- On the CH3/CF3 substitution effect. The gas-phase structure of 1,1,1,3,3,3-hexafluoropropane
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The gas-phase structure of CF3CH2CF3 was determined by electron diffraction.The experimental intensities are consistent with a structure possessing C2v symmetry and the following geometric parameters (ra distances in Angstroem and α angles in degrees, error limits are 3? values): C-H=1.082 (18), C-C=1.518 (4), C-F=1.333 (2), CCC=113.9 (6), FCF=107.7 (1) and HCH=108.7 (not refined).The CF3 groups are tilted by 1.8 (8) deg away from each other.Comparison of these results with the structures of propane, 2-fluoropropane, 2.2-difluoropropane and perfluoropropaneallows a discussion of the effects of fluorination on the C-C- bond lengths and CCC bond angles in this series.The geometries of these compounds have been optimized by ab initio calculations in the HF approximation using different basis sets (3-21G, 6-31G* and 6-311G*).The effect of CH3/CF3 substitution on the C-C-bond lengths is reproduced correctly only with basis sets including polarization functions.
- Mack, Hans-Georg,Oberhammer, Heinz,Grosser, Martin,Dakkouri, Marwan
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Read Online
- Chlorodefluorination of Fluoromethanes and Fluoroolefins at a Lewis Acidic Aluminum Fluoride
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Chlorodefluorination reactions of fluoromethanes and fluoroolefins catalysed by the highly Lewis acidic nanoscopic aluminum chlorofluoride (ACF, AlClxF3?x, x≈0.05–0.3) in the presence of ClSiEt3 were studied. Both fluoromethanes and fluoroolefins convert under mild reaction conditions by fluorine-chlorine exchange steps into chlorinated fluoro derivatives. MAS NMR studies provided information on the interaction of silanes and hexafluoropropene with the ACF surface.
- Braun, Thomas,Pan, Xinzi,Scholz, Gudrun,Talavera, Maria
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- Preparation method of 1, 1, 1, 3, 3, 3-hexafluoropropane
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The invention discloses a preparation method of 1, 1, 1, 3, 3, 3-hexafluoropropane. The method includes: (1) reacting a halogenated inorganic salt with heptafluoroisobutenyl methyl ether in an aproticsolvent, then adding water and performing stirring, conducting cooling and filtering, and rectifying the filtrate to obtain hexafluoroisobutyric acid; and (2) heating the hexafluoroisobutyric acid obtained in step (1), collecting the generated gaseous product and performing cooling to obtain the 1, 1, 1, 3, 3, 3-hexafluoropropane product. The method provided by the invention has the advantages ofsimple process, environmental friendliness, low cost, green and environmental protection.
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Paragraph 0043-0046
(2019/05/08)
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- PROCESS FOR PRODUCING FLUORINE-CONTAINING OLEFIN
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In the production of fluorine-containing olefins using a chlorine-containing alkane or a chlorine-containing alkene as a starting material, a process for producing a plurality of useful fluorine-containing olefins with high selectivity using the same raw material, the same equipment, and the same conditions is provided. The present invention provides a process for producing fluorine-containing olefins, the process comprising reacting a chlorine-containing compound represented by a specific formula and anhydrous hydrogen fluoride in the presence of oxidative gas and a fluorination catalyst, wherein the fluorination catalyst is a catalyst in which at least one metal element M selected from the group consisting of Group VIII and Group IX is present together with chromium. This production process can simultaneously produce two or more fluorine-containing olefin compounds, including HFO-1234yf and HFO-1234ze, with high selectivity.
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Paragraph 0090-0093; 0097
(2016/12/22)
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- Method for co-preparation of 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene from hexafluoropropylene
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2, 3, 3, 3-hexafluoro propylene, the 1, 3, 3, 3-and -1234z3 (HFO-1234yf) (HFP) from -1234z3 (HFO-1234ze, E-form) simultaneous manufacturing method is provided. (by machine translation)
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Paragraph 0160; 0161; 0162; 0163
(2017/01/05)
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- PROCESSES FOR SEPARATION OF FLUOROOLEFINS FROM HYDROGEN FLUORIDE BY AZEOTROPIC DISTILLATION
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The present disclosure relates to a process for separating a fluoroolefin from a mixture comprising hydrogen fluoride and fluoroolefin, comprising azeotropic distillation both with and without an entrainer. In particular are disclosed processes for separating any of HFC-1225ye, HFC-1234ze, HFC-1234yf or HFC-1243zf from HF.
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Page/Page column 21-22
(2008/06/13)
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- Catalytic isomerization processes of 1,3,3,3-tetrafluoropropene for making 2,3,3,3-tetrafluoropropene
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The present invention relates to a process of catalyzed isomerization of HFC-1234ze to make HFC-1234yf. The process comprises contacting HFC-1234ze with a suitable catalyst in a reactor to obtain a product mixture comprising HFC-1234yf.
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Page/Page column 3
(2008/06/13)
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- 1,1,1,3,3,3-hexafluoropropane purification with photochlorination equipment
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A continuous, vapor phase method for purifying a crude mixture of 1,1,1,3,3,3-hexafluoropropane and one or more unsaturated fluorocarbon compounds, the process comprising: a) providing a photochlorinator vessel comprising 1) a UV lamp unit comprising a UV lamp located in a transparent inner well, the transparent inner well being located within a transparent outer well, the outer well being provided with material for cooling walls of the inner and outer wells; the inner well and the outer well defining separate chambers isolated from each other; and 2) a reaction vessel into which the UV lamp unit has been inserted; b) introducing into the reaction vessel a gaseous mixture of Cl2 and a distillation inseparable mixture of 1,1,1,3,3,3-hexafluoropropane and one or more unsaturated fluorocarbon compounds; c) reacting, in the gaseous state and in the presence of UV light from the photochlorinator, the mixture with Cl2 with the distillation inseparable mixture of 1,1,1,3,3,3-hexafluoropropane and one or more unsaturated compounds to saturate unsaturated fluorocarbons into a reacted mixture, and d) separating a purified 1,1,1,3,3,3-hexafluoropropane product containing less than 1000 ppm, most preferably less than 100 ppm unsaturated fluorocarbons.
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Page/Page column 8; sheet 1-3
(2008/06/13)
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- PROCESS FOR THE PRODUCTION OF 1,1,1,3,3,3-HEXAFLUOROPROPANE
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A process for the preparation of 1,1,1,3,3,3-hexafluoropropane is disclosed. The process involves (a) contacting at least one halopropane of the formula CF3CH2CHyX3-y (where each X is independently F, Cl or Br, and y is 3, 2, or 1) with Cl?2#191 in the presence of light or a free radical initiator to produce a mixture comprising CF3CH2CCIyX3-y; (b) contacting the CF3CH2CCIyX3-y produced in step (a) with HF, optionally in the presence of a fluorination catalyst, to produce a product mixture comprising CF3CH2CF3; and (c) recovering CF3CH2CF3 from the mixture produced in step (b).
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Page/Page column 14-15
(2008/06/13)
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- PROCESS FOR THE PREPARATION OF 1,1,1,3,3,3-HEXAFLUOROPROPANE AND AT LEAST ONE OF 1,1,1,2,3,3-HEXAFLUOROPROPANE AND 1,1,1,2,3,3,3-HEPTAFLUOROPROPANE
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A process is disclosed for the manufacture of 1,1,1,3,3,3-hexafluoropropane (HFC-236fa) and at least one 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). The process involves (a) reacting HF, Cl2, and at least one halopropene of the formula CX3CCl=CX2 (where each X is independently F or Cl) to produce a product including both CF3CCl2CF3 and CF3CClFCClF2; (b) reacting CF3CCl2CF3 and CF3CClFCClF2 produced in (a) with hydrogen to produce a product comprising CF3CH2CF3 and at least one compound selected from the group consisting of CHF2CHFCF3, and CF3CHFCF3; and (c) recovering from the product produced in (b), CF3CH2CF3 and at least one compound selected from the group consisting of CHF2CHFCF3 and CF3CHFCF3. In (a), the CF3CCl2CF3 and CF3CClFCClF2 are produced in the presence of a chlorofluorination catalyst including a ZnCr2O4/crystalline α-chromium oxide composition, a ZnCr2O4/crystalline α-chromium oxide composition which has been treated with a fluorinating agent, a zinc halide/α-chromium oxide composition and/or a zinc halide/α-chromium oxide composition which has been treated with a fluorinating agent.
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Page/Page column 16; 19
(2008/06/13)
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- Method of making 1,1,3,3,3-pentafluoropropene
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The invention provides an economic process for the manufacture of the hydrofluorocarbon 1,1,3,3,3-pentafluoropropene (HFC-1225zc). HFC-1225zc can be made from the dehydrochlorination of 1-chloro-1,1,3,3,3-pentafluoropropane (HCFC-235fa). Alternatively, HFC-1225zc can also be made from the dehydrofluorination of 1,1,1,3,3,3-hexafluoropropane (HFC-236fa). HFC-1225zc) is a compound that has the potential to be used as a low Global Warming Potential refrigerant, blowing agent, aerosol propellant, or solvent.
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Page/Page column 4
(2008/06/13)
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- Method of making fluorinated propanes
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The invention provides a process for the manufacture of fluoropropanes, and more particularly, the manufacture of 1,1,1,3,3,3-hexafluoropropane (HFC-236fa) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). The process utilizes 3-carbon by-products, i.e. waste material, from other commercial processes as raw material. The process also avoids the use of hexafluoropropane (HFP) as a reactant for making HFC-227ea, and is able to convert any three-carbon hydrocarbon (HC), hydrochlorofluorocarbon (HCFC), chlorofluorocarbon (CFC) compound or any halogenated propanes and produce high valued three-carbon hydrofluorocarbons (HFCs) at significantly lower cost than current commercial processes.
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- PROCESS FOR THE PREPARATION OF 1,1,1,3,3-PENTAFLUOROPROPANE AND 1,1,1,2,3-PENTAFLUOROPROPANE
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A process is disclosed for the manufacture of CF3CH2CHF2 and CF3CHFCH2F. The process involves (a) reacting hydrogen fluoride, chlorine, and at least one halopropene of the formula CX3CCl=CClX (where each X is independently F or Cl) to produce a product including both CF3CCl2CClF2 and CF3CClFCCl2F; (b) reacting CF3CCl2CClF2 and CF3CClFCCl2F produced in (a) with hydrogen to produce a product including both CF3CH2CHF2, and CF3CHFCH2F; and (c) recovering CF3CH2CHF2 and CF3CHFCH2F from the product produced in (b). In (a), the CF3CCl2CClF2 and CF3CClFCCl2F are produced in the presence of a chlorofluorination catalyst including a ZnCr2O4/crystalline α-chromium oxide composition, a ZnCr2O4/crystalline α-chromium oxide composition which has been treated with a fluorinating agent, a zinc halide/α-chromium oxide composition and/or a zinc halide/α-chromium oxide composition which has been treated with a fluorinating agent.
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Page/Page column 17; 19
(2008/06/13)
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- Systems and methods for producing fluorocarbons
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Systems and methods for producing fluorocarbons are provided that include contacting a saturated halogenated fluorocarbon with hydrogen and catalyst to produce a saturated hydrofluorocarbon and an unsaturated fluorocarbon. Aspects of the present invention describe systems and methods for contacting saturated halogenated fluorocarbons such as CF3CClFCF3 and/or CF3CCl2CF3 with hydrogen and catalyst. Systems and methods of the present invention also describe contacting saturated halogenated fluorocarbons with catalysts having one or more of K, Zr, Na, Ni, Cu, Ni, Zn, Fe, Mn, Co, Ti, and Pd. Aspects of the present invention also describe contacting saturated halogenated fluorocarbons with hydrogen under pressure. Saturated hydroflourocarbons and unsaturated fluorocarbons produced in accordance with the systems and methods of the present invention can include one or more of CF3CFHCF3, CF3CH2CF3, CF3CHClCF3, CF3CF═CF2, CF3CH═CF2, and CF3CCl═CF2.
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Page/Page column 3-14
(2008/06/13)
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- Process for purifying hydrofluoropropanes
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A process is disclosed for purifying a hydrofluoropropane of undesirable C2-C4 olefinic and C1-C4 saturated chlorinated impurities, comprising the steps of: contacting a first mixture of hydrofluoropropane, olefinic impurity and saturated chlorinated impurity with hydrogen and hydrogen fluoride concurrently in the presence of a bifunctional catalyst, for example an alloy of gold and palladium supported on carbon, capable of catalyzing hydrogenation and fluorination. During the contacting step, olefinic impurity is converted to saturated hydrogenated derivative and/or saturated hydrofluorinated derivativ, and saturated chlorinated impurity is converted to a saturated hydrodechlorinated derivative and/or saturated fluorinated derivative. The hydrofluoropropane thus formed is substantially free of both the olefinic and saturated chlorinated impurities and may be used as obtained or subject to further purification steps such as distillation to remove the process derivatives (e.g., hydrogenation, hydrodechlorination and hydrofluorination derivatives) from the hydrofluoropropane.
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- 2,2-Dihydroperfluoropentane (HFC 4310 mf) synthesis from HFP dimer
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The thermodynamic dimer of hexafluoropropene (HFP) may be used for the one pot synthesis of 2H-perfluoro-2-pentene, which is the starting compound for preparation of 2,2-dihydroperfluoropentane (HFC 4310 mf).
- Cheburkov, Yuri,Moore, George G.I.
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p. 227 - 231
(2007/10/03)
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- Reaction of fluoroolefins with sulfur chlorides in hydrogen fluoride-boron trifluoride system
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The reaction of tetrafluoroethylene (1), perfluorovinyl ether (3), hexafluoropropene (5), and 2-H-pentafluoropropene (7) with sulfur chlorides in anhydrous HF/BF3 system has been studied. The reaction with S2Cl2 at 40-100°C produces a mixture of the corresponding di- and trisulfides along with smaller amounts of sulfenyl- and thiosulfenyl chlorides. In case of 7 the use of BF3 catalyst results higher yields and selectivity of the process under milder conditions. The reaction of 5 and SCl2 in HF/BF3 at 100°C is selective, gives (CF3)2CFSCl, isolated in 65% yield.
- Petrov, Viacheslav A.
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p. 325 - 327
(2007/10/03)
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- Selective reduction of halopolyfluorocarbons by organosilicon hydrides
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It is demonstrated that silicon hydrides can be used for reduction of polyfluorinated halocarbons. For example, the reaction between CF3CCl2F and excess triethylsilane, catalyzed by benzoyl peroxide, leads to the formation of a mixture containing CF3CHClF (major), CF3CH2F, and ClSi(C2H5)3. On the other hand, the reaction of chlorofluoroalkanes, containing an internal -CCl2- group readily proceeds with reduction of both chlorines, leading to compounds such as (CF3)2CH2 and CF3CH2C2F5. In contrast to chlorofluoroalkanes, bromofluoroalkanes are much more reactive and reaction with hydrosilane rapidly proceeds without the catalyst at elevated temperature.
- Petrov, Viacheslav A.
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p. 7294 - 7297
(2007/10/03)
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- REACTIONS OF TRIFLUOROMETHYL AND TRIPLET METHYLENE RADICALS WITH SOME ALKYLSILANES
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The recombination of CF3 and CH2SiF3 radicals was used to prepare CF3CH2SiF3 by collisional stabilization of the initially formed hot molecule, CF3CH2SiF3*.One fate of this hot species, not so far observed, is its decomposition to give CF3CH2 and SiF3 radicals, a process which leads to additional products.In separate studies of the reactions of 3CH2 with CF3CH2SiF3, the formation of CH3SiF3 is observed, and this is suggested to be through a 5-coordinate radical exchange process.
- Bell, T. N.,Marciniak, B.,Sherwood, A. G.
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p. 3818 - 3820
(2007/10/02)
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- ROH Molecule Assisted Elimination of F- from (CF3)2CH- and (CF3)2CD- in Gas-Phase Elcb-Type Reactions
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The gas-phase reactions of the carbanion (CF3)2CH- with the following series of ROH molecules, (CF3)2CHOH, CF3CH2OH, (CH3)3COH, CH3OH, and H2O, are described.In each case, formation of ROH assisted Elcb elimination cluster ion F-(HOR)χ (χ =/> 1) was the major or exclusive reaction channel.The reactions of (CF3)2CD- with these ROH molecules were also examined to observe if D/H exchange occurred in the carbanion-HOR collisions and if deuterium was incorporated into the cluster ion of ROH assisted Elcb elimination.The results from the reactions of (CF3)2CH- and (CF3)2CD-6 with (CH3)3COH (i) the primary product ion was F-(HOC(CH3)3)2; (ii) extensive D/H exchange was observed in (CF3)2CD-, but no deuterium was observed in the fluoride cluster ion product; and (iii) D/H exchange and elimination occurred with the same rate constants> led to the proposal that coordination of (CH3)3COH occurred at two separate sites in the carbanion, C2 for D/H exchange and fluorine of a CF3 group for the ROH assisted Elcb elimination.The results from the collision limited reactions of (CF3)2CHOH and CF3CH2OH are consistent with this mechanistic proposal.The reactions of the carbanions with CH3OH and H2O were too slow to allow for detailed analysis.
- McDonald, Richard N.,McGhee, William D.,Chowdhury, A. Kasem
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p. 7334 - 7340
(2007/10/02)
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- Bis(trifluoromethyl)sulfine, (CF3)2C=SO: New Syntheses and Some Reactions
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New methods for the synthesis of bis(trifluoromethyl)sulfine (sulfoxide) (9) are reported.Pyrolysis, photolysis, and hydrolysis of the compound were investigated as well as the typical behaviour in reactions with the thiocarbonyl group (thiophosgene), with anthracene (Diels-Alder addition) and halogens.
- Elsaesser, Andreas,Sundermeyer, Wolfgang
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p. 4553 - 4560
(2007/10/02)
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- REACTION OF HYDROXY- AND CARBONYL COMPOUNDS WITH SULFUR TETRAFLUORIDE. XIV. REACTION OF ALIPHATIC OXOCARBOXYLIC ACIDS WITH SF4
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The reaction of mono- and dibasic 2-oxocarboxylic acids with sulfur tetrafluoride leads to loss of carbon monoxide.The resulting polyfluoroalkane products contain one less carbon atom than the starting oxoacid. 3-Oxopentanedioic and 4-oxopentanoic acids react with SF4 without cleavage of carbon-carbon bonds.Depending on the reaction conditions, the reaction products consist either of polyfluoroalkanes or acyl fluoride derivatives of fluorinated carboxylic acids.
- Bloshchitsa, F.A.,Burmakov, A.I.,Kunshenko, B.V.,Alekseeva, L.A.,Yagupol'skii, L.M.
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p. 1286 - 1291
(2007/10/02)
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