CN108276243B - Industrial production method of octafluorocyclopentene - Google Patents
Industrial production method of octafluorocyclopentene Download PDFInfo
- Publication number
- CN108276243B CN108276243B CN201711389280.XA CN201711389280A CN108276243B CN 108276243 B CN108276243 B CN 108276243B CN 201711389280 A CN201711389280 A CN 201711389280A CN 108276243 B CN108276243 B CN 108276243B
- Authority
- CN
- China
- Prior art keywords
- octafluorocyclopentene
- reaction
- product
- production method
- industrial production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- YBMDPYAEZDJWNY-UHFFFAOYSA-N 1,2,3,3,4,4,5,5-octafluorocyclopentene Chemical compound FC1=C(F)C(F)(F)C(F)(F)C1(F)F YBMDPYAEZDJWNY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000009776 industrial production Methods 0.000 title claims abstract description 13
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 34
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 17
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006467 substitution reaction Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 35
- DMZRCHJVWAKCAX-UHFFFAOYSA-N 1,2,3,3,4,4,5,5-octachlorocyclopentene Chemical compound ClC1=C(Cl)C(Cl)(Cl)C(Cl)(Cl)C1(Cl)Cl DMZRCHJVWAKCAX-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003682 fluorination reaction Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000005660 chlorination reaction Methods 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- ZFMWDTNZPKDVBU-UHFFFAOYSA-N 1,2,3,4-tetrachlorocyclopentane Chemical compound ClC1CC(Cl)C(Cl)C1Cl ZFMWDTNZPKDVBU-UHFFFAOYSA-N 0.000 claims description 2
- QPIRTTQWLDPXBN-UHFFFAOYSA-N 1,2-dichlorocyclopentane Chemical compound ClC1CCCC1Cl QPIRTTQWLDPXBN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000066 reactive distillation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000543 intermediate Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- SOJZMJXWEOBDIC-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5-nonafluorocyclopentane Chemical compound FC1C(F)(F)C(F)(F)C(F)(F)C1(F)F SOJZMJXWEOBDIC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001940 cyclopentanes Chemical class 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ABPBVCKGWWGZDP-UHFFFAOYSA-N 1,2-dichloro-3,3,4,4,5,5-hexafluorocyclopentene Chemical compound FC1(F)C(Cl)=C(Cl)C(F)(F)C1(F)F ABPBVCKGWWGZDP-UHFFFAOYSA-N 0.000 description 1
- MYVQKOLPIBOMHY-UHFFFAOYSA-N 1-chloro-1,2,2,3,3,4,4,5,5-nonafluorocyclopentane Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(Cl)C1(F)F MYVQKOLPIBOMHY-UHFFFAOYSA-N 0.000 description 1
- MTXFJQPFMARORW-UHFFFAOYSA-N 3-chloro-1,2,3,4,4,5,5-heptafluorocyclopentene Chemical compound FC1=C(F)C(F)(Cl)C(F)(F)C1(F)F MTXFJQPFMARORW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- FWCXQLAABAQTMM-UHFFFAOYSA-N S1(=O)(=O)CCCC1.N1=CC=CC=C1 Chemical compound S1(=O)(=O)CCCC1.N1=CC=CC=C1 FWCXQLAABAQTMM-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- VMPHUBHEXZMNGC-UHFFFAOYSA-N ethanol;thiolane 1,1-dioxide Chemical compound CCO.O=S1(=O)CCCC1 VMPHUBHEXZMNGC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/204—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being a halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
- C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an industrial production method of octafluorocyclopentene, and belongs to the field of synthesis of fine chemical intermediates. Cyclopentene, chlorine and anhydrous potassium fluoride are used as raw materials, sulfolane is used as a solvent, and the raw materials and the sulfolane are subjected to temperature programming, are gradually chlorinated, and are subjected to high-temperature substitution reaction with the potassium fluoride to generate octafluorocyclopentene. The kettle residue after the product separation can be reused by distilling the solvent sulfolane under reduced pressure; the production process has the advantages of simple steps, environmental protection, high yield, low production cost and high purity of the obtained product, and is beneficial to later-stage application.
Description
Technical Field
The invention relates to an industrial production method of octafluorocyclopentene, and belongs to the field of synthesis of fine chemical intermediates.
Background
The 1,2,3,3,4,4,5, 5-octafluorocyclopentene is abbreviated as octafluorocyclopentene or perfluorocyclopentene, is mainly used for etching and cleaning semiconductors, and can participate in the preparation of organic photochromic materials. Octafluorocyclopentene is considered to be a competitive advantage as one of the next generation etching gases and the most attractive raw material for electronic devices. Octafluorocyclopentene may also be used in the synthesis of high-end dyes. It has less influence on environment and is one new kind of fluoric chemical.
The preparation method of the literature mostly uses the fluorine chloride of cyclopentene as a raw material and is prepared by multi-step fluorination reaction.
Ancient Zhuyufu et al, Ribenson ceramic nitroxide corporation, reported a process for preparing octafluorocyclopentene from octachlorocyclopentene as a starting material by a two-step fluorination reaction. Under the action of gas phase fluorination catalyst, octachlorocyclopentene and anhydrous HF are first halogen exchange reacted to produce 1, 2-dichloro-3, 3,4,4,5, 5-hexafluorocyclopentene, chloroheptafluorocyclopentene, etc. and then reacted with alkali metal fluoride in amide and sulfoxide solvent to produce octafluorocyclopentene. The reaction formula is as follows:
octachlorocyclopentene as a raw material needs to be prepared by self, and dicyclopentadiene as an initial raw material needs to be depolymerized at high temperature to obtain cyclopentadiene monomers, and then the subsequent steps can be carried out.
The synthesis process comprises the following steps:
the research group also tried to prepare octachlorocyclopentadiene as an intermediate by adopting the method, and the following problems existed:
firstly, the dicyclopentadiene which is commercially available needs to be depolymerized at the high temperature of 300-350 ℃ to prepare cyclopentadiene monomers, and the research group finds that the high temperature is not easy to be reached in a small test and is dangerous to operate. If the production is enlarged, the actual operation is more difficult. A small amount of cyclopentadiene monomer is obtained by adopting an electric heating jacket for small trial and subsequent steps are explored.
Secondly, when chlorine is introduced by using a newly prepared cyclopentadiene monomer according to the process of the literature, the cyclopentadiene monomer is easily polymerized into stable dicyclopentadiene after the temperature is increased, the reaction temperature is increased, the tar content of the system is increased, a sample is taken for GC-MS and GC analysis, only about 5 percent of target product is obtained, the reaction system is viscous, and chlorine is introduced to the reaction system and cannot be absorbed, so that the product content is not changed.
Japanese patent discloses that under the condition of using nonafluorocyclopentane chloride as raw material and using isopropanol as solvent and zinc powder, the nonafluorocyclopentane chloride can be used for preparing octafluorocyclopentene by means of dehalogenation reaction, and the isopropanol in the product can be removed by adopting 13X type molecular sieve. In the route, the raw material of the chlorononafluorocyclopentane is not suitable to be obtained. The reaction formula is as follows:
in conclusion, the existing synthesis method of octafluorocyclopentene has the problems of more reaction steps, unavailable raw materials, large amount of hydrogen fluoride, more reaction steps and low product separation yield.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an industrial production method of octafluorocyclopentene, which comprises the steps of heating cyclopentene and chlorine by a program, reacting to obtain octachlorocyclopentene, and then reacting with potassium fluoride at a high temperature to obtain the octafluorocyclopentene.
In order to achieve the purpose, the invention provides an industrial production method of octafluorocyclopentene, which is technically characterized by comprising the following steps: the method takes cyclopentene as a raw material, and obtains an octafluorocyclopentene product after temperature programming chlorination and high temperature fluorination in turn. The method comprises the following steps:
first step, chlorination reaction:
introducing chlorine into the cyclopentene, performing addition to obtain 1, 2-dichlorocyclopentane, continuously introducing the chlorine, heating the reaction to 70 ℃ for reaction to obtain 1,2,3, 4-tetrachlorocyclopentane, continuously heating the reaction to 180 ℃ and 210 ℃ for reaction to obtain a crude octachlorocyclopentene product;
in the step, the reaction is carried out in the absence of a solvent, and the molar ratio of the cyclopentene serving as the raw material to the chlorine is 1: 18-20. Stopping the reaction when the content of the intermediate is less than 2%, and purifying the product by reduced pressure distillation;
and step two, substitution fluorination:
after anhydrous potassium fluoride and sulfolane are mixed, the temperature is controlled at 140-.
In the step, qualified octafluorocyclopentene is obtained by adopting a mode of reaction and normal pressure rectification, and is received by a low-temperature cooling device at the cooling temperature of-10-0 ℃. The reaction time is usually 2-5 h; the mol ratio of octachlorocyclopentene to anhydrous potassium fluoride in the raw materials is 1: 10-12.
Through the process, the separation yield of the octafluorocyclopentene product reaches 45-55%, the content of octafluorocyclopentene in the product is more than 99%, the water content is less than 0.2%, and the detection of chloride ions is less than 0.1%.
Further, after the second step reaction, neutralizing the obtained kettle residue with alkali, centrifuging to remove inorganic salts so as to reduce the content of fluorine ions and chloride ions in the process wastewater, and finally distilling under reduced pressure to remove sulfolane and ethanol for recycling. The operation process is as follows:
cooling the material after the fluorination reaction distillation product to 50-70 ℃, adding potassium hydroxide solid to remove redundant anhydrous potassium fluoride and hydrochloride in the system, then centrifugally filtering to obtain centrifugal mother liquor and filter cake (the filter cake contains a large amount of potassium chloride and a small amount of potassium fluoride), leaching the filter cake with ethanol, and retaining the leacheate to finally obtain centrifugal mother liquor containing pyridine sulfolane and the leacheate containing ethanol sulfolane, wherein the filter cake is light yellow solid. And recovering the solvents pyridine, sulfolane and a small amount of ethanol from the filtrate by adopting a reduced pressure distillation method, wherein the recovered solvents are used for next experiment, and the solvents can be recovered for multiple times and can be used for multiple times.
The invention has the beneficial effects that:
1. the method takes cyclopentene, chlorine and anhydrous potassium fluoride as raw materials, and obtains the octafluorocyclopentene with high yield and high content after chlorination reaction and fluorination reaction in sequence, wherein the separation yield of the product can reach 45-55%, the product content is more than 99%, the water content is less than 0.1%, and the chloride ion detection is less than 0.1%.
2. Compared with the traditional process method, the method has the advantages of short process flow, convenient operation and contribution to industrial amplification.
3. In the process, the residue after the octafluorocyclopentene product is separated is neutralized by alkali and then subjected to reduced pressure distillation to respectively recover the sulfolane solvent and ethanol for leaching for reuse.
4. The production process of the invention is pollution-free, green, high in yield, beneficial to reducing production cost, high in product purity and beneficial to later application.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the specific examples.
Example 1: the synthesis route of octachlorocyclopentene in this example is shown in the following reaction formula:
the experimental steps are as follows:
adding 68g (1mol, 97%) of liquid cyclopentene into a 250ml four-port reaction kettle equipped with a mechanical stirring and reflux condensing device, and connecting with an alkaline tail gas absorption device;
when the temperature in the system is 25 ℃, chlorine gas is introduced into the kettle, the temperature of the system rises at this time, the temperature during backflow is 45 ℃ (the atmospheric boiling point of cyclopentene is 44.2 ℃), the chlorine gas is introduced to carry out addition reaction, no gas is produced during the beginning, the chlorine gas is completely absorbed, the backflow stops along with the progress of the reaction, and the ventilation speed of the chlorine gas is optimal to be 1 g/min. At this point, a sample was taken for gas phase analysis and the feed cyclopentene was < 2%. And then slowly raising the temperature in the system to 70 ℃, continuously introducing chlorine gas for deep chlorination, converting the system into a mixture of polychlorinated cyclopentane, continuously raising the temperature of the later-stage system to 180 ℃, continuously introducing chlorine gas, controlling the temperature rise speed to be 10 ℃/h, controlling the maximum reaction temperature to be 210 ℃, sampling and analyzing, and stopping the reaction when the over-chlorination state is less than 2%. The reaction product is octachlorocyclopentene and a small amount of polymer; a total of about 1420g of chlorine were passed. The utilization rate of the chlorine can be improved by adopting a continuous device during industrial amplification.
The temperature is reduced to 100 ℃, residual chlorine and hydrogen chloride gas in the system are removed by using a water pump under reduced pressure, and then the system is connected with a mechanical pump.
The reduced pressure distillation is carried out by a mechanical pump, and the product is collected (116 ℃ C./4 mmHg). 223.1g of octachlorocyclopentene is obtained, m/z is 343.6 by GC-MS detection, and other fragment peaks are consistent with those of a standard sample. The product purity is 98 percent, and the product yield is 63.6 percent.
Example 2: the synthetic route for octachlorocyclopentene in this example is an enlargement of example 1
The experimental steps are as follows:
680g (10mol, 97%) of liquid cyclopentene is added into a 2L four-port reaction kettle provided with a mechanical stirring and reflux condensing device, and then connected with an alkaline tail gas absorption device;
at room temperature, chlorine gas is introduced into the kettle, the temperature of the system rises at this time, the temperature during reflux is 45 ℃ (the atmospheric boiling point of cyclopentene is 44.2 ℃), and chlorine gas is introduced to perform addition reaction, so that no gas is produced at the beginning, the chlorine gas is completely absorbed, the reflux stops along with the reaction, and the aeration speed of the chlorine gas is optimal to be 1 g/min. At this point, a sample can be taken for gas phase analysis, and the cyclopentene raw material is less than 2%. Then slowly heating the system to 110 ℃, continuously introducing chlorine gas for deep chlorination, converting the system into a mixture of polychlorinated cyclopentane, continuously heating the system to 180 ℃ in the later period, continuously introducing chlorine gas, controlling the heating speed to 10 ℃/h and the highest reaction temperature to 210 ℃, sampling and analyzing, stopping the reaction when the excessive chlorination state is less than 2%, and obtaining reaction products of octachlorocyclopentene and a small amount of polymers; a total of 12780g of chlorine was passed in.
The temperature is reduced to 100 ℃, residual chlorine and hydrogen chloride gas in the system are removed by using a water pump under reduced pressure, and then the system is connected with a mechanical pump.
The reduced pressure distillation is carried out by a mechanical pump, and the product is collected (116 ℃ C./4 mmHg). 2140.4g of octachlorocyclopentene is obtained, the product purity is 98 percent, and the product yield is 61.7 percent.
Example 3: the synthetic route of octafluorocyclopentene in this example is shown in the following reaction formula:
the experimental steps are as follows:
290g (5mol, 99%, 10eq) of anhydrous potassium fluoride and 1012g of sulfolane are added into a 2L four-port reaction kettle provided with a mechanical stirring and rectifying condensing device, and the temperature is raised to 140 ℃ by stirring.
172g (98 percent, 0.5mol) of self-made octachlorocyclopentene and 180g of sulfolane are mixed and then are dripped into the system, the dripping time is 2 hours, the temperature of the system is slowly increased in the dripping process, the temperature increasing speed is about 5 ℃/h, the reflux of the system is obvious after the dripping is finished, and the product is extracted from the top end of a rectifying tower. The atmospheric boiling point of the product octafluorocyclopentene is 27 ℃.
When the product fraction is reduced, the temperature of the system is continuously increased to 170 ℃ at most; the product is cooled to-10-0 ℃ by a low-temperature cooling device in the product collection process, so that the evaporation loss of the product is prevented.
This example collected 79.6g of octafluorocyclopentene product, 99.7% GC, less than 0.2% moisture, less than 0.1% chloride detection, and 75% product yield. 212.0 m/z by GC-MS, F NMR spectral data: -117.048ppm (4F), -129.197ppm (2F), -148.448ppm (2F); both GC-MS and FNMR were consistent with the peak formation of the standard sample.
Example 4:
the experimental steps are as follows:
290g (5mol, 99%, 10eq) of anhydrous potassium fluoride and 1012g of sulfolane are added into a 2L four-port reaction kettle provided with a mechanical stirring and rectifying condensing device, and the temperature is raised to 150 ℃ by stirring.
172g (98 percent, 0.5mol) of self-made octachlorocyclopentene and 180g of sulfolane are mixed and then are dripped into the system, the dripping time is 1.5h, the temperature of the system is slowly increased in the dripping process, the temperature increasing speed is about 10 ℃/h, the reflux of the system is obvious after the dripping is finished, and the product is extracted from the top end of a rectifying tower.
When the product fraction is reduced, the temperature of the system is continuously increased to 170 ℃ at most; the product is cooled to-10-0 ℃ by a low-temperature cooling device in the product collection process.
The octafluorocyclopentene product 82.7g, GC 99.2% and product yield 78% are collected in the example.
Example 5:
the experimental steps are as follows:
to a 5L four port reactor equipped with mechanical stirring and rectification condensing units, 580g (10mol, 99%, 10eq) of anhydrous potassium fluoride and 2025g of sulfolane were added, and the temperature was raised to 140 ℃ with stirring.
343.7g (98 percent and 1mol) of self-made octachlorocyclopentene and 360g of sulfolane are mixed and then are dripped into the system, the dripping time is 3h, the temperature of the system is slowly increased in the dripping process, the temperature increasing speed is about 10 ℃/h, the reflux of the system is obvious after the dripping is finished, and the product is extracted from the top end of a rectifying tower.
When the product fraction is reduced, the temperature of the system is continuously increased to 170 ℃ at most, the reaction is carried out in a heat preservation way until no fraction is extracted, and the reaction is stopped; the product is cooled to-10-0 ℃ by a low-temperature cooling device in the product collection process.
In the example, 180.2g of octafluorocyclopentene product, 99.2 percent of GC and 85 percent of product yield are collected.
Example 6:
the experimental steps are as follows:
290g (5mol, 99%, 10eq) of anhydrous potassium fluoride and 1012g of sulfolane are added into a 2L four-port reaction kettle provided with a mechanical stirring and rectifying condensing device, and the temperature is raised to 150 ℃ by stirring.
172g (98 percent, 0.5mol) of self-made octachlorocyclopentene and 180g of sulfolane are mixed and then are dripped into the system, the dripping time is 2 hours, the temperature of the system is slowly increased in the dripping process, the temperature increasing speed is about 10 ℃/h, the reflux of the system is obvious after the dripping is finished, and the product is extracted from the top end of a rectifying tower.
Keeping the temperature at 170 ℃ after the dripping is finished until no fraction is discharged from the product; the product is cooled to-10-0 ℃ by a low-temperature cooling device in the product collection process.
The octafluorocyclopentene product 65.7g, GC 99.3% and product yield 62% are collected in the example. This example demonstrates that reducing the ratio of fluorinating reagent has a greater effect on yield.
Example 7:
the experimental steps are as follows:
to a 2L four port reactor equipped with a mechanical stirring and rectifying condenser, 348g (6mol, 99%, 12eq) of anhydrous potassium fluoride and 1012g of sulfolane were added, and the temperature was raised to 140 ℃ with stirring.
172g (98 percent, 0.5mol) of self-made octachlorocyclopentene and 180g of sulfolane are mixed and then are dripped into the system, the dripping time is 2 hours, the temperature of the system is slowly increased in the dripping process, the temperature increasing speed is about 10 ℃/h, the reflux of the system is obvious after the dripping is finished, and the product is extracted from the top end of a rectifying tower.
After the dripping is finished, keeping the temperature at 170 ℃ until no fraction is discharged from the product, wherein the time is 2 hours; the product is cooled to-10-0 ℃ by a low-temperature cooling device in the product collection process.
The octafluorocyclopentene product 81.6g, GC 99.2% and product yield 77% are collected in the example. This example demonstrates a fluorination reagent ratio of 10: 1 to 12: 1 does not contribute much to the yield.
And (3) solvent recovery:
and (3) cooling the rectified kettle residue to 60 ℃, centrifuging, washing a filter cake with 100mL of ethanol, wherein the filter cake mainly comprises potassium chloride, potassium fluoride and a small amount of solvent, and is light yellow and is discarded as solid waste.
And (3) carrying out reduced pressure distillation on the filtrate and the washing liquid by using an oil pump and a water pump respectively, recovering sulfolane and ethanol, wherein the recovered solvent can be reused for many times, and the recovery rate of the solvent is more than 90%.
Claims (7)
1. An industrial production method of octafluorocyclopentene is characterized by comprising the following steps: first step, chlorination reaction: introducing chlorine into the cyclopentene, performing addition to obtain 1, 2-dichlorocyclopentane, continuously introducing the chlorine, heating the reaction to 70 ℃ for reaction to obtain 1,2,3, 4-tetrachlorocyclopentane, continuously heating the reaction to 180 ℃ and 210 ℃ for reaction to obtain a crude octachlorocyclopentene product; and step two, substitution fluorination: after anhydrous potassium fluoride and sulfolane are mixed, the temperature is controlled at 140-.
2. The industrial production method of octafluorocyclopentene according to claim 1, wherein: in the first-step chlorination reaction, the reaction is carried out in the absence of a solvent, and the equivalent ratio of chlorine to cyclopentene is 18-20: 1.
3. the industrial production method of octafluorocyclopentene according to claim 1, wherein: in the first-step chlorination reaction, the crude octachlorocyclopentene is subjected to a reduced pressure rectification mode to obtain a pure octachlorocyclopentene.
4. The industrial production method of octafluorocyclopentene according to claim 1, wherein: in the second step of substitution fluorination, the molar ratio of anhydrous potassium fluoride to octachlorocyclopentene is 10-12: 1.
5. the industrial production method of octafluorocyclopentene according to claim 1, wherein: in the second step of the substitution fluorination, octafluorocyclopentene is synthesized by adopting a mode of rectifying a product while reacting, and is received by adopting a low-temperature cooling device.
6. The industrial production method of octafluorocyclopentene according to claim 1, wherein: and centrifuging and distilling the material obtained after the product is subjected to reactive distillation in the second step under reduced pressure to obtain a solvent for recycling in the next batch.
7. The industrial production method of octafluorocyclopentene according to claim 6, wherein the solvent application operation specifically comprises: naturally cooling the material after the fluorination reaction rectification product to 50-70 ℃, obtaining centrifugate and filter cake containing a large amount of potassium chloride and a small amount of potassium fluoride through centrifugal filtration, leaching the filter cake with ethanol, retaining leacheate, respectively recovering the sulfolane solution and the ethanol leacheate under reduced pressure, and recycling the obtained solvent for next use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711389280.XA CN108276243B (en) | 2017-12-20 | 2017-12-20 | Industrial production method of octafluorocyclopentene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711389280.XA CN108276243B (en) | 2017-12-20 | 2017-12-20 | Industrial production method of octafluorocyclopentene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108276243A CN108276243A (en) | 2018-07-13 |
| CN108276243B true CN108276243B (en) | 2020-08-11 |
Family
ID=62801903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711389280.XA Active CN108276243B (en) | 2017-12-20 | 2017-12-20 | Industrial production method of octafluorocyclopentene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108276243B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563545B (en) * | 2019-08-29 | 2021-10-22 | 浙江博瑞电子科技有限公司 | Continuous industrial preparation method of octafluorocyclopentene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB703202A (en) * | 1951-10-16 | 1954-01-27 | Bataafsche Petroleum | Processes for the preparation of polychloro alicyclic compounds |
| CN1270575A (en) * | 1997-09-17 | 2000-10-18 | 森陶硝子株式会社 | Method for producing perhalogenated cyclopentene |
| KR100796067B1 (en) * | 2006-05-09 | 2008-01-21 | 울산화학주식회사 | Dry etching gas for semiconductor manufacturing and manufacturing method thereof |
| CN105439806A (en) * | 2015-11-24 | 2016-03-30 | 北京宇极科技发展有限公司 | Novel octafluorocyclopentene preparation method |
| CN107188778A (en) * | 2017-05-18 | 2017-09-22 | 北京宇极科技发展有限公司 | The preparation method of octafluoro cyclopentene |
-
2017
- 2017-12-20 CN CN201711389280.XA patent/CN108276243B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB703202A (en) * | 1951-10-16 | 1954-01-27 | Bataafsche Petroleum | Processes for the preparation of polychloro alicyclic compounds |
| CN1270575A (en) * | 1997-09-17 | 2000-10-18 | 森陶硝子株式会社 | Method for producing perhalogenated cyclopentene |
| KR100796067B1 (en) * | 2006-05-09 | 2008-01-21 | 울산화학주식회사 | Dry etching gas for semiconductor manufacturing and manufacturing method thereof |
| CN105439806A (en) * | 2015-11-24 | 2016-03-30 | 北京宇极科技发展有限公司 | Novel octafluorocyclopentene preparation method |
| CN107188778A (en) * | 2017-05-18 | 2017-09-22 | 北京宇极科技发展有限公司 | The preparation method of octafluoro cyclopentene |
Non-Patent Citations (1)
| Title |
|---|
| 八氟环戊烯的制备;徐卫国;《有机氟工业》;20061231(第2期);第24-25页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108276243A (en) | 2018-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2020530051A (en) | Polyetherketone Methods for producing ketones | |
| TWI698423B (en) | Method of synthesizing 2,2,4,4-tetramethyl-1,3-cyclobutadione | |
| KR102364274B1 (en) | Continuous process for the preparation of 2-methylallyl alcohol | |
| CN110937979B (en) | Method for separating and purifying fluorobenzene by extractive distillation | |
| CN108164390B (en) | Industrial production method of perfluorocyclopentene | |
| EP3655458A1 (en) | Purification of poly ether ketone ketone by centrifugal filtration | |
| CN113896614B (en) | Method for continuously synthesizing chlorobutane in non-aqueous system | |
| CN104402709B (en) | Paraphthaloyl chloride production technology and process units thereof | |
| CN108276243B (en) | Industrial production method of octafluorocyclopentene | |
| CN107459472A (en) | Method for refining dimethyl sulfoxide solvent in carbon fiber precursor production process | |
| CN105384596A (en) | Preparation method of vinylidene fluoride (VDF) | |
| CN115772069A (en) | Synthesis method of vinyl methyl ether | |
| CN104529721B (en) | Industrial preparation method of sevoflurane | |
| CN112441926B (en) | Method for co-producing m-methylbenzoic acid nitride and m-phthalic acid | |
| CN109400506B (en) | Synthesis method of high-purity chlorosulfonyl isocyanate | |
| CN116216647B (en) | Method for preparing anhydrous hydrogen fluoride green by using aqueous hydrofluoric acid through multistage sulfuric acid analysis method | |
| CN108017574B (en) | A kind of method of the chloro- 2,4,6- trifluoromethyl pyridine continuous production of fluroxypramide intermediate 3,5- bis- | |
| JPH05507688A (en) | Method for producing 1,1-dichloro-1-fluoroethane | |
| CN101052616A (en) | Method for producing fluorine-containing fluorosulfonyl alkylvinyl ether | |
| CN111187145B (en) | Preparation method of hexafluorobutadiene | |
| JP4817542B2 (en) | Production method of fluorinated vinyl ether | |
| CN112409127A (en) | Water removal method in tetrachloroethylene production process | |
| CN114409499B (en) | Process for preparing 1, 1-difluoroethylene | |
| CN111518033B (en) | Preparation method of 4,6-dichloropyrimidine | |
| CN111333490A (en) | Method for removing butyraldehyde impurities in ethanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |