Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
  • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
  • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
  • C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
  • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur

Definitions

• This invention is directed to a method for preparing imides from compounds having a sulfonyl fluoride functional group.
• the imides so prepared are useful in a variety of catalytic and electrochemical applications.
• BACKGROUND OF THE INVENTION Compounds having a sulfonyl fluoride functional group are well known in the art.
• vinyl ethers and olefins having a fluorosulfonyl fluoride group have been found to be particularly useful as monomers for copolymerization with tetrafluoroethylene, ethylene, vinylidene fluoride and other olefinic and fluoroolefmic monomers to form polymers which, upon hydrolysis are converted to highly useful ionomers.
• X CH or N
• Z H, K, Na, or Group I or II metal
• R one or more fluorocarbon groups including fluorocarbon ethers and/or sulfonyl groups and or perfluoro non-oxy acid groups
• Y perfluoroalkyl or F
• m 0 or 1.
• CF 2 CF-OCF 2 CF 2 SO 2 Cl
• CF 3 SO 2 NHNa CF 3 SO 2 NHNa
• Xue's method is not applicable to the sulfonyl fluoride species without first protecting the double bond.
• CF 3 SO 2 NNa 2 made by combining CF 3 SO 2 NHNa and NaH in THF and reacting for four hours at room temperature. The inventors hereof have determined that Xue's method of preparation provides a conversion of less than 10% from CF 3 SO 2 NHNa to CF 3 SO 2 NNa 2 .
• CF 2 CF-OCF 2 CF 2 SO 2 N(Na)SO 2 CF 3 .
• CF 2 CFOCF 2 CF 2 SO 2 F and CF 3 SO 2 NHNa to produce an unusable complex mixture of products. Xue makes no suggestion that CF 3 SO 2 NNa 2 is effective at converting sulfonyl fluoride containing compounds to imides.
• MeuBdoerffer et al. Chemiker Science, 96. Jahrgang (1972) No. 10, 582-583 discloses a method for synthesizing RSO 2 NH 2 wherein R is perfluoroalkyl.
• Feiring et al., WO 9945048(A1 ) provides a method for imidizing fluorinated vinyl ether monomers containing a sulfonyl fluoride group by first protecting the double bond and then converting the sulfonyl fluoride into an imide.
• Armand et al, EPO 0 850 920 A2 discloses a method for imidizing sulfonyl fluoride and chloride species containing aromatic rings.
• R 3 is a diradical selected from the group consisting of fluorinated or non- fluorinated alkenyl. including oxyalkenyl or fluorooxyalkenyl, and each Z is independently hydrogen or halogen, and the Zs need not be the same; and, causing them to react to form a non-polymeric imide composition represented by the formula
• R 3 is a diradical selected from the group consisting of fluorinated or non-fluorinated alkenyl, including oxyalkenyl or fluorooxyalkenyl, each Z is independently hydrogen or halogen, wherein the Z's need not be the same;
• R 2 is aryl, fluoro-aryl, or XCF 2 - where X is H, halogen, fluorinated or non- fluorinated linear or cyclic alkyl radicals having 1-10 carbons, optionally substituted by one or more ether oxygens;
• M is an alkali when y is 1 or an alkaline earth metal when y is 2.
• reacting is intended to mean allowing or to allow at least two components in a reaction mixture to react to form at least one product. "Reacting” may optionally include stirring and/or heating or cooling.
• BRIEF DESCRIPTION OF DRAWING Figure 1 is a representation of the apparatus employed for determining the volume of hydrogen gas evolved from the reactions described in the specific embodiments herein.
• the process of the present invention represents a simple method of providing a very wide range of imides which can be readily and variously ion exchanged to provide superacid catalysts, electrolytes, and ionomers useful for electrochemical applications.
• Equally useful is the imidization of a polymer comprising monomer units of vinylidene fluoride and monomer units comprising a pendant group having sulfonyl fluoride functionality, particularly a perfluorovinyl ether perfluoroalkoxysulfonyl fluoride, such as described in Doyle et al., WO 9941292(A1).
• a polymer comprising monomer units of vinylidene fluoride and monomer units comprising a pendant group having sulfonyl fluoride functionality, particularly a perfluorovinyl ether perfluoroalkoxysulfonyl fluoride, such as described in Doyle et al., WO 9941292(A1).
• the methods of the art for converting sulfonyl fluorides to imides are not applicable to the copolymers of WO 9941292(A1) and others embodiments containing vinylidene fluoride monomer units because of the base instability of the
• the method of the present invention provides for conversion of sulfonyl fluoride to imide in vinylidene fluoride containing polymers without degradation of the polymer backbone.
• the term "hydrocarbyl” is employed to mean a monoradical consisting of carbon and hydrogen. Included in the term “hydrocarbyl” are alkyl, cycloalkyl, aryl, aryl alkyl and the like. Similarly, the term “hydrocarbenyl” is employed to mean a diradical consisting of carbon and hydrogen.
• hydrocarbyl and hydrocarbenyl radicals may contain one or more unsaturated carbon-carbon bonds, one or more ether oxygens, and may be partially or fully fluorinated.
• any hydrocarbyl or hydrocarbenyl radical is suitable for the practice of the invention except that radicals containing perfluorolefin functionality are not suitable for the practice of the invention.
• Perfluorovinyl ether functionality however is preferred.
• dimetal sulfonyl amide salts having the formula (R SO 2 NM b )3_ b M' c (III) are found to be highly effective agents for preparing imides from a wide variety of compounds having a sulfonyl fluoride functionality, both from polymeric and non-polymeric species.
• R 2 is fluoroalkyl having 1-4 carbons; most preferably R 2 is CF 3 -.
• the process of the invention may be conducted in the absence of an inert liquid diluent when a sufficient excess of a liquid R 1 (SO 2 F) m is provided to ensure good mixing.
• a liquid R 1 (SO 2 F) m is provided to ensure good mixing.
• the reaction may proceed inhomogeneously, and is potentially subject to sudden decomposition. Therefore, it is preferred to conduct the process of the invention in an inert liquid diluent.
• Numerous aprotic organic liquids are suitable for use as an inert liquid diluent for the process of the invention; the requirements are not strict beyond liquidity and inertness.
• Preferred liquids are ethers, including THF, nitriles, DMSO, amides, and sulfolanes. Ethers are more preferred, with THF most preferred.
• the reaction may be conducted at any temperature between the freezing and boiling point of the inert liquid diluent.
• Room temperature has been found to be satisfactory in the preferred embodiment of the invention. Temperatures from room temperature to 80°C are suitable, with room temperature to 60°C more preferred.
• the reaction mixture is preferably stirred or otherwise agitated according to means commonly employed in the art.
• the product of the process is most preferably as represented by the formula
• CF 2 CFO-[CF 2 CF(CF 3 )-O] n -CF 2 CF 2 SO 2 N(Na)SO 2 CF 3 (Vffl)
• n 0 or 1. It is a particularly surprising aspect of the present invention that the conversion of the -SO 2 F group may be effected without the necessity of protecting the double bond.
• the product so-formed, (VILT) may advantageously be employed as a comonomer with fluorinated olefins, non-fluorinated olefins, fluorinated vinyl ethers, non-fluorinated vinyl ethers, and combinations thereof.
• Preferred comonomers include ethylene, tetrafluoroethylene, hexafluoro- propylene, perfluoroalkyl vinyl ether, vinylidene fluoride, and vinyl fluoride.
• Copolymerizing the monomer (VIE) with a variety of co-monomers may be effected for example according to the teachings of DesMarteau, op.cit. or of Feiring et al., op.cit. or, more broadly, may be effected according the methods of Connolly et al., op.cit.
• the ionomers so formed are useful in a wide variety of electrochemical applications.
• the product monomer, (VIII) may be ion exchanged to the lithium form by contacting the monomer (VIII) with a dilute solution of LiCl in THF.
• the polymerizations indicated above may then be effected.
• the polymerizations may first be effected, followed by ion exchange with LiCl in THF.
• the preferred sodium imide of the invention can be treated with aqueous acid to form the acid followed by treatment with aqueous lithium salt to form the lithium ion composition.
• a sulfonyl fluoride polymer composition is contacted with the dimetal sulfonyl amide salt (III) in liquid dispersion or solution to form a reaction mixture.
• the polymer comprises monomer units represented by the formula
• R 3 is a diradical selected from the group consisting of fluorinated or non- fluorinated alkenyl, including oxyalkenyl or fluorooxyalkenyl, and each Z is independently hydrogen or halogen, and need not be the same.
• R 3 is oxyalkenyl.
• V is represented by the formula
• the polymer comprising the monomer units (IX) may comprise up to 50 mol % of said monomer units (IX).
• Comonomer units incorporated therewith may be derived from numerous olefinically unsaturated species as identified in the art including, ethylene, vinylidene fluoride- (VF 2 ), vinyl fluoride, and combinations thereof to form terpolymers. Additional termonomers include tetrafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ethers, and such other ethylenically unsaturated species as are known in the art.
• Particularly preferred for the practice of the invention is a copolymer comprising up to 50 mol %, most preferably up to 20 mol %, of comonomer units (IX) and comonomer units derived from VF 2 , most preferably at least 50 mol % of monomer units derived from VF 2 . It is a surprising aspect of the present invention that the copolymer of (IX) with at least 50 mol % of units derived from VF 2 can be successfully reacted according to the process of the invention to form the corresponding imide.
• Oligomeric polymers may themselves be liquids at or near room temperature and therefore are well-suited as the liquid dispersing medium of the process. However, it is generally preferred to employ an inert diluent, preferably a solvent for the polymer. As the molecular weight of the polymer increases, solubility and solution viscosity become increasingly difficult problems, making homogeneous reaction difficult.
• the preferred copolymer of VF 2 and comonomer (IX) is particularly well-suited to the practice of the present invention because of the relatively higher solubility of
• VF -containing polymers in non-fluorinated solvents than other fluoropolymers.
• Numerous aprotic organic liquids are suitable for use as solvents for the sulfonyl fluoride polymer composition in the process of the invention.
• solubility of the polymer reactant is a limiting factor.
• Preferred solvents are ethers, including THF, nitriles, DMSO, amides, and sulfolanes. Ethers are more preferred, with THF most preferred. Because of the limitations on solubility associated with high molecular weight, lower molecular weight polymers are preferred.
• Suitable and preferred reaction temperatures are as in the case of the non- polymeric reactant hereinabove described.
• R 3 is a diradical selected from the group consisting of fluorinated or non-fluorinated alkenyl, including oxyalkenyl or fluorooxyalkenyl, each Z is independently hydrogen or halogen, wherein the Zs need not be the same;
• R 2 is aryl, fluoro-aryl, or XCF 2 - where X is H, halogen, fluorinated or non- fluorinated linear or cyclic alkyl radicals having 1-10 carbons, optionally substituted by one or more ether oxygens;
• M is an alkaline earth metal.
• the process of the present invention is preferably practiced with a purified form of the dimetal sulfonyl amide salt (III).
• Xue, op.cit. teaches only a process which "provides very small amounts of highly contaminated (III).
• the inventors of the present invention have determined by ordinary methods of chemical analysis that Xue's process produced CF 3 SO 2 NNa 2 with conversion of less than 10%, most of the remainder of his reaction product being unconverted starting material. No method is provided in the art for preparing (III) in pure form.
• the dimetal sulfonyl amide salt starting material R 2 SO 2 NM ) 3 .
• the inventor hereof has found that surprisingly the dimetal sulfonyl amide salt (IU.) can be made at much higher purities than in Xue's process, purity of greater than 50%, preferably greater than 90%, most preferably greater than 95%, by contacting a sulfonyl amide or monometal sulfonyl amide salt thereof having the formula (R 2 SO 2 NH) 3 .
• a M",(VII) with at least one alkali or alkaline earth metal hydride and an aprotic liquid to form a reaction mixture which is permitted to react to any desired degree of conversion up to 100%, which is preferred.
• a 1 or 2
• R 2 is aryl, fluoro-aryl, or XCF 2 - where X is H, halogen, or a fluorinated or non-fluorinated linear or cyclic alkyl radical having 1-10 carbons, optionally substituted by one or more ether oxygens.
• the hydride may be a mixture of more than one alkali or alkaline earth hydrides, or a mixture of alkali and alkaline earth hydrides. If preferred, the reaction may proceed in stages with different hydrides being fed to the reaction at different times.
• R 2 is perfluoroalkyl, most preferably trifluoromethyl, and M" is sodium.
• CF 3 SO 2 NH 2 is the preferred starting material for preparing the CF 3 SO NNa 2 preferred for the process of the present invention.
• the preferred aprotic liquid is acetonitrile.
• the reaction to produce the CF SO 2 NNa 2 is continued until one or the other starting material is completely consumed and reaction stops. More preferably the stoichiometry is adjusted so that only trace amounts of either starting material remain when reaction is complete. Most preferably, the hydride is added at slightly below stoichiometric quantity.
• the sulfonyl amide and monometal salt thereof (VII) are soluble in the aprotic solvents employed in the process of preparing the dimetal sulfonyl amide salt (III), but the dimetal sulfonyl amide salt (III) itself is not.
• the solubility difference is exploited herein to separate the reaction product from the reaction mixture and obtain a composition comprising sulfonyl amide salts at least 50 mol %, preferably at least 90 mol %, most preferably at least 95 mol %, of which salts are represented by the formula (R 2 SO 2 NM b ) 3 . b M c ', (III), as hereinabove defined.
• any convenient method known in the art for separating solids from liquids may be employed, including filtration, centrifugation and, distillation. While it is preferred to permit the synthesis of (III) to run to completion, this may not always be practical depending upon the aprotic solvent chosen. In neat acetonitrile, 100% conversion is achieved in ca. 4 hours at room temperature. However, in neat THF, six days of reaction are required for 100% conversion. In the latter case, it may be desired to separate the reaction product before the reactants have fully reacted. The method of separation based upon the heretofore unknown solubility difference hereinabove described provides a practical method for isolating the dimetal sulfonyl amide salt (HI) at high purity when conversion has been low.
• HI dimetal sulfonyl amide salt
• the CF 3 SO 2 NNa 2 preferred for the process of the present invention is substantially free of contamination by NaH. This is achieved by employing slightly less than the stoichiometric amount of NaH in its preparation, thereby insuring that when the reaction achieves full conversion, the NaH will be exhausted. Any excess of the soluble intermediate CF 3 SO 2 NHNa is easily separated by washing/filtration cycles, preferably using fresh aliquots of solvent.
• the components of the reaction mixture may be combined in any order, but that it is preferred to first mix the sulfonyl amide or a monometal salt thereof (II), with the aprotic liquid to form a solution, following with addition of the hydride after the solution has formed. First mixing the hydride with the aprotic solvent has resulted in poor reaction or slower than expected conversion.
• a suitable temperature for preparing the dimetal sulfonyl amide salt (III) will lie between the melting point and the boiling point of the aprotic liquid selected. It has been found to be satisfactory for the practice of the invention to conduct the process of the invention at room temperature. However, somewhat highertemperatures result in faster reaction.
• acetonitrile is employed as the solvent at a temperature between 0°C and 80°C, preferably between room temperature and 80°C, most preferably between room temperature and 60°C.
• Aprotic solvents suitable for preparing the dimetal sulfonyl amide salt (III) should be substantially free of water.
• Water causes the reaction to go in the wrong direction, for example to form CF 3 SO 2 NHNa and NaOH, and provides a route for making a sulfonate instead of an imide.
• it has been found satisfactory to employ acetonitrile having water content less than or equal to ca 500 ppm, with water content less than or equal to ca. 50 ppm more preferred.
• Acetonitrile is quite hygroscopic, and care should be taken in handling to avoid water contamination from the atmosphere.
• the preferred aprotic solvent for the preparation of the dimetal sulfonyl amide salt (III) comprises acetonitrile.
• Acetonitrile has been found to accelerate the conversion by a considerable amount over other aprotic solvents. In neat acetonitrile, essentially quantitative conversion is achieved in ca. 4 hours. In the presence of as little as 5% acetonitrile in the THF taught by Xue,op.cit., essentially quantitative conversion is achieved in ca. 25 h. These results contrast starkly with the six days required under the conditions taught by Xue.
