CN110511242A - A kind of preparation method of high-purity monoalkylphosphinic acids - Google Patents
A kind of preparation method of high-purity monoalkylphosphinic acids Download PDFInfo
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- CN110511242A CN110511242A CN201910775182.2A CN201910775182A CN110511242A CN 110511242 A CN110511242 A CN 110511242A CN 201910775182 A CN201910775182 A CN 201910775182A CN 110511242 A CN110511242 A CN 110511242A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
Abstract
The invention discloses a kind of preparation method of high-purity monoalkylphosphinic acids, include the following steps: that (1) mixes hypophosphites and organic solvent I, oil bath is stirred to hypophosphites and is completely dissolved, and mixed liquor is obtained；(2) catalyst is added into mixed liquor, temperature is added alcoholic solution, filters after reaction, obtain crude product；(3) organic solvent II is added into crude product, shakes up standing and is divided into 2 layers, upper and lower level separate collection；(4) aqueous slkali is added in organic phase, shakes up rear stratification, collects lower layer's aqueous phase liquid, upper organic phase does liquid waste processing, and lower layer's aqueous phase liquid is merged with the aqueous phase solution that step (3) is collected；(5) organic solvent II I is added in aqueous phase solution after merging to be extracted, collects upper organic phase extracted, then rotate organic solvent II I, high-purity monoalkylphosphinic acids can be obtained.The present invention has monoalkylphosphinic acids purity is high, and reagent toxicity is small, environmental protection, feature at low cost, easy to operate.
Description
Technical field
The present invention relates to a kind of preparation method of monoalkylphosphinic acids, especially a kind of preparation of high-purity monoalkylphosphinic acids
Method.
Background technique
It is Guizhou Province's phosphate rock resource and the maximum mining area of rare earth resources reserves, middle rare earth storage that golden phosphorus ore is knitted in Guizhou
Up to 144.6 ten thousand tons of amount, and based on the rare earths such as yttrium, lanthanum, cerium, neodymium, these rare earth elements are to develop new high-tech material and national defence, boat
Irreplaceable strategic resource in the sophisticated technologies such as empty space flight.Therefore, the extracting and developing rare earth element from phosphorus ore, to raising phosphorus
The utilization rate of ore resources and the sustainable development of rare earth resources all have significance.It is generally used in Extraction of rare eart industry at present
Extractant be P507, Cyanex272, exist long to heavy rare-earth extraction equilibration time, back extraction acid concentration is high, back extraction not exclusively or
It is easy to the disadvantages of emulsifying, is expensive.
As people's environmental protection, safe and healthy consciousness are increasingly enhanced, countries in the world start using environment friendly flame retardant as grinding
Study carefully the emphasis of development and application, monoalkylphosphinic acid salt and dialkylphosphinic salts have good thermal stability and anti-flammability
Halogen-free flame retardants is widely used as the substitute of bromide fire retardant.In addition, alkyl phosphinic acid is floating in mineral
Choosing, rare-earth extractant and field of hydrometallurgy also play an important role, and wherein monoalkylphosphinic acids intermediate is the pass of synthesis
Key, and single group can generate simultaneously with biradical product in organophosphinic acids preparation process, the two physical property is extremely similar, such as
What regulation reaction generates the product needed, and separates two kinds of substances of single, double group and directly affect practical effect, therefore,
How separating-purifying is carried out when preparing monoalkylphosphinic acids, and removal dialkyl phosphinic acid is to need to overcome the problems, such as.
Chinese patent CN201410168815.0 discloses a kind of monoalkylphosphinic acids and asymmetric dialkyl phosphinic acid
Synthetic method, but the disubstituted by-product in this patent monoalkylphosphinic acids crude product is removed using amantadine method, adamantane
Toxicity is big, and liquid waste processing is difficult after purification, and not environmentally, expensive reagents are at high cost, and purification operations process is cumbersome.Chinese patent
CN201310068664.7 discloses a kind of monoalkyl/dialkylphosphinic salts and preparation method thereof, which is reaction with water
Medium reacts at being 70~90 DEG C in temperature with alkene I under initiator I effect by hypophosphites, obtains monoalkylphosphinic acids
Salt.Patent CN201310068662.8 using organic solvent as reaction medium, by hypophosphites initiator I effect under with alkene I
It is reacted at being 70 ~ 90 DEG C in temperature, obtains the monoalkylphosphinic acid salt above method since olefine reaction is needed in certain pressure item
It is carried out under part, needs higher equipment investment, and there are some potential safety problemss.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of high-purity monoalkylphosphinic acids.The present invention has monoalkyl
Phosphinic acids purity is high, reagent toxicity is small, environmental protection, feature at low cost, easy to operate.
Technical solution of the present invention: a kind of preparation method of high-purity monoalkylphosphinic acids includes the following steps:
(1) hypophosphites and organic solvent I are mixed, 60-80 DEG C of oil bath, which is stirred to hypophosphites, to be completely dissolved, and mixed liquor is obtained；
(2) catalyst is slowly added into the mixed liquor of step (1), temperature rises to 90-110 DEG C after addition, then slowly
Alcoholic solution is added to be reacted, reaction is filtered after terminating, and is able to the crude product based on monoalkylphosphinic acids；
(3) organic solvent II is added into crude product made from step (2), shakes up standing and is divided into 2 layers, upper and lower level separate collection,
Upper layer is organic phase solution, and lower layer is aqueous phase solution；
(4) aqueous slkali is added in the organic phase that step (3) are collected, shakes up rear stratification, collect lower layer's aqueous phase liquid, upper layer
Organic phase does liquid waste processing, and lower layer's aqueous phase liquid is merged with the aqueous phase solution that step (3) is collected；
(5) organic solvent II I is added in the aqueous phase solution after step (4) merge to be extracted, collecting upper layer extracted has
Then machine phase rotates organic solvent II I, high-purity monoalkylphosphinic acids can be obtained.
The preparation method of high-purity monoalkylphosphinic acids above-mentioned, organic solvent I described in step (1) are hydrochloric acid, sulfuric acid, phosphorus
One of acid, formic acid, acetic acid, propionic acid, butyric acid or isobutyric acid or more than one.
The preparation method of high-purity monoalkylphosphinic acids above-mentioned, the matter of hypophosphites and organic solvent I described in step (1)
Amount volume ratio is 1:1.5-1:2.5.
The preparation method of high-purity monoalkylphosphinic acids above-mentioned, catalyst described in step (2) are the concentrated sulfuric acid, nitric acid, salt
One of acid or hydrogen peroxide.
The preparation method of high-purity monoalkylphosphinic acids above-mentioned, the dosage of step (2) described catalyst and hypophosphites
Volume mass ratio is 1:0.5-1:1.5.
The preparation method of high-purity monoalkylphosphinic acids above-mentioned, the mass body of step (2) hypophosphites and alcoholic solution
Product also contains acid and organic peroxy initiator in alcoholic solution, alcohol, acid and organic peroxy therein draw than being 1:1-1:2.5
The volume ratio for sending out agent is 3:6-9:1.1-1.3；
The acid be one of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid or isobutyric acid or more than one；
The alcohol is in methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, octanol, isooctanol, the tert-butyl alcohol or cyclohexanol
It is a kind of；
The organic peroxide evocating agent is perbenzoic acid, peroxylauric acid, di-tert-butyl peroxide, peroxidating
Carbonic ester crosses oxalic acid, tert-butyl hydroperoxide isobutyrate, the peroxidating pivalic acid tert-butyl ester, peroxidating spy pentyl ester or azo two
One of isobutyronitrile or more than one.
The preparation method of high-purity monoalkylphosphinic acids above-mentioned, step (2) described alcoholic solution are finished in 20-40h addition.
The preparation method of high-purity monoalkylphosphinic acids above-mentioned, organic solvent II described in step (3) are hexamethylene, petroleum
One of ether, n-hexane, pentane, isopentane or normal heptane are 1:1 with crude product mass ratio.
