CN102887919B - Production method of triphenylphosphine - Google Patents
Production method of triphenylphosphine Download PDFInfo
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- CN102887919B CN102887919B CN201110207368.1A CN201110207368A CN102887919B CN 102887919 B CN102887919 B CN 102887919B CN 201110207368 A CN201110207368 A CN 201110207368A CN 102887919 B CN102887919 B CN 102887919B
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- toluene
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- triphenylphosphine
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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 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000003756 stirring Methods 0.000 claims abstract description 46
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 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 26
- 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
- 238000006073 displacement reaction 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
- 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 16
- 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
- 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
- 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
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- 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 object of the invention is to invent the production method of triphenylphosphine of a kind of reacting balance, safety and environmental protection.The main method that current production triphenyl is seen has magnesium processes and sodium method two kinds, but is that requirement is high with sodium method manufacture sodium sand, and the security incidents such as the reaction of sodium and chlorinated benzene is violent, easily sets off an explosion, fire; Magnesium processes is then gentle due to reaction conditions, safer, but in phosphine tri chloride titration process, because reactant viscosity is high, heat transfer is slow, easily causes side reaction, cause that product purity is not high, yield is low, therefore needing to solve provides a kind of new method, solves magnesium processes Problems existing.
Summary of the invention
According to the deficiencies in the prior art, technical problem to be solved by this invention is: the production method providing a kind of triphenylphosphine, 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: the production method providing a kind of triphenylphosphine, it is characterized in that comprising the following 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 sealing manhole, adds phenyl-magnesium-chloride initiation solution 10 parts, fill nitrogen deoxygenation, repeats displacement 2-3 time; Heating makes temperature in the kettle remain on 80 ± 5 DEG C, at the uniform velocity drips chlorinated benzene and amount to 220-260 part under stirring, when dripping about to 1/4-1/2 chlorinated benzene, be warming up to 100-105 DEG C and keep about 30 minutes, then be cooled to 80 ± 5 DEG C, when continuing the chlorinated benzene dripping remaining 1/2-3/4, during dropping, maintain material temperature 80 ± 5 DEG C, dropwise, slowly be warming up to 100-105 DEG C, to there is gentle reflux, keep temperature 4 hours, be cooled to 50-80 DEG C, still in another reactor of suction;
(2) open sufficient water coolant, when being cooled to 50 DEG C in still, drip phosphorus trichloride 10-12 part, toluene 6 parts of mixtures, keep material temperature 50 DEG C ± 5 DEG C, phosphorus trichloride toluene mixture liquid dropwises, and heating material temperature to 85 DEG C-95 DEG C of degree, are incubated 4 hours;
(3) be cooled to room temperature-50 DEG C, start the hydrochloric acid 6-10 part dripping massfraction 4-8%, maintain the temperature at room temperature-50 DEG C, stir 30 minutes again after dropwising, leave standstill 60 minutes, separate bottom aqueous layer, again with the washing of water 15-30 part, operate the same twice totally;
(4) stir lower heating and distill out tetrahydrofuran (THF) and toluene, until solvent has distilled, in still, material has been heated to 140 DEG C, opens vacuum pump vacuum distillation, and when vacuum reaches 0.9mpa, temperature of charge reaches 140-180 DEG C without when refluxing, and underpressure distillation terminates;
(5) temperature of charge is cooled to room temperature-50 DEG C, adds massfraction 30% hydrochloric acid 75 parts, stirs 30 minutes, leave standstill 15-20 minute, triphenyl phosphorus is all dissolved, filter elimination triphenylphosphine oxide and other impurity, 80 parts of softening waters are added in filtrate, then centrifugal, isolate triphenylphosphine;
(6) toluene 70-80 part is added in still, drop into isolated triphenylphosphine 25 parts, be warming up to 50 DEG C, stirring and dissolving, add 0.5 part of hydrochloric acid, stir 15 minutes, leave standstill 15-30 minute, divide acid of desalting, add water 0.5 part, stir 15 minutes, leave standstill 15 minutes, branch vibration layer, 0.5 part, hydro-oxidation sodium, neutralization, add 2 parts of water washings again, distill out toluene, concentrated solution press filtration is entered in another still, 70-80 part methyl alcohol is added in advance in still, then stirring heating, to reacting kettle inner pressure reaches 0.2Mpa, be incubated 30 minutes, 0-30 DEG C is progressively cooled under stirring, triphenyl is seen crystallization, centrifugation, oven dry can obtain triphenylphosphine product.
2 parts of water washings 1-5 time are added again described in step (6).
The distillation of the toluene described in 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 processes produces triphenylphosphine, overcome traditional magnesium processes produce yield low, cost is high, heavy-polluted problem, present method production process safety simultaneously, the Peril Incidents such as blast can not be produced, overcome traditional magnesium processes produce yield low, cost is high, heavy-polluted problem, by adding a certain amount of solvent in advance in a kettle., phenyl-magnesium-chloride grignard reagent adds in reactor in batches, quantitatively drip the mode of phosphorus trichloride at low temperatures, solve the problem that yield is low; By the improvement to aftertreatment technologys such as product triphenylphosphine purifications, avoid and add the pollution of mineral acid to environment in a large number, whole technique is more reasonable, is applicable to large-scale industrial and produces.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
(1) tetrahydrofuran (THF) 26 parts, toluene 80 parts mix in reactor, drop into magnesium chips 6 parts from manhole, and sealing manhole, adds phenyl-magnesium-chloride initiation solution 10 parts, fill nitrogen deoxygenation, repeat displacement 2 times; Heating makes temperature in the kettle remain on 80 ± 5 DEG C, at the uniform velocity drips chlorinated benzene and amount to 220 parts, when dropping to three/monochloro-benzene under stirring, be warming up to 100 DEG C and keep about 30 minutes, then be cooled to 80 ± 5 DEG C, continue to drip remaining chlorinated benzene of 2/3rds, during dropping, maintain material temperature 80 ± 5 DEG C, dropwise, slowly be warming up to 100 DEG C, to there is gentle reflux, keep temperature 4 hours, be cooled to 50 DEG C, still in another reactor of suction;
(2) open sufficient water coolant, when being cooled to 50 DEG C in still, drip phosphorus trichloride 10 parts, toluene 6 parts of mixtures, keep material temperature 50 DEG C ± 5 DEG C, phosphorus trichloride toluene mixture liquid dropwises, and heating material temperature to 85 DEG C DEG C degree, is incubated 4 hours;
(3) be cooled to 45 DEG C, start the hydrochloric acid 6 parts dripping massfraction 4%, maintain the temperature at 45 DEG C, after dropwising, stir 30 minutes again, leave standstill 60 minutes, separate bottom aqueous layer, then with the washing of 15 parts, water, operate the same twice totally.
(4) stir lower heating and distill out tetrahydrofuran (THF) and toluene, until solvent has distilled, in still, material has been heated to 140 DEG C, opens vacuum pump vacuum distillation, and when vacuum reaches 0.9mpa, temperature of charge reaches 140 DEG C without when refluxing, and underpressure distillation terminates;
(5) temperature of charge is cooled to 45 DEG C, adds massfraction 30% hydrochloric acid 75 parts, stirs 30 minutes, leave standstill 15 minutes, triphenyl phosphorus is all dissolved, filter elimination triphenylphosphine oxide and other impurity, 80 parts of softening waters are added in filtrate, then centrifugal, isolate triphenylphosphine;
(6) toluene 70 parts is added in still, drop into isolated triphenylphosphine 25 parts, be warming up to 50 DEG C, stirring and dissolving, add 0.5 part of hydrochloric acid, stir 15 minutes, leave standstill 15 minutes, divide acid of desalting, add water 0.5 part, stir 15 minutes, leave standstill 15 minutes, branch vibration layer, 0.5 part, hydro-oxidation sodium, neutralization, add 2 parts of water washings again, distill out toluene, concentrated solution press filtration is entered in another still, 70 parts of methyl alcohol are added in advance in still, then stirring heating, to reacting kettle inner pressure reaches 0.2Mpa, be incubated 30 minutes, 0 DEG C is progressively cooled under stirring, triphenyl is seen crystallization, centrifugation, oven dry can obtain triphenylphosphine product.
2 parts of water washings 1 time are added again described in step (6).
The distillation of the toluene described in 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 | 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) tetrahydrofuran (THF) 30 parts, toluene 100 parts mix in reactor, drop into magnesium chips 7 parts from manhole, and sealing manhole, adds phenyl-magnesium-chloride initiation solution 10 parts, fill nitrogen deoxygenation, repeat displacement 3 times; Heating make temperature in the kettle remain on 80 ± 5 DEG C, at the uniform velocity drip chlorinated benzene under stirring and amount to 240 parts, drip about 1/4 chlorinated benzene time, be warming up to 105 DEG C and keep about 30 minutes, then be cooled to 80 ± 5 DEG C, continue to drip remaining chlorinated benzene of 3/4, during dropping, maintain material temperature 80 ± 5 DEG C, dropwise, slowly be warming up to 105 DEG C, to there is gentle reflux, keep temperature 4 hours, be cooled to 70 DEG C, still in another reactor of suction;
(2) open sufficient water coolant, when being cooled to 50 DEG C in still, drip phosphorus trichloride 11 parts, toluene 6 parts of mixtures, keep material temperature 50 DEG C ± 5 DEG C, phosphorus trichloride toluene mixture liquid dropwises, and heating material temperature to 90 DEG C degree, is incubated 4 hours;
(3) be cooled to room temperature, start the hydrochloric acid 8 parts dripping 6%, maintain the temperature at room temperature, after dropwising, stir 30 minutes again, leave standstill 60 minutes, separate bottom aqueous layer, then with the washing of 20 parts, water, operate the same twice totally.
(4) stir lower heating and distill out tetrahydrofuran (THF) and toluene, until solvent has distilled, in still, material has been heated to 140 DEG C, opens vacuum pump vacuum distillation, and when vacuum reaches 0.9mpa, temperature of charge reaches 160 DEG C without when refluxing, and underpressure distillation terminates;
(5) temperature of charge is cooled to room temperature, adds massfraction 30% hydrochloric acid 75 parts, stirs 30 minutes, leave standstill 15-20 minute, triphenyl phosphorus is all dissolved, filter elimination triphenylphosphine oxide and other impurity, 80 parts of softening waters are added in filtrate, then centrifugal, isolate triphenylphosphine;
(6) toluene 75 parts is added in still, drop into isolated triphenylphosphine 25 parts, be warming up to 50 DEG C, stirring and dissolving, add 0.5 part of hydrochloric acid, stir 15 minutes, leave standstill 20 minutes, divide acid of desalting, add water 0.5 part, stir 15 minutes, leave standstill 15 minutes, branch vibration layer, 0.5 part, hydro-oxidation sodium, neutralization, add 2 parts of water washings again, distill out toluene, concentrated solution press filtration is entered in another still, 75 parts of methyl alcohol are added in advance in still, then stirring heating, to reacting kettle inner pressure reaches 0.2Mpa, be incubated 30 minutes, 10 DEG C are progressively cooled under stirring, triphenyl is seen crystallization, centrifugation, oven dry can obtain triphenylphosphine product.
2 parts of water washings 3 times are added again described in step (6).
The distillation of the toluene described in 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 | 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) tetrahydrofuran (THF) 35 parts, toluene 120 parts mix in reactor, drop into magnesium chips 8.5 parts from manhole, and sealing manhole, adds phenyl-magnesium-chloride initiation solution 10 parts, fill nitrogen deoxygenation, repeat displacement 3 times; Heating make temperature in the kettle remain on 80 ± 5 DEG C, at the uniform velocity drip chlorinated benzene under stirring and amount to 260 parts, drip about 1/3 chlorinated benzene time, be warming up to 103 DEG C and keep about 30 minutes, then be cooled to 80 ± 5 DEG C, continue to drip remaining chlorinated benzene of 2/3, during dropping, maintain material temperature 80 ± 5 DEG C, dropwise, slowly be warming up to 103 DEG C, to there is gentle reflux, keep temperature 4 hours, be cooled to 80 DEG C, still in another reactor of suction;
(2) open sufficient water coolant, when being cooled to 50 DEG C in still, drip phosphorus trichloride 12 parts, toluene 6 parts of mixtures, keep material temperature 50 DEG C ± 5 DEG C, phosphorus trichloride toluene mixture liquid dropwises, and heating material temperature to 95 DEG C degree, is incubated 4 hours;
(3) be cooled to 40 DEG C, start the hydrochloric acid 10 parts dripping massfraction 8%, maintain the temperature at 40 DEG C, after dropwising, stir 30 minutes again, leave standstill 60 minutes, separate bottom aqueous layer, then with the washing of 30 parts, water, operate the same twice totally.
(4) stir lower heating and distill out tetrahydrofuran (THF) and toluene, until solvent has distilled, in still, material has been heated to 140 DEG C, opens vacuum pump vacuum distillation, and when vacuum reaches 0.9mpa, temperature of charge reaches 180 DEG C without when refluxing, and underpressure distillation terminates;
(5) temperature of charge is cooled to 40 DEG C, adds massfraction 30% hydrochloric acid 75 parts, stirs 30 minutes, leave standstill 20 minutes, triphenyl phosphorus is all dissolved, filter elimination triphenylphosphine oxide and other impurity, 80 parts of softening waters are added in filtrate, then centrifugal, isolate triphenylphosphine;
(6) toluene 80 parts is added in still, drop into isolated triphenylphosphine 25 parts, be warming up to 50 DEG C, stirring and dissolving, add 0.5 part of hydrochloric acid, stir 15 minutes, leave standstill 30 minutes, divide acid of desalting, add water 0.5 part, stir 15 minutes, leave standstill 15 minutes, branch vibration layer, 0.5 part, hydro-oxidation sodium, neutralization, add 2 parts of water washings again, distill out toluene, concentrated solution press filtration is entered in another still, 80 parts of methyl alcohol are added in advance in still, then stirring heating, to reacting kettle inner pressure reaches 0.2Mpa, be incubated 30 minutes, 25 DEG C are progressively cooled under stirring, triphenyl is seen crystallization, centrifugation, oven dry can obtain triphenylphosphine product.
2 parts of water washings 5 times are added again described in step (6).
The distillation of the toluene described in 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 | White particle crystallization | 80.5℃ | 96 | 0.0098 | 0.0004 | 0.0003 | 0.00099 | 0.0012 | 0.0003 | 0.4 | 0.099 |
Claims (1)
1. a production method for triphenylphosphine, is characterized in that comprising the following 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 sealing manhole, adds phenyl-magnesium-chloride initiation solution 10 parts, fill nitrogen deoxygenation, repeats displacement 2-3 time; Heating makes temperature in the kettle remain on 80 ± 5 DEG C, at the uniform velocity drips chlorinated benzene and amount to 220-260 part, when dropping to 1/4-1/2 chlorinated benzene under stirring, be warming up to 100-105 DEG C and keep about 30 minutes, then be cooled to 80 ± 5 DEG C, when continuing to drip remaining chlorinated benzene of 1/2-3/4, during dropping, maintain material temperature 80 ± 5 DEG C, dropwise, slowly be warming up to 100-105 DEG C, to there is gentle reflux, keep temperature 4 hours, be cooled to 50-80 DEG C, still in another reactor of suction;
(2) open sufficient water coolant, when being cooled to 50 DEG C in still, drip phosphorus trichloride 10-12 part, toluene 6 parts of mixtures, keep material temperature 50 DEG C ± 5 DEG C, phosphorus trichloride toluene mixture liquid dropwises, and heating material temperature to 85 DEG C-95 DEG C of degree, are incubated 4 hours;
(3) be cooled to room temperature-50 DEG C, start the hydrochloric acid 6-10 part dripping massfraction 4-8%, maintain the temperature at room temperature-50 DEG C, stir 30 minutes again after dropwising, leave standstill 60 minutes, separate bottom aqueous layer, again with the washing of water 15-30 part, operate the same twice totally;
(4) stir lower heating and distill out tetrahydrofuran (THF) and toluene, until solvent has distilled, in still, material has been heated to 140 DEG C, opens vacuum pump vacuum distillation, and when vacuum reaches 0.9mpa, temperature of charge reaches 140-180 DEG C without when refluxing, and underpressure distillation terminates;
(5) temperature of charge is cooled to room temperature-50 DEG C, adds massfraction 30% hydrochloric acid 75 parts, stirs 30 minutes, leave standstill 15-20 minute, triphenyl phosphorus is all dissolved, filter elimination triphenylphosphine oxide and other impurity, 80 parts of softening waters are added in filtrate, then centrifugal, isolate triphenylphosphine;
(6) toluene 70-80 part is added in still, drop into isolated triphenylphosphine 25 parts, be warming up to 50 DEG C, stirring and dissolving, add 0.5 part of hydrochloric acid, stir 15 minutes, leave standstill 15-30 minute, divide acid of desalting, add water 0.5 part, stir 15 minutes, leave standstill 15 minutes, branch vibration layer, 0.5 part, hydro-oxidation sodium, neutralization, add 2 parts of water washings again, distill out toluene, concentrated solution press filtration is entered in another still, 70-80 part methyl alcohol is added in advance in still, then stirring heating, to reacting kettle inner pressure reaches 0.2Mpa, be incubated 30 minutes, 0-30 DEG C is progressively cooled under stirring, triphenyl is seen crystallization, centrifugation, oven dry can obtain triphenylphosphine product,
2 parts of water washings 1-5 time are added again described in step (6);
The distillation of the toluene described in step (6) is air distillation or underpressure distillation.
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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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| 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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| CN102887919A CN102887919A (en) | 2013-01-23 |
| CN102887919B true CN102887919B (en) | 2015-07-22 |
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| 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 |
| 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 |
| CN108069448B (en) * | 2017-12-27 | 2020-11-10 | 安徽金善化工科技有限公司 | Preparation method of magnesium chloride solution |
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| CN108178773A (en) * | 2017-12-27 | 2018-06-19 | 安徽金善化工科技有限公司 | A kind of triphenylphosphine |
| 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 |
| CN117024452B (en) * | 2023-08-08 | 2024-05-14 | 浙江万盛股份有限公司 | Preparation process of phenyl magnesium chloride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4045494A (en) * | 1975-03-06 | 1977-08-30 | M&T Chemicals Inc. | Method for preparing triogranophosphines |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB837329A (en) * | 1957-07-22 | 1960-06-09 | Metal & Thermit Corp | Improvements in the production of organophosphorus compounds |
| US3499039A (en) * | 1966-11-10 | 1970-03-03 | Advance Prod Gmbh | Preparation of tertiary phosphines |
| RU2221805C1 (en) * | 2002-07-09 | 2004-01-20 | Институт органической и физической химии им. А.Е. Арбузова Казанского научного центра РАН | Method for preparing triphenylphosphine |
| CN101210031B (en) * | 2006-12-29 | 2010-10-13 | 中国石油大学(北京) | Method for producing triphenylphosphine |
| CN101481389B (en) * | 2009-01-15 | 2011-08-17 | 宁波工程学院 | Method for recycling triphenyl phosphine oxide and triphenylphosphine from waste slag |
-
2011
- 2011-07-22 CN CN201110207368.1A patent/CN102887919B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4045494A (en) * | 1975-03-06 | 1977-08-30 | M&T Chemicals Inc. | Method for preparing triogranophosphines |
Non-Patent Citations (1)
| Title |
|---|
| 徐克勋.第五编 元素有机化合物 三苯基膦.《精细有机化工原料及中间体手册》.1998,第5-10页. * |
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