1,1,3,3,3-pentafluoroprop-1-ene

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Fluorinated saturated and olefinic compounds formed by contacting HCC-230fa with HF in step (1) can include, for example, 1-chloro-1,3,3,3-tetrafluoro-1-propene (HCFC-1224zb), 1,1-dichloro-1,3,3,3-tetrafluoropropane (HCFC-234fb), 1,3-dichloro-1,1,3,3-tetrafluoropropane (HCFC-234fa), 1,1-dichloro-3,3,3-trifluoro-1-propene (HCFC-1223za), 1,1,1-trichloro-3,3,3-trifluoropropane (HCFC-233fb), 1,1,3-trichloro-1,3,3-trifluoropropane (HCFC-233fa), 1,1,3-trichloro-3,3-difluoro-1-propene (HCFC-1222za), 3,3,3-trichloro-1,1-difluoro-1-propene (HCFC-1222zc), 1,1,1,3-tetrachloro-3,3-difluoropropane (HCFC-232fb), 1,1,3,3-tetrachloro-1,3-difluoropropane (HCFC-232fa), 1,1,3,3-tetrachloro-3-fluoro-1-propene (HCFC-1221za), 1,3,3,3-tetrachloro-1-fluoro-1-propene (HCFC-1221zb) and 1,1,1,3,3-pentachloro-3-fluoropropane (HCFC-231fa). In addition, small amounts of 1-chloro-1,1,3,3,3-pentafluoropropane (HCFC-235fa), and 1,1,3,3,3-pentafluoro-1-propene (HFC-1225zc) may also be formed, particularly if a catalyst is present. When CCl3CH2CCl3 is used as the starting material, small amounts of CCl3CH=CCl2 (another possible starting material) can be formed in addition to fluorinated compounds. The step (1) reaction is controlled to provide a fluorinated product which includes no more than about 40 mole percent HFC-236fa. Fluorinated saturated and olefinic compounds formed

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The present process produces a 1:1 molar mixture of HF and CF3CH═CF2 in the reactor exit stream. The reactor exit stream can also contain unconverted reactant, CF3CH2CF3. The components of the reactor exit stream can be separated by conventional means, such as distillation. Hydrogen fluoride and CF3CH═CF2 form a homogenous low-boiling azeotrope containing about 60 mole percent CF3CH═CF2. The present process reactor exit stream can be distilled and the low-boiling HF and CF3CH═CF2 azeotrope taken off as a distillation column overhead stream, leaving substantially pure CF3CH2CF3 as a distillation column bottom stream. Recovered CF3CH2CF3 reactant may be recycled to the reactor. CF3CH═CF2 can be separated from its azeotrope with HF by conventional procedures, such as pressure swing distillation or by neutralization of the HF with caustic. The present process produces a 1 The components of the reactor exit stream can be separated by conventional means, such as distillation

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 100 mL Hastelloy shaker tube was loaded with 26.5 g (0.227 mole) chlorosulfuric acid, cooled in liquid nitrogen, evacuated and loaded with 30 g (0.225 mole) of 1,1,3,3,3-pentafluoropropene. The reaction vessel was allowed to warm and kept on a shaker at 40° C. at autogenous pressure for 6 hours. The pressure tube was unloaded, and the reaction mixture was added drop by drop into the flask containing 60 ml of ethanol at −10° C. over a 15 minute period. The reaction mixture was stirred overnight at 20° C. and then was poured into 200 ml of ice water. The organic layer was separated, washed with sodium bicarbonate, water, and dried under MgSO4. Distillation gave 31 g of CF3CH2COOEt (87%), bp 108-109° C. cooled in liquid nitrogen evacuated to warm the reaction mixture was added drop by drop into the flask The organic layer was separated washed with sodium bicarbonate, water dried under MgSO4 Distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 250 mL Hastelloy shaker tube was loaded with 60 g (0.51 mole) chlorosulfuric acid (HOSO2Cl), cooled in liquid nitrogen, evacuated and loaded with 60 g (0.45 mole) of 1,1,3,3,3-pentafluoropropene. The reaction vessel was allowed to warm and kept on a shaker at 20° C. at autogenous pressure for 24 hours. After 24 hours, the pressure tube was unloaded, and the reaction mixture quenched by ice and the organic layer washed with 5% sodium bicarbonate, water and dried under MgSO4. After distillation, 81.3 g of CF3CH2CF2OSO2Cl was obtained containing 6% of CF3CH2CF2OSO2F. cooled in liquid nitrogen evacuated to warm After 24 hours the reaction mixture quenched by ice the organic layer washed with 5% sodium bicarbonate, water dried under MgSO4 After distillation

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 100 mL Hastelloy shaker tube was loaded with 26.5 g (0.227 mole) chlorosulfuric acid, cooled in liquid nitrogen, evacuated and loaded with 30 g (0.225 mole) of 1,1,3,3,3-pentafluoropropene. The reaction vessel was allowed to warm and kept on a shaker at 40° C. at autogenous pressure for 6 hours. The pressure tube was unloaded, and the reaction mixture was added drop by drop into the flask containing 60 ml of ethanol at −10° C. over a 15 minute period. The reaction mixture was stirred overnight at 20° C. and then was poured into 200 ml of ice water. The organic layer was separated, washed with sodium bicarbonate, water, and dried under MgSO4. Distillation gave 31 g of CF3CH2COOEt (87%), bp 108-109° C. cooled in liquid nitrogen evacuated to warm the reaction mixture was added drop by drop into the flask The organic layer was separated washed with sodium bicarbonate, water dried under MgSO4 Distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 250 mL Hastelloy shaker tube was loaded with 60 g (0.51 mole) chlorosulfuric acid (HOSO2Cl), cooled in liquid nitrogen, evacuated and loaded with 60 g (0.45 mole) of 1,1,3,3,3-pentafluoropropene. The reaction vessel was allowed to warm and kept on a shaker at 20° C. at autogenous pressure for 24 hours. After 24 hours, the pressure tube was unloaded, and the reaction mixture quenched by ice and the organic layer washed with 5% sodium bicarbonate, water and dried under MgSO4. After distillation, 81.3 g of CF3CH2CF2OSO2Cl was obtained containing 6% of CF3CH2CF2OSO2F. cooled in liquid nitrogen evacuated to warm After 24 hours the reaction mixture quenched by ice the organic layer washed with 5% sodium bicarbonate, water dried under MgSO4 After distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The present process produces a 1:1 molar mixture of HF and CF3CH═CF2 in the reactor exit stream. The reactor exit stream can also contain unconverted reactant, CF3CH2CF3. The components of the reactor exit stream can be separated by conventional means, such as distillation. Hydrogen fluoride and CF3CH═CF2 form a homogenous low-boiling azeotrope containing about 60 mole percent CF3CH═CF2. The present process reactor exit stream can be distilled and the low-boiling HF and CF3CH═CF2 azeotrope taken off as a distillation column overhead stream, leaving substantially pure CF3CH2CF3 as a distillation column bottom stream. Recovered CF3CH2CF3 reactant may be recycled to the reactor. CF3CH═CF2 can be separated from its azeotrope with HF by conventional procedures, such as pressure swing distillation or by neutralization of the HF with caustic. The present process produces a 1 The components of the reactor exit stream can be separated by conventional means, such as distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under nitrogen, into a quartz reactor equipped with a dry-ice condenser was added anhydrous methanol (100 g, 3.10 mol) and di-tertiarybutylperoxide (3.95 g, 0.015 mol). The quartz reactor tube was placed in a Rayonet UV photochemical reactor and HFC 1225, CF3CH═CF2 (57.9 g, 0.438 mol) was added drop-wise via a dry-ice condenser (−78° C.) over a period of ˜5 hours while being irradiated at 254 nm. After complete addition, the reaction mixture was irradiated for additional hour. Then the reaction mixture was concentrated under reduced pressure, the residue (˜65 g) was mixed well with 120 mL aq. Na2SO3 (20%), separated the lower layer, and washed with brine (40 mL). The crude product was then distilled under reduced pressure (24-28 mm Hg) to afford 55 g CF3CH2CF2CH2OH (yield 77% based on HFC 1225). Under nitrogen, into a quartz reactor equipped with a dry-ice condenser was added drop-wise via a dry-ice condenser (−78° C.) over a period of ˜5 hours while being irradiated at 254 nm After complete addition the reaction mixture was irradiated for additional hour Then the reaction mixture was concentrated under reduced pressure the residue (˜65 g) was mixed well with 120 mL aq. Na2SO3 (20%) separated the lower layer washed with brine (40 mL) The crude product was then distilled under reduced pressure (24-28 mm Hg)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under nitrogen, into a quartz tube equipped with a dry-ice condenser was added anhydrous methanol (20 g, 0.62 mol) and di-tertiarybutylperoxide (.79 g, 0.003 mol). The quartz tube was placed in a Rayonet UV photochemical reactor and HFC 1225, CF3CH═CF2 (7 g, 0.05 mol) was added drop-wise via a dry-ice condenser (−78° C.) over a period of ˜30 minutes while being irradiated at 254 nm. After complete addition, the reaction mixture was irradiated for ˜30 minutes. The reaction mixture was concentrated under reduced pressure. The residue was extracted in diethyl ether (˜50 mL), washed with 20 mL aq. Na2SO3 (20%) and brine (10 mL). The ether layer was then concentrated to afford 7 g of the crude material which was distilled under reduced pressure (24-28 mm Hg) to afford CF3CH2CF2CH2OH (4.6 g, mol) as a colorless liquid. Yield=52% based on HFC 1225. Boiling point, 62° C./24-28 mm Hg. GC-MS: m/e 164 (C4H5F5O) for M+;19F and 1H NMR spectra are consistent with the structure. 19 F NMR (CDCl3)δ=−62.4 (3F, tt overlaps), −106.5 (2F, m) ppm; 1H NMR (CDCl3)δ=2.7 (1H, t), 2.9 (2H, m), 3.8 (2H, m) ppm. Under nitrogen, into a quartz tube equipped with a dry-ice condenser was added drop-wise via a dry-ice condenser (−78° C.) over a period of ˜30 minutes while being irradiated at 254 nm After complete addition the reaction mixture was irradiated for ˜30 minutes The reaction mixture was concentrated under reduced pressure The residue was extracted in diethyl ether (˜50 mL) washed with 20 mL aq. Na2SO3 (20%) and brine (10 mL) The ether layer was then concentrated to afford 7 g of the crude material which was distilled under reduced pressure (24-28 mm Hg)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A VF2/PMVE/TFE/2-HPFP fluoroelastomer was prepared by a continuous emulsion polymerization process of the invention in a well-stirred 4.0-liter stainless steel liquid full reaction vessel at 110° C. An aqueous solution, consisting of 3.5 g/hour (g/h) ammonium persulfate, 2.0 g/h sodium hydroxide, 8.4 g/h Zonyl® FS-62 fluorosurfactant (25 wt. % A.I.) solution, and 2.4 g/h isopropanol in deionized water, was fed to the reactor at a rate of 8 L/hour. The reactor was maintained at a liquid-full level at a pressure of 6.2 MPa by means of a back-pressure control valve in the effluent line. After 30 minutes, polymerization was initiated by introduction of a gaseous monomer mixture consisting of 185 g/h tetrafluoroethylene (TFE), 1237 g/h vinylidene fluoride (VF2), and 835 g/h perfluoro(methyl vinyl) ether (PMVE) fed through a diaphragm compressor. After 15 minutes more, 2-hydropentafluoropropylene (2-HPFP) was introduced into the remainder of the gaseous mixture and added at a rate of 68.5 g/h. After 2.0 hours, collection of the resulting fluoroelastomer latex was begun and continued for 6 hours. The latex, which had a pH of 5.23 and contained 22.6 wt. % solids, was separated from residual monomers in a degassing vessel at atmospheric pressure. Fluoroelastomer crumb product was isolated from the latex by reducing the pH to about 3 with dilute sulfuric and coagulating with aluminum sulfate solution. The coagulated fluoroelastomer polymer was allowed to settle, supernatant serum was removed, and the polymer was washed by reslurrying in water twice before filtering. The wet crumb was dried in an air oven at approximately 50°-65° C. to a moisture content of less than 1 wt. %. About 14 kg of fluoroelastomer was recovered at an overall conversion of 97.1%. The product, containing 8.2 wt. % TFE units, 54.1 wt. % VF2 units, 35.9 wt. % PMVE units and 1.84 wt. % 2-HPFP units, was an amorphous elastomer having a glass transition temperature of −30° C., as determined by DSC (heating mode, 10° C./minute, inflection point of transition). Inherent viscosity of the elastomer was 0.89 dL/g, measured at 30° C. in methyl ethyl ketone, and Mooney viscosity, ML (1+10), was 53. The reactor was maintained at a liquid-full level at a pressure of 6.2 MPa by means of a back-pressure control valve in the effluent line polymerization After 15 minutes more added at a rate of 68.5 g/h After 2.0 hours collection of the resulting fluoroelastomer continued for 6 hours was separated from residual monomers in a degassing vessel at atmospheric pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The test procedure described in Example 2 was repeated except that the catalyst was 0.5% Pd on alumina, the reaction temperature was held to approximately 150° C. and the duration of the test was approximately 12.6 hours. The mole ratio of hydrogen to CF3CCl2CF2Cl introduced into the quartz reactor was approximately 1.09. The reaction product was collected and its composition was determined. The reaction resulted in a conversion of CF3CCl2CF2Cl of about 97.8%, with a selectivity for CF3CH═CF2 of 6.8%, for CF3CCl═CF2 of 85.4%, and for CF3CHClCF2Cl of 3.8%. was held to approximately 150° C. The reaction product was collected

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Fluorinated saturated and olefinic compounds formed by contacting HCC-230fa with HF in step (1) can include, for example, 1-chloro-1,3,3,3-tetrafluoro-1-propene (HCFC-1224zb), 1,1-dichloro-1,3,3,3-tetrafluoropropane (HCFC-234fb), 1,3-dichloro-1,1,3,3-tetrafluoropropane (HCFC-234fa), 1,1-dichloro-3,3,3-trifluoro-1-propene (HCFC-1223za), 1,1,1-trichloro-3,3,3-trifluoropropane (HCFC-233fb), 1,1,3-trichloro-1,3,3-trifluoropropane (HCFC-233fa), 1,1,3-trichloro-3,3-difluoro-1-propene (HCFC-1222za), 3,3,3-trichloro-1,1-difluoro-1-propene (HCFC-1222zc), 1,1,1,3-tetrachloro-3,3-difluoropropane (HCFC-232fb), 1,1,3,3-tetrachloro-1,3-difluoropropane (HCFC-232fa), 1,1,3,3-tetrachloro-3-fluoro-1-propene (HCFC-1221za), 1,3,3,3-tetrachloro-1-fluoro-1-propene (HCFC-1221zb) and 1,1,1,3,3-pentachloro-3-fluoropropane (HCFC-231fa). In addition, small amounts of 1-chloro-1,1,3,3,3-pentafluoropropane (HCFC-235fa), and 1,1,3,3,3-pentafluoro-1-propene (HFC-1225zc) may also be formed, particularly if a catalyst is present. When CCl3CH2CCl3 is used as the starting material, small amounts of CCl3CH=CCl2 (another possible starting material) can be formed in addition to fluorinated compounds. The step (1) reaction is controlled to provide a fluorinated product which includes no more than about 40 mole percent HFC-236fa. Fluorinated saturated and olefinic compounds formed