CN106188135B - A kind of preparation method of diisobutyl dithiophosphinic acid sodium - Google Patents

A kind of preparation method of diisobutyl dithiophosphinic acid sodium Download PDF

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CN106188135B
CN106188135B CN201610532228.4A CN201610532228A CN106188135B CN 106188135 B CN106188135 B CN 106188135B CN 201610532228 A CN201610532228 A CN 201610532228A CN 106188135 B CN106188135 B CN 106188135B
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reaction
preparation
sulphur
solvent
acid sodium
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CN106188135A (en
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文武
史华红
麦裕良
梁东
高敏
秦晓生
高茜斐
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Guangdong Research Instititute Of Petrochemical And Fine Chemical Engineering
Guangdong Synyoo New Material Co ltd
Institute of Chemical Engineering of Guangdong Academy of Sciences
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SYNYOO NEW MATERIALS CO Ltd
GUANGDONG RESEARCH INSTITUTE PETROCHEMICAL INDUSTRY
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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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/301—Acyclic saturated acids which can have further substituents on alkyl

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a kind of preparation method of diisobutyl dithiophosphinic acid sodium, it comprises the following steps：1）The preparation of grignard reagent selenium alkynide；2）Four isobutyl groups, two sulphur joins the preparation of phosphine；3）Under the action of phase transfer catalyst, four isobutyl groups, two sulphur connection phosphine and vulcanizing agent reaction, obtain diisobutyl dithiophosphinic acid sodium.The method of the present invention promotes the reaction between the reactant of several different accumulation shapes by phase transfer catalyst, two sulphur of tetraalkyl connection phosphine method is overcome because existing reaction yield is paid no attention to and thinks over a problem using solvent, reaction time is short, only need 2~4 it is small when, the high income of diisobutyl dithiophosphinic acid sodium, reaches more than 80%.

Description

A kind of preparation method of diisobutyl dithiophosphinic acid sodium
Technical field
The present invention relates to a kind of preparation method of diisobutyl dithiophosphinic acid sodium.
Background technology
At present, explored mineral resources have more than 200 to plant in the world, wherein most be located at the U.S., the former Soviet Union, China, The countries and regions such as South Africa, Australia, Canada, wherein obtain effective exploitation and utilize it is exhausted be sulphide ore mostly, mainly It is enriched with and is separated by floatation.Flotation is a kind of difference based on mineral surfaces physics and chemical property, passes through flotation Medicament is selectively enriched with the mineral with higher use value, and is allowed to be divided with the less gangue mineral of use value From sorting technology.
Only have seldom mineral that there is natural hydrophobicity, such as graphite, brightness key ore deposit and sulphurite in nature, can not Using or less using flotation reagent with regard to that can flotate, most of mineral all have certain hydrophily, it is necessary to floating by adding Select reagent and change its flotation performance to change the physico-chemical property of mineral surfaces.The species of floating agent is very much, and wherein flotation is caught Receive agent and occupy very important effect in floating operation, it can change the hydrophily of mineral surfaces and change its flotation spy Property, decides the quality of flotation effect.
The characteristics of sulfide flotation collector is that intramolecule contains sulphur atom, has collecting effect for sulfide mineral, and To gangue mineral as quartz and calcite do not have collecting effect, so during with this kind of collecting agent Flotation of Sulfide Ores thing, it is easy to just Gangue can be removed.The structure of floating agent can be expressed as RX, and wherein R represents alkyl, and X then represents close mineral base.Sulphide ore is caught The close mineral base for receiving agent is generally-SH, thiocarbonyl group, such as：Xanthate, black powder, sulphur nitrogen class and thiourethane etc..
Dialkyl dithio phosphinates is a kind of important sulfide flotation collector, has excellent flotation effect, Available for Floatation of Copper, lead sulphide ore and it is associated with the copper of rare precious metal, lead sulphide ore.However, due to dialkyl disulfides generation The manufacturing process of phosphonate is complicated, and manufacturing cost is high, it is produced and applying within a very long time all in flotation Rest on theoretical research stage, until the eighties of last century sixties Cyanamid companies develop it is a kind of to nonferrous metal sulfide mineral Flotation reagent with good flotation effect --- diisobutyl dithiophosphinic acid sodium（DTPINa）, just really realize industry Metaplasia is produced.
At present, the preparation method of diisobutyl dithiophosphinic acid sodium can be mainly summarized as：Dialkyl phosphine method, tetraalkyl Two sulphur connection phosphine method, dialkyl group chlorine phosphine sulfide method and phosphorus pentasulfide method.Wherein, two sulphur of tetraalkyl joins phosphine method with trichlorine phosphine sulfide and grignard Reagent etc. is raw material, have the advantages that raw material be easy to get, general reaction step it is less, be current main stream approach.Two sulphur of tetraalkyl Connection phosphine method includes two-step reaction：1）Four isobutyl groups, two sulphur connection phosphine is prepared with Grignard Reagent and phosphorus thiochloride reaction；2）Four isobutyl groups Two sulphur join phosphine and react to obtain diisobutyl dithiophosphinic acid sodium with vulcanization reaction thing.Although four isobutyls in second step vulcanization reaction Two sulphur of base connection phosphine is liquid, but due to other reactants（The vulcanizing agents such as nine water vulcanized sodium, sulphur）It is solid and inventory is larger, Addition Isosorbide-5-Nitrae-dioxane or water, which are needed, as solvent carrys out dispersed material and promote to react.Although solvent can be to a certain extent Dispersed material, promote reaction and shorten the reaction time, but can also reduce reaction solution concentration at the same time, causes reaction yield undesirable, The reaction yield of general diisobutyl dithiophosphinic acid sodium only has 40%~65%.
The content of the invention
It is an object of the invention to provide a kind of preparation method of diisobutyl dithiophosphinic acid sodium.
The technical solution used in the present invention is：
A kind of preparation method of diisobutyl dithiophosphinic acid sodium, comprises the following steps：
1) magnesium, iodine and solvent are added into reaction kettle, adds isobutane bromide, be stirred at reflux, fully reaction, obtain isobutyl Base magnesium bromide；
2) selenium alkynide is added into reaction kettle, nitrogen charging gas shielded, adds phosphorus thiochloride, and room temperature is fully reacted, production Thing adds dilute sulfuric acid to hydrolyze, and stands, split-phase, retains organic phase, removes the solvent in organic phase, obtains four isobutyl groups, two sulphur connection phosphine；
3) four isobutyl groups, two sulphur is joined into phosphine, vulcanizing agent and phase transfer catalyst and adds reaction kettle, stirred, heating, constant temperature fills Divide reaction, reaction product is cooled to room temperature, is extracted after adding water with organic solvent, obtains diisobutyl dithiophosphinic acid sodium.
Step 1）The isobutane bromide, the molar ratio of magnesium are 1：（1~1.05）.
Step 1）The isobutane bromide, the mass volume ratio of solvent are 1g：（3~6）mL.
Step 1）The solvent is anhydrous ether, one kind in anhydrous tetrahydro furan.
Step 2）The selenium alkynide, the molar ratio of phosphorus thiochloride are（3.8~4.2）：1.
Step 3）Four isobutyl groups, the two sulphur connection phosphine, vulcanizing agent, the molar ratio of phase transfer catalyst are 1：1：（0.01~ 0.05）.
Step 3）The vulcanizing agent is at least one of sulphur, nine water vulcanized sodium.
Step 3）The phase transfer catalyst is quaternary ammonium salt-type phase transfer catalyst.
Step 3）The temperature of the reaction is 120~140 DEG C, and the reaction time is 2~4h.
Step 3）The organic solvent is esters, one kind in halogenated hydrocarbon.
The beneficial effects of the invention are as follows：The method of the present invention promotes several different accumulation shapes by phase transfer catalyst （Solid, liquid）Reactant between reaction, overcome two sulphur of tetraalkyl connection phosphine method because using solvent and existing reaction Yield, which is paid no attention to, to think over a problem, and the reaction time is short, it is only necessary to 2~4 it is small when, the high income of diisobutyl dithiophosphinic acid sodium, reaches 80% More than.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of diisobutyl dithiophosphinic acid sodium prepared by embodiment 1.
Embodiment
A kind of preparation method of diisobutyl dithiophosphinic acid sodium, comprises the following steps：
1) magnesium, iodine and solvent are added into reaction kettle, adds isobutane bromide, be stirred at reflux, fully reaction, obtain isobutyl Base magnesium bromide；
2) selenium alkynide is added into reaction kettle, nitrogen charging gas shielded, adds phosphorus thiochloride, and room temperature is fully reacted, production Thing adds dilute sulfuric acid to hydrolyze, and stands, split-phase, retains organic phase, removes the solvent in organic phase, obtains four isobutyl groups, two sulphur connection phosphine；
3) four isobutyl groups, two sulphur is joined into phosphine, vulcanizing agent and phase transfer catalyst and adds reaction kettle, stirred, heating, constant temperature fills Divide reaction, reaction product is cooled to room temperature, is extracted after adding water with organic solvent, obtains diisobutyl dithiophosphinic acid sodium.
Preferably, step 1）The isobutane bromide, the molar ratio of magnesium are 1：（1~1.05）.
Preferably, step 1）The isobutane bromide, the mass volume ratio of solvent are 1g：（3~6）mL.
Preferably, step 1）The solvent is anhydrous ether, one kind in anhydrous tetrahydro furan.
Preferably, step 2）The selenium alkynide, the molar ratio of phosphorus thiochloride are（3.8~4.2）：1.
Preferably, step 3）Four isobutyl groups, the two sulphur connection phosphine, vulcanizing agent, the molar ratio of phase transfer catalyst are 1：1： （0.01~0.05）.
Preferably, step 3）The vulcanizing agent is at least one of sulphur, nine water vulcanized sodium.
Preferably, step 3）The phase transfer catalyst is quaternary ammonium salt-type phase transfer catalyst.
It is further preferred that step 3）The phase transfer catalyst is tetrabutylammonium chloride, tetrabutylammonium bromide, the tetrabutyl Ammonium iodide, 4-butyl ammonium hydrogen sulfate, benzyltriethylammoinium chloride, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride, At least one of tetradecyl trimethyl ammonium chloride.
Still further preferably, step 3）The phase transfer catalyst is tetrabutylammonium bromide, tetrabutylammonium iodide, benzyl At least one of triethyl ammonium chloride.
Preferably, step 3）The temperature of the reaction is 120~140 DEG C, and the reaction time is 2~4h.
Preferably, step 3）The organic solvent is esters, one kind in halogenated hydrocarbon.
It is further preferred that step 3）The organic solvent is one in dichloromethane, 1,2- dichloroethanes, ethyl acetate Kind.
The complete synthesis route of the diisobutyl dithiophosphinic acid sodium of the present invention is as follows：
The present invention is made further explanation and description with reference to specific embodiment.
Embodiment 1：
1）In the 2L there-necked flasks equipped with reflux condensing tube and constant pressure funnel, it is anhydrous to add 24.3g magnesium rods, 300mL THF and 0.1g iodine, then the mixed solution that 137g isobutane bromides and the anhydrous THF of 110mL are formed add constant pressure funnel In, first by 40mL, the mixed solution adds there-necked flask, for initiation reaction, then remaining solution is slowly added dropwise, after dripping, adds To seething with excitement, 1~2h of reflux to bubble-free is produced heat；
2）Under nitrogen protection, by step 1）Reaction solution be placed in ice-water bath and cool down, be added dropwise with constant pressure funnel The mixed solution that 44.6g phosphorus thiochlorides and the anhydrous THF of 150mL are formed, control temperature is below 10 DEG C, after dripping, continues 30min is stirred, removes ice-water bath, is heated up naturally, reaction 16h is stirred at room temperature, then is placed reaction liquid into ice-water bath, is added 10% dilute sulfuric acids of the 200mL containing ice is hydrolyzed, and stands, and separates organic phase, and water is mutually extracted with 200mL ethyl acetate, is associated with Machine phase, and be washed with water 3 times, revolving removes solvent, obtains tetra- isobutyl groups of 41.9g, two sulphur connection phosphine（Weak yellow liquid）, yield is 91.0%；
3）By step 2）Four isobutyl groups, two sulphur connection phosphine add 500mL there-necked flasks, then by 3.8g sulphur, nine water sulphur of 28.4g Change sodium and 0.4g phase transfer catalyst tetrabutylammonium bromide is added in there-necked flask after mixing, 130 DEG C of stirring reaction 3h, reaction Complete postcooling adds 150mL water, filters, filtrate is extracted with 200mL ethyl acetate, is extracted 3~4 times, until water phase to room temperature Basic odorless, merges organic phase, revolving removes solvent, dry, obtains 50.1g diisobutyl dithiophosphinic acid sodium（It is reddish brown Color solid）, yield 83.1%.
Diisobutyl dithiophosphinic acid sodium manufactured in the present embodiment1H NMR spectras are as shown in Figure 1, solve spectrum analysis such as Under：1H NMR（300MHz, D2O）：1.04ppm（D, 12H ,-CH3）, 1.94ppm（Dd, 4H ,-CH2P）, 2.15ppm（M, 2H ,- CH）.
Embodiment 2：
1）In the 2L there-necked flasks equipped with reflux condensing tube and constant pressure funnel, it is anhydrous to add 25.5g magnesium rods, 600mL THF and 0.1g iodine, the mixed solution that 137g isobutane bromides and the anhydrous THF of 220mL are formed are added in constant pressure funnel, First by 50mL, the mixed solution adds there-necked flask, for initiation reaction, then remaining solution is slowly added dropwise, after dripping, heating To boiling, 1~2h of reflux to bubble-free is produced；
2）Under nitrogen protection, by step 1）Reaction solution be placed in ice-water bath and cool down, 40g is added dropwise with constant pressure funnel The mixed solution that phosphorus thiochloride and the anhydrous THF of 150mL are formed, control temperature after dripping, continue to stir below 10 DEG C 30min, removes ice-water bath, heats up naturally, and reaction 16h is stirred at room temperature, then places reaction liquid into ice-water bath, adds 200mL and contains 10% dilute sulfuric acid of ice is hydrolyzed, and stands, and separates organic phase, and water is mutually extracted with 200mL dichloromethane, merges organic phase, and It is washed with water 3 times, revolving removes solvent, obtains tetra- isobutyl groups of 41.6g, two sulphur connection phosphine（Weak yellow liquid）, yield 90.4%；
3）By step 2）Four isobutyl groups, two sulphur connection phosphine add 500mL there-necked flasks, then by 3.8g sulphur, nine water sulphur of 28.4g Change sodium and 2.2g phase transfer catalyst tetrabutylammonium iodides are added in there-necked flask after mixing, 140 DEG C of stirring reaction 2h, reaction Complete postcooling adds 150mL water, filters, filtrate is extracted with 200mL dichloromethane, is extracted 3~4 times, until water phase to room temperature Basic odorless, merges organic phase, revolving removes solvent, dry, obtains 48.7g diisobutyl dithiophosphinic acid sodium（It is reddish brown Color solid）, yield 80.7%.
Embodiment 3：
1）In the 2L there-necked flasks equipped with reflux condensing tube and constant pressure funnel, 25g magnesium rods, the anhydrous THF of 500mL are added With 0.1g iodine, the mixed solution that 137g isobutane bromides and the anhydrous THF of 200mL are formed is added in constant pressure funnel, first By 50mL, the mixed solution adds there-necked flask, for initiation reaction, then remaining solution is slowly added dropwise, after dripping, is heated to Boiling, 1~2h of reflux to bubble-free are produced；
2）Under nitrogen protection, by step 1）Reaction solution be placed in ice-water bath and cool down, 42g is added dropwise with constant pressure funnel The mixed solution that phosphorus thiochloride and the anhydrous THF of 150mL are formed, is added dropwise control temperature below 10 DEG C, after dripping, continues to stir 30min is mixed, removes ice-water bath, is heated up naturally, reaction 16h is stirred at room temperature, then is placed reaction liquid into ice-water bath, adds 200mL 10% dilute sulfuric acid containing ice is hydrolyzed, and stands, and separates organic phase, and water is mutually extracted with 200mL ethyl acetate, merges organic phase, And be washed with water 3 times, revolving removes solvent, obtains tetra- isobutyl groups of 41.5g, two sulphur connection phosphine（Weak yellow liquid）, yield 90.2%；
3）By step 2）Four isobutyl groups, two sulphur connection phosphine add 500mL there-necked flasks, then by 3.8g sulphur, nine water sulphur of 28.4g Change sodium and 0.8g phase transfer catalyst benzyltriethylammoinium chlorides are added in there-necked flask after mixing, 120 DEG C of stirring reaction 4h, Postcooling have been reacted to room temperature, has added 150mL water, has been filtered, filtrate is extracted with 200mL ethyl acetate, is extracted 3~4 times, until The mutually basic odorless of water, merges organic phase, revolving removes solvent, dry, obtains 49.6g diisobutyl dithiophosphinic acid sodium （Red brown solid）, yield 82.2%.
