CN102887919A - Production method of triphenylphosphine - Google Patents
Production method of triphenylphosphine Download PDFInfo
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- CN102887919A CN102887919A CN2011102073681A CN201110207368A CN102887919A CN 102887919 A CN102887919 A CN 102887919A CN 2011102073681 A CN2011102073681 A CN 2011102073681A CN 201110207368 A CN201110207368 A CN 201110207368A CN 102887919 A CN102887919 A CN 102887919A
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- Prior art keywords
- toluene
- triphenylphosphine
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- temperature
- Prior art date
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 108
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011777 magnesium Substances 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 230000000977 initiatory effect Effects 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims description 17
- 150000001555 benzenes Chemical class 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 12
- 229940091250 magnesium supplement Drugs 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000002826 coolant Substances 0.000 claims description 5
- 238000006392 deoxygenation reaction Methods 0.000 claims description 5
- 238000011033 desalting Methods 0.000 claims description 5
- 230000008030 elimination Effects 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000010583 slow cooling Methods 0.000 claims description 5
- PQXSRBUXVJIPDU-UHFFFAOYSA-N toluene;trichlorophosphane Chemical compound ClP(Cl)Cl.CC1=CC=CC=C1 PQXSRBUXVJIPDU-UHFFFAOYSA-N 0.000 claims description 5
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 15
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 238000011049 filling Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- -1 phenyl-magnesium-chloride grignard reagent Chemical class 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 1
- DGWFDTKFTGTOAF-UHFFFAOYSA-N P.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl DGWFDTKFTGTOAF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a production method of triphenylphosphine, which belongs to the chemical field and is characterized by comprising the following steps of: evenly mixing tetrahydrofuran and toluene uniform, putting magnesium chips, adding initiating liquid, filling nitrogen and discharging oxygen; heating up to enable the temperature of the kettle maintain to be within a range of 80+/-5 DEG C, dropwise adding chlorobenzen at a constant speed with stirring, heating and cooling, dropwise adding chlorobenzene continously, pumping into another reaction kettle; cooling the kettle, dropwise adding phosphorus trichloride, toluene and mixture of phosphorus trichloride and toluene; cooling and dropwise adding hydrochloric acid, standing and washing with water; heating and distilling tetrahydrofuran and toluene, ending vacuum distillation; cooling materials and separating triphenylphosphine out; adding toluene and triphenylphosphine, distilling toluene, filter-pressing the concentrated liquid into another vessel, adding methyl alcohol into the kettle, separating triphenylphosphine by crystallization, centrifugally separating and drying. The product obtained by the method has the advantages of high yield, high purity and low pollution, and overcomes the problem of low yield, high production cost and large pollution in the traditional magnesium method. At the same time, the production process of the method is safe.
Description
Technical field
The present invention relates to a kind of production method of triphenylphosphine, belong to chemical field.
Background technology
The objective of the invention is to invent the production method of the triphenylphosphine of a kind of reacting balance, safety and environmental protection.Producing at present main method that triphenyl sees has two kinds of magnesium method and sodium methods, but is the requirement height with sodium method manufacture sodium sand, and the security incidents such as the reaction of sodium and chlorinated benzene is violent, sets off an explosion easily, fire; And the magnesium rule is because reaction conditions is gentle, safer, still in the phosphine tri chloride titration process, because reactant viscosity is high, it is slow to conduct heat, and causes easily side reaction, cause that product purity is not high, yield is low, therefore need to solve a kind of new method that provide, solve the problem that the magnesium method exists.
Summary of the invention
According to the deficiencies in the prior art, technical problem to be solved by this invention is: a kind of production method of triphenylphosphine is provided, and product yield is high, purity is high, it is low to pollute.
