CN108610373A - A method of preparing hexyl-didecyl phosphorous oxide - Google Patents
A method of preparing hexyl-didecyl phosphorous oxide Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims abstract description 8
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000010792 warming Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- XOQRLXHLTSYZBF-UHFFFAOYSA-N 1-decylphosphonoyldecane Chemical compound CCCCCCCCCCP(=O)CCCCCCCCCC XOQRLXHLTSYZBF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- 238000001514 detection method Methods 0.000 claims abstract description 7
- 235000019441 ethanol Nutrition 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000012044 organic layer Substances 0.000 claims abstract description 5
- 238000001953 recrystallisation Methods 0.000 claims abstract description 5
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims abstract 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical group CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 239000010865 sewage Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- 229910052770 Uranium Inorganic materials 0.000 description 10
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 8
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000638 solvent extraction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- -1 metals ion Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003747 Grignard reaction Methods 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 206010051093 Cardiopulmonary failure Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- 206010044565 Tremor Diseases 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000956 solid--liquid extraction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5304—Acyclic saturated phosphine oxides or thioxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a kind of methods preparing hexyl didecyl phosphorous oxide, and didecyl phosphine oxide, 1 hexene, acetic acid solvent and di-tert-butyl peroxide are added into polytetrafluoro reaction kettle, and a small amount of industry mixing decene is added, stirring and dissolving, 130~140 DEG C are warming up to, is reacted 12~36 hours31The reaction was complete for P NMR detections, and the demulsification washing of 5~15wt% dilute hydrochloric acid is added in reaction solution, and chloroform extraction is used in combination, organic layer is washed with water to neutrality, and chloroform and the complete alkene of unreacted is evaporated off in Rotary Evaporators, with ethyl alcohol recrystallization, filtering, vacuum drying, obtains white solid；The preparation method reaction step of the present invention is simple, and environmentally protective, Atom economy is good, and product purity is high, is easily isolated, the foreground with industrialization.Products application of the present invention is in water quality detection and sewage treatment industry.
Description
Technical field
The invention belongs to technical field of phosphorous chemical industry, and in particular to a method of preparing trialkyl phosphorus.
Background technology
Extraction refers to compound because of the solubility in two kinds of mutual solubility very littles or fairly insoluble solvent
(distribution coefficient) is different, to partially or completely enter one of which solvent.When the number of extraction is enough, compound will be complete
Enter one of which solvent entirely.
Extractant is various in style, generally comprises inorganic and organic extractant.And most of used in industrial production are
Organic extractant has good dissolubility in organic solvent.It is allowed to be dissolved in organic solvent to be waited for metal to increase it
Extract the dissolubility of object, and enhance its extraction ability, while its volatility can also be weakened, viscosity, and it is water-soluble.Organic extractant
It is largely used to non-ferrous metal hydrometallurgy industry, is mainly used for extracting copper and various noble metals and rare earth.
There are many kinds of the methods of extraction, generally comprises solvent extraction, solid-liquid extraction (leaching), chemical precipitation method, tree
Fat method, aqueous two-phase method, oxidation-reduction method, floatation and electric stripping process.
What is be wherein most widely used is the precipitation method and solvent extraction.The precipitation method are mainly used for sewage disposal, method master
If adding specific chemical reagent into sewage, it is made to react with the substance to be handled being dissolved in waste water, generated
It is insoluble in the precipitation of salts of water, to which success is removed from sewage.But due to the use of a large amount of chemical reagent, which can cause greatly
The secondary pollution of amount is unfavorable for the green environment advocated energetically now close friend and sustainable development, and is of limited application.
Solvent-extracted extraction process is full liquid process, and two kinds of liquid phases of participation process are respectively water phase and organic phase.Water
The density of phase is typically larger than used organic phase density so that after static layering, organic phase is always located in above water phase.Solvent
The element that extraction can be used to handle tonne in the industry, can be used for laboratory treatment gram and the element of milligram grade separation and
Enrichment.Solvent extraction is because of spies such as its operation is very simple while cheap, rate of extraction fast, high selectivity, separation rate height
Point has become an indispensable basic fundamental, industrially in the Separation ＆ Purification of current every field
It has been obtained for being widely applied, and wherein most has obtained good effect.Solvent extraction is research in recent years
Red heat point.
Organic phosphates extractant is one of several main extractants of solvent extraction extracting metals ion now, so far for
Only it is widely used to numerous areas.Organic phosphates extractant is various in style, various structures, but generally speaking, in being generally divided into
Property phosphorous and acidic phosphorus type two major classes.
At 1945, people have found that tributyl phosphate (TBP) has effects that extract uranium for the first time.From then on, TBP is gradually
It is taken seriously, till now, is used to post-process nuclear fuel in the world, extract the elements such as thorium therein, uranium.
TBP can degrade under high temperature and radiation and generate dibutylphosphoric acid ester (DBP) and monobutyl phosphate (MDP), but DBP and MDP to zirconium,
Niobium member is known as higher mating capability, in addition, DBP and MDP can be combined into thorium, zirconium etc. both it is not soluble in water be also insoluble in it is organic molten
The substance of agent, a large amount of precipitation can cover whole system, extraction efficiency caused to drastically reduce.Therefore, the use of TBP extractants
Service life is very short.
Therefore, people begin one's study modified technique flow, and have carried out research extensively and profoundly to phosphorus-contained extractant.People
It was found that when using D2When EHPA makees extractant, two different amine solvents are screened, such as ethylene diamine, 1,2- propane diamine, 1,3- the third two
The extraction yield of amine etc., uranium can promote 18~36 times.On the other hand, if in neutral ligand, such as dihexyl-N, N- diethyl
Tributyl phosphate and trioctylphosphine oxide are added in base-carbamyl phosphate methyl esters, the extraction efficiency of uranium ion can be greatly improved.When
Tributyl phosphate (TBP), trioctylphosphine oxide (TOPO), D2EHPA is mixed when making extractant, and effect of extracting is very good.
The uranium mill in China is all extracting uranium ion using eluex process mostly, which uses organophosphor as extraction
Agent, the i.e. di-(2-ethylhexyl)phosphoric acid (D of 0.2mol/L2EHPA) with the trialkyl phosphorus of 0.1mol/L (TRPO) system,
The uranium product purity obtained by this flow is high not enough, wherein still containing various metals impurity.This crude product need to pass through TBP
Purified product can be obtained after extraction process is refined, it is pure to reach core.
Trioctylphosphine oxide is widely used in the extraction of uranium in industry, usually with the D of different proportion2EHPA is combined, extraction effect
Rate is all very high, but has realized that industrialized trialkyl phosphorus also only has trioctylphosphine oxide therefore to research and develop other at present
The industrialized production route of trialkyl phosphorus has great importance to finding new efficient extractant.
There are two types of the methods of the synthesis trialkyl phosphorus of mainstream in the world：Grignard reagent method and hydrogen phosphide synthetic method are led to
It crosses grignard reaction and prepares trioctylphosphine oxide, the biggest advantage is to need to only can be obtained product by single step reaction, and produce
Object purity is very high.It is well known that grignard reaction has disadvantages that：Operation difficulty is high, and the condition for preparing Grignard Reagent is very tight
Lattice, for Grignard Reagent to water and oxygen all extreme sensitivities, yield is generally very low.Grignard reaction condition is too harsh, is not suitable for out very much
Send out into industrial manufacture process.Hydrogen phosphide addition process, product purity is relatively low, there is many impurity and by-product.In addition, used original
Expect phosphatization.Hydrogen is also violent in toxicity, not only irritant but also be system.Toxic agent, if sucking can be to heart, respiratory system.Kidney, intestines
Stomach, nervous system.Damaged with liver, gently then cause to shed tears, cough, dizziness, headache, the symptoms such as nausea and vomiting, it is heavy then can
It can cause to tremble, spasm, cardiorespiratory failure and death.Concentration reaches 9.7mg/m3It will cause to be poisoned above；550~
830mg/m3Dead, 2798mg/m occurs for 0.5~1.0 hour for contact3It can be rapid lethal.And the hydrogen phosphide of trace in air can
Spontaneous combustion, the aerial concentration of hydrogen phosphide reach 1.8% (26g/m3) more than can explode.
Neutral organophosphorus extractant is widely used in the extraction process of uranium, they generally have very high selectivity to uranium
With certain chemical radiation stability, but carried out currently on the market industrialized production only three n-octyl phosphorous oxides, and
Production method is more toxic or low yield, it is still desirable to be improved, and be needed to develop a greater variety of trialkyl phosphorus
Production method.
Invention content
In view of this, the purpose of the present invention is to provide a kind of method preparing hexyl-didecyl phosphorous oxide, in the hope of reducing
The pollution of reaction and toxicity, and improve yield and product purity.
To achieve the above object, the present invention provides the following technical solutions：
A method of preparing hexyl-didecyl phosphorous oxide, be added into polytetrafluoro reaction kettle didecyl phosphine oxide, 1- oneself
A small amount of industry mixing decene is added in alkene, acetic acid solvent and di-tert-butyl peroxide, and stirring and dissolving is warming up to 130~140 DEG C,
Reaction 12~36 hours,31The reaction was complete for P-NMR detections, and the demulsification washing of 5~15wt% dilute hydrochloric acid is added in reaction solution, and trichlorine is used in combination
Methane extracts, and organic layer is washed with water to neutrality, and chloroform and the complete alkene of unreacted is evaporated off in Rotary Evaporators, with ethyl alcohol weight
Crystallization is filtered, and vacuum drying obtains white solid.
Preferably, the didecyl phosphine oxide and 1- hexenes molar ratio 1: 1.1~1.3.
Preferably, the addition of the di-tert-butyl peroxide is the 3 of didecyl phosphine oxide and 1- hexene gross masses
~6%.
Preferably, the addition of the described industry mixing decene be didecyl phosphine oxide with the 2 of 1- hexene gross masses~
5%.
Preferably, stirring and dissolving is warming up to 135 DEG C, reacts 24 hours.
Preferably, the demulsification washing of 10wt% dilute hydrochloric acid is added in reaction solution.
The preparation method reaction step of the present invention is simple, and environmentally protective, Atom economy is good, and product purity is high, is easy to point
From the foreground with industrialization.
Specific implementation mode
Technical solution in the embodiment of the present invention is described in detail below, it is clear that described embodiment is only
It is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
The every other embodiment that personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
2g didecyls phosphine oxide (0.006mol), 1.26g1- hexenes are added in 25ml polytetrafluoro reaction kettles
(0.015mol), 10ml acetic acid, 0.2g di-tert-butyl peroxides mix decene on a small quantity, and stirring and dissolving is warming up to 140 DEG C, instead
It answers 12 hours.31The reaction was complete for P-NMR detections.The demulsification washing of 5wt% dilute hydrochloric acid is added in reaction solution, and chloroform extraction is used in combination, has
Machine layer is washed with water to neutrality, and chloroform and the complete alkene of unreacted is evaporated off in Rotary Evaporators.With ethyl alcohol recrystallization, filter,
Vacuum drying, obtains white solid.Yield 88.6%.
Embodiment 2
2g didecyls phosphine oxide (0.006mol), 1.26g1- hexenes are added in 25ml polytetrafluoro reaction kettles
(0.015mol), 10ml acetic acid, 0.4g di-tert-butyl peroxides mix decene on a small quantity, and stirring and dissolving is warming up to 130 DEG C, instead
It answers 36 hours.31The reaction was complete for P-NMR detections.The demulsification washing of 15wt% dilute hydrochloric acid is added in reaction solution, and chloroform extraction is used in combination,
Organic layer is washed with water to neutrality, and chloroform and the complete alkene of unreacted is evaporated off in Rotary Evaporators.With ethyl alcohol recrystallization, mistake
Filter, vacuum drying, obtains white solid.Yield 89.5%.
Embodiment 3
2g didecyls phosphine oxide (0.006mol), 1.26g1- hexenes are added in 25ml polytetrafluoro reaction kettles
(0.015mol), 10ml acetic acid, 0.3g di-tert-butyl peroxides mix decene on a small quantity, and stirring and dissolving is warming up to 135 DEG C, instead
It answers 24 hours.31The reaction was complete for P-NMR detections.The demulsification washing of 10wt% dilute hydrochloric acid is added in reaction solution, and chloroform extraction is used in combination,
Organic layer is washed with water to neutrality, and chloroform and the complete alkene of unreacted is evaporated off in Rotary Evaporators.With ethyl alcohol recrystallization, mistake
Filter, vacuum drying, obtains white solid.Yield 90.0%.
For those skilled in the art, it is clear that invention is not limited to the details of the above exemplary embodiments, and not
In the case of the spirit or essential attributes of the present invention, the present invention can be realized in other specific forms.Therefore, no matter from
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended right
It is required that rather than above description limit, it is intended that all changes that will be fallen within the meaning and scope of the equivalent requirements of the claims
Change is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiment being appreciated that.
Claims (6)
1. a kind of method preparing hexyl-didecyl phosphorous oxide, which is characterized in that include the following steps：
Didecyl phosphine oxide, 1- hexenes, acetic acid solvent and di-tert-butyl peroxide are added into polytetrafluoro reaction kettle, is added few
Amount industry mixing decene, stirring and dissolving are warming up to 130~140 DEG C, react 12~36 hours,31The reaction was complete for P-NMR detections, instead
It answers liquid that the demulsification washing of 5~15wt% dilute hydrochloric acid is added, is used in combination chloroform extraction, organic layer to be washed with water to neutrality, rotation is steamed
Chloroform and the complete alkene of unreacted is evaporated off in hair instrument, with ethyl alcohol recrystallization, filters, and vacuum drying obtains white solid.
2. according to the method described in claim 1, it is characterized in that：The didecyl phosphine oxide and 1- hexenes molar ratio 1:
1.1~1.3.
3. according to the method described in claim 1, it is characterized in that：The addition of the di-tert-butyl peroxide is didecyl
Base phosphine oxide and the 3~6% of 1- hexene gross masses.
4. according to the method described in claim 1, it is characterized in that：The addition of the industry mixing decene is didecyl oxygen
Change the 2~5% of phosphine and 1- hexene gross masses.
5. according to the method described in claim 1, it is characterized in that：Stirring and dissolving is warming up to 135 DEG C, reacts 24 hours.
6. according to the method described in claim 1, it is characterized in that：The demulsification washing of 10wt% dilute hydrochloric acid is added in reaction solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611149504.5A CN108610373A (en) | 2016-12-13 | 2016-12-13 | A method of preparing hexyl-didecyl phosphorous oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611149504.5A CN108610373A (en) | 2016-12-13 | 2016-12-13 | A method of preparing hexyl-didecyl phosphorous oxide |
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Application publication date: 20181002 |