• Suitable nitriles include higher alkyl nitriles, dinitriles such as adiponitrile, benzonitrile, and the like.
• suitable solvents include ethers, DMF, DMSO, DMAC, and amides. Combinations of suitable solvents are also suitable.
• the atmosphere to which the dimetal sulfonyl amide salt (III) is exposed should be substantially free of water as well.
• Water vapor concentrations of about 25 ppm have been found to be highly suitable. Higher levels of water vapor concentration can be tolerated, but it should be understood that the higher the water vapor concentration of the atmosphere, the greater the contamination during subsequent reaction. As a general rule, the less water, the better, in whatever form.
• inert atmosphere refers to an anhydrous atmosphere having a water vapor concentration of less than ca. 50 ppm. It is not meant to imply a non-oxidative atmosphere. Thus, the reactions herein may be accomplished in desiccated air as well as in dry nitrogen or other non-chemically active gases. Dry nitrogen, however, is preferred.
• CF 3 SO 2 NH 2 is dissolved at a concentration in the range of 5-10% by weight in acetonitrile in an inert atmosphere such as nitrogen.
• an inert atmosphere such as nitrogen.
• good mixing may become more difficult to maintain as the insoluble CF 3 SO 2 NNa 2 product begins to form, creating a dispersion. Therefore at concentrations higher than about 10% by weight, other forms of agitation may be preferred over simple stirring, such as ultrasonic agitation, or microfluidization such as may be achieved using a MicroFluidizerTM available from Microfluidics, Inc., Newton, MA.
• the dimetal sulfonyl amide salt (III) may be dried under vacuum at elevated temperature but the user must be aware of the possibility of spontaneous and violent decomposition of the material. It is highly recommended to never handle this material in a totally dry state. It is highly recommended to keep the material wet at all times. It seems that the smaller composition CF 3 SO NNa 2 is less stable than the compositions of higher molecular weight like C4F9SO 2 NNa . A suitable temperature depends upon the specific composition thereof.
• the preferred CF 3 SO 2 NNa 2 should be dried at a temperature preferably not higher than 80°C, most preferably not higher than 65°C. Certain of the compositions of the invention, including the preferred CF 3 SO 2 NNa 2 , have been observed to undergo certain decomposition aggressively when heated to the decomposition threshold but it has also been observed at one occasion that the preferred
• EXAMPLE 1 CF 3 SO 2 NH 2 was purchased from Tokyo Chemical Industry, Portland, Oregon, (TCI) and dried and purified by two cycles of sublimation under a vacuum of about 10" 3 Torr, employing a water cooled ( ⁇ 20°C) cold-finger, and an oil bath at 80°C.
• Anhydrous acetonitrile was purchased from EM Science
• the temperature of the reaction mixture increased from 21.6°C to 50.5°C during the addition process.
• the mixture was stirred at room temperature for 20 h. After about 4-5 hours the reaction medium had taken on an opaque "creamy" appearance, and no further bubbling, indicative of the evolution of hydrogen, was observed.
• the reacted mixture was filtered through a glass-filter (medium porosity) inside the dry-box.
• the white solid was washed three times with 100 ml of the anhydrous acetonitrile, transferred from the filter to a Schlenk flask and dried under vacuum (10 -2 Torr) at room temperature for 5 h, still in the dry box. Approximately 10% of the filtrate was lost in transferring from the filter to the Schlenk flask.
• the Schlenk flask was sealed, removed from the dry-box, and subject to further evacuation under oil pump vacuum (10 -3 Torr) for 15 h at room temperature.
• the Schlenk flask was then immersed in an oil bath set at 50°C and held for four hours at which time the bath was heated to 65 °C and the Schlenk flask was held therein for an additional 20 h while still subject to evacuation under oil pump vacuum (10 -3 Torr). Afterwards, the CF 3 SO 2 NNa 2 was only handled inside the dry-box.
• EXAMPLE 3 Employing the reagents and equipment of Example 1, inside the dry-box 3.123 g of the sublimed CF 3 SO NH 2 was dissolved in 100 ml of the anhydrous acetonitrile in a round-bottom flask. 1 127 g of the sodium hyd ⁇ de was slowly added to form a first reaction mixture. Addition of NaH took place over a penod of 10 mm while the first reaction mixture was stirred with a magnetic stirring bar at room temperature.
• CF 2 CFOCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 F
• PSEPVE prepared according to the method of Connolly et al., U.S. Patent No. 3,282,875, was slur ⁇ ed with P 2 O 5 and distilled. 10.002 g of the thus- treated PSEPVE was added to the mixture of CF 3 SO 2 NNa 2 and acetonitrile prepared as hereinabove to form a second reaction mixture. The second reaction mixture was stirred at room temperature.
• reaction mixture was centrifuged and then filtered through a glass filter (medium porosity).
• the residue was washed with 100 ml of anhydrous acetonitrile. All volatiles were removed under vacuum and the slightly beige residue was heated to 1 10°C for 16 h at 10- 3 Torr. Yield was 8.358 g.
• EXAMPLE 5 Benzonitrile (Aldrich)was dried by mixing with P 2 O5 and then distilling. Employing reagents and equipment of Example 1, inside the dry-box 3.008 g of the sublimed CF 3 SO 2 NH 2 was dissolved in 90 ml of the dried benzonitrile in a round-bottom flask. To form a first reaction mixture, 1.018 g of the sodium hydride was slowly added while the reaction mixture was stirred with a magnetic stirring bar at room temperature. The reaction mixture changed its appearance after 10 min. A white precipitate was formed causing a thickening of the slurry. Shortly after, the reaction mixture changed its color to yellow. After 60 min, the reaction mixture was red.
• EXAMPLE 6 In this Example, an apparatus was employed for determining the volume of hydrogen gas evolved by the reaction as a function of time.
• the apparatus is depicted in Figure 1.
• a second neck was fitted with a thermocouple probe, 4, and a third neck was fitted with a stopcock, 5.
• the stopcock, 5, was connected via a 4 cm piece of Tygon® tubing, 6, to an Aldrich Safe-purge (TM) valve, 7, containing mineral oil.
• TM Aldrich Safe-purge
• the Safe-purge valve, 7, was connected via a rubber hose, 8, to a water-filled 250 ml graduated cylinder, 9, that is deployed upside-down in a water-filled 600 ml beaker, 10.
• liquid reactants were charged to the flask through any of the necks, SRAD, 3, was charged with the desired amount of solid reactant and reaffixed to the flask, 1, in the downward-pointing position shown in the figure.
• the beaker, 10, was filled to about 50% of capacity with water while the graduated cylinder, 9, was filled completely with water.
• the stopcock, 5, was opened, and the adaptor, 3, was inverted thus delivering the solid reactant to the reactants in the flask and thereby initiating the reaction.
• As hydrogen was evolved from the reaction it displaces the water from the graduated cylinder providing a volumetric means for determining the rate and total amount of hydrogen evolution.
• Example 2 Employing the methods and material of Example 1, inside the dry-box, 0.546 g of the sublimed CF 3 SO 2 NH 2 was dissolved in 100 ml of the anhydrous acetonitrile in the three neck round bottom flask of Figure 1. 0.213 g of the sodium hydride was carefully placed in the SRAD. The flask was carefully brought outside the dry box and connected to the remainder of the apparatus of Figure 1. After all connections had been established, the stopcock to the reaction flask was opened. The reaction mixture was stirred at room temperature and the SRAD was inverted thereby feeding the NaH to the solution in the flask.
• the reaction mixture was stirred at room temperature and the SRAD was inverted thereby feeding the NaH to the solution in the flask. No immediate reaction could be observed. Over the first 150 min, only a total of 10 ml of an evolving gas could be collected. After 150 min, the formation of gas started. Over the next 105 min, additional 135 ml of gas were collected in the graduated cylinder. During this period, the appearance of the reaction mixture changed. The fine residue in the reaction mixture changed to a thicker precipitation that settled easily at the bottom of the flask when the stirring was stopped. The reaction mixture was stirred for another 14 h at room temperature. 10 ml of additional gas were collected during this period. The flask was brought into the dry box and a sample of the solution was submitted for NMR. No fluorine could be detected, indicating the complete conversion of CF 3 SO 2 NHNa into insoluble CF 3 SO 2 NNa 2 . EXAMPLE 8
• Example 10 Following the procedure of Example 10, inside the dry-box, a 250 ml three neck round bottom flask was charged with 75 ml of anhydrous acetonitrile prepared as in Example 1. 0.189 g NaH was placed in the SRAD. 0.879 g of the CF 3 SO 2 NHNa of Example 10 was dissolved in 25 ml acetonitrile prepared as in Example 1 and placed in an addition funnel which substituted for the thermocouple of Example 10. After the required connections were made, the reaction mixture was stirred at room temperature and the NaH was immediately added to the solvent. 6 ml of gas were collected over a period of 3 h. The CF 3 SO 2 NHNa solution was added and the reaction mixture was continued to be stirred at room temperature.
• the reaction was completed after six days at room temperature.
• the reaction flask was brought inside the dry-box.
• CF 2 CFOCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 N(Na)SO 2 CF 3 and excess PSEPVE.
• EXAMPLE 10 Following the procedure of Example 11 , inside the dry-box, the round bottom flask was charged with 0.633 g of the CF 3 SO 2 NHNa of Example 11. The material was dissolved in 100 ml of anhydrous acetonitrile prepared as in Example 1. 0.103 g of NaH was placed in the SRAD. After the required connections were made, the reaction mixture was stined and heated by immersing the flask in an oil-bath set at 50°C. The reaction mixture was heated for 2 h and the pressure was allowed to equalize inside the flask. No pressure was released through the bubbler for 30 min. After 2 h of heating, the NaH was added to the solution. No obvious reaction could be observed for 20 min.. After 20 min., gas was released from the reaction mixture. Evolution of ca. 83 ml of gas was calculated to conespond to complete conversion.
• the residue was dried at 110°C for 24 h at 10" 3 Ton.
• the residue was redissolved in 100 ml of anhydrous acetonitrile and filtered through a paper filter. All volatiles were removed from the solution.
• the residue was dried at 110°C for 16 h at 10 ⁇ 3 Torr.
• EXAMPLE 14 As in Example 1, a round bottom flask was charged with 3.082 g of the CF 3 S ⁇ 2 NH 2 prepared as in Example 1 and 100 ml of anhydrous acetonitrile prepared as in Example 1. 1.134 g of the NaH (Aldrich) was added slowly over a period of 5 min. The mixture was stined at room temperature for 16 h inside the dry-box. No fluorine could be detected by NMR. 2.025 g of CH 3 SO 2 F (Aldrich, as received) was added. The reaction mixture thus formed was stined at room temperature for 2 h. The reaction mixture was centrifuged and all volatiles were removed. The residue was dried at 110°C for 24 h at 10 ⁇ 3 Ton.
• EXAMPLE 15 A 400 mL Hastelloy autoclave prechilled to ⁇ -20°C was charged with PSEPVE (150 g) and 15 mL of 0.17 M hexafluoropropylene oxide dimer peroxide. The vessel was closed, evacuated, then further charged with vinylidene fluoride (64 g) and CO (150 g), and shaken at room temperature for 18 hr. Excess pressure was released and the viscous residue was analyzed by 19 F NMR (acetone d 6 ) which clearly indicated residual monomer. Estimated conversion of PSEPVE was ca. 60%. The entire sample was devolatilized at 100°C (0.5 mm) for several hours.
• CH 2 CHCH 2 CF 2 CF 2 OCF 2 CF 2 SO 2 F was synthesized according to the teachings of Guo et al, Huaxue Xuebao (1984), 42(6), 592-5.
• CH 2 CHCH 2 CF 2 ACF 2 BOCF 2 CCF 2 DSO 2 N(Na)SO 2 CF 3 E: -80.60 ppm (CF 3 , E, 3F), -82.77 ppm (CF 2 , C, 2F), -88.90 ppm (CF 2 , B, 2F), -118.31 ppm (2 X CF 2 , A + D, 4F).
• CH 2 A CHBCH 2 CCF 2 CF 2 OCF 2 ⁇ : 2.87 ppm (CH 2 , C, tdt, 2H), 5.26 ppm (CH 2 , A, 2F) and 5.74 ppm (CH 2 , B, IF).

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (7)

Applications Claiming Priority (2)

Publications (1)

Family

ID=22611911

Family Applications (1)

Country Status (9)

Cited By (1)

Families Citing this family (6)

Citations (4)

Family Cites Families (5)

• 2000
  • 2000-12-01 WO PCT/US2000/032672 patent/WO2001040174A1/en not_active Ceased
  • 2000-12-01 CN CN00816376A patent/CN1402705A/zh active Pending
  • 2000-12-01 CA CA002389385A patent/CA2389385A1/en not_active Abandoned
  • 2000-12-01 JP JP2001541861A patent/JP4723149B2/ja not_active Expired - Fee Related
  • 2000-12-01 DE DE60012225T patent/DE60012225T2/de not_active Expired - Lifetime
  • 2000-12-01 KR KR1020027006864A patent/KR20020067534A/ko not_active Withdrawn
  • 2000-12-01 US US10/129,168 patent/US6759477B2/en not_active Expired - Fee Related
  • 2000-12-01 EP EP00980900A patent/EP1237858B1/en not_active Expired - Lifetime
  • 2000-12-31 AU AU18099/01A patent/AU1809901A/en not_active Abandoned

Patent Citations (4)

Also Published As

Similar Documents

Legal Events