CN104163751B - A kind of method preparing 2-chloro-3,3,3-trifluoro propene - Google Patents
A kind of method preparing 2-chloro-3,3,3-trifluoro propene Download PDFInfo
- Publication number
- CN104163751B CN104163751B CN201310188780.2A CN201310188780A CN104163751B CN 104163751 B CN104163751 B CN 104163751B CN 201310188780 A CN201310188780 A CN 201310188780A CN 104163751 B CN104163751 B CN 104163751B
- Authority
- CN
- China
- Prior art keywords
- chloro
- tri chloropropene
- catalyst
- trifluoropropene
- prepared
- 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 method that the open one of the present invention is prepared 2 chlorine 3,3,3 trifluoro propenes by tri chloropropene, first with 1,1,3 tri chloropropene and/or 3,3,3 tri chloropropenes, HCl and O2Gas phase mixture as raw material, react under oxychlorination catalyst effect, then under fluorination catalyst effect, be passed through anhydrous HF and react further and obtain 2 chlorine 3,3,3 trifluoro propenes.2 chlorine 3,3,3 trifluoro propenes prepared by the present invention can be used for synthesizing 2,3,3,3 tetrafluoropropenes.
Description
Technical field
The present invention relates to the preparation method of a kind of Halogen alkene, especially relate to a kind of 2-chloro-3,3,3 ,-trifluoropropene
Preparation method.
Background technology
According to the regulation of Montreal Protocol, the most most widely used, GWP value (relative CO will be phased out2And
Speech, GWP value is 1340) higher fluoroether refrigerant HFC-134a.During finding HFC-134a substitute, flourishing state
Family plans to use 2, and 3,3,3-tetrafluoropropenes (HFO-1234yf) HFO-1234yf is in addition to as cold-producing medium, it is also possible to as high heat
Stability, the polymerization monomer of high resiliency thermoelasticity elastomeric material and comonomer, market capacity is big.
In the preparation process of HFO-1234yf, 2-chloro-3,3,3 ,-trifluoropropene (HCFC-1233xf) is the most useful
Intermediate mainly has following report for the preparation method of HCFC-1233xf: United States Patent (USP) US2009030244 reports to be passed through
At least one and HF in 1,1,2,3-tetrachloropropylene, 1,1,1,2,3-pentachloropropane and 2,3,3,3-tetrachloropropylene are in gas phase
Under fluorination catalyst and stabilizer function, the method for vapor-phase synthesis HCFC-1233xf.
PCT Patent WO2007079431A2 reports with CCl2=CClCH2Cl (HCC-1230xa) is raw material, urges in fluorination
Under agent effect, gas phase fluorination generates the process of HCFC-1233xf.
PCT Patent WO2009015317A1 reports with CCl2=CClCH2Cl (HCC-1230xa) or 1,1,1,2,3-pentachloro-
Propane is raw material, and under fluorination catalyst effect, fluorination generates the process of HCFC-1233xf.
United States Patent (USP) US20090287026A1 reports with 1, and 1,2,3-tetrachloropropylene is raw material, prepared by gas phase fluorination
The process of HCFC-1233xf.
PCT Patent WO2009125199A2 reports with 1, and chloro-3,3, the 3-trifluoro propane of 2-bis-are raw material, utilizes gas phase to bear
Carried catalyst takes off and utilizes de-HCl in alkali liquor to obtain the process of HCFC-1233xf in HCl or liquid phase.
PCT Patent WO2010123148A1 reports with 1, and 1,1,2,3-pentachloropropane is raw material, prepared by gas phase fluorination
The process of HCFC-1233xf.
PCT Patent WO2010123148A1 reports with 1, and 1,1,2,3-pentachloropropane is raw material, prepared by gas phase fluorination
The process of HCFC-1233xf.
PCT Patent WO2011126679A2 reports and with 1,1,1,2,2-pentachloropropane or 1,1,1,2,3-pentachloropropane is
Raw material, gas phase fluorination prepares the process of HCFC-1233xf.
PCT Patent WO2011010606A1 reports with 1, and 2 ,-two chloro-3,3,3-trifluoro propenes are raw material, hydrogenating reduction
Prepare the process of HCFC-1233xf.
Chinese patent CN102001911A1 reports with 1, and 1,2,3-tetrachloropropylene is raw material, and liquid-phase fluorination obtains
HCFC-1233xf, obtains simultaneously, 1,1,2,3-pentafluoropropane and 1, the technical process of 1,1,2,2-pentafluoropropane.
PCT Patent WO2011135416A1 reports with 1, and 1,1,2,3-pentachloropropane is raw material, in the solution liquid phase fluorine
Change the process preparing HCFC-1233xf.
Chinese patent CN102363589 reports with 1, and 1,2-tri-chloro-3-fluoropropene is raw material, prepared by gas phase fluorination
The process of HCFC-1233xf.
Chinese patent CN102247789A reports with 3, and 3,3-trifluoro propenes are raw material, are passed through Cl in the liquid phase2, at purple
Carrying out Light chlorimation synthesis under outer light irradiation and obtain 1, chloro-3,3, the 3-trifluoro propane of 2-bis-, then in alkali liquor, de-HCl obtains
The process of HCFC-1233xf.
United States Patent (USP) US2007112228 reports with propylene as raw material, and gas phase fluorination prepares 2-fluoroethane, then to this
Material carries out Light chlorimation, obtains 1,1,1,2-tetra-chloro-2-fluoropropane, then product is carried out fluorination reaction, obtains HCFC-1233xf
Process.
With 1,1,2,3-tetrachloropropylene or 1,1,1,2,3-pentachloropropane for Material synthesis HCFC-1233xf in prior art
During, raw material 1,1,2,3-tetrachloropropylene and 1, the synthesis step of 1,1,2,3-pentachloropropane is complicated, 1,1,2,3-tetrachloro
Propylene need to be eliminated HCl by glyceryl trichloride through two one-step chlorinations and two steps and obtain, 1,1,1,2,3-pentachloropropane need to by 1,
1,3-trichloropropane carries out chlorination reaction and obtains, and both approaches not only needs to use dangerous chlorine, also can obtain substantial amounts of
By-product HCl.Though this is improved by United States Patent (USP) US2010168482, using tri chloropropene is raw material, at fluorination catalyst
Under effect, react the mixture obtaining HCFC-1233xf, HFO-1234yf and HFC-245cb with chlorine and anhydrous HF.The method
Need also exist for using dangerous chlorine, and owing to this reaction is high for thermal chlorination reaction, reaction temperature, raw material 1,1,3-trichlorine third
Alkene and/or 3,3,3-tri chloropropenes and intermediate 1,1,2,3-tetrachloropropylene easily tie carbon, block reactor.
Summary of the invention
The problem that it is an object of the invention to overcome prior art to exist, it is provided that a kind of 2-chloro-3,3,3 ,-trifluoropropene
Preparation method, the method not only need not use the chlorine of danger, safety and environmental protection, additionally it is possible to makes reactions steps simplify, avoid knot
Burnt, comprehensive utilization by-product HCl, has that synthetic route is novel, raw material is easy to get, selectivity, conversion ratio advantages of higher
For reaching goal of the invention the technical solution used in the present invention it is:
A kind of method being prepared 2-chloro-3,3,3 ,-trifluoropropene by tri chloropropene, in fixed bed reactors, makes 1,1,3-
Tri chloropropene and/or 3,3,3-tri chloropropene, HCl and O2Gas phase mixture as raw material first under oxychlorination catalyst effect
Reaction, then react further with anhydrous HF under fluorination catalyst effect and obtain 2-chloro-3,3,3 ,-trifluoropropene；Described oxychlorination
Active component in catalyst includes main active CuCl2And Supplementary active ingredients, described Supplementary active ingredients is selected from
MgCl2、KCl、LaCl3、ScCl3And CeCl3In one, two or three combination of the above；Described 1,1,3-tri chloropropene and/
Or 3,3,3-tri chloropropene, O2, mol ratio between HF and HCl be 0.8～1.2:1.1～2.0:5～15:1.
Active component in the oxychlorination catalyst that the present invention uses includes main active CuCl2Become with auxiliary activity
Point, described Supplementary active ingredients is selected from MgCl2、KCl、LaCl3、ScCl3And CeCl3In one, more than two or three group
Close, preferably MgCl2、LaCl3And CeCl3In one, two or three；Main active CuCl2Account for the matter of active component
Amount percentage composition is preferably 10～90%；The load capacity of active component is preferably 0.1～15%, and more preferably 2～6%；Catalysis
Agent carrier is preferably aluminium oxide or activated carbon.
Present invention also offers a kind of method that sedimentation method prepare oxychlorination catalyst, comprise the following steps:
(1) by the CuCl of metering2It is dissolved in deionized water, wiring solution-forming with the salt of Supplementary active ingredients；
(2) aluminium-hydroxide powder of metering is dissolved in sodium hydroxide solution, reacts at 50～100 DEG C, obtain hydrogen-oxygen
Change sodium with aluminium sesquioxide concentration than the solution being 1.2～1.8:1；
(3) solution that step (1) obtains is joined in the solution of step (2), high-speed stirred 1～2 hours, add phase
When in amount of solution 2～the water of 4 times, stirring 4～6 hours, then precipitate, obtain catalyst granules；
(4) the catalyst granules deionized water that step (3) obtains is washed, until electrical conductivity is more than 400 Ω
cm-1；
(5) catalyst granules that step (4) obtained filters, and dries 2～3 hours at 100～150 DEG C, then 350～
450 DEG C of roastings 0.5～2 hours, obtain oxychlorination catalyst.
The fluorination catalyst used is not specially required by the present invention, and conventional catalysts for gas phase fluorination all can use, excellent
Elect fluorine chromium oxide gas-like phase fluorination catalyst as.The fluorine needed for the present invention can be prepared according to the method for patent CN01141970.9
Change catalyst.
Physical behavior is not had particular/special requirement, common ball, lamellar and graininess all may be used by the catalyst that the present invention uses
To use.The oxychlorination catalyst prepared through preparation method of the present invention can directly use.Fluorination catalyst is before use
Preferably process through HF activity, some oxide of catalyst surface so can be made to be converted into fluoride.This activation process step
Fluorination catalyst can be realized with HF in suitable hydrogen-catalyst reactor, first make HF pass through dried fluorination catalyst
To make fluorination catalyst fractional saturation with HF, anhydrous HF e.g., from about 200～500 DEG C, can be led to by this by a certain temperature
Cross fluorination catalyst 15～process for 400 minutes.
In the method being prepared 2-chloro-3,3,3 ,-trifluoropropene by tri chloropropene that the present invention provides, raw material 1,1,3-trichlorine
Propylene and/or 3,3,3-tri chloropropene, O2, mol ratio between HF and HCl be preferably 0.8～1.2:1.1～2.0:5～
15:1, more preferably 1.1～1.2:1.10～1.15:5～15:1.Raw material tri chloropropene by 1,1,3-tri chloropropene and 3,
3,3-tri chloropropene two kinds compositions, the 1 of any ratio, 1,3-tri chloropropene and 3, the mixture of 3,3-tri chloropropenes could be used for
The present invention.
In preparation method of the present invention, if reaction temperature is too low, reaction conversion ratio can be made relatively low, if reaction temperature mistake
Height, the most easily causes raw material to tie carbon on a catalyst, causes catalysqt deactivation, it is therefore preferable that reaction temperature is 200～350
DEG C, more preferably 250～350 DEG C.If feed space velocity is too low, it is meant that the time that raw material contacts with catalyst is longer, easily
Cause knot carbon inactivation or the organic cracking of catalyst, cause target product selectivity to reduce, if feed space velocity is too high, then contact
Time is the shortest, causes conversion ratio the lowest, it is therefore preferable that feed space velocity is 200～600h-1, more preferably 200～300h-1。
The fixed bed reactors that the present invention uses, are divided into two sections, one section of filling oxychlorination catalyst, the filling fluorination of another section
Catalyst, as preferred mode, the oxychlorination catalyst volume of filling and the volume ratio of fluorination catalyst are 1:1～1.5.
The raw material that the present invention uses the most first is preheated to 250 DEG C before adding fixed bed reactors, raw material tri chloropropene,
O2, and HCl preferably add from reactor head, HF preferably adds in the middle part of fixed bed reactors, and HF so can be avoided the
One step participates in reaction, generates impurity, HCl and O in simultaneous reactions2As carrier gas, decrease the knot carbon of tri chloropropene.
Reactor involved in foregoing invention, distillation column and feed line, delivery pipe and phase that they are correlated with
Close unit to be made up of resistant material.It is typically constructed material and includes nickel-containing alloys, rustless steel and copper plated steel.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses and potentially included in Claims scope
All alternatives, improvement project and equivalents.
The preparation of embodiment 1 oxychlorination catalyst
Weigh the CuCl of 125 grams2·2H2O, the MgCl of 63 grams2It is dissolved in 1000ml deionized water, makes solution A；Weigh
40 grams of aluminium-hydroxide powders, join in the sodium hydroxide solution of 50 DEG C under stirring, stir 15min, make solution B；Under stirring
Solution A is joined in solution B, stir 20min after adding, then precipitate, wash with deionized water, until electrical conductivity is big
In 400 Ω cm-1, then filtration drying；Present for catalyst granules after washing 150 DEG C are dried 2 hours, then 450 DEG C of roastings
Burn 2 hours, finally dried catalyst granules is made cylindric, can use.
Prepared by embodiment 2 HCFC-1233xf
Material molar ratio is CCl2=CHCH2Cl:HCl:O2: HF=1:1.2:2.4:10, reaction temperature 200-350 DEG C, reaction
Pressure 0.3MPa, air speed 400h-1, oxychlorination catalyst as shown in example 1, loadings 200ml, fluorination catalyst loadings 200ml,
Outlets products is through washing, carrying out GC analysis after drying, and result of the test is as shown in table 1.
Table 1
Prepared by embodiment 3 HCFC-1233xf
Material molar ratio is CH2=CHCCl3:HCl:O2: HF=1:1.2:2.4:10, reaction temperature 260 DEG C, reaction pressure
0.3MPa, raw material relative oxychlorination catalyst and air speed 200-600h of fluorination catalyst respectively-1, oxychlorination catalyst such as example 1
Shown in, loadings 200ml, fluorination catalyst loadings 200ml, outlets products, through washing, carrying out GC analysis after drying, is tested
Result is as shown in table 2.
Table 2
Prepared by embodiment 4 HCFC-1233xf
Operational approach is with embodiment 1, except for the difference that by the MgCl of 63 grams2Change respectively and be LaCl3 76g,SrCl3·
9H2O82.6g、CeCl3·9H2O 76.4g、ScCl369g, KCl 23g, other components are constant.Material molar ratio: CCl2=
CHCH2Cl:HCl:O2: HF=1:1.2:2.4:10, reaction temperature 260 DEG C, reaction pressure 0.3MPa, air speed 400h-1, oxychlorination
Catalyst such as example 1, loadings 200ml, fluorination catalyst loadings 200ml, outlets products divides through washing, carrying out GC after drying
Analysis, result of the test is as shown in table 3.
Table 3
Claims (11)
1. the method being prepared 2-chloro-3,3,3 ,-trifluoropropene by tri chloropropene, it is characterised in that in fixed bed reactors,
Make 1,1,3-tri chloropropene and/or 3,3,3-tri chloropropene, HCl and O2Gas phase mixture be first catalyzed in oxychlorination as raw material
React under agent effect, then react further with anhydrous HF under fluorination catalyst effect and obtain 2-chloro-3,3,3 ,-trifluoropropene；Institute
The active component stated in oxychlorination catalyst includes main active CuCl2And Supplementary active ingredients, described auxiliary activity becomes
It is selected from MgCl2、KCl、LaCl3、ScCl3And CeCl3In one, two or three combination of the above；Described 1,1,3-trichlorine third
Alkene and/or 3,3,3-tri chloropropene, O2, mol ratio between HF and HCl be 0.8～1.2:1.1～2.0:5～15:1.
