CN112409130A - Production process of 2, 2-difluoropropanol - Google Patents
Production process of 2, 2-difluoropropanol Download PDFInfo
- Publication number
- CN112409130A CN112409130A CN202010973203.4A CN202010973203A CN112409130A CN 112409130 A CN112409130 A CN 112409130A CN 202010973203 A CN202010973203 A CN 202010973203A CN 112409130 A CN112409130 A CN 112409130A
- Authority
- CN
- China
- Prior art keywords
- difluoropropanol
- methanol
- reaction
- difluorochloroethylene
- rectifying
- 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.)
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- CKLONJANQGBREW-UHFFFAOYSA-N 2,2-difluoropropan-1-ol Chemical compound CC(F)(F)CO CKLONJANQGBREW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 15
- HTHNTJCVPNKCPZ-UHFFFAOYSA-N 2-chloro-1,1-difluoroethene Chemical group FC(F)=CCl HTHNTJCVPNKCPZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical group CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- PMWGIVRHUIAIII-UHFFFAOYSA-N 2,2-difluoropropanoic acid Chemical compound CC(F)(F)C(O)=O PMWGIVRHUIAIII-UHFFFAOYSA-N 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 229940017219 methyl propionate Drugs 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- OIQOUHIUUREZOM-UHFFFAOYSA-N 1,1-dichloro-1,2-difluoroethane Chemical compound FCC(F)(Cl)Cl OIQOUHIUUREZOM-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- -1 dicumyl hydroperoxide Chemical compound 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
-
- 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
- C07C29/58—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of halogen, e.g. by hydrogenolysis, splitting-off
-
- 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
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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 a production process of 2, 2-difluoropropanol, which comprises the following steps: with N2Replacing air in the autoclave, adding methanol and a cross-linking agent, heating to 130 ℃, slowly introducing difluorochloroethylene under 0.5MPa, controlling the kettle pressure not to exceed 0.5MPa, and reacting for 24 hours; step two, hydrogenation reaction: adding catalyst palladium-carbon into a reaction kettle, using methanol as a solvent, adding triethylamine, introducing hydrogen, pressurizing to 2MPa, reacting for 24 hours at 110 ℃, filtering and recovering the palladium-carbon after the reaction is finished, and rectifying at 95 ℃ and normal pressure to recover the methanol; rectifying at 120 deg.C under normal pressure to obtainAnd (5) producing the product. Compared with the traditional 2, 2-difluoropropionate reduction method, the method has the advantages of cheap raw materials, less three wastes, high yield of the prepared product, good purity, easily obtained raw materials, simple process, good stability and simple requirement on equipment, and the prepared 2, 2-difluoropropanol is more suitable for industrial production.
Description
Technical Field
The invention particularly relates to a production process of 2, 2-difluoropropanol.
Background
Difluorodichloroethane (R132b) is a byproduct in industrial production of R123a, and in recent years, with the application of R123a, the waste of fluorine resources caused by the treatment of R132b as hazardous waste is increasing. The invention synthesizes difluorochloroethylene prepared by R132b into 2, 2-propanol, which is an important way to change waste into valuable.
The traditional 2, 2-propanol process is to use 2, 2-difluoro methyl propionate to reduce and generate 2, 2-propanol, but the preparation of 2, 2-difluoro methyl propionate needs to use expensive dust reagent, so that the cost of 2, 2-propanol is greatly increased. Compared with the traditional reduction method using 2, 2-difluoro methyl propionate, the process has the advantages of cheap raw materials, less three wastes, high yield of prepared products, good purity, easily obtained raw materials, simple process, good stability and simple requirement on equipment, and the prepared 2, 2-difluoro propanol is more suitable for industrial production.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the defects of the prior art, the invention provides a production process of 2, 2-difluoropropanol.
The technical scheme is as follows: a production process of 2, 2-difluoropropanol comprises the following steps:
step one, addition reaction: with N2Replacing air in the autoclave, adding methanol and a cross-linking agent, heating to 130 ℃, slowly introducing difluorochloroethylene under 0.5MPa, controlling the kettle pressure not to exceed 0.5MPa, and reacting for 24 hours;
step two, hydrogenation reaction: adding catalyst palladium carbon into a reaction kettle, wherein the mass ratio of difluorochloroethylene to palladium carbon is 1: 0.5, taking methanol as a solvent, adding triethylamine, wherein the mass ratio of the triethylamine to the difluorochloroethylene is 2: 1, introducing hydrogen, pressurizing to 2MPa, reacting for 24 hours at 110 ℃, filtering and recovering palladium-carbon after the reaction is finished, and rectifying and recovering methanol at 95 ℃ and normal pressure; rectifying at 120 ℃ and normal pressure to obtain the product 2, 2-difluoropropanol.
As an optimization: in the first step, the more crosslinking agents used in production are dicumyl peroxide, benzoyl peroxide, dicumyl hydroperoxide and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane. The invention determines that the best effect is achieved when the cross-linking agent is 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
As an optimization: in the first step, the mass ratio of difluorochloroethylene to methanol is controlled to be 1: 1-1: 10, the reaction can be carried out, and the invention determines that the reaction is carried out at a mass ratio of 1: 4-1: the best effect is obtained after 6 times.
As an optimization: in the second step, the acid-binding agent generally comprises organic base and inorganic base, wherein the organic base comprises triethylamine, DIEA, pyridine and the like, and the inorganic base comprises sodium acetate, sodium carbonate, potassium carbonate and the like. The invention determines that triethylamine is used as an acid-binding agent, and the effect of absorbing hydrochloric acid generated by reaction is optimal.
Has the advantages that: the product prepared by the method has the advantages of high yield, good purity, easily obtained raw materials, simple process, good stability and simple requirement on equipment, and the prepared 2, 2-difluoropropanol is more suitable for industrial production.
Detailed Description
Examples
A production process of 2, 2-difluoropropanol comprises the following steps:
step one, addition reaction: with N2Replacing air in the autoclave, adding methanol and a crosslinking agent, wherein the crosslinking agent is 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, heating to 130 ℃, slowly introducing difluorochloroethylene under 0.5MPa, and controlling the mass ratio of the difluorochloroethylene to the methanol to be 1: 4-1: 6, controlling the kettle pressure not to exceed 0.5MPa, and reacting for 24 hours;
step two, hydrogenation reaction: adding catalyst palladium carbon into a reaction kettle, wherein the mass ratio of difluorochloroethylene to palladium carbon is 1: 0.5, taking methanol as a solvent, adding triethylamine, taking triethylamine as an acid-binding agent to absorb hydrochloric acid generated by the reaction, wherein the mass ratio of the triethylamine to the difluorochloroethylene is 2: 1, introducing hydrogen, pressurizing to 2MPa, reacting for 24 hours at 110 ℃, filtering and recovering palladium-carbon after the reaction is finished, and rectifying and recovering methanol at 95 ℃ and normal pressure; rectifying at 120 ℃ and normal pressure to obtain the product 2, 2-difluoropropanol.
The product prepared by the method has the advantages of high yield, good purity, easily obtained raw materials, simple process, good stability and simple requirement on equipment, and the prepared 2, 2-difluoropropanol is more suitable for industrial production.
The technical solutions in the embodiments of the present invention are clearly and completely described above, so that those skilled in the art can better understand the advantages and features of the present invention, and thus the protection scope of the present invention is more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Claims (4)
1. A production process of 2, 2-difluoropropanol is characterized in that: the method comprises the following steps:
step one, addition reaction: with N2Replacing air in the autoclave, adding methanol and a cross-linking agent, heating to 130 ℃, slowly introducing difluorochloroethylene under 0.5MPa, controlling the kettle pressure not to exceed 0.5MPa, and reacting for 24 hours;
step two, hydrogenation reaction: adding catalyst palladium carbon into a reaction kettle, wherein the mass ratio of difluorochloroethylene to palladium carbon is 1: 0.5, taking methanol as a solvent, adding triethylamine, wherein the mass ratio of the triethylamine to the difluorochloroethylene is 2: 1, introducing hydrogen, pressurizing to 2MPa, reacting for 24 hours at 110 ℃, filtering and recovering palladium-carbon after the reaction is finished, and rectifying and recovering methanol at 95 ℃ and normal pressure; rectifying at 120 ℃ and normal pressure to obtain the product 2, 2-difluoropropanol.
2. The process for the production of 2, 2-difluoropropanol according to claim 1, characterized in that: in the first step, the cross-linking agent is 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
3. The process for the production of 2, 2-difluoropropanol according to claim 1, characterized in that: in the first step, the mass ratio of difluorochloroethylene to methanol is controlled to be 1: 4-1: 6.
4. the process for the production of 2, 2-difluoropropanol according to claim 1, characterized in that: and in the second step, triethylamine is used as an acid-binding agent to absorb hydrochloric acid generated by the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010973203.4A CN112409130A (en) | 2020-09-16 | 2020-09-16 | Production process of 2, 2-difluoropropanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010973203.4A CN112409130A (en) | 2020-09-16 | 2020-09-16 | Production process of 2, 2-difluoropropanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112409130A true CN112409130A (en) | 2021-02-26 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010973203.4A Pending CN112409130A (en) | 2020-09-16 | 2020-09-16 | Production process of 2, 2-difluoropropanol |
Country Status (1)
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1020421A1 (en) * | 1997-05-19 | 2000-07-19 | Daiso Co., Ltd. | Process for producing 1,2-propanediol |
| CN106866352A (en) * | 2015-12-14 | 2017-06-20 | 浙江蓝天环保高科技股份有限公司 | A kind of preparation method of the fluoro- 2- vinyl chloride of 1,1- bis- |
| CN107400040A (en) * | 2017-07-21 | 2017-11-28 | 山东飞源新材料有限公司 | A kind of preparation method of the propane diols of 2,2 difluoro 1,3 |
| CN109265313A (en) * | 2018-11-13 | 2019-01-25 | 山东华安新材料有限公司 | A kind of method that difluoro dichloroethanes synthesizes two polytrifluoromonochlorethylenes |
| CN110240536A (en) * | 2018-03-07 | 2019-09-17 | 北京先锋创新科技发展有限公司 | A kind of production of vinyl chloride and process for refining |
| CN110668918A (en) * | 2019-10-22 | 2020-01-10 | 邹平铭兴化工有限公司 | Chemical synthesis method of 3-chloro-1-propanol |
-
2020
- 2020-09-16 CN CN202010973203.4A patent/CN112409130A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1020421A1 (en) * | 1997-05-19 | 2000-07-19 | Daiso Co., Ltd. | Process for producing 1,2-propanediol |
| CN106866352A (en) * | 2015-12-14 | 2017-06-20 | 浙江蓝天环保高科技股份有限公司 | A kind of preparation method of the fluoro- 2- vinyl chloride of 1,1- bis- |
| CN107400040A (en) * | 2017-07-21 | 2017-11-28 | 山东飞源新材料有限公司 | A kind of preparation method of the propane diols of 2,2 difluoro 1,3 |
| CN110240536A (en) * | 2018-03-07 | 2019-09-17 | 北京先锋创新科技发展有限公司 | A kind of production of vinyl chloride and process for refining |
| CN109265313A (en) * | 2018-11-13 | 2019-01-25 | 山东华安新材料有限公司 | A kind of method that difluoro dichloroethanes synthesizes two polytrifluoromonochlorethylenes |
| CN110668918A (en) * | 2019-10-22 | 2020-01-10 | 邹平铭兴化工有限公司 | Chemical synthesis method of 3-chloro-1-propanol |
Non-Patent Citations (4)
| Title |
|---|
| BRUNO AMEDURI ET AL: "Synthesis of fluorinated telomers Part 7.Telomerization of 1,1-difluoro-2-chloroethylene and 1,2-difluoro-1,2 dichloroethylene with methanol", 《NEW J. CHEM》 * |
| BRUNO AMEDURI 等: "Synthesis of fluorinated telomers Part 7.Telomerization of 1,1-difluoro-2-chloroethylene and 1,2-difluoro-1,2 dichloroethylene with methanol" * |
| 刘鹰翔: "《药物合成反应新世纪第2版》", 31 August 2017, 中国中医药出版社 * |
| 罗代暄等: "《化学试剂与精细化学品合成基础有机分册》", 31 May 1991, 高等教育出版社 * |
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