The preparation method of high-purity monoalkylphosphinic acids above-mentioned, step (4) aqueous slkali are lithium hydroxide solution, hydrogen-oxygen
Change one or more in sodium solution or potassium hydroxide solution, solution concentration 2-6%, it is crude product quality that total amount, which is added,
1-2 times；The aqueous slkali is added in three times.The preparation method of high-purity monoalkylphosphinic acids above-mentioned, step have described in (5)
Solvent III be petroleum ether, ether, isopropyl ether, butyl ether, methyl phenyl ethers anisole, benzene,toluene,xylene, isopropylbenzene, diisobutyl ketone or
One of kerosene or more than one, the extraction carries out in three times, and the additional amount of each organic solvent II I is crude product quality
1/3.
Beneficial effects of the present invention
1, the present invention is by changing the preparation method of monoalkylphosphinic acids, and is successively extracted with organic solvent, aqueous slkali etc.
Separation can finally obtain the monoalkylphosphinic acids of purity is high.
2, the purification reagent that the present invention uses is smaller compared to adamantane toxicity, and cost is also lower, to substantially increase
Environment protecting reduces the production cost of monoalkylphosphinic acids.
3, the present invention is prepared and is purified by above-mentioned technique, compared with the conventional method, operates simpler, safety
It is higher.
Detailed description of the invention
Attached drawing 1 is product of the present invention1H NMR spectra；
Attached drawing 2 is product of the present invention13C NMR spectra；
Attached drawing 3 is product of the present invention31P NMR spectra.
1HNMR、13CNMR and31PNMR uses DMSO to carry out nuclear-magnetism detection as solvent.By upper figure it is found that synthesizing
Product1HNMRδ(10-6) interpretation of result is as follows: 1,0.88-0.90 (d, CH3, 6H)；2,1.84-1.94 (m, CH, 1H)；3,
1.44-1.48 (d, CH2, 2H)；4,6.4 (s, P-OH, 1H), 5,7.44 (s, P-H, 1H).Two acetic acid (solvent) peaks are removed, are closed
At three kinds of H's in the isobutyl groups of H1, H2, H3 and target product in product formula1The position HNMR is corresponding, and integral area
It is opposite with theoretical 1:2:6 than for 1:1.98:6.H4 and H5 is with P-H's in target product isobutylphosphinic and two kinds of H of P-OH1The position HNMR is corresponding, and its integral area is that 0.47:0.47 is corresponding with Theoretical Area ratio 1:1.13CNMRδ(10-6) analysis
It is as follows: 1,24.62(d, CH3)；2,23.56(s, CH)；3,41.56-42.27(d, CH2), wherein due to-CH2With the direct phase of P
Connect cause nuclear-magnetism peak be coupled to two it is unimodal.In addition, synthetic product31PNMRδ(10-6): 30.910.Single nuclear-magnetism peak
Show that only a kind of phosphorous compound is present in product, and the chemical potential phase shift with pertinent literature report target product
Unanimously, therefore substantially it can determine that the synthesized product of experiment is consistent with target product.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
The embodiment of the present invention
Embodiment 1: a kind of preparation method of high-purity monoalkylphosphinic acids, steps are as follows:
(1) 180g hypophosphites and 320ml acetic acid are mixed, 70 DEG C of oil baths are stirred to hypophosphites and are completely dissolved, and mixed liquor is obtained；
(2) it is slowly added to the 180ml concentrated sulfuric acid into mixed liquor, is unlikely to make solution vigorous reaction, temperature rises to 100 DEG C,
Then 320ml alcoholic solution is at the uniform velocity added (wherein containing alcohol, acid and organic peroxy initiator, alcohol, acid and organic peroxy in 30h
The volume ratio of initiator is 3:8:1.2, and the acid is hydrochloric acid；The alcohol is methanol；The organic peroxide evocating agent is
Perbenzoic acid) it is reacted, reaction is filtered after terminating, and obtains conversion ratio greater than 80% or more with monoalkyl time phosphine
Crude product based on acid；
(3) into crude product made from step (2), hexamethylene is added in 1:1 in mass ratio, is shaken up standing and is divided into 2 layers, upper and lower level point
Collection is opened, is operated 3 times repeatedly, upper layer is the organic phase more containing double alkyl, and lower layer is molten containing the more water phase of monoalkyl
Liquid；
(4) lithium hydroxide solution that concentration is 4% is added in three times in the organic phase that step (3) are collected, additional amount is crude product
1.5 times of quality, shake up rear stratification, collect lower layer's aqueous phase liquid, and upper layer hexamethylene mutually does liquid waste processing, and by lower water
Phase liquid merges with the aqueous phase solution that step (3) is collected；
(5) petroleum ether is added in the aqueous phase solution after step (4) merge to be extracted, the dosage of petroleum ether and the matter of crude product
Amount collects upper organic phase extracted, then rotates petroleum ether, high-purity monoalkylphosphinic acids can be obtained than being 1:3.
Embodiment 2: a kind of preparation method of high-purity monoalkylphosphinic acids, steps are as follows:
(1) 180g hypophosphites and 270ml acetic acid are mixed, 60 DEG C of oil baths are stirred to hypophosphites and are completely dissolved, and mixed liquor is obtained；
(2) 360ml hydrochloric acid is slowly added into mixed liquor, temperature rises to 90 DEG C, and then 180ml alcoholic solution (its is at the uniform velocity added in 20h
In contain alcohol, acid and organic peroxy initiator, the volume ratio of alcohol, acid and organic peroxy initiator is 3:6:1.1, described
Acid is formic acid；The alcohol is isopropanol, butanol；The organic peroxide evocating agent is di-tert-butyl peroxide) it carries out instead
It answers, reaction is filtered after terminating, and obtains the crude product based on monoalkylphosphinic acids that conversion ratio is greater than 80% or more；
(3) into crude product made from step (2), n-hexane is added in 1:1 in mass ratio, is shaken up standing and is divided into 2 layers, upper and lower level point
Collection is opened, is operated 3 times repeatedly, upper layer is the organic phase more containing double alkyl, and lower layer is molten containing the more water phase of monoalkyl
Liquid；
(4) potassium hydroxide solution that concentration is 2% is added in three times in the organic phase that step (3) are collected, additional amount is crude product
1 times of quality, shakes up rear stratification, collects lower layer's aqueous phase liquid, and upper layer hexamethylene mutually does liquid waste processing, and by lower layer's water phase
Liquid merges with the aqueous phase solution that step (3) is collected；
(5) butyl ether is added in the aqueous phase solution after step (4) merge to be extracted, the dosage of butyl ether and the mass ratio of crude product
For 1:3, upper organic phase extracted is collected, butyl ether is then rotated, high-purity monoalkylphosphinic acids can be obtained.
Embodiment 3: a kind of preparation method of high-purity monoalkylphosphinic acids, steps are as follows:
(1) 180g hypophosphites and 450ml acetic acid are mixed, 80 DEG C of oil baths are stirred to hypophosphites and are completely dissolved, must mix
Liquid；
(2) 120ml hydrogen peroxide is slowly added into mixed liquor, temperature rises to 110 DEG C, and then it is molten that 450ml alcohol is at the uniform velocity added in 40h
Liquid (wherein containing alcohol, acid and organic peroxy initiator, the volume ratio of alcohol, acid and organic peroxy initiator is 3:9:1.3,
The acid is isobutyric acid；The alcohol is cyclohexanol；The organic peroxide evocating agent is azodiisobutyronitrile) it carries out instead
It answers, reaction is filtered after terminating, and obtains the crude product based on monoalkylphosphinic acids that conversion ratio is greater than 80% or more；
(3) into crude product made from step (2), normal heptane is added in 1:1 in mass ratio, is shaken up standing and is divided into 2 layers, upper and lower level point
Collection is opened, is operated 3 times repeatedly, upper layer is the organic phase more containing double alkyl, and lower layer is molten containing the more water phase of monoalkyl
Liquid；
(4) sodium hydroxide solution that concentration is 6% is added in three times in the organic phase that step (3) are collected, additional amount is crude product
1-2 times of quality, shakes up rear stratification, collects lower layer's aqueous phase liquid, and upper layer hexamethylene mutually does liquid waste processing, and by lower water
Phase liquid merges with the aqueous phase solution that step (3) is collected；
(5) kerosene is added in the aqueous phase solution after step (4) merge to be extracted, the dosage of kerosene and the mass ratio of crude product
For 1:3, upper organic phase extracted is collected, kerosene is then rotated, high-purity monoalkylphosphinic acids can be obtained.
Claims (10)
1. a kind of preparation method of high-purity monoalkylphosphinic acids, which comprises the steps of:
(1) hypophosphites and organic solvent I are mixed, 60-80 DEG C of oil bath, which is stirred to hypophosphites, to be completely dissolved, and mixed liquor is obtained；
(2) catalyst is slowly added into the mixed liquor of step (1), temperature rises to 90-110 DEG C after addition, then slowly
Alcoholic solution is added to be reacted, reaction is filtered after terminating, and is able to the crude product based on monoalkylphosphinic acids；
(3) organic solvent II is added into crude product made from step (2), shakes up standing and is divided into 2 layers, upper and lower level separate collection,
Upper layer is organic phase solution, and lower layer is aqueous phase solution；
(4) aqueous slkali is added in the organic phase that step (3) are collected, shakes up rear stratification, collect lower layer's aqueous phase liquid, upper layer
Organic phase does liquid waste processing, and lower layer's aqueous phase liquid is merged with the aqueous phase solution that step (3) is collected；
(5) organic solvent II I is added in the aqueous phase solution after step (4) merge to be extracted, collecting upper layer extracted has
Then machine phase rotates organic solvent II I, high-purity monoalkylphosphinic acids can be obtained.
2. the preparation method of high-purity monoalkylphosphinic acids according to claim 1, it is characterised in that: described in step (1)
Organic solvent I be one of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid or isobutyric acid or more than one.
3. the preparation method of high-purity monoalkylphosphinic acids according to claim 1, it is characterised in that: described in step (1)
Hypophosphites and the mass volume ratio of organic solvent I are 1:1.5-1:2.5.
4. the preparation method of high-purity monoalkylphosphinic acids according to claim 1, it is characterised in that: described in step (2)
Catalyst is one of the concentrated sulfuric acid, nitric acid, hydrochloric acid or hydrogen peroxide.
5. the preparation method of high-purity monoalkylphosphinic acids according to claim 1, it is characterised in that: step (2) is described to urge
The dosage of agent and the volume mass ratio of hypophosphites are 1:0.5-1:1.5.
6. the preparation method of high-purity monoalkylphosphinic acids according to claim 1, it is characterised in that: step (2) described time
The mass volume ratio of phosphate and alcoholic solution is 1:1-1:2.5, also contains acid and organic peroxy initiator in alcoholic solution, wherein
Alcohol, acid and organic peroxy initiator volume ratio be 3:6-9:1.1-1.3；
The acid be one of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid or isobutyric acid or more than one；
The alcohol is in methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, octanol, isooctanol, the tert-butyl alcohol or cyclohexanol
It is a kind of；
The organic peroxide evocating agent is perbenzoic acid, peroxylauric acid, di-tert-butyl peroxide, peroxidating
Carbonic ester crosses oxalic acid, tert-butyl hydroperoxide isobutyrate, the peroxidating pivalic acid tert-butyl ester, peroxidating spy pentyl ester or azo two
One of isobutyronitrile or more than one.
7. the preparation method of high-purity monoalkylphosphinic acids according to claim 1, it is characterised in that: step (2) described alcohol
Solution is finished in 20-40h addition.
8. the preparation method of high-purity monoalkylphosphinic acids according to claim 1, it is characterised in that: described in step (3)
Organic solvent II is one of hexamethylene, petroleum ether, n-hexane, pentane, isopentane or normal heptane, with crude product mass ratio
For 1:1.
9. the preparation method of high-purity monoalkylphosphinic acids according to claim 1, it is characterised in that: step (4) described alkali
Solution is one or more kinds of in lithium hydroxide solution, sodium hydroxide solution or potassium hydroxide solution, solution concentration 2-6%,
1-2 times that total amount is crude product quality is added；The aqueous slkali is added in three times.
10. according to the preparation method of high-purity monoalkylphosphinic acids described in claim 1, it is characterised in that: step has described in (5)
Solvent III be petroleum ether, ether, isopropyl ether, butyl ether, methyl phenyl ethers anisole, benzene,toluene,xylene, isopropylbenzene, diisobutyl ketone or
One of kerosene or more than one, the extraction carries out in three times, and the additional amount of each organic solvent II I is crude product quality
1/3.
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