CN102786386B - Preparation method of 4-chloro-2-fluorotoluene - Google Patents
Preparation method of 4-chloro-2-fluorotoluene Download PDFInfo
- Publication number
- CN102786386B CN102786386B CN201210309120.0A CN201210309120A CN102786386B CN 102786386 B CN102786386 B CN 102786386B CN 201210309120 A CN201210309120 A CN 201210309120A CN 102786386 B CN102786386 B CN 102786386B
- Authority
- CN
- China
- Prior art keywords
- control temperature
- chloro
- hour
- hours
- totally
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 4-chloro-2-fluorotoluene. The preparation method has few steps and is high in yield, and obtained product is high in purity. The preparation method includes the steps of firstly, salifying, mixing anhydrous hydrofluoric acid and 5-chloro-2-methylaniline according to a mole ratio of (2-5):1 in such way that the 5-chloro-2-methylaniline is added dropwise into the anhydrous hydrofluoric acid, allowing for reaction for 1-3 hours at 5-7 DEG C after dropping so as to obtain mixture 1; secondly, diazotizing, adding sodium nitrite into the mixture 1 in such way that the sodium nitrite is added dropwise into the mixture 1, allowing for reaction for 1-3 hours at -3 DEG C to 0 DEG C after addition of the sodium nitrite so as to obtain mixture 2; and thirdly, performing thermolysis, namely heating the mixture 2 at 0-40 DEG C to decompose, wherein the sodium nitrite and the 5-chloro-2-methylaniline used in the step of salifying accord to the mole ratio of (1-1.5):1.
Description
Technical field
The present invention relates to a kind of preparation method of fluorochemicals, particularly relate to the preparation method of the chloro-2-toluene fluoride of 4-.
Background technology
4-chloro-2-toluene fluoride is a kind of important fluorochemicals, and the preparation method of the chloro-2-toluene fluoride of existing 4-comprises the following steps: 1,5-chloro-2-methyl aniline and Sodium Nitrite and hydrochloric acid carry out diazotization reaction; 2, step 1 adds cold fluoroboric acid or ammonium borofluoride, Sodium tetrafluoroborate after completing, and is settled out the NITRODIAZONIUM FLUOROBORATE compared with indissoluble; 3, reheat after separation obtains NITRODIAZONIUM FLUOROBORATE and decompose, obtain the chloro-2-toluene fluoride of 4-.
Above-mentioned preparation method has following shortcoming: the side reaction in step 3 is many, the purity of product and yield are reduced, typical side reaction product comprises goes back original product (that is: hydrogen substituted amido instead of fluorine substituted amido), chlorinated aromatic thing, even summation product (that is: biphenyl) and diazonium tar, diazonium tar refers to a kind of mixture of polyaromatic compound, in above-mentioned preparation method, diazonium tar is the primary product of reaction on the contrary sometimes.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of the chloro-2-toluene fluoride of 4-that a kind of step is few, yield is high, and this preparation method's products obtained therefrom purity is high.
The preparation method of the chloro-2-toluene fluoride of 4-of the present invention, comprises the following steps:
1, salt-forming steps: be (2-5) by mol ratio under the condition of 5-7 DEG C: the anhydrous hydrofluoric acid of 1 and the mixing of 5-chloro-2-methyl aniline, hybrid mode at the uniform velocity to drip whole 5-chloro-2-methyl aniline in 7-10 hour in anhydrous hydrofluoric acid, drip after terminating and under the condition of 5-7 DEG C, react 1-3 hour again, obtain mixture 1; Chemical equation is:
2, diazotation step: add Sodium Nitrite under the condition of-3-0 DEG C in mixture 1, in Sodium Nitrite used and salt-forming steps, the mol ratio of 5-chloro-2-methyl aniline used is (1-1.5): 1, add the mode of Sodium Nitrite at the uniform velocity to drip whole Sodium Nitrite in 8-10 hour in mixture 1, under the condition of-3-0 DEG C, react 1-3 hour again after adding Sodium Nitrite, obtain mixture 2; Chemical equation is:
3, thermal decomposition steps: by mixture 2 thermal degradation under the condition of 0-40 DEG C.Chemical equation is:
The preparation method of the chloro-2-toluene fluoride of 4-of the present invention, wherein described in thermal decomposition steps, thermal degradation is divided into four-stage: the first stage is 5 hours, and control temperature is at 0-18 DEG C; Subordinate phase is 12 hours, and control temperature is at 18-26 DEG C; Phase III is 8 hours, and control temperature is at 26-30 DEG C; Fourth stage is 5 hours, and control temperature is at 30-40 DEG C.
The preparation method of the chloro-2-toluene fluoride of 4-of the present invention, wherein described in thermal decomposition steps, thermal degradation is divided into four-stage:
Totally 5 hours first stage, control temperature is at 0-18 DEG C: the 1 hour control temperature at 0-4 DEG C, and within the 2nd hour, control temperature is at 4-8 DEG C, and within the 3rd hour, control temperature is at 8-12 DEG C, and within the 4th hour, control temperature is at 12-15 DEG C, and within the 5th hour, control temperature is at 15-18 DEG C;
Subordinate phase totally 12 hours, control temperature the 18-26 DEG C: the 1 step totally 2 hours control temperature at 18-21 DEG C, 2nd step totally 2 hours control temperature at 21-23 DEG C, the 3rd step totally 4 hours control temperature at 23-24.5 DEG C, the 4th step totally 4 hours control temperature at 24.5-26 DEG C;
Totally 8 hours phase III, control temperature the 26-30 DEG C: the 1 step totally 2 hours control temperature at 26 DEG C-27 DEG C, the 2nd step totally 2 hours control temperature at 27-28 DEG C, the 3rd step totally 2 hours control temperature at 28-29 DEG C, the 4th step totally 2 hours control temperature at 29-30 DEG C;
Fourth stage totally 5 hours, control temperature is at 30-40 DEG C: the 1 hour control temperature at 30-32 DEG C, and within the 2nd hour, control temperature is at 32-34 DEG C, and within the 3rd hour, control temperature is at 34-36 DEG C, within 4th hour, control temperature is at 36-38 DEG C, and within the 5th hour, control temperature is at 38-40 DEG C.
The preparation method of the chloro-2-toluene fluoride of 4-of the present invention, also comprises following post-processing step after wherein said thermal decomposition steps:
(1) washing neutralization: thermal decomposition steps products therefrom is down to 5 DEG C, stratification, gained upper strata is the chloro-2-toluene fluoride of thick 4-, and lower floor is spent acid, collects the chloro-2-toluene fluoride of thick 4-and carries out washing 3-5 time and add the NaOH aqueous solution after abandoning lower floor's waste water neutralizing;
(2) distill: the chloro-2-toluene fluoride of thick 4-through washing neutralization first carries out heating underpressure distillation, heat under vapour pressure is 0.02-0.05Mpa condition, when temperature reach 98-104 DEG C and backflow material terminate without steam distillation during oil droplet, carry out heating air distillation again, 158 DEG C of later cuts are 4-chloro-2-toluene fluoride finished product.
The preparation method of the chloro-2-toluene fluoride of 4-of the present invention, wherein described in washing neutralization, spent acid carries out hydrofluoric acid recovery according to following steps: mixed with 98 quality % sulfuric acid by spent acid, Sodium Nitrite 1-1.5mol is often used in diazotation step, 2-3mol98 quality % sulfuric acid is added, Distillation recovery hydrofluoric acid in this step.
The preparation method of the chloro-2-toluene fluoride of 4-of the present invention adopts the solvent of anhydrous hydrofluoric acid as reaction and the source of diazonium salt negatively charged ion, thus avoid separation and the transfer of intermediate a tetrafluoro borate, although aryldiazonium fluorochemical is unstable in the solution, but their decomposition can be controlled by control temperature in thermal degradation step, thus minimizing side reaction, improve yield.The 4-prepared by the present invention chloro-2-toluene fluoride purity can reach more than 99%, and yield also can reach 98%.This route is compared with traditional Tetrafluoroboric acid route in addition, has sizable economic advantages.
Below in conjunction with accompanying drawing, the preparation method to the chloro-2-toluene fluoride of 4-of the present invention is described further.
Accompanying drawing explanation
Fig. 1 is the mass spectrum of preparation method's products obtained therefrom of the chloro-2-toluene fluoride of 4-of the present invention;
Fig. 2 is the carbon spectrum nuclear-magnetism figure of preparation method's products obtained therefrom of the chloro-2-toluene fluoride of 4-of the present invention.
Embodiment
Embodiment 1
The preparation method of the chloro-2-toluene fluoride of 4-of the present invention, comprises the following steps:
1, salt-forming steps: at the uniform velocity drip 5-chloro-2-methyl aniline 1mol under the condition of 5-7 DEG C in 2mol anhydrous hydrofluoric acid, dropping process completed in 7 hours, to drip after terminating insulation reaction 1 hour under the condition of 5-7 DEG C again, obtains mixture 1;
2, diazotation step: at the uniform velocity drip 1mol Sodium Nitrite under the condition of-3-0 DEG C in mixture 1, dropping process completed in 8 hours, drips after terminating and reacts 1 hour under the condition of-3-0 DEG C, obtain mixture 2;
3, thermal decomposition steps: by mixture 2 thermal degradation, thermal degradation is divided into following four-stage:
Totally 5 hours first stage, control temperature is at 0-18 DEG C: the 1 hour control temperature at 0-4 DEG C, and within the 2nd hour, control temperature is at 4-8 DEG C, and within the 3rd hour, control temperature is at 8-12 DEG C, and within the 4th hour, control temperature is at 12-15 DEG C, and within the 5th hour, control temperature is at 15-18 DEG C;
Subordinate phase totally 12 hours, control temperature the 18-26 DEG C: the 1 step totally 2 hours control temperature at 18-21 DEG C, 2nd step totally 2 hours control temperature at 21-23 DEG C, the 3rd step totally 4 hours control temperature at 23-24.5 DEG C, the 4th step totally 4 hours control temperature at 24.5-26 DEG C;
Totally 8 hours phase III, control temperature the 26-30 DEG C: the 1 step totally 2 hours control temperature at 26 DEG C-27 DEG C, the 2nd step totally 2 hours control temperature at 27-28 DEG C, the 3rd step totally 2 hours control temperature at 28-29 DEG C, the 4th step totally 2 hours control temperature at 29-30 DEG C;
Fourth stage totally 5 hours, control temperature is at 30-40 DEG C: the 1 hour control temperature at 30-32 DEG C, and within the 2nd hour, control temperature is at 32-34 DEG C, and within the 3rd hour, control temperature is at 34-36 DEG C, within 4th hour, control temperature is at 36-38 DEG C, and within the 5th hour, control temperature is at 38-40 DEG C.
4, washing neutralization: thermal decomposition steps products therefrom is down to 5 DEG C, leave standstill 2 little layereds, gained upper strata is the chloro-2-toluene fluoride of thick 4-, lower floor is spent acid, collect the chloro-2-toluene fluoride of thick 4-and carry out washing 3-5 time, each amount of water is more than 2 times of volumes of the chloro-2-toluene fluoride of thick 4-, adds the 10w/v%NaOH aqueous solution and neutralize after abandoning lower floor's waste water, makes mixed solution reach neutral.
5, distill: the chloro-2-toluene fluoride of thick 4-through washing neutralization first carries out heating underpressure distillation, heat under vapour pressure is 0.02-0.05Mpa condition, when temperature reach 98-104 DEG C and backflow material terminate without steam distillation during oil droplet, carry out heating air distillation again, fraction before 158 DEG C returns washing neutralization procedure, distill with lower batch of material, 158 DEG C of later cuts are 4-chloro-2-toluene fluoride finished product.
6, the recovery of useless hydrofluoric acid: washing neutralization procedure gained spent acid is mixed with the 98 quality % sulfuric acid of 2mol, distillation, distillation temperature in the kettle from low to high, ensure that tower top temperature is in earlier stage at 40-45 DEG C, middle and later periods, tower top temperature control temperature was at 45-55 DEG C, when temperature in the kettle reaches 130 DEG C, insulation distillation, to terminating without during hydrofluoric acid.
The theoretical yield of 4-chloro-2-toluene fluoride finished product is 1mol, actual obtains 0.98mol, and yield is 98%, and the purity of the chloro-2-toluene fluoride of gas chromatographic detection gained 4-is 99.9%, mass spectrum as Fig. 1, carbon spectrum nuclear-magnetism figure (
13cNMR) as Fig. 2, determine that products obtained therefrom is the chloro-2-toluene fluoride of 4-.
Embodiment 2
Be prepared according to the preparation method of the chloro-2-toluene fluoride of 4-in embodiment 1, only change the following parameter of embodiment 1 following steps:
Salt-forming steps: at the uniform velocity drip 5-chloro-2-methyl aniline 1mol under the condition of 5-7 DEG C in 5mol anhydrous hydrofluoric acid, dropping process completed in 10 hours, to drip after terminating insulation reaction 3 hours under the condition of 5-7 DEG C again, obtains mixture 1;
Diazotation step: at the uniform velocity drip 1.5mol Sodium Nitrite under the condition of-3-0 DEG C in mixture 1, dropping process completed in 10 hours, drips after terminating and reacts 3 hours under the condition of-3-0 DEG C, obtain mixture 2;
The recovery of useless hydrofluoric acid: spent acid is mixed with the 98 quality % sulfuric acid of 3mol, distillation, distillation temperature in the kettle is from low to high, ensure that tower top temperature is in earlier stage at 40-45 DEG C, the middle and later periods, tower top temperature control temperature was at 45-55 DEG C, when temperature in the kettle reaches 130 DEG C, insulation distillation, to terminating without during hydrofluoric acid.
The theoretical yield of 4-chloro-2-toluene fluoride finished product is 1mol, actual obtains 0.97mol, and yield is 97%, and the purity of the chloro-2-toluene fluoride of gas chromatographic detection gained 4-is 99.9%, through carbon spectrum nuclear-magnetism (
13cNMR) determine that products obtained therefrom is the chloro-2-toluene fluoride of 4-.
Embodiment 3
Be prepared according to the preparation method of the chloro-2-toluene fluoride of 4-in embodiment 1, only change the following parameter of embodiment 1 following steps:
Salt-forming steps: at the uniform velocity drip 5-chloro-2-methyl aniline 1mol under the condition of 5-7 DEG C in 3.5mol anhydrous hydrofluoric acid, dropping process completed in 9 hours, to drip after terminating insulation reaction 2 hours under the condition of 5-7 DEG C again, obtains mixture 1;
Diazotation step: at the uniform velocity drip 1.5mol Sodium Nitrite under the condition of-3-0 DEG C in mixture 1, dropping process completed in 9 hours, drips after terminating and reacts 2 hours under the condition of-3-0 DEG C, obtain mixture 2;
The recovery of useless hydrofluoric acid: spent acid is mixed with the 98 quality % sulfuric acid of 3mol, distillation, distillation temperature in the kettle is from low to high, ensure that tower top temperature is in earlier stage at 40-45 DEG C, the middle and later periods, tower top temperature control temperature was at 45-55 DEG C, when temperature in the kettle reaches 130 DEG C, insulation distillation, to terminating without during hydrofluoric acid.
The theoretical yield of 4-chloro-2-toluene fluoride finished product is 1mol, actual obtains 0.96mol, and yield is 96%, and the purity of the chloro-2-toluene fluoride of gas chromatographic detection gained 4-is 99.9%, through carbon spectrum nuclear-magnetism (
13cNMR) determine that products obtained therefrom is the chloro-2-toluene fluoride of 4-.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.
Claims (3)
1. a preparation method for the chloro-2-toluene fluoride of 4-, is characterized in that comprising the following steps:
1) salt-forming steps: be (2-5) by mol ratio under the condition of 5-7 DEG C: the anhydrous hydrofluoric acid of 1 and the mixing of 5-chloro-2-methyl aniline, hybrid mode at the uniform velocity to drip whole 5-chloro-2-methyl aniline in 7-10 hour in anhydrous hydrofluoric acid, drip after terminating and under the condition of 5-7 DEG C, react 1-3 hour again, obtain mixture 1;
2) diazotation step: add Sodium Nitrite under the condition of-3-0 DEG C in mixture 1, in Sodium Nitrite used and salt-forming steps, the mol ratio of 5-chloro-2-methyl aniline used is (1-1.5): 1, add the mode of Sodium Nitrite at the uniform velocity to drip whole Sodium Nitrite in 8-10 hour in mixture 1, under the condition of-3-0 DEG C, react 1-3 hour again after adding Sodium Nitrite, obtain mixture 2;
3) thermal decomposition steps: by mixture 2 thermal degradation under the condition of 0-40 DEG C;
Described in thermal decomposition steps, thermal degradation is divided into four-stage:
Totally 5 hours first stage, control temperature is at 0-18 DEG C: the 1 hour control temperature at 0-4 DEG C, and within the 2nd hour, control temperature is at 4-8 DEG C, and within the 3rd hour, control temperature is at 8-12 DEG C, and within the 4th hour, control temperature is at 12-15 DEG C, and within the 5th hour, control temperature is at 15-18 DEG C;
Subordinate phase totally 12 hours, control temperature the 18-26 DEG C: the 1 step totally 2 hours control temperature at 18-21 DEG C, 2nd step totally 2 hours control temperature at 21-23 DEG C, the 3rd step totally 4 hours control temperature at 23-24.5 DEG C, the 4th step totally 4 hours control temperature at 24.5-26 DEG C;
Totally 8 hours phase III, control temperature the 26-30 DEG C: the 1 step totally 2 hours control temperature at 26 DEG C-27 DEG C, the 2nd step totally 2 hours control temperature at 27-28 DEG C, the 3rd step totally 2 hours control temperature at 28-29 DEG C, the 4th step totally 2 hours control temperature at 29-30 DEG C;
Fourth stage totally 5 hours, control temperature is at 30-40 DEG C: the 1 hour control temperature at 30-32 DEG C, and within the 2nd hour, control temperature is at 32-34 DEG C, and within the 3rd hour, control temperature is at 34-36 DEG C, within 4th hour, control temperature is at 36-38 DEG C, and within the 5th hour, control temperature is at 38-40 DEG C.
2. the preparation method of the chloro-2-toluene fluoride of 4-according to claim 1, is characterized in that: also comprise following post-processing step after described thermal decomposition steps:
1) washing neutralization: thermal decomposition steps products therefrom is down to 5 DEG C, stratification, gained upper strata is the chloro-2-toluene fluoride of thick 4-, and lower floor is spent acid, collects the chloro-2-toluene fluoride of thick 4-and carries out washing 3-5 time and add the NaOH aqueous solution after abandoning lower floor's waste water neutralizing;
2) distill: the chloro-2-toluene fluoride of thick 4-through washing neutralization first carries out heating underpressure distillation, heat under vapour pressure is 0.02-0.05Mpa condition, when temperature reach 98-104 DEG C and backflow material terminate without steam distillation during oil droplet, carry out heating air distillation again, 158 DEG C of later cuts are 4-chloro-2-toluene fluoride finished product.
3. the preparation method of the chloro-2-toluene fluoride of 4-according to claim 2, it is characterized in that: described in washing neutralization, spent acid carries out hydrofluoric acid recovery according to following steps: mixed with 98 quality % sulfuric acid by spent acid, Sodium Nitrite 1-1.5mol is often used in diazotation step, 2-3mol98 quality % sulfuric acid is added, Distillation recovery hydrofluoric acid in this step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210309120.0A CN102786386B (en) | 2012-08-27 | 2012-08-27 | Preparation method of 4-chloro-2-fluorotoluene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210309120.0A CN102786386B (en) | 2012-08-27 | 2012-08-27 | Preparation method of 4-chloro-2-fluorotoluene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102786386A CN102786386A (en) | 2012-11-21 |
| CN102786386B true CN102786386B (en) | 2015-01-21 |
Family
ID=47151995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210309120.0A Active CN102786386B (en) | 2012-08-27 | 2012-08-27 | Preparation method of 4-chloro-2-fluorotoluene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102786386B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108569948B (en) * | 2017-03-09 | 2021-06-04 | 辽宁天予化工有限公司 | Preparation method of 2-chloro-4-fluorotoluene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096196A (en) * | 1975-10-31 | 1978-06-20 | Olin Corporation | Diazotization-fluorination in a medium of hydrogen fluoride containing tertiary amine compounds |
| JPH03167144A (en) * | 1989-11-27 | 1991-07-19 | Mitsui Toatsu Chem Inc | Production of fluorobenzene |
| CN100384795C (en) * | 2006-03-09 | 2008-04-30 | 解卫宇 | Producer and production for aromatic fluoride compound |
| CN102234218A (en) * | 2010-04-23 | 2011-11-09 | 龙口市福尔生化科技有限公司 | Preparation method of 2,4-dichlorotoluene |
-
2012
- 2012-08-27 CN CN201210309120.0A patent/CN102786386B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096196A (en) * | 1975-10-31 | 1978-06-20 | Olin Corporation | Diazotization-fluorination in a medium of hydrogen fluoride containing tertiary amine compounds |
| JPH03167144A (en) * | 1989-11-27 | 1991-07-19 | Mitsui Toatsu Chem Inc | Production of fluorobenzene |
| CN100384795C (en) * | 2006-03-09 | 2008-04-30 | 解卫宇 | Producer and production for aromatic fluoride compound |
| CN102234218A (en) * | 2010-04-23 | 2011-11-09 | 龙口市福尔生化科技有限公司 | Preparation method of 2,4-dichlorotoluene |
Non-Patent Citations (2)
| Title |
|---|
| 氟苯的合成及应用;王志坚等;《辽宁化工》;19960520(第03期);第52-54,64页 * |
| 芳香族含氟中间体合成技术进展;梁诚;《有机氟工业》;20070330(第01期);第26-34页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102786386A (en) | 2012-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104016840B (en) | A kind of preparation method of 2-(Trifluoromethyl) benzaldehyde | |
| CN103288718B (en) | Preparation method of 2-chloro-5-tirfluoromethylpyridine | |
| CN108456155A (en) | The method for being used to prepare the imide salts containing fluorosulfonyl group | |
| CN104327037A (en) | Vinylene carbonate preparation method | |
| CN102531872A (en) | Method for preparing high purity (99.9 percent) 4,4'-difluorobenzophenone | |
| CN105408293B (en) | The manufacture method of methyl fluoride | |
| WO2020137824A1 (en) | Cyclobutene production method | |
| CN102786386B (en) | Preparation method of 4-chloro-2-fluorotoluene | |
| CN105949093A (en) | Preparation method of LiN(CF3SO2)2 salt | |
| CN107473928A (en) | A kind of fluorobenzene preparation method | |
| CN102786384B (en) | Preparation method of o-fluorotoluene | |
| CN102786385B (en) | Preparation method of m-fluorotoluene | |
| CN103254074B (en) | Preparation method of ethyl difluoroacetate and intermediate thereof | |
| WO2019194214A1 (en) | Fluoroolefin production method | |
| CN102786387B (en) | Preparation method for p-fluorotoluene | |
| CN104774227A (en) | Chlorination method for sucrose-6-ethyl ester | |
| CN105152988B (en) | One-step method prepares the new technology of N fluoro-diphenyl sulfimides | |
| CN108727154A (en) | A kind of preparation method of hexafluoropropylene dimmer | |
| CN109627165B (en) | Method for co-production of 2-fluoropropionate and ethyl difluoroacetate | |
| CN209537352U (en) | Hexafluoropropylene dimmer prepares the device of perfluor isobutyl ether | |
| CN106146302B (en) | The preparation method of propionic ester | |
| CN105753631A (en) | Synthetic method of fluorine-containing aromatic compounds | |
| CN109503362A (en) | Hexafluoropropylene dimmer prepares the device of perfluor isobutyl ether | |
| CN109232256A (en) | A kind of synthetic method of fluorine-containing carbonic ester | |
| CN104710271A (en) | Preparation method of 1-bromo-1-fluoroethylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 265713, Yantai City, Shandong province Longkou City Xu Fu Street, Ru Lin Zhuang Applicant after: SHANDONG FUER CO., LTD. Address before: 265713, Yantai City, Shandong province Longkou City Xu Fu Street, Ru Lin Zhuang Applicant before: Shandong Fuer Co., Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: SHANDONG FU ER CO., LTD. TO: SHANDONG FUER CO., LTD. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |