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
  • C08G65/02—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
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
  • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
• • 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
• • 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
• • 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
  • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
  • C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
  • C08G65/3233—Molecular halogen
  • C08G65/3236—Fluorine
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2213/06—Perfluoro polymers

Definitions

• This invention pertains to perfluoropolyethers and perhalogenated chlorofluoropolyethers that can be prepared by fluorinating addition polymers made by polymerizing epoxides. More particularly this invention pertains to perhalogenated polyethers having the general formula:
• p is an integer between 1 and 50;
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are F, Cl, a perfluoroalkyl of one to 20 carbons or a perfluoroalkyl ether of two to 20 carbons wherein one or more fluorine atoms may be substituted by a halogen atom other than fluorine; wherein R 2 and R 8 when taken together can be
• R 9 through R 12 have the values of R 1 through R 8 ;
• X and Z are the same or different and are selected from the group consisting of -(CF 2 ) r OCF 3 , -(CF 2 ) r COF, -(CF 2 ) r COOH, -(CF 2 ) C(O)OCH 3 , -(CF 2 ) r CONH 2 wherein r is an integer from 1 to 12, perfluoroalkyl, perfluoroether and perfluoropolyether; wherein one or more of the fluorine atoms may be substituted by a halogen atom other than fluorine; wherein m is an integer from 0 to 10,000; n is an integer from 1 to 10,000; provided that when m is zero, Y is -CF 2 CF 2 -, n is greater than 20, and Z is -CF 2 COOH or -CF 2 COF, then X cannot be
• R 5 and R 6 are selected from a group consisting of F and Cl; and when m is zero and Y is -CF 2 CF 2 (CF 3 )- then (YO) n cannot be isotactic; and when m Is zero, when n is less than 200. and Y is
• R 1 , R 2 , R 3 and R 4 together cannot be F.
• the perfluoropolyethers and perhalogenated chlorofluoropolyethers of this invention can be used as heat transfer fluids, vapor phase soldering fluids, hydraulic fluids, base stocks for greases, lubricants, thermal shock fluids, and in numerous other applications in which an inert, nonflammable, oxidatively stable fluid is required.
• Monofunctional polymers of the present invention can further be used for surface treatments and as surfacants.
• Difunctional polymers can be useful as intermediates for preparing elastomers, sealants and protective coatings.
• the lubricity of the polyethers can be enhanced by increasing the number of chlorine substituents on the chain.
• the chlorinated compounds of the present invention are particularly useful as hydraulic and thermal shock fluids. Description of the Invention
• This invention pertains to perhalogenated polyethers of the general formula:
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are F, Cl, a perfluoroalkyl of one to 20 carbons, preferably 1 to 10 carbon atoms, or a perfluoroalkyl ether of two to 20 carbons, preferably 2 to 10 carbon atoms.
• one or more fluorine atoms may be substituted by a halogen atom other than fluorine (preferably chlorine).
• R 2 and R 8 when taken together can be - CR 9 R 10 CR 1 1 R 12 - wherein R 9 through R 12 may be any of the groups given for R 1 through R 8 .
• X and Z are the same or different and represent the terminal groups of the oligomer or polymer and may be fluorinated alkyls such as -CF 3 , -C 2 F 5 , -C 3 F 7 , -C 4 F 9 groups or they may be functional groups such as -(CF 2 ) r COF, -(CF 2 ) r COOH, -(CF 2 ) r OCF 3 , -(CF 2 ) r CONH 2 , -(CF 2 ) r C(O)OCH 3 wherein r is an integer from 1 to 12.
• X and Z may also be simple derivatives of the functional groups listed above such as
• R' is a hydrocarbon or fluorocarbon which contains one to ten carbon atoms and which may contain one or more ether oxygens and/or chlorine subs tituents.
• m is an integer from 0 to 10,000;
• n is an integer from 1. to 10,000 and
• p is an integer from 1 to 50 with a preferred range of 3 to 5, except that the provisos below apply.
• n and m subscripts in Formula I are average Indices of composition such that when m is zero the polyether is referred to as an isotactic or atactic homopolymer being composed of the repeating unit (YO); when m and n are both greater than zero the polyether is referred to as either a random copolymer, alternating copolymer or block copolymer of (YO) and (Y'O) repeating units.
• Y is -CF 2 CF 2 -
• Z is -CF 2 COOH, -CF 2 COF
• X cannot be -C 2 F 5 .
• -CF 2 CF 2 - and Z is -CF 2 COOH or -CF 2 COF, then X cannot be -CF 2 COOH, -CF 2 COF, -CF 2 CF 2 COOH, -CF 2 CF 2 COF, -CF or -C 3 F 7 .
• perhalogenated polyethers can be prepared by fluorinating addition polymers made by polymerizing 1,2-epoxides, 1,3- epoxides and higher epoxides.
• the polymers prepared from a polymerized 1,2-epoxide would have essentially the following formula:
• perfluoro -polyethylene oxide prepared by fluorinating the polymer resulting from the polymerization of ethylene oxide. Nonelastomeric perfluoropoly (ethylene oxide) is the subject of several U.S. Patents (See e.g., U.S. Patent No, 4,760,198).
• Perfluoropoly (ethylene oxide) polymers of this invention are elastomeric and have ethylene oxide repeat units (i.e., when R 1 , R 2 , R 3 and R 4 are all F, then n is 200 or more.
• a preferred compound of Formula II which is an elastomeric perfluorinated polyether, will have 200 to 10,000 repeating tetrafluoroethylene oxide units. The elastomers will have a molecular weight of approximately 20,000 a.m.u. or above.
• a perhalogenated polymer made from a polymerized 1,3-epoxide would have essentially the following formula:
• R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 may be the same or different and may be selected from the group consisting of -Cl, -F, -CF 3 , -CF 2 Cl, -C 2 F , -C 3 F 7 , -C 4 F 9 , -OCF 3 , -OC 2 F 5 , and perfluoro- alkyl of one to 20 carbons (preferably 1 to 10 carbons), or a perfluoroalkyl ether of two to 20 carbons (preferably 2 to 10 carbons) wherein one or more of the fluorine atoms may be substituted by a halogen atom other than fluorine; wherein R 1 , R 2 , R 3 and R 4 together are not fluorine if R 5 and R 6 are selected from a group consisting of F and Cl.
• X and Z and n are as defined above.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 either
• n is an Integer from 200 to 10,000.
• perfluoropolyethers where m is zero and X, Z and n are defined above, are shown below. Polymers of this type may be isotactic or atactic homopolymers.
• perhalogenated polyethers where m and n are greater than zero and X and Z are defined above having the following compositions:
• Perfluoropolyethers and perhalogenated chloro fluoroethers can also be made having the formula:
• X, Z, R 1 , R 2 , n and p are as previously defined.
• p is an integer from 3 to 5.
• perfluoropolyethers can be made having the formula:
• X and Z are selected from the group consisting of -CF 3 , -C 2 F 5 , -C 3 F 7 , -G 6 F 13 , COF, -CF 2 OCF 3 , -CF 2 COF, -COOH, and CF 2 COOH, and wherein n is an integer from 1 to 10,000.
• This invention further pertains to a method of making perhalogenated compounds, such as perfluoropolyethers and perhalogenated chlorofluoropolyether polymers.
• Two basic types of polymers can be prepared from alkylene oxides.
• the first involves the reaction of the epoxide with compounds having one or more labile hydogens such as water, phenol, alcohols, acids, etc.
• the products obtained, generally speaking, have from 2 to 100 alkylene oxide units.
• the second type of polymer Is characterized by a much higher molecular weight often exceeding 1,000,000.
• the polymers are prepared by treating the epoxide with Lewis acids, bases, as well as numerous other catalysts.
• the hydrocarbon polyethers are best converted to fluorocarbons using fluorine gas which is commercially available at sufficiently high purity levels and at an acceptable cost.
• the fluorination reaction is generally carried out at a temperature from -40 to +150°C, preferably from -10 and +50°C. It can be carried out in a reactor containing an ultraviolet light source or in the dark. Using the preferred temperature range, it is not necessary to have an ultraviolet light source since the fluorine is sufficiently reactive. If an ultraviolet light source is used, a wavelength between 250 and 350 nm is preferred. When the reactor is radiated with an external light source, a transparent window is needed which does not react with either fluorine or hydrogen fluoride. A quartz lens coated with a thin film of fluorinated ethylene -propylene copolymer works well.
• the fluorination reaction can be carried out in a variety of ways.
