CN109942392A - A kind of preparation method of hexachloroacetone - Google Patents
A kind of preparation method of hexachloroacetone Download PDFInfo
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- CN109942392A CN109942392A CN201811636470.1A CN201811636470A CN109942392A CN 109942392 A CN109942392 A CN 109942392A CN 201811636470 A CN201811636470 A CN 201811636470A CN 109942392 A CN109942392 A CN 109942392A
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- chlorine
- hexachloroacetone
- compound
- catalyst
- preparation
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- DOJXGHGHTWFZHK-UHFFFAOYSA-N Hexachloroacetone Chemical compound ClC(Cl)(Cl)C(=O)C(Cl)(Cl)Cl DOJXGHGHTWFZHK-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 88
- 239000000460 chlorine Substances 0.000 claims abstract description 77
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 75
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 229940126062 Compound A Drugs 0.000 claims abstract description 32
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000012043 crude product Substances 0.000 claims abstract description 13
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 125000000714 pyrimidinyl group Chemical group 0.000 claims abstract description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- SMZHKGXSEAGRTI-UHFFFAOYSA-N 1,1,1-trichloropropan-2-one Chemical compound CC(=O)C(Cl)(Cl)Cl SMZHKGXSEAGRTI-UHFFFAOYSA-N 0.000 claims description 2
- DJWVKJAGMVZYFP-UHFFFAOYSA-N 1,1,3,3-tetrachloropropan-2-one Chemical group ClC(Cl)C(=O)C(Cl)Cl DJWVKJAGMVZYFP-UHFFFAOYSA-N 0.000 claims description 2
- CSVFWMMPUJDVKH-UHFFFAOYSA-N 1,1-dichloropropan-2-one Chemical compound CC(=O)C(Cl)Cl CSVFWMMPUJDVKH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- ZWILTCXCTVMANU-UHFFFAOYSA-N tetrachloroacetone Natural products ClCC(=O)C(Cl)Cl ZWILTCXCTVMANU-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 2
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 13
- 239000000498 cooling water Substances 0.000 description 12
- 239000012467 final product Substances 0.000 description 12
- 150000002576 ketones Chemical class 0.000 description 9
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 8
- ZEOVXNVKXIPWMS-UHFFFAOYSA-N 2,2-dichloropropane Chemical compound CC(C)(Cl)Cl ZEOVXNVKXIPWMS-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 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 description 1
- FILKGCRCWDMBKA-UHFFFAOYSA-N 2,6-dichloropyridine Chemical compound ClC1=CC=CC(Cl)=N1 FILKGCRCWDMBKA-UHFFFAOYSA-N 0.000 description 1
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to a kind of preparation methods of hexachloroacetone, belong to organic chemistry gas preparation technical field.Compound A is mixed with chlorine molecule B and is reacted under the action of catalyst at 30 DEG C~150 DEG C, reaction product is the mixture comprising hexachloroacetone and catalyst；Catalyst is isolated from the mixture and obtains crude product；Purification crude product is to obtain hexachloroacetone；Compound A is acetone and amount of chlorine atom is at least one of 1~5 chlroacetone；Chlorine molecule B is the mixture of chlorine or chlorine and diluent gas, and diluent gas is inert gas or nitrogen；Catalyst is pyrimidine, 2- chlorine pyrimidine, 2- nitrile pyrimidine or s-triazine.The method is easily recycled catalyst, and can obtain the extremely low hexachloroacetone of impurity content in high yield.
Description
Technical field
The present invention relates to a kind of preparation methods of hexachloroacetone, belong to organic chemistry gas preparation technical field.
Background technique
At present preparation method known patent US2199934, US2635117 of hexachloroacetone, US3265740,
JP2015556795, CN2013103226 and CN201580003850.Wherein, US2199934, US3265740 and
JP2015556795 is using pyridine as catalyst, the method for reacting acetone with chlorine molecule B；CN2013103226 is to use
Triphenylphosphine is as catalyst, the method for reacting acetone with chlorine molecule B；US2635117 and CN201580003850 is to use
Active carbon is as catalyst, the method for reacting acetone with chlorine molecule B；The chlorine molecule B is chlorine or chlorine and diluent gas
Mixture, diluent gas is the gas that inert gas or nitrogen etc. are not involved in reaction.Using pyridine, triphenylphosphine as catalysis
Agent, catalyst and its chloride are dissolved in hexachloroacetone product, therefore, it is difficult to recycle and recycle catalyst and its chloride,
In addition, even if removing catalyst and its when chloride by carrying out distilation to crude product, micro catalyst and its chlorination
Object also remains in hexachloroacetone, and therefore, it is difficult to obtain the hexachloroacetone of high-purity.Using active carbon as catalyst, chlorine atom
The acetone dichloride of number 1~5 is easy to polymerize, therefore easily generates high boiling compound, therefore hexachloroacetone yield is generally below
80%.
Summary of the invention
To overcome defect of the existing technology, the purpose of the present invention is to provide a kind of preparation method of hexachloroacetone,
The method is easily recycled catalyst, and can high yield obtain the hexachloroacetone of extremely low impurity content.
To achieve the purpose of the present invention, following technical scheme is provided.
A kind of preparation method of hexachloroacetone, the method comprises the following steps: compound A and chlorine molecule B are blended in catalyst
The lower reaction of effect, reaction product is the mixture comprising hexachloroacetone and catalyst；Catalyst is isolated from the mixture
And obtain crude product；Purification crude product is to obtain hexachloroacetone.
The compound A is acetone and amount of chlorine atom is at least one of 1~5 chlroacetone, wherein acetone is as former
Material, the chlroacetone that amount of chlorine atom is 1~5 are raw material acetone and the intermediate product that chlorine molecule B is generated during the reaction.
It is preferred that biodiversity percentage composition is 2% or less in the compound A；Mass distributary in the more preferable compound A
Measuring percentage composition is 0.5% or less；Biodiversity percentage composition is 0.1% or less in the most preferably described compound A.
The acetone includes diacetone alcohol (DAA) impurity sometimes, preferably in acetone the mass percentage of DAA be 1% with
Under, the mass percentage of DAA is 0.1% or less in more preferable acetone.
The chlorine molecule B is the mixture of chlorine or chlorine and diluent gas, and diluent gas is inert gas or nitrogen etc.
It is not involved in the gas of reaction.
It is preferred that chlorine molecule and hydrogen atom molar ratio in compound A are 1:1~1.5:1, more preferable chlorine molecule B in chlorine molecule B
Middle chlorine molecule is 1.1:1~1.2:1 with hydrogen atom molar ratio in compound A.
The catalyst is pyrimidine, 2- chlorine pyrimidine, 2- nitrile pyrimidine or s-triazine；It is preferred that the catalyst is pyrimidine or 2- chlorine
Pyrimidine.
The molar ratio of the catalyst and the compound A are 1:5~1:100；It is preferred that the catalyst and the chemical combination
The molar ratio of object A is 1:10~1:20.
The reaction is that gas-liquid mixed is reacted, can be by having the reaction kettle of stirring, tube-type reactor or board-like tower-shaped anti-
The modes such as device are answered to realize；It can also be realized by gas distributor mixed gas and liquid.
Reactive mode is intermittent or continous way.
Reaction speed can be adjusted by chlorine molecule B flow, temperature and catalyst amount etc..
Reaction temperature is 30 DEG C~150 DEG C.
When preferred compound A is that raw material acetone is reacted with chlorine molecule B, reaction temperature is 30 DEG C~40 DEG C；Add with chlorine molecule B
The increase for entering amount, when hydrogen atom molar ratio is 2:1 in chlorine molecule in chlorine molecule B and compound A, acetone conversion is a chlorine third
Ketone, dichloroacetone and trichloroacetone mixture；Catalyst is added, by reaction heat from being warming up to 110 DEG C~120 DEG C, when chlorine point
When hydrogen atom molar ratio is 5:1 in chlorine molecule and compound A in sub- B, reaction product is tetrachloroacetone, five chlroacetones and chlordene third
Alcohol/ketone mixtures；It is heated to 140 DEG C~150 DEG C.Preferred compound A is that raw material acetone reacts generation pentachloro- third with chlorine molecule B
It is 140 DEG C~150 DEG C until reaction terminates by reaction temperature after ketone.
Reaction pressure is normal pressure.
It is preferred that being passed through chlorine and hydrogen chloride that nitrogen purges out dereaction remnants after reaction.
It can separating catalyst obtains crude product from the mixture by the methods of sedimentation separation, washing or drying.
The hexachloroacetone of extremely low impurity content can be obtained by vacuum distillation purification crude product；It is preferred that vacuum distillation purification
Vacuum degree be 0.1KPa~5KPa, more preferably vacuum distillation purification vacuum degree be 0.1KPa~0.5KPa.
Beneficial effect
The present invention provides a kind of preparation method of hexachloroacetone, the method is easily recycled catalyst, and can be in high yield
Obtain the extremely low hexachloroacetone of impurity content.
Specific embodiment
The present invention is further described combined with specific embodiments below, but the present invention is not limited to following embodiments.
Embodiment 1
In the 1L glass reactor with blender, thermometer, gas introduction tube and condenser, acetone (moisture is added
0.1%wt or less) 295g (5mol), stirring, then chlorine is passed through in acetone with the flow of 4g/min, and the reactor is with cooling
Water is maintained at 30 DEG C~40 DEG C, until removing cooling water after about 710g (10mol) chlorine is passed through, it is phonetic that 20.3g (0.25mol) is added
Pyridine, by reaction heat from being warming up to 110 DEG C~120 DEG C, until being heated to 140 DEG C after about 1775g (25mol) chlorine is passed through
~150 DEG C, until being passed through nitrogen purging except dereaction residual chlorine gas and hydrogen chloride, wait urge after about 2343g (33mol) chlorine is added
Product is isolated after agent and product layering, three times, calcium chloride is dry for washing, and final product is evaporated under reduced pressure at 0.1KPa, is received
Rate is 94.5%.
Gas chromatographic detection is carried out to final product, as a result are as follows: the acetone dichloride that amount of chlorine atom is 1~4 is not detected, pentachloro- third
Ketone mass percentage is 0.02%, and high-boiling components are not detected, and hexachloroacetone mass percentage is 99.98%.
Embodiment 2
In the 1L glass reactor with blender, thermometer, gas introduction tube and condenser, acetone (moisture is added
0.1%wt or less) 295g (5mol), stirring, then chlorine is passed through in acetone with the flow of 4g/min, and reactor is protected with cooling water
It holds at 30 DEG C~40 DEG C, until removing cooling water after about 710g (10mol) chlorine is passed through, it is phonetic that 57.3g (0.50mol) 2- chlorine is added
Pyridine, by reaction heat from 110 DEG C of heating, until 140 DEG C~150 DEG C are heated to after about 1775g (25mol) chlorine is passed through,
After being added to about 2812g (39.6mol) chlorine, it is passed through nitrogen purging and removes remaining chlorine and hydrogen chloride, to catalyst and product
Product is isolated after layering, three times, calcium chloride is dry for washing, and final product, yield 94.1% are evaporated under reduced pressure at 0.1KPa.
Gas chromatographic detection is carried out to final product, as a result are as follows: the acetone dichloride that amount of chlorine atom is 1~4 is not detected, pentachloro- third
Ketone mass percentage is 0.06%, and high-boiling components are not detected, and hexachloroacetone mass percentage is 99.94%.
Embodiment 3
In the 1L glass reactor with blender, thermometer, gas introduction tube and condenser, acetone (moisture is added
0.1%wt or less) 295g (5mol), stirring, then chlorine is passed through in acetone with the flow of 4g/min, and reactor is protected with cooling water
It holds at 30 DEG C~40 DEG C, until removing cooling water after about 710g (10mol) chlorine is passed through, 36.8g (0.35mol) 2- nitrile pyrrole is added
Pyridine, by reaction heat from being warming up to 110 DEG C~120 DEG C, until being heated to 140 DEG C after about 1775g (25mol) chlorine is passed through
~150 DEG C, until be passed through nitrogen after about 2450g (34.5mol) chlorine is added and purge remaining chlorine and hydrogen chloride, to catalyst with
Product is isolated after product layering, three times, calcium chloride is dry for washing, is evaporated under reduced pressure to final product under 0.1KPa, yield is
93.8%.
Gas chromatographic detection is carried out to final product, as a result are as follows: the acetone dichloride that amount of chlorine atom is 1~4 is not detected, pentachloro- third
Ketone mass percentage is 0.05%, and high-boiling components are not detected, and hexachloroacetone mass percentage is 99.95%.
Embodiment 4
In the 1L glass reactor with blender, thermometer, gas introduction tube and condenser, acetone (moisture is added
0.1%wt or less) 295g (5mol), stirring, then chlorine is passed through in acetone with the flow of 4g/min, and reactor is protected with cooling water
It holds at 30 DEG C~40 DEG C, until removing cooling water after about 710g (10mol) chlorine is passed through, 54.8g (0.25mol) s-triazine is added,
By reaction heat from being warming up to 110 DEG C~120 DEG C, until after about 1775g (25mol) chlorine is passed through, be heated to 140 DEG C~
150 DEG C, until being passed through nitrogen purging after about 2450g (34.5mol) chlorine is added and removing remaining chlorine and hydrogen chloride, to catalyst
Product is isolated with after product layering, is washed three times, calcium chloride is dry, is evaporated under reduced pressure to final product under 0.1KPa, yield is
93.6%.
Gas chromatographic detection is carried out to final product, as a result are as follows: the acetone dichloride that amount of chlorine atom is 1~4 is not detected, pentachloro- third
Ketone mass percentage is 0.11%, and high-boiling components are not detected, and hexachloroacetone mass percentage is 99.89%.
Comparative example 1
In the 1L glass reactor with blender, thermometer, gas introduction tube and condenser, acetone (moisture is added
0.1%wt or less) 295g (5mol), stirring, then chlorine is passed through in acetone with the flow of 4g/min, and reactor, which leads to cooling water, to be protected
It holds at 30 DEG C~40 DEG C, until removing cooling water after about 710g (10mol) chlorine is passed through, 39.6g (0.50mol) pyridine is added, according to
By reaction heat from 110 DEG C of heating, until 140 DEG C~150 DEG C are heated to, until about after about 1775g (25mol) chlorine is passed through
After 2450g (34.5mol) chlorine is added, changes and be passed through the remaining chlorine of nitrogen purging removing and hydrogen chloride, to catalyst and product point
Product is isolated after layer, three times, calcium chloride is dry for washing, is evaporated under reduced pressure to final product, yield 91.3% under 0.1KPa.
Gas chromatographic detection is carried out to final product, as a result are as follows: the acetone dichloride that amount of chlorine atom is 1~4 is not detected, pentachloro- third
Ketone mass percentage is that 1.3%, 2- chloropyridine mass percentage is 0.3%, and 2,6- dichloropyridine mass percentages are
0.7%, high-boiling components are not detected, and hexachloroacetone mass percentage is 97.7%.
Comparative example 2
In the 1L glass reactor with blender, thermometer, gas introduction tube and condenser, acetone (moisture is added
0.1%wt or less) 295g (5mol), stirring, then chlorine is passed through in acetone with the flow of 4g/min, and reactor is protected with cooling water
It holds at 30 DEG C~40 DEG C, until removing cooling water after about 710g (10mol) chlorine is passed through, 65.6g (0.25mol) triphenyl is added
Phosphine, by reaction heat from 110 DEG C of heating, until 140 DEG C~150 DEG C are heated to after about 1775g (25mol) chlorine is passed through,
After being added to about 2450g (34.5mol) chlorine, it is passed through the remaining removing chlorine of nitrogen purging and hydrogen chloride, to catalyst and product
Product is isolated after layering, three times, calcium chloride is dry for washing, is evaporated under reduced pressure to final product, yield 92.4% in 0.1KPa.
Gas chromatographic detection is carried out to final product, as a result are as follows: the acetone dichloride that amount of chlorine atom is 1~4 is not detected, pentachloro- third
Ketone mass percentage is 2.3%, and phenol quality percentage composition is 0.5%, and high-boiling components are not detected, and hexachloroacetone quality percentage contains
Amount is 97.2%.
Claims (10)
1. a kind of preparation method of hexachloroacetone, it is characterised in that: the method comprises the following steps: compound A is being urged with chlorine molecule B
The lower reaction of agent effect, reaction product is the mixture comprising hexachloroacetone and catalyst；It isolates and urges from the mixture
Agent and obtain crude product；Purification crude product is to obtain hexachloroacetone；
The compound A is acetone and amount of chlorine atom is at least one of 1~5 chlroacetone；
The chlorine molecule B is the mixture of chlorine or chlorine and diluent gas, and diluent gas is inert gas or nitrogen；
The catalyst is pyrimidine, 2- chlorine pyrimidine, 2- nitrile pyrimidine or s-triazine；
Reaction temperature is 30 DEG C~150 DEG C.
2. a kind of preparation method of hexachloroacetone according to claim 1, it is characterised in that: compound A is raw material acetone
When reacting with chlorine molecule B, reaction temperature is 30 DEG C~40 DEG C；With the increase of chlorine molecule B additional amount, when chlorine molecule in chlorine molecule B
With hydrogen atom molar ratio in compound A be 2:1 when, acetone conversion be monochloroacetone, dichloroacetone and trichloroacetone mixture；Add
Enter catalyst, by reaction heat from being warming up to 110 DEG C~120 DEG C, when chlorine molecule rubs with hydrogen atom in compound A in chlorine molecule B
When you are than being 5:1, reaction product is tetrachloroacetone, five chlroacetones and hexachloroacetone mixture；It is heated to 140 DEG C~150
DEG C until reaction terminate.
3. a kind of preparation method of hexachloroacetone according to claim 1 or 2, it is characterised in that: the catalyst is phonetic
Pyridine or 2- chlorine pyrimidine.
4. a kind of preparation method of hexachloroacetone according to claim 1 or 2, it is characterised in that: chlorine in the chlorine molecule B
Molecule is 1:1~1.5:1 with hydrogen atom molar ratio in compound A；The molar ratio of the catalyst and the compound A are 1:5
~1:100.
5. a kind of preparation method of hexachloroacetone according to claim 1 or 2, it is characterised in that: chlorine molecule in chlorine molecule B
It is 1.1:1~1.2:1 with hydrogen atom molar ratio in compound A；The molar ratio of the catalyst and the compound A be 1:10~
1:20。
6. a kind of preparation method of hexachloroacetone according to claim 1 or 2, it is characterised in that: water in the compound A
Dividing mass percentage is 2% or less；The mass percentage of DAA is 1% or less in the acetone；By 0.1KPa~
5KPa vacuum distillation purifies crude product and obtains the hexachloroacetone of extremely low impurity content.
7. a kind of preparation method of hexachloroacetone according to claim 1 or 2, it is characterised in that: water in the compound A
Dividing mass percentage is 0.5% or less；The mass percentage of DAA is 0.1% or less in the acetone；By in 0.1KPa
~0.5KPa vacuum distillation purifies crude product and obtains the hexachloroacetone of extremely low impurity content.
8. a kind of preparation method of hexachloroacetone according to claim 3, it is characterised in that: chlorine point in the chlorine molecule B
Son is 1:1~1.5:1 with hydrogen atom molar ratio in compound A；The molar ratio of the catalyst and the compound A be 1:5~
1:100；
Biodiversity percentage composition is 2% or less in the compound A；In the acetone mass percentage of DAA be 1% with
Under；The hexachloroacetone of extremely low impurity content is obtained and being evaporated under reduced pressure purification crude product in 0.1KPa~5KPa.
9. a kind of preparation method of hexachloroacetone according to claim 3, it is characterised in that: chlorine point in the chlorine molecule B
Son is 1.1:1~1.2:1 with hydrogen atom molar ratio in compound A；The molar ratio of the catalyst and the compound A are 1:10
~1:20；
Biodiversity percentage composition is 0.5% or less in the compound A；The mass percentage of DAA is in the acetone
0.1% or less；The hexachloroacetone of extremely low impurity content is obtained and being evaporated under reduced pressure purification crude product in 0.1KPa~0.5KPa.
10. a kind of preparation method of hexachloroacetone according to claim 9, it is characterised in that: moisture in the compound A
Mass percentage is 0.1% or less.
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| CN115894167A (en) * | 2023-03-13 | 2023-04-04 | 泽升科技(广州)有限公司 | Preparation method of deuterated chloroform |
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