CN104177219A - Method for preparing 1,3,3,3-tetrafluoropropene - Google Patents
Method for preparing 1,3,3,3-tetrafluoropropene Download PDFInfo
- Publication number
- CN104177219A CN104177219A CN201410377685.1A CN201410377685A CN104177219A CN 104177219 A CN104177219 A CN 104177219A CN 201410377685 A CN201410377685 A CN 201410377685A CN 104177219 A CN104177219 A CN 104177219A
- Authority
- CN
- China
- Prior art keywords
- tetrafluoeopropene
- reaction
- aqueous solution
- preparing
- pentafluoropropane
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 1,3,3,3-tetrafluoropropene. The method comprises the following preparation procedures: firstly, adding 350-550g of alkaline aqueous solution into a reactor, and adding a solvent into the reactor, so as to form a solvent system for reaction; then, heating to the reaction temperature of 10-150 DEG C while stirring, adding 100-320g of 1,1,1,3,3-pentafluoropropane into the reactor after the heating is ended, and controlling the mole ratio of alkali in the alkaline aqueous solution and 1,1,1,3,3-pentafluoropropane to (0.75-7): 1; then, starting to react for 5-60 minutes, thereby finally producing the reaction product 1,3,3,3-tetrafluoropropene. According to the method, improvement is carried out based on the prior art, and the disadvantages of the existing 1,3,3,3-tetrafluoropropene preparation methods are overcome; 1,1,1,3,3-pentafluoropropane is selected as a reaction raw material and is added into the solvent containing alkaline aqueous solution for reacting, and 1,3,3,3-tetrafluoropropene is prepared finally; not only is the production efficiency remarkably increased, but also the preparation process is more economical and environment-friendly.
Description
Technical field
The present invention relates to a kind of method of preparing tetrafluoroethylene, especially relate to the method for utilizing 1,1,1,3,3-pentafluoropropane (HFC-245fa) to prepare 1,3,3,3-tetrafluoeopropene (HFC-1234ze).
Background technology
1,3,3,3-tetrafluoeopropene, has the latent value (GWP) of lower Greenhouse effect and the latent value (ODP) of zero ozone depletion, is considered to the most potential and substitutes 1,1, the 4th generation ODS substitute of 1,2-Tetrafluoroethane (HFC-134a), is widely used as refrigeration agent, whipping agent, aerosol propellant, solvent etc.In addition, 1,3,3,3-tetrafluoeopropene (HFC-1234ze) is the synthetic basic raw material with high thermal stability high-elasticity thermoplastic material, and aromatic hydrocarbons and aliphatics are had to unreactiveness, easily sulfuration, can make Coating Materials, high temperature resistant resistance to thermal insulation material, is widely used in the fields such as fire-fighting, space flight, aviation.
The known tetrafluoeopropene compound of preparing has several different methods.For example, patent US6548719B1 discloses, under phase-transfer catalyst effect, chemical formula is that the compound of CF3C (R1aR2b) C (R3cR4d) classification adopts at least one alkali metal hydroxide dehydrohalogenation to prepare the method for multiple fluoroolefins compounds, wherein R substituting group is as defined in this patent, and condition is wherein to have at least one hydrogen and on adjacent carbons, have a halogen.Disclose a kind of effectively and when being applicable to prepare the method for multiple tetrafluoeopropene compounds, this patent is not specifically openly prepared the method for 1,3,3,3-tetrafluoeopropene.Multiple preparation 1,3,3 is disclosed in patent CN200580020412.0, the method for 3-tetrafluoeopropene, the method is included under phase-transfer catalyst effect, and making chemical formula is compound dehydrohalogenation in alkali aqueous solution of CF3CH2CHFX class.The defect that this method need to be used expensive phase-transfer catalyst, has long reaction time, yield is low.
In the patents such as patent US5986151, US6124510, EP974571, CN200480027096.5, CN200780023672.2, disclose and a kind ofly prepared 1,3,3, the method of 3-tetrafluoeopropene, the method is included under the effect of metal catalyst, gas phase makes CF3CH2CF2H (HFC-245fa) dehydrofluorination, being included at relatively high temperature makes CF3CH2CF2H (HFC-245fa) contact time enough with catalyzer, make CF3CH2CF2H (HFC-245fa) change into 1,3,3,3-tetrafluoeopropene.These class methods all need to use catalyzer, and exist temperature of reaction higher, the easy coking and deactivation of catalyzer, and the continuous production cycle is shorter, the not high defect of transformation efficiency.
The method of preparation 1,3,3,3-tetrafluoeopropene is disclosed in the patents such as patent US5986151, US6124510, US6548719B1, EP974571, CN200480027096.5.These methods produce 1,3,3 for take CF3CH2CF2H (HFC-245fa) in caustic solution as raw material dehydrofluorination, and 3-tetrafluoeopropene, all exists the defect that long reaction time or reaction yield are low.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing 1,3,3,3-tetrafluoeopropene, present method is improved on existing basis, overcomes existing preparation 1,3,3, the shortcoming in 3-tetrafluoeopropene method.Selecting 1,1,1,3,3-pentafluoropropane is reaction raw materials, and 1,1,1,3,3-pentafluoropropane is added in the alkaline aqueous solution that contains solvent and reacted, and finally makes 1,3,3,3-tetrafluoeopropene.Not only production efficiency significantly improves, and preparation process environmental protection more economically.
In order to solve the problems of the technologies described above, adopt following technical scheme:
A kind of method of preparing 1,3,3,3-tetrafluoeopropene, is characterized in that comprising the process of being prepared as follows: first in reactor, add 350g～550g alkaline aqueous solution, and add solvent to reactor, form the solvent system of reaction; Then warming while stirring, to 10 ℃～150 ℃ of temperature of reaction, after intensification finishes, is added 1,1 of 100g～320g to reactor, 1,3,3-pentafluoropropane, controls the alkali and 1 in alkaline aqueous solution, the mol ratio of 1,1,3,3-pentafluoropropane is in (0.75～7): in 1 scope; Then start reaction, the reaction times is 5min～60min, final formation reaction product 1,3,3,3-tetrafluoeopropene.
Preferably, alkaline aqueous solution comprises aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical and composition thereof.Alkaline aqueous solution choose object variation, draw materials conveniently.
Preferably, the alkali weight concentration of alkaline aqueous solution is 5%～50%.Within the scope of this alkali concn, the solubility property of alkaline aqueous solution is best, has the function that promotes reaction.
Preferably, solvent comprises the organism, the organism that contains alkyl and aryl ethers that contain alkyl and aryl nitrile, contains organism of sulfoxide and composition thereof.The scope of selecting material of solvent is wide, therefore draw materials conveniently.
Preferably, solvent comprises acetonitrile, adiponitrile, 2-methyltetrahydrofuran, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), tetramethylene sulfone, diethylene glycol dimethyl ether and composition thereof.The scope of selecting material of solvent is wide, therefore draw materials conveniently.
Preferably, temperature of reaction is preferably 30 ℃～100 ℃.In this range of reaction temperature, speed of response, transformation efficiency the best, react comparatively steady.
Preferably, the reaction times is preferably 10min～30min.In this reaction time range, speed of response, transformation efficiency the best, reaction cost is lower, can avoid causing because the reaction times is long cost to increase.
Preferably, the mol ratio of the alkali in alkaline aqueous solution and 1,1,1,3,3-pentafluoropropane is preferably (1～5): 1.In this molar ratio range, the solute effect of 1,1,1,3,3-pentafluoropropane is best.
Owing to adopting technique scheme, there is following beneficial effect:
The present invention is a kind of method of preparing 1,3,3,3-tetrafluoeopropene, and present method is improved on existing basis, overcomes existing preparation 1,3,3, the shortcoming in 3-tetrafluoeopropene method.Selecting 1,1,1,3,3-pentafluoropropane is reaction raw materials, and 1,1,1,3,3-pentafluoropropane is added in the alkaline aqueous solution that contains solvent and reacted, and finally makes 1,3,3,3-tetrafluoeopropene.Not only production efficiency significantly improves, and preparation process environmental protection more economically.
Solvent has solubilization-aid effect, and 1,1,1,3,3-pentafluoropropane is not easy to dissolve in alkaline aqueous solution, adds after solvent, and solvent can help 1,1,1,3,3-pentafluoropropane is dissolved in alkaline aqueous solution, can effectively promote reaction, and speed of response, production efficiency etc. all has remarkable lifting.In reaction, water or inorganic phase be because alkali lye exists, and organic phase is solvent and a small amount of 1,1,1,3,3-pentafluoropropane, and upper organic phase can be returned reactive system and again be participated in reaction, therefore reduced solvent load, significantly reduces production costs.Simultaneously the present invention have equipment requirements simple, produce easily control, side reaction is few, solvent can recycled, production cost is lower, the advantage that yield is high.1,3,3 of reaction production, the yield of 3-tetrafluoeopropene can reach more than 95%.
Embodiment
The present invention is a kind of method of preparing 1,3,3,3-tetrafluoeopropene, and selecting 1,1,1,3,3-pentafluoropropane is that reaction raw materials prepares 1,3,3,3-tetrafluoeopropene by a series of technical process.Prepare 1,3,3,3-tetrafluoeopropene comprises its cis-isomeride and trans-isomer(ide), the chemical equation of its reaction is:
During preparation, first prepare an autoclave, this autoclave is comprised of mechanical stirrer and reflux exchanger.Should previously prepared alkaline aqueous solution before starting to feed intake: solid alkali is comprised to sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood or their mixture put in a certain amount of water, stirring prepares alkaline aqueous solution, and the weight concentration of controlling alkali by dilute with water is in 5%～50% scope, because within the scope of this alkali concn, the solubility property of alkaline aqueous solution is best, has the function that promotes reaction.
Prepare after alkaline aqueous solution, this alkaline aqueous solution is put in reactor, input amount is controlled within the scope of 350g～550g.Then to reactor, add solvent, solvent species is numerous, solvent is organism and must contains alkyl and aryl nitrile, alkyl and aryl ethers or these groups of sulfoxide, therefore be mainly taken from nitrile organism, ethers organism, sulfoxide type organism or their mixture.Concretely, solvent is selected from acetonitrile, propionitrile, butyronitrile, methyl cellosolve acetate glutaronitrile, adiponitrile, cyanobenzene, carbonic acid 1,2-ethyl, carbonic acid 1, the sub-propyl ester of 2-, methyl ethyl ketone, methyl isoamyl ketone, diisobutyl ketone, methyl-phenoxide, 2-methyltetrahydrofuran, tetrahydrofuran (THF), dioxane, diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, tetramethylene sulfone, dimethyl formamide, dimethyl sulfoxide (DMSO), perfluor-N-methylmorpholine or its mixture.Through experiment, obtain excellent preferred solvent and comprise acetonitrile, adiponitrile, 2-methyltetrahydrofuran, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), tetramethylene sulfone, diethylene glycol dimethyl ether or its mixture.
Add solvent in reactor after, form the solvent system that is applicable to reaction, then to the material warming while stirring in reactor, and be finally warming up to 10 ℃～150 ℃ of temperature of reaction, through experiment, obtaining preferred temperature of reaction is 30 ℃～100 ℃.Be warming up to after temperature of reaction, in reactor, add 1,1,1,3 of 100g～320g, 3-pentafluoropropane.In the final reaction system forming, the mol ratio of the alkali in alkaline aqueous solution and 1,1,1,3,3-pentafluoropropane is in (0.75～7): in 1 scope, obtain its preferred molar ratio for (1～5): 1 through experiment; The weight of solvent is 0.1～1 times of 1,1,1,3,3-pentafluoropropane weight.
After above-mentioned all raw materials have added, off-response still starts reaction, and the reaction times is controlled at 5min～60min, and through experiment, obtaining the preferred reaction time is 10min～30min.Finally obtain reaction product, and utilize straight cold finger Direct Sampling to on-line gas chromatography analyser, analytical reaction product component.
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1:
To the potassium hydroxide solution 380g that adds 50% in the autoclave being comprised of mechanical stirrer, reflux exchanger, dimethyl sulfoxide (DMSO) 200g, stirs and is warming up to 100 ℃, by dipping tube, adds 1,1,1,3,3-pentafluoropropane 300g.After 10min in straight cold finger place Direct Sampling to on-line gas chromatography analysis, have an appointment 99.49% 1,3,3,3-tetrafluoeopropene, 0.22% 1,1,1,3,3-pentafluoropropane.
This embodiment obtain 1,3,3,3-tetrafluoeopropene very high purity, impurity content is few, compares its speed of response, transformation efficiency has obvious lifting with existing preparation method.
Embodiment 2
To the sodium hydroxide solution 400g that adds 50% in the autoclave being comprised of mechanical stirrer, reflux exchanger, tetrahydrofuran (THF) 50g, stirs and is warming up to 45 ℃, by dipping tube, adds 1,1,1,3,3-pentafluoropropane 150g.After 20min in straight cold finger place Direct Sampling to on-line gas chromatography analysis, have an appointment 95.18% 1,3,3,3-tetrafluoeopropene, 1.78% 1,1,1,3,3-pentafluoropropane.
This embodiment obtain 1,3,3,3-tetrafluoeopropene purity is higher, impurity content is less, comparing its speed of response, transformation efficiency with existing preparation method all has faint lifting.
Embodiment 3
To the sodium carbonate solution 400g that adds 25% in the autoclave being comprised of mechanical stirrer, reflux exchanger, acetonitrile 100g, stirs and is warming up to 60 ℃, by dipping tube, adds 1,1,1,3,3-pentafluoropropane 168g.After 15min in straight cold finger place Direct Sampling to on-line gas chromatography analysis, have an appointment 96.21% 1,3,3,3-tetrafluoeopropene, 1.69% 1,1,1,3,3-pentafluoropropane.
This embodiment obtain 1,3,3,3-tetrafluoeopropene purity is high, impurity content is few, comparing its speed of response, transformation efficiency with existing preparation method all has lifting.
Embodiment 4
To the solution of potassium carbonate 400g that adds 40% in the autoclave being comprised of mechanical stirrer, reflux exchanger, tetramethylene sulfone 100g, stirs and is warming up to 60 ℃, by dipping tube, adds 1,1,1,3,3-pentafluoropropane 150g.After 30min in straight cold finger place Direct Sampling to on-line gas chromatography analysis, have an appointment 98.32% 1,3,3,3-tetrafluoeopropene, 1.43% 1,1,1,3,3-pentafluoropropane.
This embodiment obtain 1,3,3,3-tetrafluoeopropene purity is high, impurity content is few, comparing its speed of response, transformation efficiency with existing preparation method all has remarkable lifting.
Embodiment 5
To the potassium hydroxide solution 500g that adds 20% in the autoclave being comprised of mechanical stirrer, reflux exchanger, dimethyl sulfoxide (DMSO) 50g, stirs and is warming up to 100 ℃, by dipping tube, adds 1,1,1,3,3-pentafluoropropane 150g.After 30min in straight cold finger place Direct Sampling to on-line gas chromatography analysis, have an appointment 97.82% 1,3,3,3-tetrafluoeopropene, 2.00% 1,1,1,3,3-pentafluoropropane.
This embodiment obtain 1,3,3,3-tetrafluoeopropene purity is high, impurity content is few, comparing its speed of response, transformation efficiency with existing preparation method all has remarkable lifting.
These are only specific embodiments of the invention, but technical characterictic of the present invention is not limited to this.Anyly take the present invention as basis, for solving essentially identical technical problem, realize essentially identical technique effect, done ground simple change, be equal to and replace or modification etc., be all covered by among protection scope of the present invention.
Claims (8)
1. a method of preparing 1,3,3,3-tetrafluoeopropene, is characterized in that comprising the process of being prepared as follows: first in reactor, add 350g～550g alkaline aqueous solution, and add solvent to described reactor, form the solvent system of reaction; Then warming while stirring, to 10 ℃～150 ℃ of temperature of reaction, after intensification finishes, is added 1,1 of 100g～320g to described reactor, 1,3,3-pentafluoropropane, controls the alkali and described 1 in described alkaline aqueous solution, the mol ratio of 1,1,3,3-pentafluoropropane is in (0.75～7): in 1 scope; Then start reaction, the reaction times is 5min～60min, final formation reaction product 1,3,3,3-tetrafluoeopropene.
2. a kind of method of preparing 1,3,3,3-tetrafluoeopropene according to claim 1, is characterized in that: described alkaline aqueous solution comprises aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical and composition thereof.
3. a kind of method of preparing 1,3,3,3-tetrafluoeopropene according to claim 1, is characterized in that: the alkali weight concentration of described alkaline aqueous solution is 5%～50%.
4. a kind of method of preparing 1,3,3,3-tetrafluoeopropene according to claim 1, is characterized in that: described solvent comprises the organism, the organism that contains alkyl and aryl ethers that contain alkyl and aryl nitrile, contains organism of sulfoxide and composition thereof.
5. a kind ofly according to claim 4 prepare 1,3, the method of 3,3-tetrafluoeopropene, is characterized in that: described solvent comprises acetonitrile, adiponitrile, 2-methyltetrahydrofuran, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), tetramethylene sulfone, diethylene glycol dimethyl ether and composition thereof.
6. a kind of method of preparing 1,3,3,3-tetrafluoeopropene according to claim 1, is characterized in that: described temperature of reaction is preferably 30 ℃～100 ℃.
7. a kind of method of preparing 1,3,3,3-tetrafluoeopropene according to claim 1, is characterized in that: the described reaction times is preferably 10min～30min.
8. a kind of method of preparing 1,3,3,3-tetrafluoeopropene according to claim 1, is characterized in that: the alkali in described alkaline aqueous solution and described 1,1,1,3, the mol ratio of 3-pentafluoropropane is preferably (1～5): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410377685.1A CN104177219B (en) | 2014-08-01 | 2014-08-01 | A kind of method for preparing 1,3,3,3 tetrafluoropropenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410377685.1A CN104177219B (en) | 2014-08-01 | 2014-08-01 | A kind of method for preparing 1,3,3,3 tetrafluoropropenes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104177219A true CN104177219A (en) | 2014-12-03 |
| CN104177219B CN104177219B (en) | 2018-02-13 |
Family
ID=51958603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410377685.1A Active CN104177219B (en) | 2014-08-01 | 2014-08-01 | A kind of method for preparing 1,3,3,3 tetrafluoropropenes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104177219B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016197280A1 (en) * | 2015-06-11 | 2016-12-15 | 浙江衢州巨新氟化工有限公司 | Method for co-production of 2,3,3,3-tetrafluoropropylene and 1,3,3,3-tetrafluoropropylene |
| JP2018526389A (en) * | 2015-09-11 | 2018-09-13 | ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー | Dehydrohalogenation of hydrochlorofluorocarbons |
| CN112054262A (en) * | 2020-08-28 | 2020-12-08 | 甘肃电气装备集团生物科技工程有限公司 | Leaching solvent suitable for electrolyte in retired lithium battery and method for separating and recycling electrolyte from retired lithium battery by using leaching solvent |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5986151A (en) * | 1997-02-05 | 1999-11-16 | Alliedsignal Inc. | Fluorinated propenes from pentafluoropropane |
| EP0974571A2 (en) * | 1998-07-21 | 2000-01-26 | Elf Atochem North America, Inc. | Preparation of 1,1,1,3-tetrafluoropropene( 1234ze ) |
| CN1589248A (en) * | 2001-09-25 | 2005-03-02 | 霍尼韦尔国际公司 | Process for producing fluoroolefins |
| US7230146B2 (en) * | 2003-10-27 | 2007-06-12 | Honeywell International Inc. | Process for producing fluoropropenes |
| CN102112421A (en) * | 2007-05-22 | 2011-06-29 | 霍尼韦尔国际公司 | Method for producing trans-1, 3, 3, 3-tetrafluoropropene |
| CN103483142A (en) * | 2013-08-29 | 2014-01-01 | 巨化集团技术中心 | Method for realizing liquid-phase continuous preparation of 2,3,3,3-tetrafluoropropene |
-
2014
- 2014-08-01 CN CN201410377685.1A patent/CN104177219B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5986151A (en) * | 1997-02-05 | 1999-11-16 | Alliedsignal Inc. | Fluorinated propenes from pentafluoropropane |
| EP0974571A2 (en) * | 1998-07-21 | 2000-01-26 | Elf Atochem North America, Inc. | Preparation of 1,1,1,3-tetrafluoropropene( 1234ze ) |
| CN1589248A (en) * | 2001-09-25 | 2005-03-02 | 霍尼韦尔国际公司 | Process for producing fluoroolefins |
| US7230146B2 (en) * | 2003-10-27 | 2007-06-12 | Honeywell International Inc. | Process for producing fluoropropenes |
| CN102112421A (en) * | 2007-05-22 | 2011-06-29 | 霍尼韦尔国际公司 | Method for producing trans-1, 3, 3, 3-tetrafluoropropene |
| CN103483142A (en) * | 2013-08-29 | 2014-01-01 | 巨化集团技术中心 | Method for realizing liquid-phase continuous preparation of 2,3,3,3-tetrafluoropropene |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016197280A1 (en) * | 2015-06-11 | 2016-12-15 | 浙江衢州巨新氟化工有限公司 | Method for co-production of 2,3,3,3-tetrafluoropropylene and 1,3,3,3-tetrafluoropropylene |
| JP2018526389A (en) * | 2015-09-11 | 2018-09-13 | ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー | Dehydrohalogenation of hydrochlorofluorocarbons |
| CN112054262A (en) * | 2020-08-28 | 2020-12-08 | 甘肃电气装备集团生物科技工程有限公司 | Leaching solvent suitable for electrolyte in retired lithium battery and method for separating and recycling electrolyte from retired lithium battery by using leaching solvent |
| WO2022041327A1 (en) * | 2020-08-28 | 2022-03-03 | 甘肃电气装备集团生物科技工程有限公司 | Extraction solvent applied to electrolyte in decommissioned lithium battery and method for separating and recovering electrolyte from decommissioned lithium battery by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104177219B (en) | 2018-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11267772B2 (en) | Process for the preparation of 2,3,3,3-tetrafluoropropene | |
| US9102579B2 (en) | Method for producing fluorinated organic compounds | |
| EP2563751B1 (en) | Method for producing tetrafluoropropenes | |
| CN115160988A (en) | Compositions comprising trifluoroethylene | |
| CA2635806A1 (en) | Method for producing fluorinated organic compounds | |
| KR20170115106A (en) | Process for producing 1-chloro-2,3,3-trifluoropropene | |
| CN101913980A (en) | Production method of 1,1,1,3,3-pentachloropropane | |
| CN107522592B (en) | Method for coproducing various halogenated olefins and fluorinated alkanes | |
| CN104177219A (en) | Method for preparing 1,3,3,3-tetrafluoropropene | |
| EP1943204A1 (en) | Method for producing fluorinated organic compounds | |
| CN103880589B (en) | The technique of HFO-1234ze and HFC-245fa is prepared in a kind of coproduction | |
| US20180029961A1 (en) | Method for preparing 2,3,3,3-tetrafluoropropene using methyl magnesium chloride | |
| CN105152850A (en) | Method for synthesizing cis/trans-3,3,3-trifluoro-1-chloropropylene | |
| CN107337576A (en) | Constant temperature catalyzing synthesizes the fluoride trifluoro toluene of 2 bromine 5 | |
| CN105367469A (en) | Tetrabenzylthiuramdisulfide synthesis method | |
| CN104496745B (en) | A kind of preparation method for synthesizing chlorohydrocarbon | |
| CN118439923A (en) | Preparation method of 1,2, 3-tetrachloropropane | |
| CN102476982A (en) | Preparation method for 3-cyclohexene-1-carboxaldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160817 Address after: 324004 Zhejiang Province, Quzhou City Kecheng District Juhua Group Corporation Applicant after: Technology Center of Juhua Group Applicant after: Zhejiang Juhua Research Institute of new materials Co. Ltd. Address before: 324004 Zhejiang Province, Quzhou City Kecheng District Juhua Group Corporation Applicant before: Technology Center of Juhua Group |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |