CN102746109A - Preparation method of 4-Chlorobenzotrifluoride - Google Patents
Preparation method of 4-Chlorobenzotrifluoride Download PDFInfo
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- CN102746109A CN102746109A CN2012102734852A CN201210273485A CN102746109A CN 102746109 A CN102746109 A CN 102746109A CN 2012102734852 A CN2012102734852 A CN 2012102734852A CN 201210273485 A CN201210273485 A CN 201210273485A CN 102746109 A CN102746109 A CN 102746109A
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Abstract
The invention discloses a preparation method of the 4-Chlorobenzotrifluoride. The method includes step 1: placing the 4-Chlorobenzotrifluoride into a reaction unit, emptying air, feeding chlorine gas into the reaction unit after heating, adding an initiator suspension, and adding the initiator suspension at intervals continuously in the reaction process; and stopping feeding the chlorine gas when the content of dichlorotoluene parachlorotoluene is reduced to 0.5wt%, andemptying the chlorine gas to obtain p-chlorobenzotrichloride; and step 2: placing the p-chlorobenzotrichloride obtained through the step 1 into a reactor, adding hydrogen fluoride liquid, performing heating, starting to maintain constant pressure when the pressure reaches 2.2 MPa to 2.7 PMa, starting to maintain the constant temperature when the temperature reaches 90 DEG C to 105 DEG C, reducing the temperature and releasing the pressure when the temperature is maintained for 50 min to 60 min, adding hydrogen fluoride for a second time when the reactor is reduced to a normal temperature and normal pressure, repeating the reaction until the reaction is over, and obtaining the p-chlorobenzotrichloride. According to the preparation method of the p-chlorobenzotrichloride, product purity and product yield can be improved.
Description
Technical field
The invention belongs to field of chemical technology, specifically, relate to a kind of preparation method of p-chloro benzo trifluoride-99.
Background technology
P-chloro benzo trifluoride-99, English name: 4-Chlorobenzotrifluoride has another name called to chlorine trifluoro benzyl, trifluoromethyl chlorobenzene, to benzyl chloride river trifluoro, is called for short PCBTF.P-chloro benzo trifluoride-99 is important organic synthesis intermediate, can be used for synthesizing a series of fluoro-containing pesticides, like Insecticides (tech) & Herbicides (tech).Fluorine-containing aromatic hydrocarbons also can be used for synthesizing the medical drugs of Tranqilliser, diuretic(s).In addition, some fluorine-containing aromatic hydrocarbons is applied to dyeing, so that it is bright and lustrous.
The synthesis technique of present domestic p-chloro benzo trifluoride-99 generally adopts the chlorination fluorination method.Chlorination is the bottleneck of this technology in this technological process.Therefore select suitable operational path to seem particularly important.With the 4-Chlorotoluene 99.5 is that raw material makes chlorobenzotrichloride through chlorination process.This method is divided into two kinds of light chlorination, catalytic chlorination process.But these two kinds of methods all cut both ways.
1. light chlorination process: adopt UV-irradiation chlorine, produce chlorine radical, chlorine radical further causes chlorination reaction and carries out.This method can not introduced tramp material to system.But efficient is relatively low.
2. catalytic chlorination process: adopt to add the initiator method and produce chlorine radical, accomplish chlorination reaction then, this method efficient is higher, but because the decomposition of initiator can produce tramp material.
And being that general the employing with hydrogen fluoride of technology of raw material production p-chloro benzo trifluoride-99 carried out fluoridation system to chlorobenzotrichloride.This reaction generally can take place under comparatively high temps and pressure.The domestic the most frequently used method of the sector is a liquid-phase fluorination process at present; It is lower that this method has temperature of reaction, and equipment corrosion is less, and unnecessary hydrogen fluoride is easy to advantages such as recovery; But this reaction is a reversible reaction; Be difficult for deeply carrying out when reaching the chemical equilibrium afterreaction, therefore influence product yield, product content has only about 90%.
Summary of the invention
The technical problem that the present invention will solve is to above deficiency, proposes the preparation method of the high p-chloro benzo trifluoride-99 of a kind of product content height and product yield.
For solving above technical problem, technical scheme of the present invention is following:
The preparation method of p-chloro benzo trifluoride-99 may further comprise the steps:
(1) 4000-5000 weight part 4-Chlorotoluene 99.5 is got in the reaction unit, with the air emptying in the reaction unit, when being warming up to 60-120 ℃ with 90-120m
3The flow of/h feeds chlorine and adds 1 weight part initiator suspension liquid then, begins reaction, and every separated 10-15min adds 1 weight part initiator suspension liquid in the reaction process; When dichloromethyl 4-Chlorotoluene 99.5 content is reduced to 0.5wt%, stop logical chlorine, the chlorine emptying in the reaction unit is obtained chlorobenzotrichloride;
(2) the 2-5 weight part that step (1) is made gets in the reaction kettle chlorobenzotrichloride, adds 1 weight part hydrogen fluoride liquid for the first time, heats up;, pressure begins to keep constant voltage when reaching 2.2-2.7MPa; When temperature reaches 90-105 ℃, begin to keep constant temperature, cooling behind the insulation 50-60min, pressure release are after reducing to normal temperature and pressure; Add 0.4-0.6 weight part hydrogen fluoride once more; Repeat above reaction and finish, discharge the hydrogenchloride of unreacted hydrogen fluoride and generation, obtain p-chloro benzo trifluoride-99 until reaction.
As a kind of scheme, the weight ratio of said 4-Chlorotoluene 99.5 and initiator suspension liquid is 5000:1.
As a kind of scheme, said initiator suspension liquid is that 4-Chlorotoluene 99.5 and Diisopropyl azodicarboxylate are formulated by weight 4-5:1.
As further scheme, said initiator suspension liquid is that 4-Chlorotoluene 99.5 and Diisopropyl azodicarboxylate are formulated by weight 4:1.
As a kind of scheme, the chlorine temperature of said feeding reaction unit is 30-60 ℃.
As a kind of scheme, in the step (1), adopt chromatography of gases to detect dichloromethyl 4-Chlorotoluene 99.5 content, get the reacted reactant of 5ml in stopple coupon, in said stopple coupon, be blown into air row chlorine,, said reactant carries out analyzing and testing when becoming colorless.
As a kind of scheme, the weight ratio to chlorobenzotrichloride and the hydrogen fluoride liquid that adds for the first time that adds in the said step (2) is 10:3.
As a kind of scheme, the weight ratio of the hydrogen fluoride liquid of the middle adding for the first time of said step (2) and the hydrogen fluoride liquid that adds once more is 2:1.
As a kind of scheme, the said hydrogen fluoride liquid that adds once more is that unreacted hydrogen fluoride gas forms through refluxing after the condenser condenses in the reaction kettle.
As a kind of scheme,, temperature begins to keep constant temperature when reaching 103 ℃.
Owing to adopted technique scheme, the invention has the beneficial effects as follows:
The initiator that the present invention adopts is a Diisopropyl azodicarboxylate, and this initiator is a kind of radical initiator commonly used, and at a lower temperature, its decomposition reaction is a first order reaction, and no induced decomposition has advantages such as high reactivity, decomposition temperature are low.And, discharge in the process of unnecessary chlorine and can take reaction system out of through blasting drying nitrogen or air because the impurity that this decomposition of initiator produces reaches about 120 ℃ through intensification in the later stage.Help improving product gas purity.Of the present invention to chlorobenzotrichloride and hydrogen fluoride liquid in carrying out fluorination process; At first add hydrogen fluoride liquid one time, carry out initial reaction so earlier, and then add hydrogen fluoride liquid for the second time; Helping promoting balanced reaction like this moves to the line of production; Help improving the yield of product, product yield is brought up to more than 92% by 90%, product purity is brought up to 96%-98% by about 90%.The hydrogen fluoride liquid that adds for the second time can be that the hydrogen fluoride gas in the reaction tower produces through multistage chip type condenser condensing reflux, helps economizing in raw materials, and helps reaction and deepen continuously and carry out.
Embodiment
Following embodiment further specifies the present invention, its objective is and can better understand content of the present invention.But the scope that embodiment does not limit the present invention in any way.Improvement that the technician of this professional domain makes in claim scope of the present invention and adjustment also should belong to right of the present invention and protection domain:
Embodiment 1
The preparation method of p-chloro benzo trifluoride-99 may further comprise the steps:
(1) 4-Chlorotoluene 99.5 5000 gram is got in the reaction units, emptying 10min heats up, during temperature to 60 ℃ with 90m
3The flow of/h feeds chlorine and adds 1 gram initiator suspension liquid, begins reaction, and every separated 10min adds 1 gram initiator suspension liquid in the reaction process; The initiator suspension liquid comprises 0.8 gram 4-Chlorotoluene 99.5 and 0.2 gram Diisopropyl azodicarboxylate.Stop logical chlorine when dichloromethyl 4-Chlorotoluene 99.5 content reduces to 0.5% when detecting, row's chlorine obtains chlorobenzotrichloride; Through test products content is 95.3wt%, and yield is 96.4wt%.
(2) with what step (1) made chlorobenzotrichloride 200 grams are got in the reaction kettle, add 100 gram hydrogen fluoride liquid, heat up; When pressure reaches 2.2MPa, begin to keep constant voltage, when temperature reaches 90, begin to keep constant temperature, cooling behind the insulation 50min, pressure release; After reducing to normal temperature and pressure, add 40 gram hydrogen fluoride, heat up; When pressure reaches 2.2MPa, begin pressurize, when temperature reaches 90 ℃, begin insulation, insulation 50min cooling, pressure release; After reducing to normal temperature and pressure, the hydrogenchloride of discharging unreacted hydrogen fluoride and generation obtains p-chloro benzo trifluoride-99.Analyze to such an extent that p-chloro benzo trifluoride-99 content is 93.6wt%, yield is 90.7wt%.
Embodiment 2
The preparation method of p-chloro benzo trifluoride-99 may further comprise the steps:
(1) 4-Chlorotoluene 99.5 5000 gram is got in the reaction units, blasts nitrogen purge 10min then, heat up, during temperature to 60 ℃ with 90m
3The flow of/h feeds 30 ℃ chlorine and adds 1 gram initiator suspension liquid, begins reaction, and every separated 10min adds 1 gram initiator suspension liquid in the reaction process; The initiator suspension liquid comprises 0.8 gram 4-Chlorotoluene 99.5 and 0.2 gram Diisopropyl azodicarboxylate.Stop logical chlorine when dichloromethyl 4-Chlorotoluene 99.5 content reduces to 0.5% when detecting, in reaction unit, blast dry air row chlorine, obtain chlorobenzotrichloride; Through test products content is 97.6wt%, yield 98.4wt%.
(2) with what step (1) made chlorobenzotrichloride 200 grams are got in the reaction kettle, add 100 gram hydrogen fluoride liquid, heat up; When pressure reaches 2.2MPa, begin to keep constant voltage, when temperature reaches 90 ℃, begin to keep constant temperature, cooling behind the insulation 50min, pressure release; After reducing to normal temperature and pressure, add 40 gram hydrogen fluoride, heat up; When pressure reaches 2.2MPa, begin pressurize, when temperature reaches 90 ℃, begin insulation, insulation 50min cooling, pressure release; After reducing to normal temperature and pressure, blast the hydrogenchloride that air is discharged unreacted hydrogen fluoride and generation, obtain p-chloro benzo trifluoride-99.Getting p-chloro benzo trifluoride-99 content through the gas spectrum analysis is: 96.3wt%, yield are 90.7wt%.
Embodiment 3
The preparation method of p-chloro benzo trifluoride-99 may further comprise the steps:
(1) 4-Chlorotoluene 99.5 4950 gram is got in the reaction units, blasts nitrogen purge 30min then, heat up, during temperature to 90 ℃ with 115m
3The flow of/h feeds 45 ℃ chlorine and adds 1.1 gram initiator suspension liquids, begins reaction, and every separated 13min adds 1.1 gram initiator suspension liquids in the reaction process; The initiator suspension liquid comprises 0.9 gram 4-Chlorotoluene 99.5 and 0.2 gram Diisopropyl azodicarboxylate.Adopt chromatography of gases to detect dichloromethyl 4-Chlorotoluene 99.5 content, get the reacted reactant of 5ml in stopple coupon, in stopple coupon, be blown into air row chlorine, when sample becomes colorless, carry out analyzing and testing.Stop logical chlorine when dichloromethyl 4-Chlorotoluene 99.5 content reduces to 0.5% when detecting, in reaction unit, blast dry air row chlorine, obtain chlorobenzotrichloride; Through test products content is 97.7wt%, yield 99.1wt%.
