CN103772429A - Method for preparing bis(2,4,4-trimethylpentyl) phosphinic acid from hydrogen phosphide as byproduct in sodium hypophosphite production process - Google Patents
Method for preparing bis(2,4,4-trimethylpentyl) phosphinic acid from hydrogen phosphide as byproduct in sodium hypophosphite production process Download PDFInfo
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Abstract
The invention discloses a method for preparing bis(2,4,4-trimethylpentyl) phosphinic acid from hydrogen phosphide as a byproduct in a sodium hypophosphite production process. The bis(2,4,4-trimethylpentyl) phosphinic acid is prepared by the steps of implementing alkaline cleaning to hydrogen phosphide which is a byproduct in sodium hypophosphite production and freeze-drying the hydrogen phosphide to remove water; pumping the such processed hydrogen phosphide into a high-pressure reaction kettle containing diisobutylene and an initiator through a compressor, wherein the hydrogen phosphide is absorbed by the diisobutylene while hydrogen and little nitrogen in the hydrogen phosphide, instead of being absorbed, enter a combustion furnace along with tail gas, and the purified hydrogen phosphide is subjected to free radical addition reaction with the diisobutylene in the presence of the initiator to generate bis(2,4,4-trimethylpentyl) phosphine; evaporating out residual diisobutylene and monoalkyl substitute; and oxidizing rest materials through hydrogen peroxide to obtain the bis(2,4,4-trimethylpentyl) phosphinic acid.
Description
Technical field
The purifying and the organophosphorus product that the present invention relates to sodium hypophosphite by product phosphuret-(t)ed hydrogen are synthetic, are specifically related to the method for two (2,4,4-tri-methyl-amyl) phospho acid of by product phosphuret-(t)ed hydrogen preparation in a kind of Sodium hypophosphite production technique.
Background technology
There is extensive use containing the organophosphorus product of C-P bond industrial.Synthetic two paths that mainly contain of organophosphorus product.The one, from phosphorus trichloride, through Hooke reaction, tri-kinds of reactions of grignard reaction or A Erbuzuofu generate the organophosphorus product containing carbon phosphorus key.Another paths is that the Radical Addition of phosphuret-(t)ed hydrogen or Hypophosporous Acid, 50 and alkene generates the organophosphorus product containing carbon phosphorus key.Although phosphorus trichloride route can the various organophosphorus product of production quantity, this route, due to introducing and the eliminating of chlorine atom, causes a large amount of pollutions and waste when production.Grignard reaction is except raw material costliness, and reaction conditions is also restive, is one of operation being of little use in Chemical Manufacture.The Radical Addition of sodium hypophosphite or Hypophosporous Acid, 50 and alkene, relative safety and the feature of environmental protection are all higher, but unreactiveness and the constructional feature of sodium hypophosphite and Hypophosporous Acid, 50 itself, the organophosphorus product that can produce is limited to low carbon number alkyl phosphorus product just can reach commercial production scale and time requirement.And this alkyl phosphorus product only has alkyl phosphinic acid.The Radical Addition of phosphuret-(t)ed hydrogen and alkene generates alkyl phosphorus.Phosphuret-(t)ed hydrogen is inflammable and have high toxicity, but its activity is high, and long-chain olefin that can be larger with spatial obstacle generates alkyl phosphorus.In view of the importance of chain alkyl phosphorus product in modern industry, it is essential that phosphuret-(t)ed hydrogen and olefine reaction generate the path of organophosphorus product.The synthetic of two (2,4, the 4-tri-methyl-amyl) Hypophosporous Acid, 50 of organophosphorus product that output is larger can illustrate such situation.
Two (2,4,4-tri-methyl-amyl) Hypophosporous Acid, 50 is an efficient Separation of nickel and cobalt extraction agent of U.S.'s Qing Te company nineteen eighty-three exploitation, trade(brand)name Cyanex 272.Cobalt is high strength, the integral part that high temperature alloy is important.This alloy is widely used in jet airplane engine turbine, sintering metal, high tension battery and magnet etc.But cobalt is mainly distributed in nickel minerals, content is low not easily separated.Therefore the complex process of separation of cobalt in metallurgical industry all the time, productive rate is low, and cost is high.Along with the application of solvent extration in metallurgy, occur that P507 has appearred in P204, the seventies sixties in last century.Aspect separation of Cobalt and Nickel, the separation factor of P507 has improved an order of magnitude than P204, and other performance is also comparatively excellent, thereby P507 is very extensive as extraction agent application.Emerging Cyanex272 of nineteen eighty-three, the separation factor of its separation of Cobalt and Nickel has improved again an order of magnitude than P507.Thereby Cyanex272 replacement P507 has become the maximum extraction agent of cobalt nickel extraction application.Because of its high separation factor, not only reduce extraction progression, save extraction agent, reduce energy consumption, and use after extraction agent can be repeatedly used.Therefore Cyanex272 has high application and promotional value.Under the effect of radical initiator, there is addition reaction generation intermediate product two (2,4,4-tri-methyl-amyl) phosphine alkane with phosphuret-(t)ed hydrogen and diisobutylene the earliest in the synthetic of Cyanex272.Intermediate product generates two (2,4,4-tri-methyl-amyl) phospho acid (US4374780 (1983)) with hydrogen peroxide oxidation again.The raw material phosphuret-(t)ed hydrogen of the method comes from phosphuret-(t)ed hydrogen acid system to be produced, and purity is high, hardly hydrogen.Peter. Hei Siting etc. (CN102180900 (2011)) synthesize two (2 with byproduct phosphuret-(t)ed hydrogen and diisobutylene in sodium hypophosphite technique under condition of free radical, 4,4-tri-methyl-amyl) phosphine, two (2,4,4-tri-methyl-amyl) phosphine obtains two (2,4,4-tri-methyl-amyl) phospho acid through hydrogen peroxide oxidation.But because reaction yield is low, production operation and Energy Consumption Cost are very high.Shiming Wo etc. (US7049463 (2006)) react with diisobutylene and generate two (2,4,4-tri-methyl-amyl) phospho acid with sodium hypophosphite in acetic acid solution under 135 ° of C and ditertiary butyl peroxide effect.Reaction times reaches 30 hours.In product, still containing 12.1% 1 substitution product, need alkali cleaning to purify.Li Linyan etc. (CN101475588 (2009)) use sodium hypophosphite in acetic acid solution, use mixture ditertiary butyl peroxide and benzoyl peroxide instead and make initiator (based on 10 % by mole of sodium hypophosphites), at 120-140 ℃, react 10-15 hour, make straight product, yield 91-92%.Wang Xiaoji (CN102020673 (2011)) in acetic acid solution, makes initiator with Diisopropyl azodicarboxylate with sodium hypophosphite, reacts and within 10 hours, make product under reflux temperature.In product, contain 13.8% 1 substitution product.Wang Xiaoji etc. (CN102268038 (2011), CN1023211117 (2012)) will shorten to 5 hours the reaction times with mixed initiator in same system, and in product, a substituent only has 4%.But what in this individual system, work may and not lie in initiator melange effect, and is the consumption of initiator.The consumption of initiator reaches 100 % by mole based on sodium hypophosphite.This is extremely dangerous in production operation, because of but do not allow perhaps, also nonsensical economically.Zhang Baogui etc. cause the free radical reaction of sodium hypophosphite and diisobutylene, reaction times 8-20 hour at 50-80 ℃ by UV-light.Product yield and purity are not quite clear.Unconventional Light lnduced Free Radicals conversion unit is a uncertain factor in industrial scale.The more than method of synthetic two (2,4,4-tri-methyl-amyl) phospho acid, or be subject to phosphuret-(t)ed hydrogen source restriction, or while adopting sodium hypophosphite to be raw material, reaction solvent needs acid adding conventionally, cause the corrosion to equipment, the reaction times is conventionally also very long, and final product still needs purification process.Or initiator amount is very large, be unsuitable for producing, or because the unconventional property of conversion unit is difficult to a large amount of production.
