WO1994025547A1 - Lubricants containing perfluorocyclobutane rings - Google Patents
Lubricants containing perfluorocyclobutane rings Download PDFInfo
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- WO1994025547A1 WO1994025547A1 PCT/US1994/004274 US9404274W WO9425547A1 WO 1994025547 A1 WO1994025547 A1 WO 1994025547A1 US 9404274 W US9404274 W US 9404274W WO 9425547 A1 WO9425547 A1 WO 9425547A1
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- lubricant
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/17—Unsaturated ethers containing halogen
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
- C07C65/24—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups polycyclic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D157/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
- C09D157/08—Homopolymers or copolymers containing elements other than carbon and hydrogen containing halogen atoms
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- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
- C10M105/54—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen containing carbon, hydrogen, halogen and oxygen
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- 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
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- 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
- C10M131/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen
- C10M131/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen containing carbon, hydrogen, halogen and oxygen
- C10M131/10—Alcohols; Ethers; Aldehydes; Ketones
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- 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
- C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
- C10M147/04—Monomer containing carbon, hydrogen, halogen and oxygen
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/72—Protective coatings, e.g. anti-static or antifriction
- G11B5/725—Protective coatings, e.g. anti-static or antifriction containing a lubricant, e.g. organic compounds
- G11B5/7253—Fluorocarbon lubricant
- G11B5/7257—Perfluoropolyether lubricant
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/16—Dielectric; Insulating oil or insulators
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/17—Electric or magnetic purposes for electric contacts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/175—Pantographs, i.e. printing devices
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/18—Electric or magnetic purposes in connection with recordings on magnetic tape or disc
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/185—Magnetic fluids
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol fueled engines
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
- C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
Definitions
- the present invention is related to lubricants, more particularly lubricants useful over a large temperature range.
- lubricants are needed for magnetic recording media such as high density rigid disks, ultra high density floppy disks, digital audio tapes and video tapes which can be read by a magnetic recording head.
- a recording head In use of these media, a recording head is in very close proximity to the recording media and frequently contacts the recording media. Such contact causes wear of the thin layer of magnetic material on the recording media and shortens the useful life of the recording media.
- lubricants there are problems including increased friction, scratching and adhesion. More efficient internal and boundary lubricant systems would be desirable.
- Lubricants for magnetic media are known in the art, but such lubricants are generally designed for more mature counter-parts of the magnetic media such as standard audio, VHS video and standard floppy disks. Examples of such lubricants included are described in U.S. Patent No. 4,613,548 to Lum, issued on September 23, 1986, a normally liquid, low molecular weight linear or cyclic poly- fluoroalkoxy phosphazene mixtures. Such lubricants do not demonstrate solvent compatibility with a wide range of organic solvents and are not stable in water and base.
- a family of perfluoropolyether difunctional derivatives end capped with planar groups including certain carboxylic acids and esters, perfluoroalkyl ethers, hydroxyalkyl, and certain substituted phenyl groups are commercially available from Ausimont U.S.A., Inc., under the trade designation FOMBLINTM.
- Certain lubricants having cyclic phosphazenes substituted with fluorinated phenoxy moieties and perfluoroalkylphenoxy moieties are disclosed in U.S. Patent 5,015,405. Such lubricants are not stable at high temperatures (for example above 100° C ) in water and base.
- Lubricants which comprise fluorocarbon substances or other fluorine- containing compounds are desirable for their superior tribological properties characteristic of fluorine-containing substances.
- fluorinated substances such as the FomblinTM fluids available from Montedison, or the KrytoxTM fluids and waxes available from E.I. DuPont de Nemours Co.
- Freon or Halon solvents for example chlorofluorocarbon (CFC) solvents such as FreonTM 112 or FreonTM 114 commercially available from E.I. DuPont de Nemours Co.
- CFC chlorofluorocarbon
- a lubricant soluble in non-CFC solvents such as tetrahydrofuran and acetone, yet to maintain the tribological characteristics of known fluorine-containing solvents.
- the lubricant is also desirably stable in the presence of water, acid and base.
- the present invention is directed to lubricating polymers, preferably fluids, advantageously polymeric and oligomeric, preferably dimers and/or polymers thereof, said lubricants being poly(perfluorocyclobutane aryl ether) compounds, and their use as lubricants.
- the invention is further directed to lubricants comprising at least one compound having a perfluorocyclobutane group, one or more of the above- described compounds.
- lubricants comprising at least one compound having a perfluorocyclobutane group, one or more of the above- described compounds.
- the compounds and compositions of the present invention are useful as extended temperature lubricants and as lubricants for magnetic media and in engines, particularly high-temperature engines, particularly when exposed to temperatures in excess of 200°C.
- the compounds are advantageously solvent compatible, magnetic recording media lubricants. Additionally the lubricants are stable in acids, bases and water and at high temperatures, such as from 35°C to 200°C.
- the invention includes high density, state of the art recording media, such as high density rigid disks, ultra high density floppy disks, digital audio tape, 8 mm video tape and super VHS tape including a lubricant which may be used as an internal or topical lubricant system to minimize wear and improve overall performance, and to protect the media from damage from the reading and/or writing head of a disk assembly.
- high density, state of the art recording media such as high density rigid disks, ultra high density floppy disks, digital audio tape, 8 mm video tape and super VHS tape
- a lubricant which may be used as an internal or topical lubricant system to minimize wear and improve overall performance, and to protect the media from damage from the reading and/or writing head of a disk assembly.
- the magnetic recording media containing a lubricating amount of lubricants of the invention comprises a substrate; a magnetic recording media thereon which include (a) magnetic particles for recording information; a binder for suspending the magnetic particle and a poly(perfluorocyclobutane aryl ether); or (b) a metallic film for recording information and a poly(perfluorocyclobutane aryl ether) fluid.
- the media described in (a) is referred to herein as particulate media and in (b), as thin film magnetic media.
- the lubricants are referred to as internal and topical, respectively.
- the lubricant is utilized as a topical lubricant for thin film or non-porous hard and flexible magnetic media advantageously by coating a metallic alloy lamina onto a base polymeric film (for example polyester) and applying the lubricant, preferably as a solution in a volatile solvent, to the surface. After solvent evaporation, a thin lubricant layer is left absorbed or bonded to the recording lamina surface.
- the lubricant is utilized in an internally lubricated system by preparing a lubricant containing lamina for application to a recording substrate.
- the lamina is advantageously prepared by forming a dispersion of solvent, a pigment containing magnetic particles and a binder system (for example urethane-vinyl).
- the lamina is then applied to a base film (for example polyester, particularly polyethylene terephthalate polyester).
- This invention additionally includes a method of preparing magnetic media by forming a dispersion comprising a binder, a magnetic particle containing pigment, a lubricating amount of a poly(perfluorocyclobutane aryl ether), and a surfactant; orienting the magnetic particles by application of a magnetic field; evaporating the solvent; and curing the polymer binder.