(2) with what step (1) made chlorobenzotrichloride 500 grams are got in the reaction kettle, add 250 gram hydrogen fluoride liquid, heat up; When pressure reaches 2.5MPa, begin to keep constant voltage, when temperature reaches 103 ℃, begin to keep constant temperature, cooling behind the insulation 50min, pressure release; After reducing to normal temperature and pressure, add 125 gram hydrogen fluoride, heat up; When pressure reaches 2.5MPa, begin pressurize, when temperature reaches 103 ℃, begin insulation, insulation 50min cooling, pressure release; After reducing to normal temperature and pressure, blast the hydrogenchloride that air is discharged unreacted hydrogen fluoride and generation, obtain p-chloro benzo trifluoride-99.Getting p-chloro benzo trifluoride-99 content through the gas spectrum analysis is: 98.2wt%, yield are 95.6wt%.
Embodiment 4
The preparation method of p-chloro benzo trifluoride-99 may further comprise the steps:
(1) 4-Chlorotoluene 99.5 4800 gram is got in the reaction units, blasts nitrogen purge 50min then, heat up, during temperature to 120 ℃ with 120m
3The flow of/h feeds 60 ℃ chlorine and adds 1.2 gram initiator suspension liquids, begins reaction, and every separated 15min adds 1.2 gram initiator suspension liquids in the reaction process; The initiator suspension liquid comprises 1 gram 4-Chlorotoluene 99.5 and 0.2 gram Diisopropyl azodicarboxylate.Adopt chromatography of gases to detect dichloromethyl 4-Chlorotoluene 99.5 content, get the reacted reactant of 5ml in stopple coupon, in stopple coupon, be blown into air row chlorine, when sample becomes colorless, carry out analyzing and testing.Stop logical chlorine when dichloromethyl 4-Chlorotoluene 99.5 content reduces to 0.5% when detecting, in reaction unit, blast drying nitrogen row chlorine, obtain chlorobenzotrichloride; Through test products content is 83.4wt%, yield 85.2wt%.
(2) with what step (1) made chlorobenzotrichloride 500 grams are got in the reaction kettle, add 100 gram hydrogen fluoride liquid, heat up; When pressure reaches 2.7MPa, begin to keep constant voltage, when temperature reaches 105 ℃, begin to keep constant temperature, cooling behind the insulation 50min, pressure release; After reducing to normal temperature and pressure, add 60 gram hydrogen fluoride, heat up; When pressure reaches 2.7MPa, begin pressurize, when temperature reaches 105 ℃, begin insulation, insulation 50min cooling, pressure release; After reducing to normal temperature and pressure, blast the hydrogenchloride that air is discharged unreacted hydrogen fluoride and generation, obtain p-chloro benzo trifluoride-99.The hydrogen fluoride liquid that adds for the second time is to form through refluxing after the condenser condenses after the hydrogen fluoride liquid of adding for the first time gasifies in reaction kettle.Getting p-chloro benzo trifluoride-99 content through the gas spectrum analysis is 83.8wt%, and yield is 79.5wt%.
Claims (10)
1. the preparation method of p-chloro benzo trifluoride-99 is characterized in that, may further comprise the steps:
(1) 4000-5000 weight part 4-Chlorotoluene 99.5 is got in the reaction unit, with the air emptying in the reaction unit, when being warming up to 60-120 ℃ with 90-120m
3The flow of/h feeds chlorine and adds 1 weight part initiator suspension liquid then, begins reaction, and every separated 10-15min adds 1 weight part initiator suspension liquid in the reaction process; When dichloromethyl 4-Chlorotoluene 99.5 content is reduced to 0.5wt%, stop logical chlorine, the chlorine emptying in the reaction unit is obtained chlorobenzotrichloride;
(2) the 2-5 weight part that step (1) is made gets in the reaction kettle chlorobenzotrichloride, adds 1 weight part hydrogen fluoride liquid for the first time, heats up;, pressure begins to keep constant voltage when reaching 2.2-2.7MPa; When temperature reaches 90-105 ℃, begin to keep constant temperature, cooling behind the insulation 50-60mi n, pressure release are after reducing to normal temperature and pressure; Add 0.4-0.6 weight part hydrogen fluoride once more; Repeat above reaction and finish, discharge the hydrogenchloride of unreacted hydrogen fluoride and generation, obtain p-chloro benzo trifluoride-99 until reaction.
2. the preparation method of p-chloro benzo trifluoride-99 according to claim 1, it is characterized in that: the weight ratio of said 4-Chlorotoluene 99.5 and initiator suspension liquid is 5000:1.
3. the preparation method of p-chloro benzo trifluoride-99 according to claim 1, it is characterized in that: said initiator suspension liquid is that 4-Chlorotoluene 99.5 and Diisopropyl azodicarboxylate are formulated by weight 4-5:1.
4. the preparation method of p-chloro benzo trifluoride-99 according to claim 3, it is characterized in that: said initiator suspension liquid is that 4-Chlorotoluene 99.5 and Diisopropyl azodicarboxylate are formulated by weight 4:1.
5. the preparation method of p-chloro benzo trifluoride-99 according to claim 1, it is characterized in that: the chlorine temperature of said feeding reaction unit is 30-60 ℃.
6. the preparation method of p-chloro benzo trifluoride-99 according to claim 1; It is characterized in that: in the step (1); Adopt chromatography of gases to detect dichloromethyl 4-Chlorotoluene 99.5 content; Get the reacted reactant of 5ml in stopple coupon, in said stopple coupon, be blown into air row chlorine, when said reactant becomes colorless, carry out analyzing and testing.
7. the preparation method of p-chloro benzo trifluoride-99 according to claim 1 is characterized in that: the weight ratio to chlorobenzotrichloride and the hydrogen fluoride liquid that adds for the first time that adds in the said step (2) is 10:3.
8. the preparation method of p-chloro benzo trifluoride-99 according to claim 1 is characterized in that: the hydrogen fluoride liquid that adds for the first time in the said step (2) is 2:1 with the weight ratio of the hydrogen fluoride liquid of adding once more.
9. the preparation method of p-chloro benzo trifluoride-99 according to claim 1 is characterized in that: the said hydrogen fluoride liquid that adds once more is that unreacted hydrogen fluoride gas forms through refluxing after the condenser condenses in the reaction kettle.
10. the preparation method of p-chloro benzo trifluoride-99 according to claim 1 is characterized in that: in the step (2), when temperature reaches 103 ℃, begin to keep constant temperature.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058820A (en) * | 2012-12-06 | 2013-04-24 | 联化科技股份有限公司 | Preparation methods of 4-bromo-2,6-difluoro-trifluorotoluene and intermediate thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4045502A (en) * | 1976-09-29 | 1977-08-30 | Olin Corporation | Process for producing high purity para-chlorobenzotrifluoride |
| CN87100230A (en) * | 1987-02-16 | 1987-12-16 | 中国科学院上海有机化学研究所 | fluorination catalyst and application thereof |
| CN102610341A (en) * | 2011-01-24 | 2012-07-25 | 上海神沃电子有限公司 | Surface-mounted macromolecule PTC (positive temperature coefficient) element and manufacturing method thereof |
| CN102603471A (en) * | 2012-02-21 | 2012-07-25 | 南通市东昌化工有限公司 | Production method of p-trifluoromethyl chlorobenzene |
-
2012
- 2012-08-01 CN CN2012102734852A patent/CN102746109A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4045502A (en) * | 1976-09-29 | 1977-08-30 | Olin Corporation | Process for producing high purity para-chlorobenzotrifluoride |
| CN87100230A (en) * | 1987-02-16 | 1987-12-16 | 中国科学院上海有机化学研究所 | fluorination catalyst and application thereof |
| CN102610341A (en) * | 2011-01-24 | 2012-07-25 | 上海神沃电子有限公司 | Surface-mounted macromolecule PTC (positive temperature coefficient) element and manufacturing method thereof |
| CN102603471A (en) * | 2012-02-21 | 2012-07-25 | 南通市东昌化工有限公司 | Production method of p-trifluoromethyl chlorobenzene |
Non-Patent Citations (2)
| Title |
|---|
| 于康平等: "对氯苯甲酰氯的合成", 《现代农药》, vol. 6, no. 5, 10 October 2007 (2007-10-10), pages 14 - 15 * |
| 马英高: "对氯三氟甲苯合成工艺的进展", 《辽宁化工》, no. 4, 28 August 1980 (1980-08-28), pages 34 - 41 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058820A (en) * | 2012-12-06 | 2013-04-24 | 联化科技股份有限公司 | Preparation methods of 4-bromo-2,6-difluoro-trifluorotoluene and intermediate thereof |
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Application publication date: 20121024 |