CN103772429B - The method of two (2,4, the 4-tri-methyl-amyl) phospho acid of by product phosphuret-(t)ed hydrogen preparation in Sodium hypophosphite production technique - Google Patents
The method of two (2,4, the 4-tri-methyl-amyl) phospho acid of by product phosphuret-(t)ed hydrogen preparation in Sodium hypophosphite production technique Download PDFInfo
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Abstract
The invention discloses a kind of method from two (2,4, the 4-tri-methyl-amyl) phospho acid of byproduct phosphuret-(t)ed hydrogen synthesis Sodium hypophosphite production.By product phosphuret-(t)ed hydrogen in Sodium hypophosphite production through alkali cleaning, then removes moisture through lyophilize.Such phosphuret-(t)ed hydrogen processed is squeezed into the reaction under high pressure kettle that diisobutylene and initiator are housed by compressor.First absorb phosphuret-(t)ed hydrogen with diisobutylene, in phosphuret-(t)ed hydrogen, institute's hydrogen and a small amount of nitrogen are not absorbed, and enter incinerator with tail gas.Phosphuret-(t)ed hydrogen after purifying generates two (2,4,4-tri-methyl-amyl) phosphine under initiator effect with diisobutylene generation Radical Addition.Steam unnecessary diisobutylene and an alkyl substituents.Leftover materials hydrogen peroxide oxidation obtains two (2,4,4-tri-methyl-amyl) phospho acid.
Description
Technical field
The present invention relates to purifying and the synthesis of organophosphorus product of sodium hypophosphite by product phosphuret-(t)ed hydrogen, be 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
Organophosphorus product containing C-P bond industrially has extensive use.The synthesis of organophosphorus product mainly contains two paths.One is from phosphorus trichloride through Hooke reaction, and grignard reaction or A Erbuzuofu tri-kinds reaction generate the organophosphorus product containing carbon phosphorus key.Another paths is the organophosphorus product that the Radical Addition of phosphuret-(t)ed hydrogen or Hypophosporous Acid, 50 and alkene generates containing carbon phosphorus key.Although phosphorus trichloride route can the various organophosphorus product of production quantity, this route, due to the introducing of chlorine atom and eliminating, causes a large amount of pollution and waste during production.Grignard reaction is except expensive starting materials, and reaction conditions is also restive, is one of operation be 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 the unreactiveness of sodium hypophosphite and Hypophosporous Acid, 50 itself and constructional feature, the organophosphorus product that can produce is limited to lower alkyl groups 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, can generate alkyl phosphorus by the long-chain olefin larger with spatial obstacle.In view of the importance of chain alkyl phosphorus product in modern industry, the path that phosphuret-(t)ed hydrogen and olefine reaction generate organophosphorus product is essential.The synthesis of two (2,4, the 4-tri-methyl-amyl) Hypophosporous Acid, 50 of the 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 Cyanex272.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, there is P204 in the sixties in last century, occurred P507 the seventies.In separation of Cobalt and Nickel, the separation factor of P507 improves an order of magnitude than P204, and other performance is also comparatively excellent, and thus P507 is very extensive as extraction agent application.Nineteen eighty-three emerging Cyanex272, the separation factor of its separation of Cobalt and Nickel turn improves an order of magnitude than P507.Thus Cyanex272 replacement P507 has become the extraction agent that cobalt nickel extraction application is maximum.Because of the separation factor that it is high, not only reduce extraction progression, save extraction agent, reduce energy consumption, and the extraction agent after using can repeatedly use.Therefore Cyanex272 has high application and promotional value.Under the effect of radical initiator, addition reaction is there is the earliest and generates intermediate product two (2,4,4-tri-methyl-amyl) phosphine alkane in the synthesis of Cyanex272 with phosphuret-(t)ed hydrogen and diisobutylene.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 and produces, and purity is high, hardly hydrogen.Peter. Hei Siting etc. (CN102180900 (2011)) byproduct phosphuret-(t)ed hydrogen and diisobutylene in sodium hypophosphite technique synthesize two (2 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.ShimingWo etc. (US7049463 (2006)) react with diisobutylene with sodium hypophosphite and generate two (2,4,4-tri-methyl-amyl) phospho acid in acetic acid solution under 135 ° of C and ditertiary butyl peroxide effect.Reaction times reaches 30 hours.Still containing 12.1% 1 substitution product in product, alkali cleaning is needed to purify.Li Linyan etc. (CN101475588 (2009)) use sodium hypophosphite in acetic acid solution, use mixture ditertiary butyl peroxide instead and benzoyl peroxide makes initiator (based on sodium hypophosphite 10 % by mole), 10-15 hour is reacted at 120-140 DEG C, obtained straight product, yield 91-92%.Wang Xiaoji (CN102020673 (2011)) in acetic acid solution, makes initiator with Diisopropyl azodicarboxylate with sodium hypophosphite, reacts 10 hours obtained products at a reflux temperature.Containing 13.8% 1 substitution product in 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 work in this individual system may and do not lie in initiator melange effect, and be 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 at 50-80 DEG C by UV-light, reaction times 8-20 hour.Product yield and purity not quite clear.Unconventional Light lnduced Free Radicals conversion unit is a uncertain factor on a manufacturing scale.The more than method of two (2,4, the 4-tri-methyl-amyl) phospho acid of synthesis, or be subject to the restriction of phosphuret-(t)ed hydrogen source, or when adopting sodium hypophosphite to be raw material, reaction solvent needs acid adding usually, cause the corrosion to equipment, the reaction times is usually 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 that phosphuret-(t)ed hydrogen and olefine reaction synthesize organophosphorus product as far back as the fifties in last century namely to develop.But the source of phosphuret-(t)ed hydrogen is the key of this technique always.Qing Te company of the U.S. is because develop the highest acid system production method producing phosphuret-(t)ed hydrogen from yellow phosphorus 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 as in the phosphuret-(t)ed hydrogen of this process byproducts containing volume ratio up to 60% hydrogen and a small amount of nitrogen.The phosphuret-(t)ed hydrogen of such purity, as previously mentioned (CN102180900 (2011)), can only low yield ground, also be synthesize organophosphorus product wastefully, or be limited to the olefine in low carbon number Reactive Synthesis lower alkyl groups phosphorus (CN101638224 (2010)) higher with activity.This shortcoming of Sodium hypophosphite production by product phosphuret-(t)ed hydrogen makes this resource fail fully to be utilized in the synthesis of organophosphorus product.Therefore how to utilize the by product phosphuret-(t)ed hydrogen in Sodium hypophosphite production to synthesize organophosphorus product efficiently, especially high alkyl phosphorus is the problem to be solved in the present invention.
Usually thick phosphuret-(t)ed hydrogen is isolated with freezing method the hydrogen and nitrogen that are difficult to liquefy-120 DEG C to-130 DEG C liquefaction when laboratory or small-scale production high purity phosphine.But such method is uneconomic for the treatment of phosphuret-(t)ed hydrogen required in industrial production.Phosphuret-(t)ed hydrogen in the separator column absorption mixed gas of the use such as KlausJoedden filling molecular sieve is to arrive the object (CA1116537 (1982)) being separated phosphuret-(t)ed hydrogen and hydrogen.But the phosphuret-(t)ed hydrogen be separated like this needs high temperature (~ 200 DEG C) desorption and molecular sieve activation process.And molecular sieve saturated extent of adsorption only has 10% relative to molecular sieve 20 DEG C time.Such sepn process is not only loaded down with trivial details nor economical.Usual molecular sieve for removing a small amount of phosphuret-(t)ed hydrogen in mixed gas, but cannot utilize the phosphuret-(t)ed hydrogen (such as CN101318124 (2008)) of absorption.How the method for directly reacting under condition of free radical with alkene after solvent absorbing phosphuret-(t)ed hydrogen such as river, portion Xiu Ji (JP58222097 (1983)), is combined into the purifying of phosphuret-(t)ed hydrogen and reaction and operates at same reaction kettle.But this method is only for the synthesis of minority trialkyl phosphorus.
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 the solution then adding thermal 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 prior art Problems existing, the invention provides a kind of preparation method of two (2,4,4-tri-methyl-amyl) phospho acid, comprises 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 after sodium hydroxide solution process again through lyophilizer drying treatment;
3) gas after drying treatment, through the reaction under high pressure kettle of compressor press-in step 1), releases residual gas simultaneously; This gas absorption process continues 1-3 hour; To saturated to liquid-absorbent; The assimilated efficiency of phosphuret-(t)ed hydrogen absorb start time very high, but increase along with the phosphine gas of liquid-absorbent, 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 DEG C, kettle internal pressure rises to 60 ~ 70 normal atmosphere, maintains temperature of reaction 75 ~ 85 DEG C simultaneously;
5) beginning is reacted after 1 hour, add initiator solution with volume pump or add initiator solution, after initiator solution adds, continuing stirring obtains containing 2,4,4-trimethylammonium-2-amyl group phosphine, two (2 for 1 hour, 4,4-trimethylammonium-2-amyl group) intermediate product of phosphine and three (2,4,4-trimethylammonium-2-amyl group) phosphine.Temperature 75 ~ 85 DEG C and 60 ~ 70 normal atmosphere 5 ~ 8 hours are kept in the process that initiator solution adds;
6) by the alkene in the intermediate product underpressure distillation of step 5) removing reactant and a substituent, with the remaining intermediate product of hydrogen peroxide oxidation, two (2,4,4-tri-methyl-amyl) phospho acid are obtained.
Wherein, described initiator solution is the diisobutylene solution containing 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 the mixture of 2,4, the 4-trimethylammonium-1-amylenes of 75% and 2,4, the 4-trimethylammonium-2-amylenes of 25%.
Wherein, described step 3) in kettle temperature remain on-30 DEG C-25 DEG C, pressure is 1-100 normal atmosphere.For maintaining pressure, purging valve need be opened and release unabsorbed, the gas that hydrogen content is higher.
Wherein, described step 4) in kettle temperature remain on 50 DEG C-100 DEG C, 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 all can add reaction under high pressure kettle with volume pump, just adds initiator during such solution warms to 80 DEG C.Drip 5 ~ 8 hours initiator time.After initiator drips and terminates, continue to keep same temperature to stir 1 hour.Initiator also first partly can dissolve in diisobutylene, or all adds before the reaction in reaction under high pressure kettle.If initiator all adds in reaction under high pressure kettle before the reaction, then can omit in step 5) and add this step of initiator solution.
Beneficial effect: the present invention utilizes by product phosphuret-(t)ed hydrogen in sodium hypophosphite technique to obtain two (2,4, the 4-tri-methyl-amyl) Hypophosporous Acid, 50 of the efficient cobalt nickel extraction agent usually needing pure phosphuret-(t)ed hydrogen obtained.Phosphuret-(t)ed hydrogen purification process process of the present invention makes alkyl phosphorus products all in the phosphatization Hydrogen Energy in Hypophosporous Acid, 50 technique and various olefine reaction compound probability.Through one step absorb phosphuret-(t)ed hydrogen utilization ratio 50%.But same absorption can repeatedly be carried out, the utilization ratio of phosphuret-(t)ed hydrogen can up to 95%.Like this, present invention achieves the target of synthesizing various alkyl phosphorus product with 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, concrete material proportion, processing condition and result thereof described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
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.The thick phosphuret-(t)ed hydrogen of by product (hereinafter referred to as thick phosphuret-(t)ed hydrogen) from Sodium hypophosphite production enters after lyophilizer lyophilize at 0-3 DEG C dewaters and enters reaction under high pressure kettle through compressor after the alkali cleaning of 30%NaOH solution.In kettle, temperature remains on-30 ~-20 DEG C.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 less than-20 DEG C.This process is kept to stop after 1.5 hours inputting thick phosphine gas.Pressure release to 40 normal atmosphere, absorbs 900 grams, phosphuret-(t)ed hydrogen (input general gas flow 2090 grams) in reaction under high pressure kettle.During heating high-pressure reaction kettle to 70 DEG C, the solution that 61.5 grams of benzoyl peroxides are dissolved in 1146 grams of diisobutylene is added by volume pump, and keep reaction under high pressure kettle at 80 DEG C, kettle internal pressure rises to 70 normal atmosphere, 5 as a child after above-mentioned whole initiator solution add in reaction under high pressure kettle by volume pump, keep temperature 80 DEG C 2 hours.Cooling sampling.Sample P-NMR analytical results: two (2,4,4-trimethylammonium-2-amyl group) phosphine 8.23 % by mole, 2,4,4-trimethylammonium-2-amyl group phosphine 8.30 % by mole, three (2,4,4-trimethylammonium-2-amyl group) phosphine 2.15 % by mole, all the other are diisobutylene.Gained reaction mass is through underpressure distillation removing residue diisobutylene and 2,4,4-trimethylammonium-2-amyl group phosphine.Leftover materials drip 30% hydrogen peroxide at 60 DEG C.566 grams are dripped in 2 hours.Temperature is slowly raised to 105 DEG C from 60 DEG C.Evaporated under reduced pressure material obtains two (2,4, the 4-tri-methyl-amyl) phospho acid 746 grams of weak yellow liquid product.
Embodiment 2
50 grams of benzoyl peroxides are dissolved in 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 DEG C dewaters and enters reaction under high pressure kettle through compressor after the alkali cleaning of 50%NaOH solution.In kettle, temperature remains on-15 DEG C ~-20 DEG C.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 the thick phosphine gas of input.Pressure release to 40 normal atmosphere in reaction under high pressure kettle, absorbs 1361 grams, phosphuret-(t)ed hydrogen (input general gas flow 3404 grams) in reaction under high pressure kettle.During heating high-pressure reaction kettle to 80 DEG C, kettle internal pressure rises to 60 ~ 70 normal atmosphere, the solution that 75.6 grams of benzoyl peroxides are dissolved in 1360 grams of diisobutylene is added by volume pump, and keep reaction under high pressure kettle at 80 ~ 85 DEG C, 5 as a child after above-mentioned whole initiator add reaction under high pressure kettle by volume pump.Keep temperature 80 ~ 85 DEG C reaction 2 hours.Be cooled to room temperature, stopped reaction.Sample P-NMR analytical results: two (2,4,4-trimethylammonium-2-amyl group) phosphine 23.70 % by mole, 2,4,4-trimethylammonium-2-amyl group phosphine 16.19 % by mole, three (2,4,4-trimethylammonium-2-amyl group) phosphine 3.39 % by mole, all the other are diisobutylene.Gained reaction mass is through underpressure distillation removing residue diisobutylene and 2,4,4-trimethylammonium-2-amyl group phosphine.Leftover materials drip 20% hydrogen peroxide at 60 DEG C.1740 grams are dripped in 3 hours.Temperature is slowly raised to 95 DEG C from 60 DEG C.Evaporated under reduced pressure material obtains two (2,4, the 4-tri-methyl-amyl) phospho acid 2350 grams of weak yellow liquid product.
Embodiment 3
136 grams of benzoyl peroxides are dissolved in 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 DEG C 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 DEG C.When kettle internal pressure rises to 70 normal atmosphere, open purging valve to keep kettle this pressure inherent.Keep this process 2 hours, stop the thick phosphine gas of input.Pressure release to 40 normal atmosphere in reaction under high pressure kettle, absorbs 1603 grams, phosphuret-(t)ed hydrogen (input general gas flow 3730 grams) in reaction under high pressure kettle.Heating high-pressure reaction kettle also maintains the temperature at 80-85 DEG C, 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: two (2,4,4-trimethylammonium-2-amyl group) phosphine 20.58 % by mole, 2,4,4-trimethylammonium-2-amyl group phosphine 20.97 % by mole, three (2,4,4-trimethylammonium-2-amyl group) phosphine 2.52 % by mole, all the other are diisobutylene.Gained reaction mass is through underpressure distillation removing residue diisobutylene and 2,4,4-trimethylammonium-2-amyl group phosphine.Leftover materials drip 30% hydrogen peroxide at 60 DEG C.1270 grams are dripped in 3 hours.Temperature is slowly raised to 95 DEG C from 60 DEG C.Evaporated under reduced pressure material obtains two (2,4, the 4-tri-methyl-amyl) phospho acid 1700 grams of weak yellow liquid product.
Embodiment 4
86.3 grams of benzoyl peroxides are dissolved in 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 DEG C dewaters and enters reaction under high pressure kettle through compressor after the alkali cleaning of 30%NaOH solution.In kettle, temperature remains on-15 DEG C.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 the thick phosphine gas of input.Reaction under high pressure kettle internal pressure pressure release to 40 normal atmosphere, absorbs 1761 grams, phosphuret-(t)ed hydrogen (input general gas flow 3567 grams) in reaction under high pressure kettle.During heating high-pressure reaction kettle to 80 DEG C, keep 80-85 DEG C 1 hour, the solution that 75.6 grams of benzoyl peroxides are dissolved in 1360 grams of diisobutylene is added by volume pump, and keep reaction under high pressure kettle at 80-85 DEG C, kettle internal pressure rises to 60 ~ 70 normal atmosphere, 5 as a child after all initiator add in reaction under high pressure kettle by volume pump, keeps temperature 80-85 DEG C of reaction 1 hour.Be cooled to room temperature, stopped reaction.Sample P-NMR analytical results: two (2,4,4-trimethylammonium-2-amyl group) phosphine 20.03 % by mole, 2,4,4-trimethylammonium-2-amyl group phosphine 25.38 % by mole, three (2,4,4-trimethylammonium-2-amyl group) phosphine 3.23 % by mole, all the other are diisobutylene.Gained reaction mass is through underpressure distillation removing residue diisobutylene and 2,4,4-trimethylammonium-2-amyl group phosphine.Leftover materials drip 30% hydrogen peroxide at 60 DEG C.1880 grams are dripped in 3 hours.Temperature is slowly raised to 95 DEG C from 60 DEG C.Evaporated under reduced pressure material obtains two (2,4, the 4-tri-methyl-amyl) phospho acid 2550 grams of weak yellow liquid product.
Claims (4)
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 after sodium hydroxide solution process again through lyophilizer drying treatment;
3) gas after drying treatment, through the reaction under high pressure kettle of compressor press-in step 1), releases residual gas simultaneously;
4) heating high-pressure reaction kettle reaction;
5) beginning is reacted after 1 hour, add initiator solution with volume pump or add initiator solution, after initiator solution adds, continuing stirring obtains containing 2,4,4-trimethylammonium-2-amyl group phosphine, two (2 for 1 hour, 4,4-trimethylammonium-2-amyl group) intermediate product of phosphine and three (2,4,4-trimethylammonium-2-amyl group) phosphine;
6) by the alkene in the intermediate product underpressure distillation of step 5) removing reactant and a substituent, with the remaining intermediate product of hydrogen peroxide oxidation, two (2,4,4-tri-methyl-amyl) phospho acid are obtained;
Described initiator solution is the diisobutylene solution containing initiator;
Described step 1) in diisobutylene be 2,4,4-trimethylammonium-1-amylene and 2,4,4-trimethylammonium-2-pentene mixture;
Described step 3) in kettle temperature remain on-30 DEG C-25 DEG C, pressure is 1-100 normal atmosphere;
Described step 4) in kettle temperature remain on 50 DEG C-100 DEG C, pressure is 1-100 normal atmosphere.
2. the preparation method of two (2,4,4-tri-methyl-amyl) phospho acid according to claim 1, it is characterized in that, described initiator is organic azo and organic peroxide evocating agent.
3. the preparation method of two (2,4,4-tri-methyl-amyl) Hypophosporous Acid, 50 according to claim 1, it is characterized in that, described initiator is benzoyl peroxide.
4. 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 |
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| 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 |
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| US4374780A (en) * | 1981-05-14 | 1983-02-22 | American Cyanamid Company | Di-2,4,4'-trimethylpentylphosphinic acid and its preparation |
| CN101638224B (en) * | 2008-07-31 | 2011-09-14 | 中国石油化工股份有限公司 | Method for purifying phosphine by-product and application method of phosphine by-product |
| 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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| US4374780A (en) * | 1981-05-14 | 1983-02-22 | American Cyanamid Company | Di-2,4,4'-trimethylpentylphosphinic acid and its preparation |
| CN101638224B (en) * | 2008-07-31 | 2011-09-14 | 中国石油化工股份有限公司 | Method for purifying phosphine by-product and application method of phosphine by-product |
| 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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