- the invention includes a method of lubricating magnetic recording media using a composition comprising at least one poly(perfluorocyclobutane aryl ether) compound.
- the invention also includes a process of preparing a lubricating poly(perfluorocyclobutane aryl ether) composition comprising heating, to a temperature of at least 50 ° C and sufficient to form perfluorocyclobutane rings from perfluorovinyl groups, a mixture of at least one of the following: (a) monomers having two dimerizable perfluorovinyl groups and end-capping agents having one dimerizable perfluorovinyl group;
- Recording media containing the lubricant of the present invention advantageously have improved physical and magnetic durabilities from more effective lubrication.
- the lubricants are solvent compatible in organic solvents such as toluene, acetone ethanol and tetrahydrofuran. This makes the product more practical to produce.
- the lubricants are advantageously stable in acids, bases and water.
- the poly(perfluorocyclobutane aryl ethers (hereinafter lubricant polymers) of the invention are formed by thermal reaction (dimerization) of monomers having at least one dimerizable perfluorovinyl group such that at least one perfluorocyclobutane group is formed.
- Lubricant polymers of the invention are preferably formed by the reaction of monomers having two or more dimerizable perfluorovinyl groups with other monomers having one dimerizable perfluorovinyl group in order to prepare oligomeric compounds which are end-capped with unsubstituted or optionally inertly or reactively substituted aryl ether groups where inert substitution is any substitution which does not interfere undesirably with the formation of the polymers and their lubricating ability and reactive substitution may interfere somewhat but has an advantage of providing better adhesion of the lubricant to a surface being lubricated.
- reactive substituents include hydroxyl, amine, and carboxylic acid groups.
- a dimerizable perfluorovinyl group is a perfluorovinyl group which reacts with another such group to form a perfluorocyclobutane ring.
- resulting dimers have one and polymers have at least two perfluorocyclobutane groups, in particular, sufficient perfluorocyclobutane groups to achieve physical and tribological properties desired for specific uses of the polymers.
- polymer is used herein to refer to any compound having at least two perfluorocyclobutane groups formed from perfluorovinyl groups, and includes oligomers which have from 2 to 1000 repeating units and preferably have a molecular weight of from 300 to 600,000.
- Fluids used in the practice of the invention are advantageously of weight average molecular weights less than 75,000, preferably from 348 to 10,000, more preferably from 348 to 3000; solid thermoplastic polymers useful as lubricants in the practice of the invention advantageously have weight average molecular weights equal to or greater than 75,000, preferably from 60,000 to 600,000, more preferably from 60,000 to 200,000; cured thermoset polymers of the invention are useful when sufficiently cured to form solids, advantageously as a layer on a surface to be lubricated, the molecular weight of which layer is not measurable as weight average molecular weight and is referred to as infinite molecular weight because of crosslinking.
- the number of perfluorocyclobutane groups can vary from as few as two up to hundreds.
- lubricant compositions comprising dimers of perfluorovinyl compounds, said dimers having a perfluorocyclobutane group.
- the relative proportion by weight of the perfluorocyclobutane groups to the other molecular components of the resulting products can vary over a wide range of from 3 to 1 to 0.01 to 1 , preferably from 3 to 1 to 0.05 to 1 and most preferably from 1 to 1 to 0.1 to 1.
- High proportions of perfluorocyclobutane groups are desirable, for instance, when fluorocarbon character such as low dielectric constant is beneficial in the products.
- Exemplary of such products are low dielectric fluids and lubricants.
- the poly(perfluorocyclobutane aryl ethers) (lubricant polymers) of the present invention are preferably mixtures of polymeric and dimeric compounds although lower and higher oligomers such as trimers and tetramers are optionally used.
- the polymeric lubricants preferably have weight average molecular weights (M w ) corresponding to greater than 30 repeating units, more preferably greater than 35 repeating units.
- M w weight average molecular weights
- the number of units is preferably sufficiently small that that the lubricants are pourable liquids at room temperature and yet maintain a low volatility, usually of a M w corresponding to less than 200 repeating units, preferably less than 100, more preferably less than 50 repeating units.
- Polymeric and/or oligomeric perfluorocyclobutane ring containing lubricants include linear molecular structures prepared from a mixture of monomers having two dimerizable perfluorovinyl groups and end-capping agents having one dimerizable perfluorovinyl group; and branched molecular structures prepared from a mixture of monomers having three or more dimerizable perfluorovinyl groups and end-capping agents having one dimerizable perfluorovinyl group, or mixtures of linear and branched structures prepared from a mixture of monomers having two or more dimerizable perfluorovinyl groups and end-capping agents having one dimerizable perfluorovinyl group.
- molar ratios of monomers having two dimerizable perfluorovinyl groups to end-capping agents are advantageously from 1 : 10 to 10: 1 , preferably from 1 :5 to 5: 1 , more preferably from 1 :4 to 4:1 .
- the branched molecular structures are advantageously prepared from a mixture wherein the ratio of monomers having three or more dimerizable perfluorovinyl groups to end-capping agents are preferably from 1 :20 to 1 :1.5, more preferably from 1 : 15 to 1 :2, most preferably from 1:3 to 1 :10.
- the mixtures of linear and branched structures are prepared from a mixture having ratios of monomers having two dimerizable perfluorovinyl groups to monomers having more than two dimerizable perfluorovinyl groups to end-capping agents advantageously of from 1 :0.1 : 1.5 to 1 :200:2000, preferably from 1 :0.5:2 to 1 :100:500, more preferably from 1 :1 :5 to 1 :10:400.
- Lubricants which are prepared from the ratios stated above do not necessarily correspond to these ratios of monomer units in the final lubricant composition, because volatile components comprising primarily the dimer of the end capping agent may optionally be removed from the lubricant by distillation or vacuum evaporation.
- Linear molecular structures are advantageously easy to prepare in high yields, while the branched molecular structures often perform better as lubricants under higher temperature or higher stress conditions when compared to lubricants which have substantially linear molecular structures.
- Monomers useful in the practice of the invention are suitably prepared by any method which links molecular structures having perfluorovinyl groups to other molecular structures or which forms perfluorovinyl groups. Useful syntheses are given, for instance in U.S. Patent 5,037,917 which is incorporated herein by reference in its entirety.
- perfluorovinyl aryl ethers are preferred.
- the monomers have structures such that resulting polymers have hydrocarbyl groups (preferably aromatic rings), perfluorocyclobutane rings and at least one non- carbon atom such as oxygen, silicon, boron, phosphorus, nitrogen, selenium, tellurium and/or sulfur atom (each optionally substituted) in the backbones, preferably between the aromatic (aryl) group and the perfluorovinyl group.
- the monomers preferably have a structure represented by Formula I:
- R represents an, optionally inertly substituted aromatic group
- each X is independently any group which links R and a perfluorovinyl group (hereinafter linking structures) preferably an oxygen or sulfur atom, said structures being inert
- m is an integer of from
- inert it is meant that the structures or substituents do not react undesirably with perfluorovinyl groups or interfere undesirably with polymerization (perfluorocyclobutane formation) of the monomers.
- R is suitably any inert molecular structure, preferably a molecular structure which facilitates formation of perfluorocyclobutane rings and/or imparts desirable physical properties to polymers or oligomers prepared from the monomers.
- at least one carbon atom of R is in the molecular chain between X's and is part of an aromatic nucleus.
- Aromatic groups are desirable because of improved physical properties of the polymers and ease of manufacture of the monomers.
- each X is preferably independently sulfur or oxygen.
- the aromatic group can be any molecular structure having aromatic character, advantageously having at least one six membered aromatic ring, suitably having any number of such six-membered rings fused together or connected by bonds or linking structures.
- R preferably has from 1 to 50 such rings, more preferably from
- R 1 to 10 rings, more preferably containing from 6 to 25 carbon atoms, most preferably R has at least 2 to 4 aromatic rings to impart properties such as hardness and/or stiffness to a polymer.
- the aromatic fragment is suitably unsubstituted or inertly substituted.
- Inert substituents on an aromatic R include, for instance, the inert substituents listed for R generally.
- R contains groups or has substituents which are inert, that is which do not undesirably interfere with the formation of perfluorocyclobutane rings from perfluorovinyl groups.
- Inert substituents include ether, carbonyl, ester, tertiary amide, carbonate, sulfide, sulfoxide, sulfone, nitrile, alkyl phosphonate, tertiary amine, alkyl phosphate, alkyl silyl, chlorine, bromine, fluorine, alkyl, arylalkyl, alkylaryl, cycloalkyl, fluoroalky, perfluoroalkyi, aromatic, heterocyclic, alkoxyl, and aryloxy groups, which inert substituents are suitably in any position, for instance, in a polymer backbone between X's and/or appended to such a backbone.
- R and substituents on R are advantageously fluorinated in order to increase the fluorine content of the lubricant and thereby improve it's tribological properties. This may be achieved by substituting the R group with such substituents as fluorine, trifluoromethyl (CF3) , perfluoroalkyi or perfluoroalkoxy, or pentafluorosuifanyl.
- substituents on R preferably contain from 1 to 50, more preferably from 1 to 12 carbon atoms because of the stability and ease of working with monomers of lower molecular weight.
- R including inert substituents preferably has a molecular weight (MW) of from 14 to 20,000, more preferably from 75 to 15,000 and most preferably from 75 to 5,000. These ranges include monomeric and oligomeric R groups. In the case of monomers which are other than oligomeric, R preferably has from 1 to 50, more preferably from 6 to 25, carbon atoms because molecular weights above this reduce the contribution to properties made by the fluorine-containing substituents when R is alkyl or aromatic hydrocarbon. As previously discussed, the nature of R as well as the perfluorocyclobutane content of the polymers can vary broadly according to the type of products desired.
- Exemplary aromatic molecular fragments include, for instance, perchlorophenylene, phenylene, biphenylene, naphthylene, dichlorophenylene, benzophenone, nitrophenylene, p,p'(2,2-diphenylene propane) [-C6 H 4" C ( CH 3)2- C 6 H 4]; p,p'-(2,2-diphenylene-1 ,1 ,1 ,3,3,3 hexafluoropropane), [-C6H4-C(CF3)2-C6H4-], 1 ,4-bis(hexafluoroisopropyl)benzene [-C(CF3)2-CeH4- C(CF 3 )2-], 1 ,3-bis(hexafluoroisopropyl)benzene [-C(CF 3 )2-C6H4-C(CF 3 )2-], preferably biphenylene; phenylene; 9,9'-diphenylfluorene, oxydip
- At least one aromatic carbon atom of R is bonded directly to X, most preferably aromatic carbon atoms of R are bonded directly to each X because perfluorovinyl groups bonded to X, said X being bonded to aromatic groups are generally more reactive in forming perfluorocyclobutane rings.
- Polymers produced from the preferred monomers preferably have a formula represented by Formula 2:
- each of R, and R"' are the same or different aromatic groups referred to herein as end capping groups because they are derived from monomers having one dimerizable perfluorovinyl group;
- R' is a branching group derived from a compound having at least 3 dimerizable perfluorovinyl groups;
- R" is an unbranched chain extending group derived from compounds having 2 dimerizable perfluorovinyl groups;
- Q is a cyclobutane group;
- X is defined as for Formula 1.
- a corresponds to the number of dimerizable perfluorvinyl groups on R' minus 2.
- Preferred polymers for this purpose are those having a structure represented by Formulas 3 or 4:
- J is H, an inert or reactive substituent.
- J is a reactive group or other group capable of substantial dipolar interaction such as hydrogen bonding or strong Vander Waals forces, such groups advantageously serve to adhere the lubricant fluid or polymer more strongly to the media surface.
- Substituents J are preferably selected from hydrogen, trifluoromethyl, pentafluorosulfanyl, fluorine, perfluoroalkoxy, tetrafluoroethoxy, trifluoromethoxy, methoxy, cyano, carboxylic acid, carboxylate alkyl ester, sulfonate alkyl ester, alkyl or aryl sulfones, amide, alkyl phosphonates, piperanyl, amino and alcohol groups.
- an alkyl or alkoxy group preferably has from 1 to 12 carbon atoms
- an aryl group preferably has from 6 to 20 carbon atoms.
- K is an unsubstituted or inertly substituted hydrocarbyl group (aryl, arylalkyi, alkylaryl, linear, branched or cyclic aliphatic), preferably selected from methyl, phenyl, or trifluoromethyl; and J is as described for Formula 3, preferably selected from hydrogen, perfluoroalkoxy, tetrafluoroethoxy, trifluoromethyl, pentafluorosulfanyl, fluorine, trifluoromethoxy, methoxy, cyano, carboxylic acid, carboxylate alkyl ester, sulfonate alkyl ester, alkyl or aryl sulfones, amide, alkyl phosphonates, piperanyl, amino and alcohol groups.
- aryl, arylalkyi, alkylaryl, linear, branched or cyclic aliphatic preferably selected from methyl, phenyl, or trifluoromethyl
- J is as
- the monomers are heated to a temperature and for a time sufficient to form perfluorocyclobutane rings.
- Temperatures suitable for forming perfluorocyclobutane rings differ with the structure of the monomer. In general, temperatures above 40°C are suitable for formation of perfluorocyclobutane rings, preferably the temperature is above 50°C, more preferably above 100°C, because these temperatures result in formation of the rings at successively faster rates. Temperatures above 450°C are preferably avoided because perfluorocyclobutane groups are generally thermally unstable above such temperatures.
- a temperature of from 130° to 230° is generally most preferred for cyclization of perfluorovinyl aromatic or aliphatic ethers or sulfides, while a temperature of from 50°C to 80°C is needed to form perfluorocyclobutane groups when the perfluorovinyl group is attached directly to an aromatic ring.
- temperature of at least 300°C, preferably at least 350°C is generally required.
- perfluorovinyl compounds are capable of radical initiated addition polymerization
- conditions conducive to free radical polymerization for example presence of oxygen, ozone, peroxygen compounds and other free radical generating compounds are avoided so that the perfluorovinyl groups will dimerize into perfluorocyclobutane groups rather than undergoing addition polymerization.
- Compounds known in the art for stabilization against free radical polymerization are alternatively used.
- compounds which supply such anions or cations are avoided.
- fluoride ions for example from carbonyl fluorides or metal fluorides
- hydroxide for example, phenoxide
- phenoxide are preferably avoided.
- oxidative conditions such as presence of oxygen, hypochlorite, dichromate, permanganate are preferably avoided because perfluorovinyl groups are known to oxidize to form carbonyl fluorides.
- Perfluorovinyl ethers, thioethers, sulfones, sulfoxides are relatively stable with regard to addition polymerization and oxidation; and, therefore, such precautions are generally unnecessary when such perfluorovinyl compounds are used.
- Monomers or admixtures thereof are suitably neat or, optionally, in admixture with other materials such as in solution, in emulsion, in dispersions or in any other form in which monomer molecules can be contacted with one another to form a polymer.
- Liquid admixtures are advantageous for maintaining contact between monomer molecules such that higher molecular weight polymers are formed. This is particularly useful when linear thermoplastic polymers are the products. Neat polymerizations or oligomerizations are also generally preferred to form relatively low molecular weight fluid products.
- the polymerization or oligomerization may be carried out in the presence of a large excess of the end-capping agent, which compound contains only one dimerizable perfluorovinyl group.
- This synthetic method creates an excess of the fluid product containing one perfluorocyclobutane ring, which then acts as a solvent for the production of the branched lubricant prepared from the end-capped monomer containing three or more dimerizable perfluorovinyl groups.
- This method also advantageously maintains a low molecular weight in the branched lubricant fluid.
- Suitable solvents are those which are inert to the conditions encountered in the polymerization reaction and include perfluorotetradecahydrophenanthrene (MULTIFLUORTM APF 215 commercially available from Air Products Corp.). At atmospheric pressure, preferred solvents are those which attain temperatures of 170°-250°C such as dichlorobenzene, trichlorobenzene, diphenyl oxide, perfluorotetradecahydrophenanthrene, and mesitylene. Although solvents such as 1 ,2-dichlorobenzene and 1 ,2,4-trichlorobenzene give less satisfactory results such as discoloration of the finished polymer, they are suitably used when their disadvantages are tolerable in a final product. When a solvent is used the concentration of monomers in solvent is advantageously from 0.1 to 99.9 weight percent preferably, from 10 to 90 percent by weight monomer.
- Polymerization or dimerization suitably takes place at any pressure. Pressures are generally chosen such that the monomers and any solvents and/or dispersing media remain liquid at the temperatures used for polymerization.
- the monomers or other materials evaporate at temperatures used, then it is generally preferable to maintain a pressure at least sufficient to maintain the materials liquid.
- the compounds of the present invention are described as single molecules having specified substituents present in a stated ratio, it will be realized by one skilled in the art that the compounds will exist as statistical mixtures of molecules. Some of these molecules will have the specified ratio of substituents while others will have higher or lower ratios. However, the perfluorocyclobutane ring containing fluids will, within these statistical mixtures, have substituents present at the specified ratios.
- the product is then recovered using conventional techniques, such as by evaporation of the polymerization solvent or light components of the polymerization under reduced pressure, including the end-capping compound which contained one dimerizable perfluorovinyl group, as well as the dimer of the end-capping compound which contained one dimerizable perfluorovinyl group.
- the compounds of this invention are useful as lubricants over extended temperature ranges. They may be used alone and also may be used in conjunction with various additives to improve their performance. Additionally, they may themselves be used as additives with other base stocks.
- the polymers are used at temperatures of from 50°C to 350°C, preferably from 20°C to 200°C.
- the poly(perfluorocyclobutane aryl ether) of the present invention When used as an additive to a base stock, the poly(perfluorocyclobutane aryl ether) of the present invention must be compatible with the base stock.
- compatible it is meant that the poly(perfluorocyclobutane aryl ether) of the present invention is readily dispersible or soluble in the base stock, either with or without the addition of an appropriate surfactant.
- Examples of known lubricant base stocks useful in the compositions of this invention include organic oils and greases within the skill in the art.
- the base stocks are poly alpha olefins, polyglycols, polyphenyl ethers and polyol esters. It is more preferred that the base stocks are polyphenyl ethers such as 5P4E (a polyphenyl ether having 5 phenyl rings with 4 ether linkages, such as that commercially available from Monsanto Corp. under the trade designation OS-124).
- Other preferred base stocks include polyol esters such as pentaerythritol tetra C5-C9 esters (PET), and poly alpha olefins.
- the lubricant compositions of this invention comprise from 0.1 to 100 weight percent of the poly(perfluorocyclobutane aryl ether) of the invention. That is, the poly(perfluorocyclobutane aryl ether) of this invention may be used as a lubricant base stock [i.e., lubricant composition is up to 100 weight percent poly(perfluorocyclobutane aryl ether)] or they may be used as additives with other lubricants [i.e., lubricant composition contains at least 0.1 weight percent poly(perfluorocyclobutane aryl ether)].
- poly(perfluorocyclobutane aryl ethers) of this invention are used as lubricant additives, it is preferred that they are used in amounts of at least 0.5 weight percent, more preferably at least 5 weight percent. It is also preferred that the poly(perfluorocyclobutane aryl ethers) of the present invention, when used as additives, are used in amounts of no greater than 50 weight percent, preferably no greater than 20 weight percent.
- the poly(perfluorocyclobutane aryl ethers) of the present invention may be used as lubricants themselves, either alone or with the addition of additives or other lubricants known in the art.
- additives useful in high temperature lubricants may be added.
- the poly(perfluorocyclobutane aryl ethers) of this invention comprise at least 50 weight percent, more preferably at least 95 weight percent of the composition with one or more additives making up the remainder of the lubricant composition.
- the poly(perfluorocyclobutane aryl ethers) of this invention may be blended with other base stocks to prepare lubricants.
- a preferred embodiment of the present invention is a magnetic recording media comprising a substrate having a magnetic recording lamina thereon, the lamina comprising magnetic particles with a binder in the case of particulate media or without a binder in the case of thin film media, for instance nickel-cobalt.
- the lamina includes a lubricating amount of at least one poly(perfluorocyclo- butane aryl ether) which may be used as either an internal or topical lubricant.
- Effective poly(perfluorocyclobutane aryl ethers) for this purpose are preferably substituted with fluorine, trifluoromethyl, trifluoromethoxy, tetrafluoroethoxy, perfluoroalkyoxy, methoxy, cyano, carboxylic acid, carboxylate alkyl ester, sulfonate alkyl ester, alkyl or aryl sulfones, amide, pentafluorosulfanyl, alkyl phosphonates, piperanyl, amino and alcohol groups.
- an alkyl or alkoxy group preferably has from 1 to 12 carbon atoms
- an aryl group preferably has from 6 to 20 carbon atoms.
- Thin film magnetic recording media generally include a substrate which may be a non-magnetic metal or a plastic such as a polyester (for example polyethylene terephthalate).
- a magnetic film such as a metal or a metal alloy such as cobalt-nickel is applied to the substrate.
- the thickness of the magnetic layer is on the order of 0.20 micrometers.
- the lubricant is preferably on the surface of the magnetic layer preferably 10 to 1000 Angstrons (10" 9 to 10' 7 m), more preferably from 2.0 nanometers to 0.20 micrometers (2x10" 9 to 2x10 _7 m).
- Particulate magnetic recording media generally include a substrate which may be a non- magnetic metal or a plastic such as polyester. Magnetic particle containing pigments such as cobalt gamma Fe2 ⁇ 3, barium ferrite or iron metal, with a binder are applied to the substrate.
- the amount of pigment can vary from 17.0 to 21.0 weight percent based on total formulation weight. The preferred range is from 17.0 to 19.0 weight percent.
- the binder is advantageously a thermosetting resin such as urethane, vinyl or a combination thereof, present in an amount between 2.5 and 6.0 weight percent, based on total formulation weight. The preferred range is between 3.0 and 6.0 weight percent.
- the poly(perfluorocyclobutyl aryl ether) lubricant When used as a topical lubricant for either particulate or thin film media, the poly(perfluorocyclobutyl aryl ether) lubricant is conveniently applied to the surface either neat or in solution with a volatile solvent.
- suitable solvents for the lubricant include aromatic hydrocarbons (for example toluene), ethers (for example diethyl ether, dimethoxyethane, dioxane, tetrahydrofuran, diethoxyethane), halogenated hydrocarbons (for example dichloromethane), alcohols (for example methanol or ethanol), ketones, (for example acetone), esters (for example ethyl acetate), alicyclic hydrocarbons (for example cyclohexane), dimethylformamide, dimethylsulfoxide, and silicone fluids.
- aromatic hydrocarbons for example toluene
- the poly(perfluorocyclobutane aryl ether) lubricant when used as an internal lubricant in particulate magnetic media, is included in the composition of the mixture applied to the substrate to form the recording lamina.
- This mixture includes binder, pigment containing magnetic particles and a volatile solvent together with the lubricant polymer. Suitable solvents for the lubricant include those listed for topical uses.
- Magnetic media containing polymer lubricants of the invention are advantageously prepared in the following way: a dispersion comprising a urethane-vinyl binder and a magnetic particle containing pigment is prepared, for example in tetrahydrofuran solvent.
- Preferred pigments include iron metal, barium ferrite and cobalt gamma Fe2U3.
- Pigment to binder ratios are preferably between 3:1 and 8:1.
- Pigment is preferably present in an amount from 2.5 to 6.0 weight percent based on total formulation weight.
- Lubricant is added to the dispersion in an amount preferably between 0 and 5 weight percent, more preferably from 0.1 to 2 weight percent of total formulation weight.
- a surfactant is added to the composition in an amount preferably between 0.50 and 1.0 weight percent of total formulation weight.
- the magnetic particles are advantageously oriented by application of a magnetic field. Conveniently, the solvent is evaporated and the polymer binder is cured by a thermal process.
- the lubricant described herein is used topically in thin film, or non-porous hard and flexible magnetic media.
- Coatings of polymeric lubricants are alternatively applied as described in U.S. Patent 5,246,782.
- Surface treated thin film media containing the lubricant of the present invention compare favorably with media surfaces treated with a hexafluoropropylene epoxide polymer available from E.I. DuPont de Nemours Co. under the trade designation KrytoxTM 143 AC and tetrafluoroethylene epoxide polymers commercially available from Ausimont, U.S.A., Inc., under the trade designation FomblinTM AM 2001. Physical properties including sliding friction and scratch resistance were evaluated to assess surface durability. The results of these comparisons are set forth in Example 8.
- the magnetic recording media containing the lubricant polymer of the present invention demonstrate improved surface durability. This is shown in the laboratory sample test results set forth in Examples 8 and 9.
- the cobalt-nickel thin film magnetic media (tape) coated with poly(perfluorocyclobutane aryl ether) lubricants demonstrate equivalent or improved friction and scratch resistance, when compared to cobalt-nickel thin film magnetic media (tape) coated with KrytoxTM 143AC, FomblinTM AM 2001 , or no lubricant.
- poly(perfluorocyclobutane aryl ether) lubricants do not require the use of FreonTM or other halogenated solvents in the coating process, whereas FreonTM or other halogenated solvents are needed in the coating process with such lubricants as KrytoxTM 143AC and FomblinTM AM 2001.
- Magnetic media containing poly(perfluorocyclobutane aryl ether) lubricants are advantageous in comparison to other commercially available products in that the lubricants of the invention provide optimal physical and magnetic performance such as low static and dynamic coefficients of friction and high coercivitey of underlying or surrounding magnetic media and are economical to produce.
- a dynamic coefficient of friction obtained is preferably less than 2, more preferably less than 0.5, even more preferably less than 0.25, most preferably less than 0.16.
- a static coefficient of friction less than 0.25.
- poly(perfluorocyclobutane aryl ether)polymers exhibit advantageous enhanced lubricant stability in bases and water.
- the following examples are provided for illustrative purposes only and should not be construed as limiting the invention in any way. Unless stated otherwise, all parts, ratios and percentages are by weight. Examples (Ex) of the invention are designated numerically while comparative samples (C.S.) are not examples of the invention and are designated alphabetically.
- EXAMPLE 1 PREPARATION OF A FLUID POLYMER OF 1.3- BISfTRIFLUOROVINYLOXY ENZENE AND 3-TRIFLUOROVINYLOXY-1'.1'.1'- TRIFLUOROTOLUENE
- DMSO 1000 ml
- toluene 250 ml
- 3-trifluoromethylphenol 200g, 1.23 mole
- Potassium hydroxide 45 percent solution, 153.3g, 1.23 mole was added to the flask all at once, and a line to supply nitrogen was attached to a reflux condenser which was placed on top of the Dean-Stark trap. The mixture was then heated to 85°C and water was removed azeotropically under a mild vacuum of 100 mm Hg (13.33 kPa) absolute pressure. When water ceased to collect in the Dean-Stark trap, the temperature of the reaction was increased to 125°C at 100 mm Hg (13.33 kPa) absolute pressure and 100 ml of toluene was removed by distillation, leaving a reaction mixture in the flask.
- reaction mixture was cooled to room temperature, and 1 ,2- dibromotetrafluoroethane (132.0g, 0.51 mole) was added slowly using a dropping addition funnel.
- the mixture was heated to 65°C overnight, then allowed to cool to room temperature.
- a liquid suspension of potassium bromide (KBr) a by- product of the reaction of 1 ,2-dibromotetrafluoroethane and potassium 3- trifluoromethyl phenoxide and DMSO (dimethylsulfoxide) was added to a 1.5 times voiumetric excess of water in a separatory funnel and shaken vigorously. The product formed a separate, lower layer at the bottom of the funnel and was removed. This crude product (lower layer) was washed again with an equal volume of water.
- the product of the above reaction (248 g, 0.73 mole) was combined with granular zinc (59.0g, 0.90 mole) in dry acetonitrile (600 ml) and stirred at 83°C for 4 hours to form a reaction mixture.
- the mixture was cooled to room temperature and filtered on a 15 micrometer sintered glass filter funnel to remove the zinc salts from the acetonitrile solution of the product.
- the acetonitrile was distilled out of the crude reaction mixture under reduced pressure (28°C, 150 mm Hg (20 kPa) absolute pressure) after which the product was recovered by distillation at 80°C and 100 mm Hg (13.33 kPa) absolute pressure to give 158 g (889.7 percent yield) of the product, m-trifluorovinyloxy-l'.l'.V-trifluorotoluene, which was 97.8 percent pure by GC (gas chromatographic) analysis, with the remainder of the product being the by-product m-(1 ,1 ,2,2,-tetrafluoroethoxy)-1 , ,1',1 '-trifluorotoluene.
- a mixture was prepared from 1.25 ml of 1 ,3-bis(trifluorovinyloxy)benzene (as prepared in U.S. Patent 5,023,380) and 8.75 ml of 3-trifluorovinyloxy-1',1 ',1 '- trifluorotoluene to make a total of 10 ml.
- This mixture was placed in a 50 ml round bottom flask fitted with a nitrogen padded reflux condenser and was refluxed under nitrogen for 20 hours.
- the resulting product was analyzed by GC/MS (gas chromatographic mass spectroscopy) and found to be a mixture of hexafluorocyclobutane products whose major components were 1 ,2-bis(3'-trifluoromethylphenoxy) hexafluorocyclobutane and 1 ,3-bis(2'-[3"-trifluoromethylphenoxy] hexafluorocyclobuty phenyl ether (having two perfluorocyclobutane rings), with a trace amount of 1 ,2-bis(3'-[2"- ⁇ 3"'- trifluoromethylphenoxy ⁇ hexafluorocyclobutyloxy]phenyl)hexafluorocyclobutyl ether (having three perfluorocyclobutane rings). By vacuum distillation two fractions were collected.
- the first fraction contained primarily mono-perfluorocyclobutane material consisting of two isomers (cis and trans 1 ,2-substituted hexafluorocyclobutane) with similar mass spectra (given for one isomer only): m/e: 484 (20.2 percent); 465 (12.9 percent); 273 (29.2 percent); 242 (30.1 percent); 207 (11.2 percent); 195 (13.0 percent); 145 (100.0 percent);
- the second fraction contained predominantly di-perfluorocyclobutane material, consisting mainly of three isomers (cis-cis, cis-trans, and trans-trans) of 1 ,2-substituted hexafluorocyclobutanes, and small amounts of four isomers of a product containing one 1 ,2-substituted hexafluorocyclobutane ring and one 1,3- substituted hexafluorocyclobutane ring (cis-1,2 cis-1,3; cis-1,2 trans-1,3; trans-1,2 cis-1 ,3; and trans-1 ,2 trans-1 ,3).
- the second fraction also contained a small amount of material containing three perfluorocyclobutane rings, consisting of six isomers (cis-cis-cis, cis-cis- trans, cis-trans-cis, cis-trans-trans, trans-cis-trans, and trans-trans-trans) of 1 ,2- substituted hexafluorocyclobutanes. Because of the small amount of this product present in the mixture, the corresponding products containing one or more 1 ,3- substituted hexafluorocyclobutane rings were not detected. The mass spectra of the six isomers showed roughly the same peaks in slightly differing intensities.
- This example shows that a compound containing one trifluorovinyl group can be combined with a compound containing two trifluorovinyl groups (the mixture then heated to cause cyclization of the trifluorovinyl groups) to provide a fluid containing perfluorocyclobutane groups.
- Such fluids are of the type useful as low dielectric hydraulic fluids or lubricants.
- EXAMPLE 2 PREPARATION OF A FLUID POLYMER OF 1.3- BISrrRIFLUOROVINYLOXY ) BENZENE f1 '.1 '.2 , .2'.TETRAFLUOROETHOXY ) - TRIFLUOROVINYLOXYBENZENE AND 1.3-B1SM '.1 '.2'.2'- TETRAFLUOROETHOXY ⁇ BENZENE
- the resulting viscous oil was checked by GC and was found to contain unreacted 1 ,3- bis(1',1',2',2',-tetrafluoroethoxy)benzene and tetraglyme, as well as mixtures of isomers of heavy components. After removal of the light, unreacted components, two fractions were cleanly separated by fractional distillation and each was analyzed by GC/MS.
- the first fraction was found to contain primarily 1 ,2-bis(3'-[1",1 ",2",2"- tetrafluoroethoxy]phenoxy)hexafluorocyclobutane as two isomers (cis and trans substituted hexafluorocyclobutane) followed by small amounts (1-2 percent each) of two 1 ,3-substituted hexafluorocyclobutane products (cis and trans), all having roughly similar mass spectra.
- the second fraction contained 1 ,3-bis(2'-[3"- ⁇ 1 "',1” , ,2 , ",2"'- tetrafluoroethoxy ⁇ phenoxy]hexa- fluorocyclobutyl)phenyl ether, primarily as three isomers of 1,2-substftuted hexafluorocyclobutanes with a small amount of four isomers of the product with one 1 ,2-substituted and one 1 ,3-substituted hexafluorocyclobutane ring. The seven isomers all gave roughly the same peaks in their mass spectra in differing intensities.
- n is from 0 to 20, preferably 0 or from 1 to 20; each L is independently trifluoromethyl, fluorine, trifluoromethoxy, tetrafluoroethoxy, perfluoroalkoxy, methoxy, cyano, carboxylic acid, carboxylate alkyl ester, sulfonate alkyl ester, alkyl or aryl sulfones, amide, pentafluorosulfanyl, alkyl phosphonate, piperaryl, amino or alcohol groups, preferably, and in this example, trifluoromethyl.
- each alkyl group is preferably from 1 to 12 carbon atoms and each aryl group is preferably from 6 to 20 carbon atoms.
- Samples of 1 , 1 , 1-tris(4-trifluoroethenyloxyphenyl)ethane (as prepared in U.S. Patent 5,023,380) (60.3g, 0. 1 1 0 mole) and 3-trifluoroethenyloxy- V-V-V- trifluorotoluene (as prepared in Example 1) (213.9g, 0.884 mole) were combined in a 250 ml round bottomed flask containing a magnetic stirring bar. A thermocouple was inserted through one neck of the flask into the solution to monitor the temperature.
- thermocouple was attached to a temperature controller which controlled the power output to a heating mantle on the flask through a Variac rheostat power source.
- a gas dispersion tube was inserted into the flask below the liquid level, and the liquid was deoxygenated by bubbling nitrogen into the flask with stirring for 15 minutes.
- the solution was stirred and heated according to the following schedule: 125°C for 3 hours; 130°C for 1 hour; 137°C for 1 hour; 140°C for 15 hours; 145°C for 1.5 hours; 150°C for 3 hours; 160°C for 5 hours; 175°C for 14 hours; 180°C for 3 hours.
- the residue from the evaporation was analyzed by gel permeation chromatography (GPC, as standardized against polystyrene) and was found to contain a number of low molecular weight fractions.
- Lubricant 2 in Examples 7 and 9.
- the anti-wear and extreme-pressure characteristics of the poly(perfluorocyclobutane aryl ether) lubricant polymers of this invention were measured by pin-on-disk testing.
- a silicon nitride (SiN) pin with hemispherical tip geometry was slided against a disk made of a film of biphenyl perfluorocyclobutyl ether polymer as prepared in U.S. Patent 5,023,380.
- Test load range was 2-15 Newtons (0.44 to 3.3 pounds).
- the sliding speed was 50 cm/sec and each test was run for 120 seconds at 25°C.
- the torque as a fraction of the wear cycles was monitored on a real time data acquisition basis for data analysis to yield the coefficient of friction.
- the average dynamic coefficient of friction of the biphenyl perfluorocyclobutyl ether polymer was 1.23 ⁇ 0.20.
- the average dynamic coefficient of friction of a 2 mil film of KaptonTM polyimide (commercially available from E.I. Du Pont de Nemours Co.) was 0.90 ⁇ 0.15.
- thermoset polymer prepared from 1 ,1 ,1 ,-tris(4-trifluorovinyloxyphenyl) ethane as prepared in U.S. Patent 5,023,380 as the disk composition.
- thermoset polymer prepared from 1 ,1 ,1-tris(4-trifluorovinyloxyphenyl)ethane was 0.97 ⁇ 0.20.
- average dynamic coefficient of friction of a 2 mil film of KaptonTM polyimide commercially available from E.I. Du Pont de Nemours Co.
- thermoset polymer performs favorably when compared to a leading polymeric lubricant film.
- the anti-wear and extreme pressure characteristics of the compounds and compositions of this invention were measured using the four-ball test using a Falex friction and wear tester according to the manufacturer's directions.
- this Example 1 , 2-bis(3-trifluoromethylphenyloxy) hexafluorocyclobutane as prepared in Example 3 (with various amounts of a polyphenyl ether, 5P4E (commercially available from Monsanto, Corp. under the trade designation OS-124), the amounts indicated in Table 1 was tested.
- the four-ball bearing balls used in this test were made of M-50 steel.
- the test load was 135 Newtons (30 pounds).
- the test speed was 1200 rpm and each test was run for 1 hour unless noted otherwise.
- Table 1 demonstrates the effectiveness of a compound of the invention as an additive to improve the tribological properties of known lubricants.
- Example 6 The procedure of Example 6 was followed with the exception that the poly(perfluorocyclobutane aryl ether) Lubricant 2 as prepared in Example 3 was used in place of 1 ,2-bis(3-trifluoromethylphenyloxy)hexafluorocyclobutane (Lubricant 1) used in Example 6. The results obtained were reported in Table 2.
- Coefficient of friction was measured by the procedure of ASTM D-3028 using a frictionometer commercially available from Custom Scientific Instruments, Inc.
- Scratch appearance force and scratch depth were measured by a scratch test performed according to the procedure of ASTM D-2197 except that it was miniaturized by a factor of 10 " 3 to measure micrometer rather than millimeter scratches.
- a loaded stylus was dragged across a sample surface, and the sample was inspected under 30X magnification to determine whether there was a visible scratch.
- Stylus load was varied from 0 to 40 mg in 10 mg steps.
- a commercial profilometer with a stylus radius of 2.5 ⁇ m was used for the test and was used to measure the depth of a scratch when one was observed. Depth was measured by retracing the scratch at 90 degrees to the observed scratch with a stylus load 10 mg less than the load used to make the scratch so that the measuring stylus does not increase the scratch depth.
- Test results show test Lubricant 1 and Lubricant 2 which were described in EXAMPLE 3 were effective as topical lubricants for thin film magnetic media and were effectively applied from methyl ethyl ketone rather than a chlorofluorocarbon.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6524352A JPH08509765A (en) | 1993-04-26 | 1994-04-19 | Lubricant containing perfluorocyclobutane ring |
EP94916541A EP0696309A1 (en) | 1993-04-26 | 1994-04-19 | Lubricants containing perfluorocyclobutane rings |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/054,647 | 1993-04-26 | ||
US08/054,647 US5364547A (en) | 1989-06-09 | 1993-04-26 | Lubricants containing perfluorocyclobutane rings |
Publications (1)
Publication Number | Publication Date |
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WO1994025547A1 true WO1994025547A1 (en) | 1994-11-10 |
Family
ID=21992557
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1994/004274 WO1994025547A1 (en) | 1993-04-26 | 1994-04-19 | Lubricants containing perfluorocyclobutane rings |
Country Status (5)
Country | Link |
---|---|
US (1) | US5364547A (en) |
EP (1) | EP0696309A1 (en) |
JP (1) | JPH08509765A (en) |
CA (1) | CA2160700A1 (en) |
WO (1) | WO1994025547A1 (en) |
Cited By (2)
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Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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US8609739B2 (en) * | 2011-02-17 | 2013-12-17 | GM Global Technology Operations LLC | Poly(perfluorocyclobutane) ionomer with phosphonic acid groups for high temperature fuel cells |
JP6374867B2 (en) * | 2013-08-07 | 2018-08-15 | ニチアス株式会社 | Cross-linking agent and fluorine-containing aromatic compound |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1990015082A1 (en) * | 1989-06-09 | 1990-12-13 | The Dow Chemical Company | Process for preparing a polymer having perfluorocyclobutane rings and polymers containing perfluorocyclobutane rings |
EP0490335A2 (en) * | 1990-12-10 | 1992-06-17 | The Dow Chemical Company | Laminates of polymers having perfluorocyclobutane rings and polymers containing perfluorocyclobutane rings |
Family Cites Families (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE23425E (en) * | 1951-10-30 | Polyfluorinated compounds | ||
US3114778A (en) * | 1963-12-17 | Fluorinated vinyl ethers and their | ||
US2848504A (en) * | 1954-07-21 | 1958-08-19 | Du Pont | Alkyl hexafluorocyclobutanes and process for preparing them |
US2958685A (en) * | 1957-08-09 | 1960-11-01 | Du Pont | Polymers of perfluoropropylene |
US2982786A (en) * | 1958-07-09 | 1961-05-02 | Du Pont | Novel cyclic dimers of perfluorovinyl ethers |
US3022356A (en) * | 1958-10-16 | 1962-02-20 | Du Pont | Process for preparing bis (omega-hydroperfluoroalkyl) carbinols |
US3316312A (en) * | 1959-04-10 | 1967-04-25 | Du Pont | Perfluorinated dialkyl cyclobutanes |
US3111509A (en) * | 1961-10-05 | 1963-11-19 | Goodrich Co B F | Stable, high softening, vinyl cyclobutane homopolymers and method for preparing same |
US3277068A (en) * | 1962-07-31 | 1966-10-04 | Leo A Wall | Perfluorovinylphenylethers and their polymers |
US3303145A (en) * | 1963-01-11 | 1967-02-07 | Du Pont | Fluorocarbon polyethers |
US3310606A (en) * | 1963-08-28 | 1967-03-21 | Du Pont | Thermosetting perfluorinated divinyl ether resins |
FR1481730A (en) * | 1965-06-02 | 1967-05-19 | Du Pont | Perfluorinated polyethylene glycol divinyl ethers and their polymers |
US3397191A (en) * | 1965-06-02 | 1968-08-13 | Du Pont | Fluorocarbon ethers |
US3549606A (en) * | 1966-01-10 | 1970-12-22 | Monsanto Co | Fluoroalkyl ethers of alicyclic fluoroolefins |
US4154753A (en) * | 1966-01-12 | 1979-05-15 | Imperial Chemical Industries Limited | Fluorinated compounds containing functional groups |
US3505411A (en) * | 1966-10-11 | 1970-04-07 | Minnesota Mining & Mfg | Perfluoroalkylene oxide polymers |
GB1185564A (en) * | 1968-03-06 | 1970-03-25 | Du Pont | Improvements relating to Perfluorinated Ethers |
US3696154A (en) * | 1970-06-12 | 1972-10-03 | Dow Chemical Co | Perfluorinated ether sulfides |
US3900380A (en) * | 1972-03-02 | 1975-08-19 | Dow Chemical Co | Preparation of fluorinated cyclobutenyl alkyl ether copolymers |
US3840603A (en) * | 1972-03-02 | 1974-10-08 | Dow Chemical Co | Fluorinated cyclobutenyl alkyl ether copolymers |
DE3024018A1 (en) * | 1979-06-29 | 1981-01-08 | Ciba Geigy Ag | Pesticidal tri:halo-vinyl-oxy-benzene derivs. - esp. for protecting keratin materials against insects |
US4423249A (en) * | 1981-08-26 | 1983-12-27 | The Dow Chemical Company | Preparation of halofluoroalkyl ethers |
US4377711A (en) * | 1981-11-04 | 1983-03-22 | Rhone-Poulenc Industries | Novel aromatic bromopolyfluoroalkyl ethers and method for the preparation thereof |
US4897457A (en) * | 1987-08-14 | 1990-01-30 | Asahi Glass Company Ltd. | Novel fluorine-containing cyclic polymer |
US5037919A (en) * | 1989-06-09 | 1991-08-06 | The Dow Chemical Company | Reactive compounds containing perfluorovinyl groups |
US5198513A (en) * | 1989-06-09 | 1993-03-30 | The Dow Chemical Company | Reactive compounds containing perfluorovinyl groups |
US5210265A (en) * | 1989-06-09 | 1993-05-11 | The Dow Chemical Company | Reactive compounds containing perfluorocyclobutane rings |
US5021602A (en) * | 1989-06-09 | 1991-06-04 | The Dow Chemical Company | Reactive compounds containing perfluorocyclobutane rings |
US5037918A (en) * | 1989-12-15 | 1991-08-06 | The Dow Chemical Company | Perfluorocyclobutane ring-containing polymers with crosslinking |
US5037917A (en) * | 1989-06-09 | 1991-08-06 | The Dow Chemical Company | Perfluorocyclobutane ring-containing polymers |
US5066746A (en) * | 1989-06-09 | 1991-11-19 | The Dow Chemical Company | Perfluorocyclobutane ring-containing polymers |
US5023380A (en) * | 1989-06-09 | 1991-06-11 | The Dow Chemical Company | Perfluorovinyl compounds |
US5162468A (en) * | 1989-06-09 | 1992-11-10 | The Dow Chemical Company | Perfluorovinyl compounds |
US5159036A (en) * | 1989-12-15 | 1992-10-27 | The Dow Chemical Company | Perfluorocyclobutane ring-containing polymers with crosslinking |
-
1993
- 1993-04-26 US US08/054,647 patent/US5364547A/en not_active Expired - Lifetime
-
1994
- 1994-04-19 JP JP6524352A patent/JPH08509765A/en active Pending
- 1994-04-19 EP EP94916541A patent/EP0696309A1/en not_active Withdrawn
- 1994-04-19 WO PCT/US1994/004274 patent/WO1994025547A1/en not_active Application Discontinuation
- 1994-04-19 CA CA002160700A patent/CA2160700A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1990015082A1 (en) * | 1989-06-09 | 1990-12-13 | The Dow Chemical Company | Process for preparing a polymer having perfluorocyclobutane rings and polymers containing perfluorocyclobutane rings |
EP0490335A2 (en) * | 1990-12-10 | 1992-06-17 | The Dow Chemical Company | Laminates of polymers having perfluorocyclobutane rings and polymers containing perfluorocyclobutane rings |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007005355A1 (en) * | 2005-07-01 | 2007-01-11 | Bausch & Lomb Incorporated | Trifluorovinyl aromatic containing poly (alkyl ether) prepolymers |
US7538160B2 (en) | 2005-07-01 | 2009-05-26 | Bausch & Lomb Incorporated | Trifluorovinyl aromatic containing poly(alkyl ether) prepolymers |
US8198375B2 (en) | 2005-07-01 | 2012-06-12 | Bausch & Lomb Incorporated | Trifluorovinyl aromatic containing poly(alkyl ether) prepolymers |
US10654779B2 (en) | 2016-09-27 | 2020-05-19 | Tosoh Finechem Corporation | Substituted bis(trifluorovinyl)benzene compound |
Also Published As
Publication number | Publication date |
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US5364547A (en) | 1994-11-15 |
EP0696309A1 (en) | 1996-02-14 |
JPH08509765A (en) | 1996-10-15 |
CA2160700A1 (en) | 1994-11-10 |
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