The technique of the synthetic organophosphorus product of phosphuret-(t)ed hydrogen and olefine reaction as far back as the fifties in last century with exploitation.But the source of phosphuret-(t)ed hydrogen is the key of this technique always.Qing Te company of the U.S. is because developed the highest acid system production method from yellow phosphorus generation phosphuret-(t)ed hydrogen of yield in phosphuret-(t)ed hydrogen production method, the Cheng Liao world of the said firm alkyl phosphorus product largest production business.The by product of sodium hypophosphite technique is another important sources of phosphuret-(t)ed hydrogen.But in the phosphuret-(t)ed hydrogen as this process byproducts, contain volume ratio up to 60% hydrogen and a small amount of nitrogen.The phosphuret-(t)ed hydrogen of purity like this, (CN102180900 (2011)) as previously mentioned, can only be low yield ground, also be to synthesize wastefully organophosphorus product, or be limited to the olefine in low carbon number higher with activity and react synthesizing low-carbon and count alkyl phosphorus (CN101638224 (2010)).This shortcoming of Sodium hypophosphite production by product phosphuret-(t)ed hydrogen makes this resource fail fully in organophosphorus product is synthetic, to be utilized.Therefore how to utilize the by product phosphuret-(t)ed hydrogen synthetic organophosphorus product efficiently in Sodium hypophosphite production, especially high carbon number alkyl phosphorus is the problem to be solved in the present invention.
When laboratory or small-scale production high purity phosphine, conventionally with freezing method, thick phosphuret-(t)ed hydrogen is isolated to the hydrogen and the nitrogen that are difficult to liquefaction-120 ℃ to-130 ℃ liquefaction.But such method is uneconomic for the treatment of required phosphuret-(t)ed hydrogen in industrial production.Klaus Joedden etc. separate the object (CA1116537 (1982)) of phosphuret-(t)ed hydrogen and hydrogen with arrival with the phosphuret-(t)ed hydrogen in the separator column absorption mixed gas of filling molecular sieve.But the phosphuret-(t)ed hydrogen separating like this needs high temperature (~ 200 ℃) desorption and molecular sieve activation treatment.And molecular sieve saturated extent of adsorption only has 10% with respect to molecular sieve weight in the time of 20 ℃.Such sepn process is not only loaded down with trivial details nor economical.Conventionally molecular sieve is used for removing a small amount of phosphuret-(t)ed hydrogen of mixed gas, but cannot utilize the phosphuret-(t)ed hydrogen (such as CN101318124 (2008)) of absorption.The method of how directly reacting under condition of free radical with alkene after the use solvent absorbing phosphuret-(t)ed hydrogen such as the river Xiu Ji of portion (JP58222097 (1983)), is combined into the purifying of phosphuret-(t)ed hydrogen and reaction at same reaction kettle and operates.But this method is synthesizing for minority trialkyl phosphorus only.
Summary of the invention
Goal of the invention: for the problems referred to above, the object of this invention is to provide a kind of preparation method of two (2,4,4-tri-methyl-amyl) phospho acid.The present invention adopts diisobutylene to absorb phosphuret-(t)ed hydrogen under normal temperature and certain pressure, and then the solution of heating absorption phosphuret-(t)ed hydrogen causes free radical reaction, obtains two (2,4,4-tri-methyl-amyl) phosphorus of intermediate product of high yield.Intermediate product obtains two (2,4,4-tri-methyl-amyl) phospho acid through hydrogen peroxide oxidation again.
Technical scheme: in order to solve the problem of prior art existence, the invention provides a kind of preparation method of two (2,4,4-tri-methyl-amyl) phospho acid, comprise the following steps:
1) diisobutylene or initiator solution are sucked in reaction under high pressure kettle;
2) by the by product phosphuret-(t)ed hydrogen in Sodium hypophosphite production through sodium hydroxide solution process after again through lyophilizer drying treatment;
3) gas after drying treatment is pressed into the reaction under high pressure kettle of step 1) through compressor, emits residual gas simultaneously; This gas absorption process continues 1-3 hour; To saturated to liquid-absorbent; The assimilated efficiency of phosphuret-(t)ed hydrogen is very high in the time absorbing beginning, but along with the phosphine gas of liquid-absorbent increases, part phosphuret-(t)ed hydrogen runs off with tail gas.Multistage absorption can effectively utilize the phosphuret-(t)ed hydrogen in thick phosphine gas, and utilization ratio can reach 95%.