2. according to the method being prepared 2-chloro-3,3,3 ,-trifluoropropene by tri chloropropene described in claim 1, it is characterised in that institute
State in oxychlorination catalyst, main active CuCl2The weight/mass percentage composition accounting for active component is 10～90%, described auxiliary
Active component is selected from MgCl2、LaCl3And CeCl3In one, two or three.
3. according to the method being prepared 2-chloro-3,3,3 ,-trifluoropropene by tri chloropropene described in claim 1, it is characterised in that institute
Stating in oxychlorination catalyst, the load capacity of active component is 0.1～15%, and carrier is aluminium oxide or activated carbon.
4. according to the method being prepared 2-chloro-3,3,3 ,-trifluoropropene by tri chloropropene described in claim 3, it is characterised in that institute
The load capacity stating active component is 2～6%.
5., according to the preparation method of the oxychlorination catalyst described in claim 1, comprise the following steps:
(1) by the CuCl of metering2It is dissolved in deionized water, wiring solution-forming with the salt of Supplementary active ingredients；
(2) aluminium-hydroxide powder of metering is dissolved in sodium hydroxide solution, reacts at 50～100 DEG C, obtain sodium hydroxide
With aluminium sesquioxide concentration than the solution being 1.2～1.8:1；
(3) solution that step (1) obtains is joined in the solution of step (2), high-speed stirred 1～2 hours, add and be equivalent to
Amount of solution 2～the water of 4 times, stir 4～6 hours, then precipitate, obtain catalyst granules；
(4) the catalyst granules deionized water that step (3) obtains is washed, until electrical conductivity is more than 400 Ω cm-1；
(5) catalyst granules step (4) obtained filters, and dries 2～3 hours at 100～150 DEG C, then at 350～450 DEG C
Roasting 0.5～2 hours, obtain oxychlorination catalyst.
6. according to the method being prepared 2-chloro-3,3,3 ,-trifluoropropene by tri chloropropene described in claim 1, it is characterised in that institute
Stating fluorination catalyst is fluorine chromium oxide gas-like phase fluorination catalyst.
7. according to the method being prepared 2-chloro-3,3,3 ,-trifluoropropene by tri chloropropene described in claim 1, it is characterised in that institute
Stating the oxychlorination catalyst volume of filling in fixed bed reactors is 1:1～1.5 with the volume ratio of fluorination catalyst.
8. according to the method being prepared 2-chloro-3,3,3 ,-trifluoropropene by tri chloropropene described in claim 1, it is characterised in that institute
State 1,1,3-tri chloropropene and/or 3,3,3-tri chloropropene, O2, mol ratio between HF and HCl be 1.1～1.2:1.10～
1.15:5～15:1.
9. according to the method being prepared 2-chloro-3,3,3 ,-trifluoropropene by tri chloropropene described in claim 1, it is characterised in that anti-
Answering temperature is 200～350 DEG C, and reaction velocity is 200～600h-1。
10. according to the method being prepared 2-chloro-3,3,3 ,-trifluoropropene by tri chloropropene described in claim 9, it is characterised in that
Described reaction temperature is 250～350 DEG C, and reaction velocity is 200～300h-1。
11. according to the method being prepared 2-chloro-3,3,3 ,-trifluoropropene by tri chloropropene described in claim 1, it is characterised in that
Raw material is first preheated to 250 DEG C before adding fixed bed reactors, and HF adds in the middle part of fixed bed reactors, 1,1,3-tri chloropropene
And/or 3,3,3-tri chloropropene, HCl and O2Add from reactor head.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310188780.2A CN104163751B (en) | 2013-05-17 | 2013-05-17 | A kind of method preparing 2-chloro-3,3,3-trifluoro propene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310188780.2A CN104163751B (en) | 2013-05-17 | 2013-05-17 | A kind of method preparing 2-chloro-3,3,3-trifluoro propene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104163751A CN104163751A (en) | 2014-11-26 |
| CN104163751B true CN104163751B (en) | 2016-09-28 |
Family
ID=51907755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310188780.2A Active CN104163751B (en) | 2013-05-17 | 2013-05-17 | A kind of method preparing 2-chloro-3,3,3-trifluoro propene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104163751B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101242899A (en) * | 2005-08-18 | 2008-08-13 | 雅宝荷兰有限责任公司 | Catlytic oxychlorination |
| CN101874009A (en) * | 2007-07-25 | 2010-10-27 | 霍尼韦尔国际公司 | Produce 2-chloro-3,3,3-trifluoro propene (HCFC-1233xf) improves one's methods |
| US20120053371A1 (en) * | 2006-01-03 | 2012-03-01 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8318992B2 (en) * | 2006-10-31 | 2012-11-27 | E I Du Pont De Nemours And Company | Processes for the production of fluoropropanes and halopropenes |
-
2013
- 2013-05-17 CN CN201310188780.2A patent/CN104163751B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101242899A (en) * | 2005-08-18 | 2008-08-13 | 雅宝荷兰有限责任公司 | Catlytic oxychlorination |
| US20120053371A1 (en) * | 2006-01-03 | 2012-03-01 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| CN101874009A (en) * | 2007-07-25 | 2010-10-27 | 霍尼韦尔国际公司 | Produce 2-chloro-3,3,3-trifluoro propene (HCFC-1233xf) improves one's methods |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104163751A (en) | 2014-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107250088B (en) | The manufacturing method of the chloro- 2,3,3- trifluoro propene of 1- | |
| CN103946192B (en) | For the method manufacturing HF hydrocarbon | |
| CN101679154B (en) | Process for isomerising a (hydrohalo) fluoroalkene | |
| CN102282114B (en) | Isomerization of 1,1,3,3-tetrafluoropropene | |
| JP6362705B2 (en) | Process for simultaneous production of 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene | |
| CN105008042B (en) | Catalyst for the chloro- 1,1,1,2- tetrafluoropropanes dehydrochlorinations of 2- | |
| JP7090000B2 (en) | Fluorine compound manufacturing method | |
| JP5905967B2 (en) | Method for producing 2,3,3,3-tetrafluoropropene | |
| JP2010532762A (en) | Preparation of fluorinated olefins by catalyzed dehydrohalogenation of halogenated hydrocarbons. | |
| JP2015500327A (en) | Process for preparing 2,3,3,3-tetrafluoropropene | |
| CN104284874A (en) | Process for producing 2,3,3,3-tetrafluoropropene | |
| CN109503315A (en) | The preparation method of tetrafluoropropene | |
| CN101980993B (en) | Method for preparing fluorinated compounds | |
| CN110590496A (en) | Method for continuously synthesizing cis-1, 1,1,4,4, 4-hexafluoro-2-butene in gas phase | |
| CN105753638B (en) | The synthetic method of 2,3,3,3- tetrafluoropropenes | |
| CN104163751B (en) | A kind of method preparing 2-chloro-3,3,3-trifluoro propene | |
| WO2015126584A1 (en) | Process for the manufacture of hydrochlorofluoroolefins | |
| JP5500261B2 (en) | Method for producing fluorine-containing alkene | |
| CN104010999A (en) | Method for preparing fluorinated olefin compounds | |
| CN105189422B (en) | The method for being used to prepare fluoroolefin | |
| CN108610233B (en) | Preparation method of 3, 3, 3-trifluoropropene | |
| JP6197637B2 (en) | (E) Method for producing 1,3,3,3-tetrafluoropropene | |
| JP6216832B2 (en) | Process for preparing 2,3,3,3-tetrafluoropropene | |
| CN104163750B (en) | The preparation method of 1,1,1,2,3-pentachloropropane and 1,1,2,3-tetrachloropropylene | |
| CN101983183B (en) | Process for producing fluoroalkyl iodide telomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |