CN1075709A - 1,1, the preparation technology of 1-three fluoro-2-monochloroethane - Google Patents
1,1, the preparation technology of 1-three fluoro-2-monochloroethane Download PDFInfo
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- CN1075709A CN1075709A CN 92108335 CN92108335A CN1075709A CN 1075709 A CN1075709 A CN 1075709A CN 92108335 CN92108335 CN 92108335 CN 92108335 A CN92108335 A CN 92108335A CN 1075709 A CN1075709 A CN 1075709A
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- fluoro
- monochloroethane
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- promotor
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Abstract
The present invention relates to prepare 1,1, the technology of ' 1-three fluoro-2-monochloroethane, being included in antimony pentachloride catalyzer and molecular formula is R
fSO
2M promotor have down trieline and hydrogen fluoride reacting by heating.R in the formula
fBe X (CF
2)
2r+2OCF
2CF
2Or X (CF
2)
2z, X is F, and Cl or I, Y are 0 or 1-6, and Z is 1-6, and M is F, Cl or OH.
Description
The invention relates to the trieline is feedstock production 1,1, the synthesis technique of 1-three fluoro-2-monochloroethane.
1,1,1-three fluoro-2-monochloroethane are preparation cooling agent 1,1,1, the raw material of 2-Tetrafluoroethane.
With liquid phase method is catalyzer with the antimony pentachloride, and trieline and anhydrous hydrogen fluoride react under heating up, and generates 1,1,1-three fluoro-2-monochloroethane.E.T.McBee etc. (Industrial and Engineering Chemistry 39(3) 409(1947)) under 170-190 ℃ of temperature, react, generate 1,1 of 32% content, 1-three fluoro-2-monochloroethane products.High temperature and low-yield make preparation become difficult.The patent of Bayer company (Brit Patent, 1585938,1978) adopts solid chemical compounds such as adding mercury perchloride, chromium trifluoride to make promotor, can make 130 ℃ of reactions, and reaction yield brings up to 90%.But the promotor that adds solid phase in antimony pentachloride has increased difficulty in operation.And reaction requires to use higher hydrogen fluoride amount.
The present invention makes catalyzer with antimony pentachloride with trieline and hydrogen fluoride reaction the time, using simultaneously has the organism of following structure to make promotor
R
fSO
2M
Because R
fSO
2M is a liquid, and whole reaction system becomes homogeneous phase, and is favourable to operation.
In the promotor provided by the invention, R
fCan be X(CF
2)
2Y+2OCF
2CF
2-, wherein X is F, Cl, I, Y=0,1-6.Also can adopt R
fBe X(CF
2)
2ZWherein X is F, Cl, I, Z=1-6.M is F, Cl, OH.
Promotor consumption used in the present invention is 0.0001 to 0.1 mole ratio of raw material trieline usage quantity.Wherein usage quantity is the 0.001-0.01 mole ratio preferably.
The present invention uses antimony pentachloride as catalyzer.The mole ratio of antimony pentachloride usage quantity and raw material trieline is 0.001～0.1.
The present invention uses commercially available trieline to be raw material, not treated can directly the use.
The anhydrous hydrogen fluoride that the present invention uses is the anhydrous fluorine human relations of technical grade hydrogen, and its water content is no more than the 0.1%(weight ratio).The mole ratio of hydrogen fluoride amount of Shi Yonging and raw material trieline is 4～10: 1 in the present invention, wherein with 4.5～6: the 1st, proper.
Temperature of reaction of the present invention is 100～160 ℃, and reasonable is 110～135 ℃, and the reaction times needs 0.5～4 hour.The longer reaction times does not influence reaction result.
The product that the present invention produced through gas chromatographic analysis, does not have the raw material trieline.
Except generating 1,1,1-three fluoro-2-monochloroethane are as outside the principal product, and also producing content in reaction product is 1 of 1-10%, 1-two fluoro-1, the 2-ethylene dichloride exists as impurity, particularly when the hydrogen fluoride consumption is low, can generate with 1,1-two chloro-1,2-ethylene dichloride are main product.
The product that the present invention generated is through alkali cleaning, washing, again through vitriol oil bubble drying, freezing collection promptly get contain greater than 95% 1,1,1-three fluoro-2-monochloroethane products.And 1,1,1-three fluoro-2-monochloroethane and 1,1-two fluoro-1,2-ethylene dichloride sum surpasses 99%.
In order to guarantee smooth implementation of the present invention, reactive system should keep dry.Following example is used for illustrating enforcement concrete operations of the present invention and result.
Example one. in the churned mechanically autoclave of 0.5 liter band, pass through drying treatment in advance, add the commercially available trifluoro-ethylene of 220 grams, add 6 gram promotor Cl(CF
2CF
2)
3-OCF
2CF
2SO
2F adds antimony pentachloride 10 grams again, and autoclave is added a cover fastening, with dry ice-ethanol cryogen cooling autoclave, be evacuated to the 10-20 mmhg pressure, behind the several minutes, stop vacuumizes, connect the hydrogen fluoride steel cylinder, under autoclave cooling situation, feed 170 gram anhydrous hydrogen fluorides.Under agitation be heated to 130 ℃, this moment, reactor pressure progressively rose to 100-130MPa.Reaction was through 2 hours, and stop reacts.Be cooled to 50 ℃, open the control valve of autoclave and emit gaseous product.Gaseous product is through the alkali lye wash bottle, after vitriol oil wash bottle feeds by dry ice-ethanol cryogen refrigerative cold-trap again and collects.Obtaining crude product is 190 grams.The gas-chromatography content analysis shows in the product 1,1, and 1-three fluoro-2-monochloroethane account for 95%, (productive rate 91%), 6.9 ℃ of boiling points.1,1-two fluoro-1, the 2-ethylene dichloride accounts for 4%(productive rate 3.4%), 47 ℃ of boiling points.
Example two. by example one device and operation, the 220 gram trielines of packing into, 5 gram promotor ICF
2CF
2OCF
2CF
2SO
2OH, 10 gram antimony pentachlorides and 170 gram anhydrous hydrogen fluorides.130 ℃ of reactions 2 hours, obtain crude product 183 grams.Gas chromatographic analysis shows and contains 93%1,1,1-three fluoro-2-monochloroethane (productive rate 86%), and 1,1-two fluoro-1,2-ethylene dichloride content accounts for 6%(productive rate 4.9%).
Example three. by example one device and operation, the trichloroethane of 220 grams of packing into, 6 gram promotor ClCF
2CF
2CF
2CF
2CF
2CF
2SO
2Cl, 10 gram antimony pentachlorides and 170 gram anhydrous hydrogen fluorides.130 ℃ of reactions 2 hours, obtain crude product 193 gram, gas chromatographic analysis shows, contain 97% 1,1,1-three fluoro-2-monochloroethane (productive rate 94%), 1,1-two fluoro-1, the content of 2-ethylene dichloride is 2.2%(productive rate 1.9%).
Example four. by example one device and operation, the 220 gram trichloroethane of packing into, 6 gram promotor Cl
-(CFCF
2)
3OCF
2CF
2SO
2F, 10 gram antimony pentachlorides and 65 gram anhydrous hydrogen fluorides.130 ℃ of reactions 2 hours, obtain crude product 153 gram, gas chromatographic analysis shows in the product 1,1-two fluoro-1,2-ethylene dichloride content is 95.6%(productive rate 65%).1,1,1-three fluoro-2-monochloroethane content are 2.3%.
Example five. by example one device, still stay in the reactor through example one reacted antimony pentachloride and promotor, do not adding in addition under the situation of antimony pentachloride and promotor, adding 220 gram trielines and 170 gram anhydrous hydrogen fluorides, 130 ℃ of reactions 2 hours, obtain 175 gram crude products, gas chromatographic analysis shows in the product 1,1, and 1-three fluoro-2-monochloroethane account for 90%(productive rate 79%) and 9.1% 1,1-two fluoro-1, the 2-ethylene dichloride.
Claims (8)
1, a kind of from trieline and hydrogen fluoride reaction preparation 1,1, the technology of 1-three fluoro-2-monochloroethane, this technology are included in the antimony pentachloride catalyzer and carry out reacting by heating under existing, and it is characterized in that catalyzer is is R by antimony pentachloride and molecular formula
fSO
2The two components of the promotor of M are formed R in the promotor molecular formula
fBe X (CF
2)
2Y+2OCF
2CF
2Or X (CF
2)
2X, X is F in the formula, and Cl or I, Y are 0 or 1-6, and Z is 1-6, and M is F, Cl or OH, the mole ratio of trieline, hydrogen fluoride, catalyzer antimony pentachloride and promotor is 1: 4-10: 0.001-0.1: 0.0001-0.1.
2, a kind of preparation as claimed in claim 11,1, the technology of 1-three fluoro-2-monochloroethane is characterized in that promotor mol consumption is the 0.001-0.01 of trieline.
3, a kind of preparation as claimed in claim 11,1, the technology of 1-three fluoro-2-monochloroethane, the mole ratio that it is characterized in that hydrogen fluoride and trieline is 4.5-6: 1.
4, a kind of preparation as claimed in claim 11,1, the technology of 1-three fluoro-2-monochloroethane is characterized in that temperature of reaction is 100-160 ℃.
5, a kind of preparation as claimed in claim 41,1, the technology of 1-three fluoro-2-monochloroethane is characterized in that temperature of reaction is 110-135 ℃.
6, a kind of preparation as claimed in claim 11,1, the technology of 1-three fluoro-2-monochloroethane is characterized in that reaction times 0.5-4 hour.
7, a kind of preparation as claimed in claim 11,1, the technology of 1-three fluoro-2-monochloroethane is characterized in that product is through alkali cleaning, washing, vitriol oil bubble drying, freezing collection.
8, a kind of as claim 1 or 7 described preparations 1,1, the technology of 1-three fluoro-2-monochloroethane is characterized in that reactive system keeps dry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92108335A CN1037172C (en) | 1992-02-24 | 1992-02-24 | Preparation process for 1, 1, 1-trifluoro-2-chloroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92108335A CN1037172C (en) | 1992-02-24 | 1992-02-24 | Preparation process for 1, 1, 1-trifluoro-2-chloroethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1075709A true CN1075709A (en) | 1993-09-01 |
| CN1037172C CN1037172C (en) | 1998-01-28 |
Family
ID=4943447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92108335A Expired - Fee Related CN1037172C (en) | 1992-02-24 | 1992-02-24 | Preparation process for 1, 1, 1-trifluoro-2-chloroethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1037172C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073884C (en) * | 1998-07-16 | 2001-10-31 | 中国科学院上海有机化学研究所 | Catalyst for preparing 1,1,1-trifluoro-2-ethane chloride and its application |
| CN101696149A (en) * | 2009-10-29 | 2010-04-21 | 江苏康泰氟化工有限公司 | Method for preparing 1,1,1-trifluoro-2-chloroethane |
| CN101696147B (en) * | 2009-10-29 | 2013-01-09 | 江苏蓝色星球环保科技股份有限公司 | Method for preparing 1,1,1-trifluoro-2-chloroethane |
| CN103508841A (en) * | 2012-06-15 | 2014-01-15 | 中化蓝天集团有限公司 | Method for preparing 1,1-difluoro-1,2-dichloroethane |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4129603A (en) * | 1978-02-07 | 1978-12-12 | Imperial Chemical Industries Limited | Manufacture of halogenated compounds |
| US4851595A (en) * | 1987-07-07 | 1989-07-25 | E. I. Du Pont De Nemours And Company | Liquid phase halogen exchange process for the manufacture of 1,1,1,2-tetrafluoroethane |
-
1992
- 1992-02-24 CN CN92108335A patent/CN1037172C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073884C (en) * | 1998-07-16 | 2001-10-31 | 中国科学院上海有机化学研究所 | Catalyst for preparing 1,1,1-trifluoro-2-ethane chloride and its application |
| CN101696149A (en) * | 2009-10-29 | 2010-04-21 | 江苏康泰氟化工有限公司 | Method for preparing 1,1,1-trifluoro-2-chloroethane |
| CN101696147B (en) * | 2009-10-29 | 2013-01-09 | 江苏蓝色星球环保科技股份有限公司 | Method for preparing 1,1,1-trifluoro-2-chloroethane |
| CN103508841A (en) * | 2012-06-15 | 2014-01-15 | 中化蓝天集团有限公司 | Method for preparing 1,1-difluoro-1,2-dichloroethane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1037172C (en) | 1998-01-28 |
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| C06 | Publication | ||
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Addressee: Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences Document name: Patent specification |
|
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
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| DD01 | Delivery of document by public notice |
Addressee: Wu Zhenzhong Sun Cuifang Document name: payment instructions |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |