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WO1998018804A1 - Phenoxy phosphazenes fonctionnalises et leur utilisation en tant que lubrifiant - Google Patents

Phenoxy phosphazenes fonctionnalises et leur utilisation en tant que lubrifiant Download PDF

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Publication number
WO1998018804A1
WO1998018804A1 PCT/US1997/016651 US9716651W WO9818804A1 WO 1998018804 A1 WO1998018804 A1 WO 1998018804A1 US 9716651 W US9716651 W US 9716651W WO 9818804 A1 WO9818804 A1 WO 9818804A1
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Prior art keywords
phosphazene
nhc
phenoxy
functionalized
phosphazenes
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PCT/US1997/016651
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English (en)
Inventor
Ted A. Morgan
Chester E. Pawloski
Kishore Kar
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The Dow Chemical Company
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Publication of WO1998018804A1 publication Critical patent/WO1998018804A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
    • C07F9/65814—Cyclic phosphazenes [P=N-]n, n>=3 n = 3 or 4
    • 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
    • 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
    • C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
    • 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
    • G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
    • G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
    • G11B5/71—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the lubricant
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • 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
    • C10N2040/32—Wires, ropes or cables lubricants
    • 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
    • C10N2040/34—Lubricating-sealants
    • 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
    • C10N2040/36—Release agents or mold release agents
    • 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
    • C10N2040/38—Conveyors or chain belts
    • 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
    • C10N2040/40—Generators or electric motors in oil or gas winning field
    • 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
    • C10N2040/42—Flashing oils or marking oils
    • 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
    • C10N2040/44—Super vacuum or supercritical use
    • 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
    • C10N2040/50—Medical uses

