CN104447864B - A kind of method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl - Google Patents
A kind of method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl Download PDFInfo
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- CN104447864B CN104447864B CN201410577208.XA CN201410577208A CN104447864B CN 104447864 B CN104447864 B CN 104447864B CN 201410577208 A CN201410577208 A CN 201410577208A CN 104447864 B CN104447864 B CN 104447864B
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Abstract
Invention describes a kind of method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl, the described iso-octyl phosphonic acids named O of di-isooctyl standard, O bis-(2 ethylhexyl) 2 ethylhexyl phosphonate, phosphonous acid di-isooctyl and caustic alcohol react and obtain phosphorous acid di-isooctyl sodium, phosphorous acid di-isooctyl sodium again with chloro-iso-octane iodine alkali metal salt be catalyzed under 150 ~ 160 DEG C reaction 2 ~ 4h, then saponification, separatory, distillation obtain target product iso-octyl phosphonic acids di-isooctyl；Phosphorous acid di-isooctyl sodium that is two (2 ethylhexyl) phosphite ester sodium；Phosphonous acid di-isooctyl that is two (2 ethylhexyl) phosphinate, chloro-iso-octane i.e. chloro 2 ethyl hexane.This method is compared with conventional method, and chloro-iso-octane consumption reduces 1/2, and close to theoretical amount；Reaction temperature reduces, and the reaction time is shorter so that by-products content reduces, and the production cycle shortens；The yield of iso-octyl phosphonic acids di-isooctyl raises, up to 92.3%.
Description
Technical field
The present invention relates to a kind of iso-octyl phosphonic acids di-isooctyl synthetic technology, a kind of method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl, the named O of standard, O-bis-(2-the ethylhexyl)-2-ethylhexyl phosphonate of described iso-octyl phosphonic acids di-isooctyl..
Background technology
Iso-octyl phosphonic acids di-isooctyl is a kind of important chemical intermediate, through the available iso-octyl phosphine monooctyl acid monooctyl ester of hydrolysis, trade name P507 of iso-octyl phosphine monooctyl acid monooctyl ester, i.e. O-(2-ethylhexyl)-2-ethylhexyl phosphonate, it it is a kind of important hydrometallurgical extraction agent, it is widely used in the separation of copper-zinc, nickel-cobalt, the packet of rare earth element and the separating-purifying of single rare earth metal, rare earth and the aspect such as non-rare earth separates.
Industrial general elder generation is with phosphonous acid di-isooctyl and caustic alcohol synthesizing phosphorous acid di-isooctyl sodium, and phosphorous acid di-isooctyl sodium is synthesized iso-octyl phosphonic acids di-isooctyl again with chloro-iso-octane.Owing to chloro-iso-octane activity is not high enough, this reaction must at high temperature be carried out, and the reaction time is longer, and chloro-iso-octane is the most excessive, while it is true, the yield of iso-octyl phosphonic acids di-isooctyl is again below 80%.
Summary of the invention
The technical problem to be solved is to provide a kind of method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl, improve the technical process of conventional synthesis iso-octyl phosphonic acids di-isooctyl, reduce chloro-iso-octane consumption, reduce reaction temperature, reduce the reaction time, improve the yield of iso-octyl phosphonic acids di-isooctyl.The iso-octyl phosphonic acids named O of di-isooctyl standard described in this patent, O-bis-(2-ethylhexyl)-2-ethylhexyl phosphonate, described phosphorous acid di-isooctyl sodium standard named two (2-ethylhexyl) phosphite ester sodium；Described phosphonous acid di-isooctyl standard named two (2-ethylhexyl) phosphinate；Described chloro-iso-octane standard named chloro-2-ethyl hexane.
In order to realize solving the purpose of above-mentioned technical problem, present invention employs following technical scheme:
A kind of method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl of the present invention, the described iso-octyl phosphonic acids named O of di-isooctyl standard, O-bis-(2-ethylhexyl)-2-ethylhexyl phosphonate, comprise the steps:
(1), synthesizing phosphorous acid di-isooctyl sodium technique: using phosphonous acid di-isooctyl to react with caustic alcohol, synthesis obtains phosphorous acid di-isooctyl sodium, is cooled to normal temperature；Described phosphorous acid di-isooctyl sodium standard named two (2-ethylhexyl) phosphite ester sodium；Described phosphonous acid di-isooctyl standard named two (2-ethylhexyl) phosphinate；This step is prior art；
(2), catalytic reaction technique: at normal temperatures, it is cooled to the phosphorous acid di-isooctyl sodium of normal temperature adds according to this base metal catalysts and the chloro-iso-octane of iodine to step (), described chloro-iso-octane standard named chloro-2-ethyl hexane, chloro-iso-octane is (1 ~ 1.2) with the mol ratio of phosphorous acid di-isooctyl sodium: 1, it is to slowly warm up to 150 ~ 160 DEG C, is incubated 2 ~ 4h；
(3), aftertreatment technology: after completion of the reaction, reactant liquor obtains target product iso-octyl phosphonic acids di-isooctyl through saponification, separatory, distillation.
Concrete, the base metal catalysts of described iodine is KI and sodium iodide.The most concrete, described catalyst amount is the 1 ~ 3% of the amount of phosphonous acid di-isooctyl material.
Concrete, described aftertreatment technology is: after catalytic reaction, treat that temperature is down to less than 90 DEG C, adding quantitative sodium hydrate aqueous solution in reactant liquor, phosphonous acid di-isooctyl is (4 ~ 5) with the mol ratio of NaOH: be to slowly warm up to 70 ~ 90 DEG C in 1,30min, saponification 30 ~ 45min, separatory, vacuum decompression distills, collects corresponding cut and be iso-octyl phosphonic acids di-isooctyl.
The most concrete, the mass fraction of described sodium hydrate aqueous solution is 3 ~ 5%,
The most concrete, the vacuum of vacuum decompression distillation is 720 ~ 740mmHg, and the cut collecting about 180 ~ 230 DEG C is iso-octyl phosphonic acids di-isooctyl.
Concrete preferred, described synthesizing phosphorous acid di-isooctyl sodium technique is: in reactor add mol ratio be 1:(1 ~ 1.1) phosphonous acid di-isooctyl and caustic alcohol, directly heat distillation removing ethanol, be slowly heated to 95-105 DEG C in 1 ~ 1.5h, obtain phosphorous acid di-isooctyl sodium.
The most concrete, the range request that was slowly heated of described catalytic reaction technique is: be to slowly warm up to 150 ~ 160 DEG C in 30 ~ 60min.
These technical schemes can also be combined with each other or combine, thus reaches superior technique effect.
By using technique scheme, the present invention has a following beneficial effect:
First, chloro-iso-octane consumption reduces 1/2, and close to theoretical amount；Second, reaction temperature reduces, and the reaction time is shorter so that by-products content reduces, and the production cycle shortens；3rd, the yield of iso-octyl phosphonic acids di-isooctyl raises, up to 92.3%.
Detailed description of the invention
Below in conjunction with embodiment, this patent is further explained.But the protection domain of this patent is not limited to specific embodiment.
Embodiment 1
In equipped with the 1000mL four-hole bottle of thermometer, it is sequentially added into 183.9g (0.6mol) phosphonous acid di-isooctyl and 44.9g (0.66mol) caustic alcohol, agitating heating, after distillation removing ethanol, obtains phosphorous acid di-isooctyl sodium.It is cooled to 25 DEG C, 2.9g (0.018mol) KI and 108.0g (0.72mol) chloro-iso-octane it is sequentially added in four-hole bottle, it is to slowly warm up to 160 DEG C, used time 1h, insulation 3h, after reaction terminates, is cooled to 80 DEG C, 100g 5% sodium hydrate aqueous solution is added in four-hole bottle, 80 DEG C it are to slowly warm up in 30min, it is incubated 30min, separatory, decompression distillation, the cut collecting 180 ~ 230 DEG C (vacuum is 720 ~ 740mmHg) is iso-octyl phosphonic acids di-isooctyl, obtains 231.9g, yield is 92.3%, and gas chromatographic purity is 95.7%.Iso-octyl phosphonic acids di-isooctyl yield described in this patent, is all the yield calculated with phosphonous acid di-isooctyl.
Embodiment 2
By the method for example 1, catalyst changes sodium iodide into, and its inventory is 2.7g (0.018mol), is incubated 2h, and other conditions are constant, obtain product 230.6g, yield 91.8%, and gas chromatographic purity is 94.2%.
Embodiment 3
By the method for example 1, the inventory of chloro-iso-octane changes 90.0g (0.6mol) into, and other conditions are constant, obtains product 226.3g, yield 90.1%, and gas chromatographic purity is 94.9%.
Embodiment 4
By the method for example 2, the inventory of chloro-iso-octane changes 90.0g (0.6mol) into, and other conditions are constant, obtains product 223.3g, yield 88.9%, and gas chromatographic purity is 93.5%.
Embodiment 5
In equipped with the 1000mL four-hole bottle of thermometer, it is sequentially added into 183.9g phosphonous acid di-isooctyl and 44.9g caustic alcohol, agitating heating, after distillation removing ethanol, obtains phosphorous acid di-isooctyl sodium.It is cooled to 25 DEG C, 2.9g KI and 130g chloro-iso-octane it is sequentially added in four-hole bottle, it is to slowly warm up to 150 DEG C, used time 0.5h, insulation 4h, after reaction terminates, is cooled to 90 DEG C, 100g 4% sodium hydrate aqueous solution is added in four-hole bottle, 70 DEG C it are to slowly warm up in 30min, it is incubated 30min, separatory, decompression distillation, the cut collecting 180 ~ 230 DEG C (vacuum is 720 ~ 740mmHg) is iso-octyl phosphonic acids di-isooctyl, obtains 232.1g, yield is 92.4%, and gas chromatographic purity is 95.3%.
Embodiment 6
By the method for example 5, catalyst changes sodium iodide into, and its inventory is 1.0g, and other conditions are constant, obtains product 228.3g, yield 90.8%, and gas chromatographic purity is 95.2%.
Embodiment 7
By the method for example 5, the inventory of chloro-iso-octane changes 90.0g into, and other conditions are constant, obtains product 229.3g, yield 92.2%, and gas chromatographic purity is 94.7%.
Embodiment 8
By the method for example 6, the inventory of chloro-iso-octane changes 90.0g into, and other conditions are constant, obtains product 223.8g, yield 89.2%, and gas chromatographic purity is 95.1%.
Claims (7)
1. the method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl, the described iso-octyl phosphonic acids di-isooctyl named O of its standard, O-bis-(2-ethylhexyl)-
2-ethylhexyl phosphonate, is characterized in that comprising the steps:
(1), synthesizing phosphorous acid di-isooctyl sodium technique: using phosphonous acid di-isooctyl to react with caustic alcohol, synthesis obtains phosphorous acid di-isooctyl sodium, is cooled to normal temperature；Described phosphorous acid its standard of di-isooctyl sodium named two (2-ethylhexyl) phosphite ester sodium；Described its standard of phosphonous acid di-isooctyl named two (2-ethylhexyl) phosphinate；
(2), catalytic reaction technique: at normal temperatures, it is cooled to the phosphorous acid di-isooctyl sodium of normal temperature adds according to this base metal catalysts and the chloro-iso-octane of iodine to step (), its standard of described chloro-iso-octane named chloro-2-ethyl hexane, chloro-iso-octane is (1 ~ 1.2) with the mol ratio of phosphorous acid di-isooctyl sodium: 1, it is to slowly warm up to 150 ~ 160 DEG C, is incubated 2 ~ 4h；
(3), aftertreatment technology: after completion of the reaction, reactant liquor obtains target product iso-octyl phosphonic acids di-isooctyl through saponification, separatory, distillation.
The most according to claim 1, the method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl, is characterized in that: the base metal catalysts of described iodine is KI and sodium iodide, and catalyst amount is the 1 ~ 3% of the amount of phosphonous acid di-isooctyl material.
3. the method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl according to any one of claim 1 or 2, it is characterized in that: described aftertreatment technology is: after catalytic reaction, treat that temperature is down to less than 90 DEG C, adding quantitative sodium hydrate aqueous solution in reactant liquor, phosphonous acid di-isooctyl is (4 ~ 5) with the mol ratio of NaOH: be to slowly warm up to 70 ~ 90 DEG C in 1,30min, saponification 30 ~ 45min, separatory, vacuum decompression distills, collects corresponding cut and be iso-octyl phosphonic acids di-isooctyl.
The most according to claim 3, the method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl, is characterized in that: the vacuum of described vacuum decompression distillation is 720 ~ 740mmHg, and the cut collecting about 180 ~ 230 DEG C is iso-octyl phosphonic acids di-isooctyl.
The most according to claim 3, the method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl, is characterized in that: the mass fraction of described sodium hydrate aqueous solution is 3 ~ 5%.
6. the method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl according to any one of claim 1 or 2, it is characterized in that: described synthesizing phosphorous acid di-isooctyl sodium technique is: in reactor add mol ratio be 1:(1 ~ 1.1) phosphonous acid di-isooctyl and caustic alcohol, directly heat distillation removing ethanol, it is slowly heated to 95-105 DEG C in 1 ~ 1.5h, obtains phosphorous acid di-isooctyl sodium.
7. the method catalyzing and synthesizing iso-octyl phosphonic acids di-isooctyl according to any one of claim 1 or 2, is characterized in that: the range request that was slowly heated of described catalytic reaction technique is: be to slowly warm up to 150 ~ 160 DEG C in 30 ~ 60min.
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| CN115028660A (en) * | 2022-06-20 | 2022-09-09 | 三门峡中达化工有限公司 | Method for synthesizing 2-ethylhexyl phosphonic acid di (2-ethyl) hexyl ester by taking 2-ethylhexyl sodium alkoxide as alkali |
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