• the polyether can be coated on a sodium fluoride powder to give a free-flowing powder which can be fluorinated in either a stationary tube, in a rotating drum- type reactor, or in a fluidizing bed. See U.S. Patent No. 4,755,567.
• the polyether can be fluorinated in a liquid phase fluorination reactor. See U.S.
• a typical laboratory- size reactor for example, has a volume of about 10 liters and contains approximately 2 to 8 liters of a suitable fluorine-inert liquid.
• Perhalogenated chlorofluorocarbons are typically used as the fluorine- inert fluorination medium.
• perfluorocarbons such as FluorinertTM FC75 (3M
• Fluorination can be carried out in a batch mode where the hydrocarbon precusor which is to be
• the reactor is charged with the liquid fluorination medium, placed in a constant temperature bath and purged with an inert gas, such as nitrogen gas. If 1,1,2-trichlorotrifluoroethane is used as the liquid medium, a condenser is placed downstream from the reactor and is maintained at -35°C.
• the hydrocarbon polyether may be fed into the reactor neat, if it has a sufficiently low viscosity, or it may be diluted with a suitable solvent. If the fluorination is being carried out in 1,1,2-trichlorotrifluoroethane, the organic feed can be conveniently diluted with the same solvent. If the hydrocarbon is insoluble in the fluorination medium, it can usually be fluorinated as an emulsion or suspension in the liquid fluorination medium. For example, a polyether such as a 2000 MW polyethylene glycol can be dissolved in an equal volume of 1,1,2-trichlorotri- fluoroethane if a small amount of chloroform is added (10 to 20 volume percent). The diluted polymer solution when fed into a fluorination reactor containing 1,1,2-trichlorotrifluoroethane forms an emulsion which can be conveniently fluorinated.
• a polyether such as a 2000 MW polyethylene glycol can be dissolved in an equal volume of 1,1,2-t
• solvents with high solvating power for polyethers which consume little if any fluorine include trichloroe thane, trifluoroacetic acid, trifluoroacetic anhydride, etc.
• the polyether is fed into the reactor at a rate of 10 to 60 grams per hour.
• Fluorine gas is delivered to the vigorously stirred reactor at a rate sufficient to react with all of the organic feed plus an additional 5 to 10 percent.
• the fluorine gas is diluted with an inert gas such as nitrogen. This is of particular importance if a liquid fluorination medium such as 1,1,2-trichlorotrifluoroethane is used. It is imperative to keep the fluorine concentration low so that the liquid fluorination medium and fluorine in the vapor space do not form a flammable mixture.
• the flammability limits of various solvents in fluorine gas can be determined by spark testing.
• a fluorine concentration of 10 to 40% works well. If operating properly, the fluorine concentration in the exit gas will be between 2 and 4%.
• the continuous addition reactor may be operated in a batch or continuous mode. If operating continuously, a small portion of the reactor contents is removed continuously or periodically. The product is recovered by distillation and the fluorination liquid is returned to the reactor.
• a hydrogen fluoride scavenger such as sodium fluoride or potassium fluoride may or may not be present in the solution to scavenge the by-product hydrogen fluoride.
• the preferred mode for carrying out the reaction for many polyethers is with a sufficient quantity of a hydrogen fluoride scavenger being present to complex with all of the hydrogen fluoride formed.
• Polyethers containing sterically hindered oxygens and/or chlorine in the vicinity of the oxygen can be fluorinated in high yield without having a hydrogen fluoride scavenger present. Naturally, these reactions are more amenable to continuous processes than those reactions requiring a hydrogen fluoride scavenger.
• the polymers prepared according to the method of the invention range in molecular weight from about 300 to 1,000,000 a.m.u. in size. Generally speaking, products having an average molecular weight below 10,000 a.m.u. are liquids while those having a molecular weight above 10,000 are solids.
• the perhalogenated of the present invention have distinct advantages over the materials prepared by the prior art.
• High molecular weight polymers can be prepared thereby making it possible to make elastomers directly. Due to the versatility of the process, a wide variety of structures can be prepared giving fluids and elastomers with greatly varying physical properties.
• compounds of the present invention which are useful as hydraulic fluids will have a molecular weight range of from about 200 to about 2,000 a.m.u. and a preferred molecular weight range of from about 500 to about
• the polyethers are typically oils. They can be used as base oils in lubricant compositions and can be admixed with optional additives and fillers to enhance the performance of the lubricant composition.
• Particularly suitable base oils are perhalogenated chlorofluoropolyethers, such as perfluoropolyepichlorohydrin having a molecular weight of from about 500 to about 5000 a.m.u. (See U.S. Patent Application Serial No. 07/355,771, filed May 23, 1989, the teachings of which are incorporated by reference.)
• Perhalogenated polyethers of this invention which can be useful as lubricants or hydraulic fluids will have inert terminal groups, such as perfluoroalkyl groups.
• the terminal groups are determined by the repeat unit.
• a polymer comprising essentially tetraethylene oxide repeat units can have terminal groups of -CF 3 or -C 2 F 5 .
• a high molecular weight perfluoropoly (ethylene oxide) elastomeric solid can be prepared by
• polymers made by polymerization of tetrafluoroethylene oxide are generally either fluids or low melting waxes.
• the polymerization of tetrafluoroethylene oxide is quite hazardous and has on several occasions resulted in unexplained explosions.
• the fluorination of heptaglyme can be carried out with a yield in excess of 50% to give perfluoroheptaglyme- a potentially useful vapor phase soldering fluid (b.p. 205°C).
• the compounds of this invention which are useful as vapor phase soldering fluids will have boiling points sufficiently high to melt the solder, a molecular weight range of from about 400 to 1,500 a.m.u. and a preferred molecular weight range of from about 600 to about 1000.
• perfluoropolyether polymers having a variety of terminal groups.
• treatment of a hydroxyl terminated polymer prior to fluorination with thionyl chloride gives a CF 2 Cl terminated polymer.
• Reaction of a diol with acrylonitrile in the presence of base followed by acid catalyzed alcoholysis gives -OCH 2 CH 2 C(O) OR terminal groups.
• the above difunctional fluid can be subjected to a Hunsdelcker reaction to give stable Iodine- terminated prepolymers.
• a polyether terminated with hydroxyl groups can be treated with methacrylonitrile in the presence of a base to give a polymer which upon acid catalyzed alcoholysis gives a
• Perfluoroalkyl pendant groups are known to sterically protect functional groups from attack by nucleophiles.
• poly (propylene glycol) further demonstrates the versatility of the present invention. If an isotactic polymer is fluorinated, a polymer is prepared with a structure essentially identical to that of the fluid prepared by polymerization of hexafluoropropylene oxide. One can also prepare an atactic perfluoropolypropylene oxide.
• Propylene oxide typically polymerizes in a randlo(rn fashion with head- to -head, head-to-tail and tail- to-tail addition occuring.
• Atactic perfluoropoly- (propylene oxide) has slightly improved low temperature properties than the isotactic polymer.
• Polymers having properties intermediate between perfluoropoly (ethylene oxide) and perfluoropoly- (propylene oxide) can be prepared by fluorinating copolymers of ethylene oxide and propylene oxide.
• the hydrocarbon polyethers can be prepared with a wide variety of ethylene oxide and propylene oxide ratios.
• the copolymers can be both random copolymers or block copolymers.
• Fluorinated telomers of epichlorohydrin and 3,3- bis (chloromethyl) oxetane can be prepared by the method of this invention.
• These fluids contain a significant amount of chlorine placed on primary carbons.
• the oxidative stability and oxidationcorrosion behavior of these materials are similar to that of perfluoropolyethers which do not contain chlorine.
• the chlorine increases the lubricity of the fluid and significantly increases the bulk modulus of the material making these fluids promising nonflammable hydraulic fluid candidates.
• other nonflammable hydraulic fluids presently being considered such as those based on telomers of chlorotrifluoroethylene are much less stable owing to the wide variety of chlorinated structures within the fluid. Many of these structures have limited high temperature stability.
• the amount of chlorine substitution on the primary carbons depends upon what the perhalogenated compound will be used for. For example, hydraulic fluids will typically contain from about 20 to about 40% chlorine atoms.
• Fluorine gas diluted with nitrogen to give a concentration of 20%, was bubbled through the vigorously stirred fluorination liquid at a rate 10 to 15% higher than that required to theoretically repace all of the hydrogen on the hydrocarbon being pumped into the reactor. Following the reaction, the reactor was purged with several volumes of nitrogen to remove the unreacted fluorine gas. Next, 154g methanol was pumped into the reactor. The reactor warmed slightly as the perfluorodiester reacted with the methanol to give the hydrolytically more stable dimethyl ester. The product was filtered to remove the sodium
• a perfluoropolyether elastomer was prepared by dissolving 146g of an 18,500 a.m.u poly (ethylene glycol) in 354g of chloroform containing 564g of 1,1,2-trichlorotrifluoroethane. The viscous solution was slowly pumped into a 10°C reactor containing 5 liters of 1,1,2-trichlorotrifluoroethane and 800g of sodium fluoride. Twenty percent fluorine, diluted with nitrogen, was metered into the reactor
• Example 2 Using the procedures outlined in Example 1, a solution consisting of 280g of poly (tetramethylene ether) glycol (terminal groups treated witht acetyl chloride to give a diester) having an average molecular weight of 2000 and 550 ml of 1,1,2-trichlorotrifluoroethane was slowly metered, over a 32 hour period, into a 5°C fluorination reactor containing 5 liters of 1,1,2-trichlorotrifluoroethane and 1400g of sodium fluoride powder. Upon completing the reaction, the reactor was purged with several volumes of nitrogen to remove the unreacted fluorine gas. Methanol (150g) was added to the reactor.
• a high molecular weight perfluoropolyepichlorohydrin fluid having properties similar to those required for a vacuum pump fluid, was prepared by reacting 50g 2-chloroethanol (0.63 mol) with 462g epichlorohydrin (5.0 mol) using a catalytic amount of SnCl 4 .
• the product (402g) diluted with 275g chloro- form and 175g 1,1,2-trichlorotrifluoroethane, was metered into a fluorination reactor over a 20 hour period.
• the reactor a 10 liter stirred tank, contained 5.7 liters 1,1,2-trichlorotrifluoroethane.
• the temperature was maintained near 20°C while 20% fluorine was delivered to the reactor at a rate sufficient to react with all of the hydrogens on the product being pumped in.
• the fluorinated product (573g, 89.8% yield) was separated from the solvent via an atmospheric distillation.
• the product was treated at 200°C for 12 hours to remove any residual hydrogen and to convert any carbonyl groups present to difluoromethylenes.
• the portion of the product approximately 25%, having a boiling point between 200 and 300°C at 0.05 mm Hg was collected.
• the average molecular weight by 19 F NMR end group analysis was approximately 3000.
• the fluid had a pour point of -22°C.
• a random copolymer of perfluoro (propylene oxide) and perfluoroepichlorohydrin was prepared by treatment of perfluoropolyepichlorohydrin with fluorine at high temperatures. For example, 300g of the product from the previous example was treated with 30% fluorine for 24 hours at 300°C to give 285g of fluid in which approximately 30% of the chlorine was replaced by fluorine. Average molecular weight by 19 F NMR end group analysis was 2800 a.m.u.
• the crude product (275g) has a melting point of 60°C.
• a 3 liter flask was charged with 267g of trichloropentaerythritol and 1 ml of boron trifluorideetherate.
• To this was added 347g of epichlorohydrin (3.75 mol) dropwise over a one hour period while the reaction temperature was maintained below 50oC throughout the addition.
• the ure was stirred for an additional 12 hours at amb temperature resulting in a viscous oil.
• a low molecular weight polymer of 3,3-bis- (chloromethyl)oxetane was prepared by mixing 200g of 3,3-bis(chloromethyl)oxetane with a catalytic amount of boron trifluoride-etherate.
• the polymer was mixed with 1100g sodium fluoride powder and placed in a 20 liter rotating aluminum reactor.
• the polymer was fluorinated at 0°C with 20% fluorine in a 22 hour reaction.
• the reactor temperature was slowly increased to 80°C over the next 20 hour period.
• the reactor contents were then exposed to pure fluorine (400cc/min) for 10 hours.
• the reactor was cooled and purged with several volumes of nitrogen prior to opening.
• the reaction mixture was extracted with 1,1,2-trichloro- trifluoroethane to give 310g of a medium viscosity oil.
• the insoluble portion was mixed with water and refiltered to give 53g of a solid polymer having a structure believed to be identical to that of the lower molecular weight fluid.
• the total yield was 363g which corresponds to a yield of 94% based on the following structure:
• the fraction having a boiling point between 90 and 210°C at 50mm Hg was collected and considered as a potentially useful nonflammable hydraulic fluid.
• the fluid had a viscosity of 9.5 cst. at 100°F.
• 480g of high molecular weight (1 million) polyethylene oxide was mixed with 2,400g sodium fluoride powder (passed over a 100 mesh sieve) and placed in a rotating drum reactor. After purging for two hours at 3 liters per minute nitrogen flow, the fluorine flow was set at 480 liters per minute. These conditions were maintained for about 36 hours after which time the nitrogen flow was reduced to 1.5 liters per minute and the fluorine flow was held at 480 cc/min. These conditions were maintained for about 8 hours and then the nitrogen flow was cut off and the reactor contents were exposed to pure fluorine (480 cc/min) for 4 additional hours or until a significant amount of fluorine comes out of the reactor.
• the perfluoropoly ( ethylene oxide) was separated from the NaF/NaHF 2 by washing with approximately 15 gallons of water. About 1050g of per fluoropoly (ethylene oxide) solids were obtained (83%).
• Butoxyethoxyethanol (300g, 1.85 mol) was treated with 200g acetyl chloride (2.54 mol) to give an ester which was separated from the product mixture by distillation.
• a portion of the product (250g) was diluted to a volume of 610 ml with 1,1,2-trichlorotrifluoroethane, then pumped into a -10°C reactor over a 23 hour period.
• a diacetate ester of tetraethylene glycol was prepared by slowly adding 600g acetyl chloride to 500g tetraethylene glycol in a stirred 2-liter flask. Upon addition of the acetyl chloride, the reaction mixture was heated to 50°C and held at that
• a diacetate ester of triethylene glycol was prepared by slowly adding 400g acetyl chloride (5.1 mol) to 300g triethylene glycol (2.0 mol) in a stirred 1 liter flask. The reaction mixture was kept below 50°C throughout the addition. The product was recovered by first bubbling dry nitrogen through the solution to remove most of the hydrogen chloride followed by a distillation.
• the product from the above reaction (250g) was diluted to 600ml with 1,1,2-trichlorotrifluoroethane then pumped into a -20°C reactor containing 5 liters of 1,1,2-trichlorotrifluoroethane and 1200g sodium fluoride powder. Fluorine, diluted with nitrogen, was bubbled through the liquid fluorination medium throughout the addition which required approximately 18 hours. After purging the reactor for approximately 30 minutes, 240g methanol was added and the reactor was warmed to room temperature. Distillation of the reactor contents gave 355 grams (95% yield) of a product with the following composition.
• a 200g sample of polypropylene glycol having an average molecular weight of 425 was diluted to 350 ml with 1,1,2-trichlorotrifluoroethane and slowly pumped into a 20°C fluorination reactor over a 22 hour period.
• the reactor contained 4 liters of 1,1,2- trichlorotr ifluoroethane as the fluorination liquid.
• 1000g sodium fluoride pellets were placed.
• a teflon-diaphragm air pump was used to circulate the gases present in the reactor through the sodium fluoride bed and back into the fluorination reactor.
• the perfluorinated fluids described in this example and the previous one were atactic polymers of hexafluoropropylene oxide.
• the hexafluoropropylene oxide units were attached in a head to tail, head to head and tail to tail fashion.
• 1,1,2,2-tetramethylethylene oxide was prepared by reacting 200g tetramethylethylene with 450g of 40% peracetic acid in 300ml methylene chloride containing 400g anhydrous sodium carbonate.
• the epoxide was polymerized with borontrifluoride etherate at -78°C to give a hard, insoluble polymer which can be ground to a fine powder.
• a po lymer having an average molecular we ight of approximately 2000 a.m.u. was prepared by polymerizing 1,4-epoxycyclohexane with a catalytic amount of trifluoromethane sulfonic anhydride. Fluorination of the polymer gave a 75% yield of a perfluoropolyether having the structure:

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• 1989
  • 1989-09-28 CA CA000613892A patent/CA1339144C/en not_active Expired - Lifetime
  • 1989-09-28 KR KR1019900701119A patent/KR0164217B1/ko not_active IP Right Cessation
  • 1989-09-28 WO PCT/US1989/004212 patent/WO1990003409A1/en not_active Application Discontinuation
  • 1989-09-28 EP EP89911202A patent/EP0436628A1/en not_active Withdrawn
  • 1989-09-28 JP JP1510459A patent/JP3069112B2/ja not_active Expired - Lifetime
  • 1989-09-28 AU AU43414/89A patent/AU4341489A/en not_active Abandoned

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