4-bromo-3,3,4,4-tetrafluorobut-1-ene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:170.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: An autoclave was charged with 108.5 g of dicyclopentadiene and 322.4 g of 1-bromo-1,1,2,2-tetrafluoro-3-butene. A solution of 0.3 g of 4-methoxyphenol dissolved in 5 ml of toluene was added to the autoclave as a polymerization inhibitor and the mixture was stirred for 5 hours at 170° C. The reaction product was purified by distillation under reduced pressure at 85° C. and 0.1 mmHg to obtain 226 g of 1-bromo-1,1,2,2-tetrafluoro-2-(tetracyclo[4.4.0.12,5.17,10]dodec-3-en-8-yl)ethane as a clear liquid (hereinafter referred to as “compound (5-a)”). was added to the autoclave as a polymerization inhibitor The reaction product was purified by distillation under reduced pressure at 85° C.

反応条件: temp:170.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: An autoclave was charged with 108.5 g of dicyclopentadiene and 322.4 g of 1-bromo-1,1,2,2-tetrafluoro-3-butene. A solution of 0.3 g of 4-methoxyphenol dissolved in 5 ml of toluene was added to the autoclave as a polymerization inhibitor and the mixture was stirred for 5 hours at 170° C. The reaction product was purified by distillation under reduced pressure at 85° C. and 25 mmHg to obtain 326 g of 1-bromo-1,1,2,2-tetrafluoro-2-(norborn-5-en-2-yl)ethane as a clear liquid (hereinafter referred to as “compound (1-a)”). was added to the autoclave as a polymerization inhibitor The reaction product was purified by distillation under reduced pressure at 85° C.

反応条件: temp:170.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: An autoclave was charged with 108.5 g of dicyclopentadiene and 322.4 g of 1-bromo-1,1,2,2-tetrafluoro-3-butene. A solution of 0.3 g of 4-methoxyphenol dissolved in 5 ml of toluene was added to the autoclave as a polymerization inhibitor and the mixture was stirred for 5 hours at 170° C. The reaction product was purified by distillation under reduced pressure at 85° C. and 25 mmHg to obtain 326 g of 1-bromo-1,1,2,2-tetrafluoro-2-(norborn-5-en-2-yl)ethane as a clear liquid (hereinafter referred to as “compound (1-a)”). was added to the autoclave as a polymerization inhibitor The reaction product was purified by distillation under reduced pressure at 85° C.

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A VF2/PMVE/TFE copolymer fluoroelastomer was prepared by a continuous emulsion polymerization process, carried out at 105° C. in a well-stirred 2.0-liter stainless steel liquid full reaction vessel. An aqueous solution, consisting of 1.98 g/hour (g/h) ammonium persulfate initiator and 0.79 g/h sodium hydroxide, was fed to the reactor at a rate of 4 L/hour. The reactor was maintained at a liquid-full level at a pressure of 6.2 MPa by means of a backpressure control valve in the effluent line. After 30 minutes, polymerization was initiated by introduction of a gaseous monomer mixture consisting of 569 g/h vinylidene fluoride (VF2), 393 g/h perfluoro(methyl vinyl ether) (PMVE), and 101 g/h tetrafluoroethylene (TFE), fed through a diaphragm compressor. Fifteen minutes after polymerization commenced, 4-bromo-3,3,4,4-tetrafluoro-1-butene (BTFB) was fed into the reactor at a rate of 10.0 g/h. After a further 1.75 hours, collection of effluent dispersion was begun and collection continued for 5 hours. The effluent polymer latex, which had a pH of 8.88 and contained 21.3 wt. % solids, was separated from residual monomers in a degassing vessel at atmospheric pressure. carried out at 105° C. in a well-stirred 2.0-liter stainless steel liquid full reaction vessel The reactor was maintained at a liquid-full level at a pressure of 6.2 MPa by means of a backpressure control valve in the effluent line polymerization Fifteen minutes after polymerization After a further 1.75 hours collection of effluent dispersion collection continued for 5 hours was separated from residual monomers in a degassing vessel at atmospheric pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Also, the sulfonic acid salt of formula (1) can be synthesized by starting with 4-bromo-3,3,4,4-tetrafluoro-1-butene which is readily available in the industry, effecting hydroboration with a borane such as 9-borabicyclo[3.3.1]-nonane (9-BBN) in a solvent such as n-hexane or tetrahydrofuran by a standard technique, treating the product with an oxidizing agent such as aqueous hydrogen peroxide in the presence of a base such as sodium hydroxide to form 4-bromo-3,3,4,4-tetrafluorobutanol, and esterifying it with carboxylic halide in the presence of a base such as triethylamine.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Also, the sulfonic acid salt of formula (1) can be synthesized by starting with 4-bromo-3,3,4,4-tetrafluoro-1-butene which is readily available in the industry, effecting hydroboration with a borane such as 9-borabicyclo[3.3.1]-nonane (9-BBN) in a solvent such as n-hexane or tetrahydrofuran by a standard technique, treating the product with an oxidizing agent such as aqueous hydrogen peroxide in the presence of a base such as sodium hydroxide to form 4-bromo-3,3,4,4-tetrafluoro-1-butanol, followed by conversion into a sulfinic acid form and subsequently into a sulfonic acid form.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A VF2/PMVE/TFE/BTFB fluoroelastomer was prepared by a continuous emulsion polymerization of the invention in a well-stirred 4.0-liter stainless steel liquid full reaction vessel at 110° C. An aqueous solution, consisting of 10.32 g/hour (g/h) ammonium persulfate, 4.53 g/h sodium hydroxide, and 8.9 g/h Zonyl® FS-62 fluorosurfactant (25 wt. % A.I) solution in deionized water, was fed to the reactor at a rate of 10 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 667 g/h tetrafluoroethylene (TFE), 872 g/h vinylidene fluoride (VF2), and 1138 g/h perfluoro(methyl vinyl) ether (PMVE) fed through a diaphragm compressor. After 15 minutes more, 4-bromo-3,3,4,4-tetrafluorobutene-1 (BTFB) added at a rate of 40.0 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 3.87 and contained 20.7 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 three times 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 15 kg of fluoroelastomer was recovered at an overall conversion of 96.0%. The product, containing 25.3 wt. % TFE units, 33.1 wt. % VF2 units, 40.0 wt. % PMVE units and 1.54 wt. % BTFB units, was an amorphous elastomer having a glass transition temperature of −22° C., as determined by DSC (heating mode, 10° C./minute, inflection point of transition). Inherent viscosity of the elastomer was 0.66 dL/g, measured at 30° C. in methyl ethyl ketone, and Mooney viscosity, ML (1+10), was 77. 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 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

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Also, the sulfonic acid salt of formula (1) can be synthesized by starting with 4-bromo-3,3,4,4-tetrafluoro-1-butene which is readily available in the industry, effecting hydroboration with a borane such as 9-borabicyclo[3.3.1]nonane (9-BBN) in a solvent such as n-hexane or tetrahydrofuran by a standard technique, treating the product with an oxidizing agent such as aqueous hydrogen peroxide in the presence of a base such as sodium hydroxide to form 4-bromo-3,3,4,4-tetrafluoro-1-butanol, followed by conversion into a sulfonic acid form and subsequently into a sulfonic acid form.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A VF2/PMVE/TFE copolymer fluoroelastomer was prepared by a continuous emulsion polymerization process, carried out at 105° C. in a well-stirred 2.0-liter stainless steel liquid full reaction vessel. An aqueous solution, consisting of 1.98 g/hour (g/h) ammonium persulfate initiator and 0.79 g/h sodium hydroxide, was fed to the reactor at a rate of 4 L/hour. The reactor was maintained at a liquid-full level at a pressure of 6.2 MPa by means of a backpressure control valve in the effluent line. After 30 minutes, polymerization was initiated by introduction of a gaseous monomer mixture consisting of 569 g/h vinylidene fluoride (VF2), 393 g/h perfluoro(methyl vinyl ether) (PMVE), and 101 g/h tetrafluoroethylene (TFE), fed through a diaphragm compressor. Fifteen minutes after polymerization commenced, 4-bromo-3,3,4,4-tetrafluoro-1-butene (BTFB) was fed into the reactor at a rate of 10.0 g/h. After a further 1.75 hours, collection of effluent dispersion was begun and collection continued for 5 hours. The effluent polymer latex, which had a pH of 8.64 and contained 20.7 wt. % solids, was separated from residual monomers in a degassing vessel at atmospheric pressure. carried out at 105° C. in a well-stirred 2.0-liter stainless steel liquid full reaction vessel The reactor was maintained at a liquid-full level at a pressure of 6.2 MPa by means of a backpressure control valve in the effluent line polymerization Fifteen minutes after polymerization After a further 1.75 hours collection of effluent dispersion collection continued for 5 hours was separated from residual monomers in a degassing vessel at atmospheric pressure