonic acid;
Described toluene consumption is 4.5 ~ 5.5 times of ammonium hypophosphite quality, ammonium hypophosphite and trifluoromethanesulfonic acid mol ratio are 20:1 ~ 35:1, the mol ratio of ammonium hypophosphite and hexamethyldisilazane is 1:1.2 ~ 1:1.5, the mol ratio of ethene and hydrogen bromide is 1:1.2 ~ 1:1.5, and the mol ratio of diethyl phospho acid and Tai-Ace S 150 is 1:0.22 ~ 1:0.25;
The mass percentage of obtained aluminum diethylphosphinate is 94.2-98.3%; Yield is 83.5-89.7%.
2. the synthetic method of aluminum diethylphosphinate according to claim 1, is characterized in that: adopt washing, suction filtration, drying step to purify to the aluminum diethylphosphinate generated, and described washing process carries out in a crystallizer.
3. the synthetic method of aluminum diethylphosphinate according to claim 1, is characterized in that: described sulfuric acid is 30wt% dilute sulphuric acid.
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| CN110746455A (en) * | 2019-11-25 | 2020-02-04 | 岳阳富和科技有限公司 | Preparation method of aluminum bis (2, 4, 4-trimethylpentyl) phosphinate |
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| CN102050835A (en) * | 2010-12-30 | 2011-05-11 | 金发科技股份有限公司 | Preparation method of dialkyl hypophosphite |
| CN102718798A (en) * | 2012-05-21 | 2012-10-10 | 金发科技股份有限公司 | Salts of dialkylphosphinic acid, preparation method and application |
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| CN102050835A (en) * | 2010-12-30 | 2011-05-11 | 金发科技股份有限公司 | Preparation method of dialkyl hypophosphite |
| CN102718798A (en) * | 2012-05-21 | 2012-10-10 | 金发科技股份有限公司 | Salts of dialkylphosphinic acid, preparation method and application |
Non-Patent Citations (1)
| Title |
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| Simple method for the preparation of dialkylphosphonic acids;Ragulin V. V. et al.;《Seriya Khimicheskaya》;19881130(第11期);2652 * |
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