The technical solution adopted for the present invention to solve the technical problems is: a kind of production method of triphenylphosphine is provided, it is characterized in that may further comprise the steps:
(1) tetrahydrofuran (THF) 26-35 part, toluene 80-120 part mix in reactor, drop into magnesium chips 6-8.5 part from manhole, and the sealing manhole adds 10 parts of phenyl-magnesium-chloride initiation solutions, fills the nitrogen deoxygenation, repeats to replace 2-3 time; Heating makes temperature in the kettle remain on 80 ± 5 ℃, at the uniform velocity drips chlorinated benzene under stirring and amounts to 220-260 part, when dripping approximately to the 1/4-1/2 chlorinated benzene, be warming up to 100-105 ℃ and kept about 30 minutes, then be cooled to 80 ± 5 ℃, when continuing to drip the chlorinated benzene of remaining 1/2-3/4, keep 80 ± 5 ℃ of material temperatures during the dropping, dropwise, slowly be warming up to 100-105 ℃, till gentle reflux occurring, kept temperature 4 hours, it is cooled to 50-80 ℃, still in another reactor of suction;
(2) open sufficient water coolant, when being cooled to 50 ℃ in the still, drip phosphorus trichloride 10-12 part, 6 parts of mixtures of toluene, keep 50 ℃ ± 5 ℃ of material temperatures, the phosphorus trichloride toluene mixture liquid dropwises, and heating material temperature to 85 ℃-95 ℃ of degree are incubated 4 hours;
(3) be cooled to room temperature-50 ℃, begin to drip hydrochloric acid 6-10 part of massfraction 4-8%, maintain the temperature at room temperature-50 ℃, dropwise rear restir 30 minutes, left standstill 60 minutes, tell the bottom water layer, again water 15-30 part washing operates the same twice totally;
(4) stir lower heating and distill out tetrahydrofuran (THF) and toluene, until solvent distill, material is heated to 140 ℃ in the still, opens the vacuum pump vacuum distillation, and when vacuum reaches 0.9mpa, temperature of charge reaches 140-180 ℃ when refluxing, the underpressure distillation end;
(5) temperature of charge is cooled to room temperature-50 ℃, adds 75 parts of massfraction 30% hydrochloric acid, stirs 30 minutes, left standstill 15-20 minute, triphenyl phosphorus is all dissolved, filter elimination triphenylphosphine oxide and other impurity, add 80 parts of softening waters in the filtrate, then centrifugal, isolate triphenylphosphine;
(6) add toluene 70-80 part in the still, drop into 25 parts of isolated triphenylphosphines, be warming up to 50 ℃, stirring and dissolving adds 0.5 part of hydrochloric acid, stirs 15 minutes, left standstill 15-30 minute, and divided the acid of desalting, add 0.5 part in water, stirred 15 minutes, and left standstill branch vibration layer 15 minutes, 0.5 part in hydro-oxidation sodium, 2 parts of water washings are added in neutralization again, distill out toluene, the concentrated solution press filtration is entered in another still, add in advance 70-80 part methyl alcohol in the still, then stirring heating, till reaching 0.2Mpa to reacting kettle inner pressure, be incubated 30 minutes, stir lower Slow cooling to 0-30 ℃, the triphenyl crystallization of seeing, centrifugation, oven dry can obtain the triphenylphosphine product.
Add again 2 parts of water washings 1-5 time described in the step (6).
The distillation of the toluene described in the step (6) is air distillation or underpressure distillation.
The invention has the beneficial effects as follows: product yield is high, purity is high, pollute the processing method that low magnesium method is produced triphenylphosphine, overcome traditional magnesium method and produce that yield is low, cost is high, heavy-polluted problem, while present method production process safety, can not produce the Peril Incidents such as blast, overcome traditional magnesium method and produce that yield is low, cost is high, heavy-polluted problem, by in reactor, adding in advance a certain amount of solvent, the phenyl-magnesium-chloride grignard reagent adds in the reactor in batches, quantitatively drip at low temperatures the mode of phosphorus trichloride, solve the low problem of yield; By the improvement to aftertreatment technologys such as product triphenylphosphine purifications, avoided a large amount of adding mineral acids to the pollution of environment, whole technique is more reasonable, is fit to large-scale industrial production.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) 80 parts of 26 parts of tetrahydrofuran (THF)s, toluene mix in reactor, drop into 6 parts of magnesium chips from manhole, and the sealing manhole adds 10 parts of phenyl-magnesium-chloride initiation solutions, fills the nitrogen deoxygenation, repeats to replace 2 times; Heating makes temperature in the kettle remain on 80 ± 5 ℃, stirs lower 220 parts altogether of the chlorinated benzene that at the uniform velocity drip, when dropping to three/monochloro-benzene, be warming up to 100 ℃ and kept about 30 minutes, then be cooled to 80 ± 5 ℃, continue to drip remaining chlorinated benzene of 2/3rds, keep 80 ± 5 ℃ of material temperatures during the dropping, dropwise, slowly be warming up to 100 ℃, till gentle reflux occurring, kept temperature 4 hours, it is cooled to 50 ℃, still in another reactor of suction;
(2) open sufficient water coolant, when being cooled to 50 ℃ in the still, drip 10 parts of phosphorus trichlorides, 6 parts of mixtures of toluene, keep 50 ℃ ± 5 ℃ of material temperatures, the phosphorus trichloride toluene mixture liquid dropwises, and heating material temperature to 85 ℃ ℃ degree is incubated 4 hours;
(3) be cooled to 45 ℃, begin to drip 6 parts of the hydrochloric acid of massfraction 4%, maintain the temperature at 45 ℃, dropwise rear restir 30 minutes, left standstill 60 minutes, tell the bottom water layer, again 15 parts of washings of water operate the same twice totally.
(4) stir lower heating and distill out tetrahydrofuran (THF) and toluene, until solvent distill, material is heated to 140 ℃ in the still, opens the vacuum pump vacuum distillation, and when vacuum reaches 0.9mpa, temperature of charge reaches 140 ℃ when refluxing, the underpressure distillation end;
(5) temperature of charge is cooled to 45 ℃, adds 75 parts of massfraction 30% hydrochloric acid, stirs 30 minutes, left standstill 15 minutes, triphenyl phosphorus is all dissolved, filter elimination triphenylphosphine oxide and other impurity, add 80 parts of softening waters in the filtrate, then centrifugal, isolate triphenylphosphine;
(6) add 70 parts of toluene in the still, drop into 25 parts of isolated triphenylphosphines, be warming up to 50 ℃, stirring and dissolving adds 0.5 part of hydrochloric acid, stirs 15 minutes, left standstill 15 minutes, and divided the acid of desalting, add 0.5 part in water, stirred 15 minutes, and left standstill branch vibration layer 15 minutes, 0.5 part in hydro-oxidation sodium, 2 parts of water washings are added in neutralization again, distill out toluene, the concentrated solution press filtration is entered in another still, add in advance 70 parts of methyl alcohol, then stirring heating in the still, till reaching 0.2Mpa to reacting kettle inner pressure, be incubated 30 minutes, stir lower Slow cooling to 0 ℃, the triphenyl crystallization of seeing, centrifugation, oven dry can obtain the triphenylphosphine product.
Add again 2 parts of water washings 1 time described in the step (6).
The distillation of the toluene described in the step (6) is air distillation.
Product data
| Title: | Content % | Outward appearance | Fusing point | Percentage transmittance | Iron | Magnesium | Sodium | Tin | Muriate | Sulphur | Weight loss on drying | Ignition residue |
| Index: | 99.5 | The white particle crystallization | 79.5℃ | 97 | 0.0095 | 0.0005 | 0.0005 | 0.00095 | 0.0015 | 0.0005 | 0.5 | 0.01 |
Embodiment 2
(1) 100 parts of 30 parts of tetrahydrofuran (THF)s, toluene mix in reactor, drop into 7 parts of magnesium chips from manhole, and the sealing manhole adds 10 parts of phenyl-magnesium-chloride initiation solutions, fills the nitrogen deoxygenation, repeats to replace 3 times; Heating makes temperature in the kettle remain on 80 ± 5 ℃, stirs lower 240 parts altogether of the chlorinated benzene that at the uniform velocity drip, when dripping about 1/4 chlorinated benzene, be warming up to 105 ℃ and kept about 30 minutes, then be cooled to 80 ± 5 ℃, continue to drip remaining chlorinated benzene of 3/4, keep 80 ± 5 ℃ of material temperatures during the dropping, dropwise, slowly be warming up to 105 ℃, till gentle reflux occurring, kept temperature 4 hours, it is cooled to 70 ℃, still in another reactor of suction;
(2) open sufficient water coolant, when being cooled to 50 ℃ in the still, drip 11 parts of phosphorus trichlorides, 6 parts of mixtures of toluene, keep 50 ℃ ± 5 ℃ of material temperatures, the phosphorus trichloride toluene mixture liquid dropwises, and heating material temperature to 90 ℃ degree is incubated 4 hours;
(3) be cooled to room temperature, begin to drip 8 parts of 6% hydrochloric acid, maintain the temperature at room temperature, dropwise rear restir 30 minutes, left standstill 60 minutes, tell the bottom water layer, again 20 parts of washings of water operate the same twice totally.
(4) stir lower heating and distill out tetrahydrofuran (THF) and toluene, until solvent distill, material is heated to 140 ℃ in the still, opens the vacuum pump vacuum distillation, and when vacuum reaches 0.9mpa, temperature of charge reaches 160 ℃ when refluxing, the underpressure distillation end;
(5) temperature of charge is cooled to room temperature, adds 75 parts of massfraction 30% hydrochloric acid, stirs 30 minutes, left standstill 15-20 minute, triphenyl phosphorus is all dissolved, filter elimination triphenylphosphine oxide and other impurity, add 80 parts of softening waters in the filtrate, then centrifugal, isolate triphenylphosphine;
(6) add 75 parts of toluene in the still, drop into 25 parts of isolated triphenylphosphines, be warming up to 50 ℃, stirring and dissolving adds 0.5 part of hydrochloric acid, stirs 15 minutes, left standstill 20 minutes, and divided the acid of desalting, add 0.5 part in water, stirred 15 minutes, and left standstill branch vibration layer 15 minutes, 0.5 part in hydro-oxidation sodium, 2 parts of water washings are added in neutralization again, distill out toluene, the concentrated solution press filtration is entered in another still, add in advance 75 parts of methyl alcohol, then stirring heating in the still, till reaching 0.2Mpa to reacting kettle inner pressure, be incubated 30 minutes, stir lower Slow cooling to 10 ℃, the triphenyl crystallization of seeing, centrifugation, oven dry can obtain the triphenylphosphine product.
Add again 2 parts of water washings 3 times described in the step (6).
The distillation of the toluene described in the step (6) is underpressure distillation.
Product data
| Title: | Content % | Outward appearance | Fusing point | Percentage transmittance | Iron | Magnesium | Sodium | Tin | Muriate | Sulphur | Weight loss on drying | Ignition residue |
| Index: | 99.6 | The white particle crystallization | 80.1℃ | 97 | 0.0099 | 0.0003 | 0.0004 | 0.00097 | 0.0014 | 0.0004 | 0.3 | 0.097 |
Embodiment 3
(1) 120 parts of 35 parts of tetrahydrofuran (THF)s, toluene mix in reactor, drop into 8.5 parts of magnesium chips from manhole, and the sealing manhole adds 10 parts of phenyl-magnesium-chloride initiation solutions, fills the nitrogen deoxygenation, repeats to replace 3 times; Heating makes temperature in the kettle remain on 80 ± 5 ℃, stirs lower 260 parts altogether of the chlorinated benzene that at the uniform velocity drip, when dripping about 1/3 chlorinated benzene, be warming up to 103 ℃ and kept about 30 minutes, then be cooled to 80 ± 5 ℃, continue to drip remaining chlorinated benzene of 2/3, keep 80 ± 5 ℃ of material temperatures during the dropping, dropwise, slowly be warming up to 103 ℃, till gentle reflux occurring, kept temperature 4 hours, it is cooled to 80 ℃, still in another reactor of suction;
(2) open sufficient water coolant, when being cooled to 50 ℃ in the still, drip 12 parts of phosphorus trichlorides, 6 parts of mixtures of toluene, keep 50 ℃ ± 5 ℃ of material temperatures, the phosphorus trichloride toluene mixture liquid dropwises, and heating material temperature to 95 ℃ degree is incubated 4 hours;
(3) be cooled to 40 ℃, begin to drip 10 parts of the hydrochloric acid of massfraction 8%, maintain the temperature at 40 ℃, dropwise rear restir 30 minutes, left standstill 60 minutes, tell the bottom water layer, again 30 parts of washings of water operate the same twice totally.
(4) stir lower heating and distill out tetrahydrofuran (THF) and toluene, until solvent distill, material is heated to 140 ℃ in the still, opens the vacuum pump vacuum distillation, and when vacuum reaches 0.9mpa, temperature of charge reaches 180 ℃ when refluxing, the underpressure distillation end;
(5) temperature of charge is cooled to 40 ℃, adds 75 parts of massfraction 30% hydrochloric acid, stirs 30 minutes, left standstill 20 minutes, triphenyl phosphorus is all dissolved, filter elimination triphenylphosphine oxide and other impurity, add 80 parts of softening waters in the filtrate, then centrifugal, isolate triphenylphosphine;
(6) add 80 parts of toluene in the still, drop into 25 parts of isolated triphenylphosphines, be warming up to 50 ℃, stirring and dissolving adds 0.5 part of hydrochloric acid, stirs 15 minutes, left standstill 30 minutes, and divided the acid of desalting, add 0.5 part in water, stirred 15 minutes, and left standstill branch vibration layer 15 minutes, 0.5 part in hydro-oxidation sodium, 2 parts of water washings are added in neutralization again, distill out toluene, the concentrated solution press filtration is entered in another still, add in advance 80 parts of methyl alcohol, then stirring heating in the still, till reaching 0.2Mpa to reacting kettle inner pressure, be incubated 30 minutes, stir lower Slow cooling to 25 ℃, the triphenyl crystallization of seeing, centrifugation, oven dry can obtain the triphenylphosphine product.
Add again 2 parts of water washings 5 times described in the step (6).
The distillation of the toluene described in the step (6) is air distillation.
Product data
| Title: | Content % | Outward appearance | Fusing point | Percentage transmittance | Iron | Magnesium | Sodium | Tin | Muriate | Sulphur | Weight loss on drying | Ignition residue |
| Index: | 99.7 | The white particle crystallization | 80.5℃ | 96 | 0.0098 | 0.0004 | 0.0003 | 0.00099 | 0.0012 | 0.0003 | 0.4 | 0.099 |
Claims (3)
1. the production method of a triphenylphosphine is characterized in that may further comprise the steps:
(1) tetrahydrofuran (THF) 26-35 part, toluene 80-120 part mix in reactor, drop into magnesium chips 6-8.5 part from manhole, and the sealing manhole adds 10 parts of phenyl-magnesium-chloride initiation solutions, fills the nitrogen deoxygenation, repeats to replace 2-3 time; Heating makes temperature in the kettle remain on 80 ± 5 ℃, at the uniform velocity drips chlorinated benzene under stirring and amounts to 220-260 part, when dropping to the 1/4-1/2 chlorinated benzene, be warming up to 100-105 ℃ and kept about 30 minutes, then be cooled to 80 ± 5 ℃, when continuing to drip the chlorinated benzene of remaining 1/2-3/4, keep 80 ± 5 ℃ of material temperatures during the dropping, dropwise, slowly be warming up to 100-105 ℃, till gentle reflux occurring, kept temperature 4 hours, it is cooled to 50-80 ℃, still in another reactor of suction;
(2) open sufficient water coolant, when being cooled to 50 ℃ in the still, drip phosphorus trichloride 10-12 part, 6 parts of mixtures of toluene, keep 50 ℃ ± 5 ℃ of material temperatures, the phosphorus trichloride toluene mixture liquid dropwises, and heating material temperature to 85 ℃-95 ℃ of degree are incubated 4 hours;
(3) be cooled to room temperature-50 ℃, begin to drip hydrochloric acid 6-10 part of massfraction 4-8%, maintain the temperature at room temperature-50 ℃, dropwise rear restir 30 minutes, left standstill 60 minutes, tell the bottom water layer, again water 15-30 part washing operates the same twice totally;
(4) stir lower heating and distill out tetrahydrofuran (THF) and toluene, until solvent distill, material is heated to 140 ℃ in the still, opens the vacuum pump vacuum distillation, and when vacuum reaches 0.9mpa, temperature of charge reaches 140-180 ℃ when refluxing, the underpressure distillation end;
(5) temperature of charge is cooled to room temperature-50 ℃, adds 75 parts of massfraction 30% hydrochloric acid, stirs 30 minutes, left standstill 15-20 minute, triphenyl phosphorus is all dissolved, filter elimination triphenylphosphine oxide and other impurity, add 80 parts of softening waters in the filtrate, then centrifugal, isolate triphenylphosphine;
(6) add toluene 70-80 part in the still, drop into 25 parts of isolated triphenylphosphines, be warming up to 50 ℃, stirring and dissolving adds 0.5 part of hydrochloric acid, stirs 15 minutes, left standstill 15-30 minute, and divided the acid of desalting, add 0.5 part in water, stirred 15 minutes, and left standstill branch vibration layer 15 minutes, 0.5 part in hydro-oxidation sodium, 2 parts of water washings are added in neutralization again, distill out toluene, the concentrated solution press filtration is entered in another still, add in advance 70-80 part methyl alcohol in the still, then stirring heating, till reaching 0.2Mpa to reacting kettle inner pressure, be incubated 30 minutes, stir lower Slow cooling to 0-30 ℃, the triphenyl crystallization of seeing, centrifugation, oven dry can obtain the triphenylphosphine product.
2. the production method of triphenylphosphine according to claim 1 is characterized in that adding 2 parts of water washings 1-5 time described in the step (6) again.
3. the production method of triphenylphosphine according to claim 1 is characterized in that the distillation at the toluene described in the step (6) is air distillation or underpressure distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110207368.1A CN102887919B (en) | 2011-07-22 | 2011-07-22 | Production method of triphenylphosphine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110207368.1A CN102887919B (en) | 2011-07-22 | 2011-07-22 | Production method of triphenylphosphine |
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| Publication Number | Publication Date |
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| CN102887919A true CN102887919A (en) | 2013-01-23 |
| CN102887919B CN102887919B (en) | 2015-07-22 |
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| CN (1) | CN102887919B (en) |
Cited By (10)
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| CN104370962A (en) * | 2014-01-03 | 2015-02-25 | 江西省驰邦药业有限公司 | Flake triphenylphosphine and production method and application thereof |
| CN108033467A (en) * | 2017-12-27 | 2018-05-15 | 安徽金善化工科技有限公司 | A kind of preparation method of anhydrous magnesium chloride |
| CN108046975A (en) * | 2017-12-27 | 2018-05-18 | 安徽金善化工科技有限公司 | A kind of preparation method of biphenyl |
| CN108069448A (en) * | 2017-12-27 | 2018-05-25 | 安徽金善化工科技有限公司 | A kind of preparation method of magnesium chloride solution |
| CN108083967A (en) * | 2017-12-27 | 2018-05-29 | 安徽金善化工科技有限公司 | A kind of distillation recovery method of toluene |
| CN108084225A (en) * | 2017-12-27 | 2018-05-29 | 安徽金善化工科技有限公司 | A kind of preparation method of triphenylphosphine |
| CN108178773A (en) * | 2017-12-27 | 2018-06-19 | 安徽金善化工科技有限公司 | A kind of triphenylphosphine |
| CN109970789A (en) * | 2019-04-25 | 2019-07-05 | 大连理工大学 | A kind of preparation method of triaryl phosphine compound |
| CN111454292A (en) * | 2020-05-08 | 2020-07-28 | 绍兴华威化工有限公司 | Preparation method of triphenylphosphine |
| CN117024452A (en) * | 2023-08-08 | 2023-11-10 | 浙江万盛股份有限公司 | Preparation process of phenyl magnesium chloride |
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|---|---|---|---|---|
| CN104370962A (en) * | 2014-01-03 | 2015-02-25 | 江西省驰邦药业有限公司 | Flake triphenylphosphine and production method and application thereof |
| CN104370962B (en) * | 2014-01-03 | 2016-06-29 | 江西省驰邦药业有限公司 | Lamellar triphenylphosphine and production method thereof and application |
| CN108084225A (en) * | 2017-12-27 | 2018-05-29 | 安徽金善化工科技有限公司 | A kind of preparation method of triphenylphosphine |
| CN108046975A (en) * | 2017-12-27 | 2018-05-18 | 安徽金善化工科技有限公司 | A kind of preparation method of biphenyl |
| CN108069448A (en) * | 2017-12-27 | 2018-05-25 | 安徽金善化工科技有限公司 | A kind of preparation method of magnesium chloride solution |
| CN108083967A (en) * | 2017-12-27 | 2018-05-29 | 安徽金善化工科技有限公司 | A kind of distillation recovery method of toluene |
| CN108033467A (en) * | 2017-12-27 | 2018-05-15 | 安徽金善化工科技有限公司 | A kind of preparation method of anhydrous magnesium chloride |
| CN108178773A (en) * | 2017-12-27 | 2018-06-19 | 安徽金善化工科技有限公司 | A kind of triphenylphosphine |
| CN109970789A (en) * | 2019-04-25 | 2019-07-05 | 大连理工大学 | A kind of preparation method of triaryl phosphine compound |
| CN109970789B (en) * | 2019-04-25 | 2021-05-07 | 大连理工大学 | Preparation method of triarylphosphine compound |
| CN111454292A (en) * | 2020-05-08 | 2020-07-28 | 绍兴华威化工有限公司 | Preparation method of triphenylphosphine |
| CN117024452A (en) * | 2023-08-08 | 2023-11-10 | 浙江万盛股份有限公司 | Preparation process of phenyl magnesium chloride |
| CN117024452B (en) * | 2023-08-08 | 2024-05-14 | 浙江万盛股份有限公司 | Preparation process of phenyl magnesium chloride |
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