4) heating high-pressure reaction kettle reaction; Make temperature in kettle reach 75 ~ 85 ℃, kettle internal pressure rises to 60 ~ 70 normal atmosphere, maintains 75 ~ 85 ℃ of temperature of reaction simultaneously;
5) reaction started after 1 hour, add initiator solution or add initiator solution with volume pump, after initiator solution adds, continue to stir and within 1 hour, obtain containing 2,4,4-trimethylammonium-2-amyl group phosphine, two (2,4,4-trimethylammonium-2-amyl group) intermediate product of phosphine and three (2,4,4-trimethylammonium-2-amyl group) phosphine.In the process that initiator solution adds, keep 75 ~ 85 ℃ of temperature and 60 ~ 70 normal atmosphere 5 ~ 8 hours;
6) the intermediate product underpressure distillation of step 5) is removed to alkene and the substituent in reactant, with the remaining intermediate product of hydrogen peroxide oxidation, obtain two (2,4,4-tri-methyl-amyl) phospho acid.
Wherein, described initiator solution is the diisobutylene solution that contains initiator.
Wherein, described step 1) in diisobutylene be the mixture of 2,4,4-trimethylammonium-1-amylene and 2,4,4-trimethylammonium-2-amylene; As preferably, diisobutylene is 75% 2,4,4-trimethylammonium-1-amylene and 25% 2,4, the mixture of 4-trimethylammonium-2-amylene.
Wherein, described step 3) in kettle temperature remain on-30 ℃-25 ℃, pressure is 1-100 normal atmosphere.For maintaining pressure, need unlatching purging valve to release unabsorbed, the gas that hydrogen content is higher.
Wherein, described step 4) in kettle temperature remain on 50 ℃-100 ℃, pressure is 1-100 normal atmosphere.
Wherein, described initiator is organic azo and organic peroxide evocating agent.
Wherein, described initiator is benzoyl peroxide (BPO).
Wherein, described step 6) in hydrogen peroxide concentration be 20%-35%.
Wherein, initiator can all add reaction under high pressure kettle with volume pump, just adds initiator when solution is warming up to 80 ℃ like this.Drip 5 ~ 8 hours initiator time.After initiator drips and finishes, continue to keep same temperature to stir 1 hour.Initiator also can first partly dissolve in diisobutylene, or all adds in reaction under high pressure kettle before reaction.If initiator has all added in reaction under high pressure kettle before reaction, in step 5), can omit and add this step of initiator solution.
Beneficial effect: the present invention utilizes by product phosphuret-(t)ed hydrogen in sodium hypophosphite technique to make two (2,4,4-tri-methyl-amyl) Hypophosporous Acid, 50 of efficient cobalt nickel separating and extracting agent that the pure phosphuret-(t)ed hydrogen of common needs makes.Phosphuret-(t)ed hydrogen purification process process of the present invention makes alkyl phosphorus products all in phosphatization Hydrogen Energy in Hypophosporous Acid, 50 technique and various olefine reaction compound probability.The phosphuret-(t)ed hydrogen utilization ratio absorbing through a step is 50%.But same absorption can repeatedly be carried out, and the utilization ratio of phosphuret-(t)ed hydrogen can be up to 95%.Like this, the present invention has realized the target with the synthetic various alkyl phosphorus products of the byproduct phosphuret-(t)ed hydrogen in Sodium hypophosphite production.
Embodiment
According to following embodiment, the present invention may be better understood.But, those skilled in the art will readily understand, the described concrete material proportion of embodiment, processing condition and result thereof be only for the present invention is described, and should also can not limit the present invention described in detail in claims.
Embodiment 1
7000 grams of diisobutylene (75% 2,4,4-trimethylammonium-1-amylene, 25% 2,4,4-trimethylammonium-2-amylene) are sucked in stainless steel reaction under high pressure kettle.After the alkali cleaning of 30%NaOH solution, enter after lyophilizer lyophilize at 0-3 ℃ dewaters and enter reaction under high pressure kettle through compressor from the thick phosphuret-(t)ed hydrogen of by product (hereinafter referred to as thick phosphuret-(t)ed hydrogen) of Sodium hypophosphite production.In kettle, temperature remains on-30 ~-20 ℃.When kettle internal pressure rises to 50 normal atmosphere, open purging valve to keep 50 normal atmosphere in kettle.In reaction under high pressure kettle, solution temperature maintains below-20 ℃.Keep this process after 1.5 hours, to stop inputting thick phosphine gas.Pressure release to 40 normal atmosphere, absorbs 900 grams, phosphuret-(t)ed hydrogen (2090 grams of input general gas flows) in reaction under high pressure kettle.When heating high-pressure reaction kettle to 70 ℃, add 61.5 grams of benzoyl peroxides to be dissolved in the solution of 1146 grams of diisobutylene by volume pump, and keep reaction under high pressure kettle at 80 ℃, kettle internal pressure rises to 70 normal atmosphere, 5 as a child after above-mentioned whole initiator solutions added in reaction under high pressure kettle by volume pump, keep 80 ℃ of temperature 2 hours.Cooling sampling.Sample P-NMR analytical results: 8.23 % by mole of two (2,4,4-trimethylammonium-2-amyl group) phosphines, 8.30 % by mole of 2,4,4-trimethylammonium-2-amyl group phosphines, 2.15 % by mole of three (2,4,4-trimethylammonium-2-amyl group) phosphines, all the other are diisobutylene.Gained reaction mass is removed residue diisobutylene and 2,4,4-trimethylammonium-2-amyl group phosphine through underpressure distillation.Leftover materials drip 30% hydrogen peroxide at 60 ℃.In 2 hours, drip 566 grams.Temperature is slowly raised to 105 ℃ from 60 ℃.Evaporated under reduced pressure material obtains 746 grams of two (2,4,4-tri-methyl-amyl) phospho acid of weak yellow liquid product.
Embodiment 2
50 grams of benzoyl peroxides are dissolved in to 7000 grams of diisobutylene (75% 2,4,4-trimethylammonium-1-amylene, 25% 2,4,4-trimethylammonium-2-amylene).Gained solution sucks in stainless steel reaction under high pressure kettle.Thick phosphuret-(t)ed hydrogen enters after lyophilizer lyophilize at 0-3 ℃ dewaters and enters reaction under high pressure kettle through compressor after the alkali cleaning of 50%NaOH solution.In kettle, temperature remains on-15 ℃ ~-20 ℃.When kettle internal pressure rises to 60 normal atmosphere, open purging valve to keep 60 normal atmosphere in kettle.Keep this process 2 hours, stop inputting thick phosphine gas.Pressure release to 40 normal atmosphere in reaction under high pressure kettle, absorbs 1361 grams, phosphuret-(t)ed hydrogen (3404 grams of input general gas flows) in reaction under high pressure kettle.When heating high-pressure reaction kettle to 80 ℃, kettle internal pressure rises to 60 ~ 70 normal atmosphere, add 75.6 grams of benzoyl peroxides to be dissolved in the solution of 1360 grams of diisobutylene by volume pump, and keep reaction under high pressure kettle at 80 ~ 85 ℃, 5 as a child after above-mentioned whole initiators added reaction under high pressure kettle by volume pump.Keep 80 ~ 85 ℃ of reactions of temperature 2 hours.Be cooled to room temperature, stopped reaction.Sample P-NMR analytical results: 23.70 % by mole of two (2,4,4-trimethylammonium-2-amyl group) phosphines, 16.19 % by mole of 2,4,4-trimethylammonium-2-amyl group phosphines, 3.39 % by mole of three (2,4,4-trimethylammonium-2-amyl group) phosphines, all the other are diisobutylene.Gained reaction mass is removed residue diisobutylene and 2,4,4-trimethylammonium-2-amyl group phosphine through underpressure distillation.Leftover materials drip 20% hydrogen peroxide at 60 ℃.In 3 hours, drip 1740 grams.Temperature is slowly raised to 95 ℃ from 60 ℃.Evaporated under reduced pressure material obtains 2350 grams of two (2,4,4-tri-methyl-amyl) phospho acid of weak yellow liquid product.
Embodiment 3
136 grams of benzoyl peroxides are dissolved in to 7000 grams of diisobutylene (75% 2,4,4-trimethylammonium-1-amylene, 25% 2,4,4-trimethylammonium-2-amylene).Gained solution sucks in stainless steel reaction under high pressure kettle.Thick phosphuret-(t)ed hydrogen enters after lyophilizer lyophilize at 0-3 ℃ dewaters and enters reaction under high pressure kettle through compressor after the alkali cleaning of 40%NaOH solution.In kettle, temperature remains on-15 ~-20 ℃.When kettle internal pressure rises to 70 normal atmosphere, open purging valve to keep inherent this pressure of kettle.Keep this process 2 hours, stop inputting thick phosphine gas.Pressure release to 40 normal atmosphere in reaction under high pressure kettle, absorbs 1603 grams, phosphuret-(t)ed hydrogen (3730 grams of input general gas flows) in reaction under high pressure kettle.Heating high-pressure reaction kettle also maintains the temperature at 80-85 ℃, and kettle internal pressure rises to 60 ~ 70 normal atmosphere, 7 hours time.Be cooled to room temperature, stopped reaction.Sample P-NMR analytical results: 20.58 % by mole of two (2,4,4-trimethylammonium-2-amyl group) phosphines, 20.97 % by mole of 2,4,4-trimethylammonium-2-amyl group phosphines, 2.52 % by mole of three (2,4,4-trimethylammonium-2-amyl group) phosphines, all the other are diisobutylene.Gained reaction mass is removed residue diisobutylene and 2,4,4-trimethylammonium-2-amyl group phosphine through underpressure distillation.Leftover materials drip 30% hydrogen peroxide at 60 ℃.In 3 hours, drip 1270 grams.Temperature is slowly raised to 95 ℃ from 60 ℃.Evaporated under reduced pressure material obtains 1700 grams of two (2,4,4-tri-methyl-amyl) phospho acid of weak yellow liquid product.
Embodiment 4
86.3 grams of benzoyl peroxides are dissolved in to 7000 grams of diisobutylene (75% 2,4,4-trimethylammonium-1-amylene, 25% 2,4,4-trimethylammonium-2-amylene).Gained solution sucks in stainless steel reaction under high pressure kettle.Thick phosphuret-(t)ed hydrogen enters after lyophilizer lyophilize at 0-3 ℃ dewaters and enters reaction under high pressure kettle through compressor after the alkali cleaning of 30%NaOH solution.In kettle, temperature remains on-15 ℃.When kettle internal pressure rises to 70 normal atmosphere, open purging valve to keep 70 normal atmosphere in kettle.Keep this process 2 hours, stop inputting thick phosphine gas.Reaction under high pressure kettle internal pressure pressure release to 40 normal atmosphere, absorbs 1761 grams, phosphuret-(t)ed hydrogen (3567 grams of input general gas flows) in reaction under high pressure kettle.When heating high-pressure reaction kettle to 80 ℃, keep 80-85 ℃ 1 hour, add 75.6 grams of benzoyl peroxides and be dissolved in the solution of 1360 grams of diisobutylene by volume pump, and keep reaction under high pressure kettle at 80-85 ℃, kettle internal pressure rises to 60 ~ 70 normal atmosphere, 5 as a child after all initiators added in reaction under high pressure kettle by volume pump, keep 80-85 ℃ of reaction of temperature 1 hour.Be cooled to room temperature, stopped reaction.Sample P-NMR analytical results: 20.03 % by mole of two (2,4,4-trimethylammonium-2-amyl group) phosphines, 25.38 % by mole of 2,4,4-trimethylammonium-2-amyl group phosphines, 3.23 % by mole of three (2,4,4-trimethylammonium-2-amyl group) phosphines, all the other are diisobutylene.Gained reaction mass is removed residue diisobutylene and 2,4,4-trimethylammonium-2-amyl group phosphine through underpressure distillation.Leftover materials drip 30% hydrogen peroxide at 60 ℃.In 3 hours, drip 1880 grams.Temperature is slowly raised to 95 ℃ from 60 ℃.Evaporated under reduced pressure material obtains 2550 grams of two (2,4,4-tri-methyl-amyl) phospho acid of weak yellow liquid product.
Claims (8)
1. the preparation method of two (2,4,4-tri-methyl-amyl) phospho acid, is characterized in that comprising the following steps:
1) diisobutylene or initiator solution are sucked in reaction under high pressure kettle;
2) by the by product phosphuret-(t)ed hydrogen in Sodium hypophosphite production through sodium hydroxide solution process after again through lyophilizer drying treatment;
3) gas after drying treatment is pressed into the reaction under high pressure kettle of step 1) through compressor, emits residual gas simultaneously;
4) heating high-pressure reaction kettle reaction;
5) reaction started after 1 hour, add initiator solution or add initiator solution with volume pump, after initiator solution adds, continue to stir and within 1 hour, obtain containing 2,4,4-trimethylammonium-2-amyl group phosphine, two (2,4,4-trimethylammonium-2-amyl group) intermediate product of phosphine and three (2,4,4-trimethylammonium-2-amyl group) phosphine;
6) the intermediate product underpressure distillation of step 5) is removed to alkene and the substituent in reactant, with the remaining intermediate product of hydrogen peroxide oxidation, obtain two (2,4,4-tri-methyl-amyl) phospho acid.
2. the preparation method of two (2,4,4-tri-methyl-amyl) phospho acid according to claim 1, is characterized in that, described initiator solution is the diisobutylene solution that contains initiator.
3. the preparation method of two (2,4,4-tri-methyl-amyl) phospho acid according to claim 1, is characterized in that described step 1) in diisobutylene be 2,4,4-trimethylammonium-1-amylene and 2,4,4-trimethylammonium-2-amylene mixture.
4. the preparation method of two (2,4,4-tri-methyl-amyl) phospho acid according to claim 1, is characterized in that described step 3) in kettle temperature remain on-30 ℃-25 ℃, pressure is 1-100 normal atmosphere.
5. the preparation method of two (2,4,4-tri-methyl-amyl) phospho acid according to claim 1, is characterized in that described step 4) in kettle temperature remain on 50 ℃-100 ℃, pressure is 1-100 normal atmosphere.
6. the preparation method of two (2,4,4-tri-methyl-amyl) phospho acid according to claim 2, is characterized in that, described initiator is organic azo and organic peroxide evocating agent.
7. the preparation method of two (2,4,4-tri-methyl-amyl) Hypophosporous Acid, 50 according to claim 2, is characterized in that, described initiator is benzoyl peroxide.
8. the preparation method of two (2,4,4-tri-methyl-amyl) Hypophosporous Acid, 50 according to claim 1, is characterized in that described step 6) in hydrogen peroxide concentration be 20%-35%.
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| CN104402923A (en) * | 2014-11-14 | 2015-03-11 | 南开大学 | One-step synthesis method of dialkylphosphinic acid mixture |
| CN112142782A (en) * | 2019-06-27 | 2020-12-29 | 南京韦福化工技术有限公司 | Preparation method of dialkyl phosphinic acid |
| CN112142780A (en) * | 2019-06-27 | 2020-12-29 | 南京韦福化工技术有限公司 | Preparation method of bis (2, 4, 4-trimethylpentyl) dithiophosphinic acid |
| CN114105112A (en) * | 2021-11-30 | 2022-03-01 | 湖北兴发化工集团股份有限公司 | Purification method of byproduct phosphine of sodium hypophosphite |
| CN114163473A (en) * | 2021-11-08 | 2022-03-11 | 湖北兴发化工集团股份有限公司 | Method for preparing diisobutylphosphine from liquid phosphine |
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| CN102180900A (en) * | 2011-03-10 | 2011-09-14 | 常熟新特化工有限公司 | Method for preparing bis(2,4,4-trimethylpentyl)phosphonic acid |
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| CN104402923A (en) * | 2014-11-14 | 2015-03-11 | 南开大学 | One-step synthesis method of dialkylphosphinic acid mixture |
| CN112142782A (en) * | 2019-06-27 | 2020-12-29 | 南京韦福化工技术有限公司 | Preparation method of dialkyl phosphinic acid |
| CN112142780A (en) * | 2019-06-27 | 2020-12-29 | 南京韦福化工技术有限公司 | Preparation method of bis (2, 4, 4-trimethylpentyl) dithiophosphinic acid |
| CN114163473A (en) * | 2021-11-08 | 2022-03-11 | 湖北兴发化工集团股份有限公司 | Method for preparing diisobutylphosphine from liquid phosphine |
| CN114163473B (en) * | 2021-11-08 | 2024-07-05 | 湖北兴发化工集团股份有限公司 | Method for preparing diisobutylphosphine from liquid hydrogen phosphide |
| CN114105112A (en) * | 2021-11-30 | 2022-03-01 | 湖北兴发化工集团股份有限公司 | Purification method of byproduct phosphine of sodium hypophosphite |
| CN114105112B (en) * | 2021-11-30 | 2024-03-12 | 湖北兴发化工集团股份有限公司 | Purification method of sodium hypophosphite byproduct phosphine |
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