Comparative example 1：
Isosorbide-5-Nitrae-dioxane solvent method
1）In the 2L there-necked flasks equipped with reflux condensing tube and constant pressure funnel, 25g magnesium rods, the anhydrous THF of 500mL are added With 0.1g iodine, the mixed solution that 137g isobutane bromides and the anhydrous THF of 200mL are formed is added in constant pressure funnel, first By 50mL, the solution adds there-necked flask, for initiation reaction, then remaining solution is slowly added dropwise, after dripping, is heated to seething with excitement, Flow back 1~2h to bubble-free produce；
2）Under nitrogen protection, by step 1）Reaction solution be placed in ice-water bath and cool down, 42g is added dropwise with constant pressure funnel The mixed solution that phosphorus thiochloride and the anhydrous THF of 150mL are formed, control temperature after dripping, continue to stir below 10 DEG C 30min, removes ice-water bath, heats up naturally, and reaction 16h is stirred at room temperature, then places reaction liquid into ice-water bath, adds 200mL and contains 10% dilute sulfuric acid of ice is hydrolyzed, and stands, and separates organic phase, and water is mutually extracted with 200mL ethyl acetate, merges organic phase, and It is washed with water 3 times, revolving removes solvent, obtains tetra- isobutyl groups of 41.7g, two sulphur connection phosphine（Weak yellow liquid）, yield 90.7%；
3）By step 2）Four isobutyl groups, two sulphur connection phosphine add 1L there-necked flasks in, add nine water of 3.8g sulphur and 28.4g Vulcanized sodium, and 200mL Isosorbide-5-Nitraes-dioxane is added as reaction dissolvent, 140 DEG C of back flow reaction 8h, are filtered while hot after having reacted Fall remaining insoluble matter, filtrate is cooled to room temperature, and separates out diisobutyl dithiophosphinic acid sodium（Red brown solid）, filter, it is dry, Obtain 36.7g products, yield 60.8%.
Comparative example 2：
Water-soluble fluorine
1）In the 2L there-necked flasks equipped with reflux condensing tube and constant pressure funnel, 25g magnesium rods, the anhydrous THF of 500mL are added With 0.1g iodine, the mixed solution that 137g isobutane bromides and the anhydrous THF of 200mL are formed is added in constant pressure funnel, first By 50mL, the solution adds there-necked flask, for initiation reaction, then remaining solution is slowly added dropwise, after dripping, is heated to seething with excitement, Flow back 1~2h to bubble-free produce；
2）Under nitrogen protection, by step 1）Reaction solution be placed in ice-water bath and cool down, 42g is added dropwise with constant pressure funnel The mixed solution that phosphorus thiochloride and the anhydrous THF of 150mL are formed, control temperature after dripping, continue to stir below 10 DEG C 30min, removes ice-water bath, heats up naturally, and reaction 16h is stirred at room temperature, then places reaction liquid into ice-water bath, adds 200mL and contains 10% dilute sulfuric acid of ice is hydrolyzed, and stands, and separates organic phase, and water is mutually extracted with 200mL ethyl acetate, merges organic phase, and It is washed with water 3 times, revolving removes solvent, obtains tetra- isobutyl groups of 41.2g, two sulphur connection phosphine（Weak yellow liquid）, yield 89.5%；
3）By step 2）Four isobutyl groups, two sulphur connection phosphine add 1L there-necked flasks in, add nine water of 3.8g sulphur and 28.4g Vulcanized sodium, and 200mL water is added as reaction dissolvent, 100 DEG C of back flow reaction 12h, filter out remaining insoluble while hot after having reacted Thing, filtering, filtrate are extracted with 200mL ethyl acetate, are extracted 3~4 times, until the mutually basic odorless of water, merge organic phase, revolving Solvent is removed, it is dry, obtain 31.8g diisobutyl dithiophosphinic acid sodium（Red brown solid）, yield 52.7%.
Comparative example 3：
Solventless method（Do not add phase transfer catalyst）
1）In the 2L there-necked flasks equipped with reflux condensing tube and constant pressure funnel, 25g magnesium rods, the anhydrous THF of 500mL are added With 0.1g iodine, the mixed solution that 137g isobutane bromides and the anhydrous THF of 200mL are formed is added in constant pressure funnel, first By 50mL, the solution adds there-necked flask, for initiation reaction, then remaining solution is slowly added dropwise, after dripping, is heated to seething with excitement, Flow back 1~2h to bubble-free produce；
2）Under nitrogen protection, by step 1）Reaction solution be placed in ice-water bath and cool down, 42g is added dropwise with constant pressure funnel The mixed solution that phosphorus thiochloride and the anhydrous THF of 150mL are formed, control temperature after dripping, continue to stir below 10 DEG C 30min, removes ice-water bath, heats up naturally, and reaction 16h is stirred at room temperature, then places reaction liquid into ice-water bath, adds 200mL and contains 10% dilute sulfuric acid of ice is hydrolyzed, and stands, and separates organic phase, and water is mutually extracted with 200mL ethyl acetate, merges organic phase, and It is washed with water 3 times, revolving removes solvent, obtains tetra- isobutyl groups of 41.5g, two sulphur connection phosphine（Weak yellow liquid）, yield 90.2%；
3）By step 2）Four isobutyl groups, two sulphur connection phosphine add 500mL there-necked flasks in, add 3.8g sulphur and 28.4g nine Water vulcanized sodium, 120 DEG C of back flow reaction 14h, have reacted postcooling and have added 150mL water, and filtering, filtrate is with 200mL ethyl acetate Extraction, extracts 3~4 times, until the mutually basic odorless of water, merges organic phase, revolving removes solvent, dry, and it is different to obtain 32.5g bis- Butyl dithiophosphinic acid sodium（Red brown solid）, yield 53.9%.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (7)

  1. A kind of 1. preparation method of diisobutyl dithiophosphinic acid sodium, it is characterised in that：Comprise the following steps：
    1) magnesium, iodine and solvent are added into reaction kettle, adds isobutane bromide, be stirred at reflux, fully reaction, obtain isobutyl bromide Change magnesium；
    2) selenium alkynide is added into reaction kettle, nitrogen charging gas shielded, adds phosphorus thiochloride, and room temperature is fully reacted, and product adds Dilute sulfuric acid hydrolyzes, and stands, split-phase, retains organic phase, removes the solvent in organic phase, obtains four isobutyl groups, two sulphur connection phosphine；
    3) four isobutyl groups, two sulphur is joined into phosphine, vulcanizing agent and phase transfer catalyst and adds reaction kettle, stirred, heated, constant temperature is fully anti- Should, reaction product is cooled to room temperature, is extracted after adding water with organic solvent, obtains diisobutyl dithiophosphinic acid sodium；
    Step 2) the selenium alkynide, the molar ratio of phosphorus thiochloride are (3.8~4.2)：1；
    Step 3) four isobutyl groups, the two sulphur connection phosphine, vulcanizing agent, the molar ratio of phase transfer catalyst are 1：1：(0.01~0.05)；
    The temperature of the step 3) reaction is 120~140 DEG C, and the reaction time is 2~4h.
  2. 2. preparation method according to claim 1, it is characterised in that：Step 1) the isobutane bromide, the molar ratio of magnesium For 1：(1~1.05).
  3. 3. preparation method according to claim 1, it is characterised in that：Step 1) the isobutane bromide, the quality of solvent Volume ratio is 1g：(3~6) mL.
  4. 4. the preparation method according to claim 1 or 3, it is characterised in that：Step 1) the solvent is anhydrous ether, anhydrous One kind in tetrahydrofuran.
  5. 5. preparation method according to claim 1, it is characterised in that：Step 3) the vulcanizing agent is sulphur, nine water vulcanize At least one of sodium.
  6. 6. preparation method according to claim 1, it is characterised in that：Step 3) the phase transfer catalyst is quaternary ammonium salt Phase transfer catalyst.
  7. 7. preparation method according to claim 1, it is characterised in that：Step 3) the organic solvent is esters, halogenated hydrocarbons One kind in class.
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二烷基二硫代次膦酸的合成;于奉先;《合成化学》;20081231;第16卷(第5期);第558-560页 *

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