Definitions

  • the present invention relates to functionalized-phenoxy phosphazenes and their use as lubricants on magnetic recording media.
  • Phosphazene fluids are known to be useful as lubricants, hydraulic fluids, fuel additives, flame retardants and for many other purposes.
  • Polyfluorosubstituted cyclophosphazenes are particularly useful as lubricants and lubricant additives.
  • tribological performance is unpredictable and dependent upon many different variables.
  • the lubricants used must be capable of forming into a thin film and having durability under the required operating conditions.
  • a recording head is positioned in very close proximity to the recording media and frequently contacts the recording media. This contact causes wear of the thin layer of magnetic material on the recording media and shortens the useful life of the recording media.
  • problems result including increased friction, scratching, and adhesion. Therefore, new efficient lubricants are desirable.
  • the first embodiment of the present invention is a group of phosphazenes useful as lubricants or lubricant additives.
  • these compounds are useful as lubricants on magnetic media.
  • the phosphazene(s) of the present invention corresponds to Formulae:
  • each X is independently -F, -(CF 2 ) n CF 3 , -OCF 2 CF 2 Br
  • each X is located in the ortho, meta or para position; preferably the meta position.
  • the phosphazene is of Formula I.
  • q is one.
  • each R is independently a linear or a branched C] to C 3 aliphatic hydrocarbon moiety.
  • n is 0.
  • perfluoropolyethereal chain as used above means substituents composed of repeating units selected from:
  • a perfluoro moiety includes perfluoroalkyl, perfluoropolyetherial groups or a combination thereof.
  • the perfluoropolyetherial chain is preferably from 400 to 4,000 grams/mole.
  • a second embodiment of this invention is a magnetic recording medium comprising a substrate having a magnetic recording lamina deposited thereon, wherein the lamina comprises magnetic particles and a phosphazene as described in the first embodiment of the present invention.
  • a third embodiment of this invention is a process for lubricating a surface by applying to the surface a functionalized-phenoxy phosphazene corresponding to the first embodiment. Due to the combination of substituents on the phosphazenes of this invention, these phosphazenes provide good adsorption properties. Good adsorption prevents the lubricant from migrating significantly on the surface under normal operating conditions.
  • the functionalized-phenoxy phosphazenes of this invention are those of the first embodiment of this invention as described above.
  • the term "phosphazene” refers to a ring with alternating phosphorus and nitrogen atoms which ring has two substituents on each phosphorus atom.
  • triazatriphosphorine is a cyclic phosphazene containing three alternating phosphorus and nitrogen atoms with two substituents on each of the three phosphorus atoms.
  • the phosphazenes of this invention comprise phosphazenes having functionalized-phenoxy groups.
  • a phenoxy group is a substituent of formula -O(C 6 H 5 ).
  • the term "functionalized-phenoxy group” as used herein refers to a substituent on a phosphorus atom of a phosphazene ring such that the substituent is of formula -O(C 6 H 5 _ q )(X) q . This structure is depicted in Formulae I and II.
  • the X substituents are of formula: -F, -CF 3 , -OH, -OR, -NH 2 , -NR 2 , -NO 2 , -CO 2 H, -CO 2 R, -C(O)R, -CN, -SH, -SR, -SO 2 NR 2 , -SO 2 R, -NHC(O)R, -NHC(O)OR, -NHC(O)NH 2 , -OCF 3 , -CH(O) or -C(O)NR 2 .
  • these substituents may be called fluoro, trifluoromethyl, hydroxy, alkoxy, amino, dialkylamino, nitro, carboxy, alkoxy carbonyl, acetyl, cyano, mercapto, alkylthio, dialkylsulfamoyl, alkylsulfonyl, alkanomido, (alkoxycarbonyl)amino, trifluoromethoxy, formyl, and formamido.
  • At least one X group is preferably a perfluoroalkyl substituent: -(CF 2 ) n CF 3 where n is zero to three. Most preferably, n is 0 and the perfluoroalkyl substituent is a 3-trifluoromefhylphenoxy group.
  • This X group may be derived from a functionalized phenol of formula HO(C 6 H 4 )(CF 2 ) n CF 3 where n is zero to three.
  • the term "functionalized phenol” refers to a molecule of formula Z(C 6 H 4 )OH where Z is fluoro, a perfluoroalkyl substituent, or a substituent from which a desired substituent, X, can be derived.
  • Functionalized phenols wherein n is zero are known in the art.
  • Functionalized phenols of formula HO(C 6 H 4 )(CF 2 ) n CF wherein n is one to three may be prepared from commercially available starting materials and as described in I&EC Product Research and 5 Development, "Synthesis and Properties of Some m-bis[m(perfluoroalkyl)phenoxy] benzenes", (1968) pp. 101-107.
  • At least one X is -CF 3 ; at least one X is -F; and at least one X is -(CH 2 ) n OH, -(CH 2 ) n OR, -(CH 2 ) n NH 2 , -(CH 2 ) n NR 2 , -(CH 2 ) n NO 2 , o -(CH 2 ) n CO 2 H, -(CH 2 ) instructCO 2 R, -(CH 2 ) dislikeC(O)R, -(CH 2 ) n CN, -(CH 2 ) n -(CH 2 ) n SH, -(CH 2 ) n SR,
  • At least one X is -OH, -NH 2 , -CH 2 CO 2 CH 3 , -CN, -NO 2 , -C(O)CH 3 , -SO 2 NR 2 , 5 -OCH 2 CH 2 OH, or -C(O)NR 2 .
  • at least one X is -CF 3 ; at least one X is -F; and at least one X is -NH 2 , -OH, -CH 2 CO 2 CH 3 , -CN, -(CH 2 ) 2 OH, or -OCH 2 CH 2 OH.
  • the phosphazene of the present invention comprises three different types of X substituents.
  • the phosphazene is preferably fully substituted with -F, -CF 3 , and o one other type of X substituent.
  • the third type of X substituent is of formula -O(CH 2 CH 2 O) n H; or of formula -(CH 2 ) distractCN wherein n is 0 to 3.
  • substituents is a phosphazene corresponding to Formula I or Formula II wherein each X is independently -F, -(CF 2 ) n CF 3 , 5 -(CH 2 ) 2 OH, -NHC(O)CH 3 , or -CH 2 CO 2 CH 3 ; with the proviso that at least one X is
  • n is 0.
  • the functionalized-phenoxy phosphazenes of the present invention are prepared by reacting suitable functionalized phenols (preferably including 3-trifluoromethylphenol) and a suitable cyclic phosphazene (preferably hexachloro-l,3,5-triaza-2,4,6-triphosphorine) in an inert organic solvent along with a hydrogen chloride acceptor such as potassium carbonate, under conditions and for a time period sufficient to yield the desired phenate which then reacts with the cyclic phosphazene to produce a functionalized-phenoxy phosphazene.
  • phenate refers to the salt of a functionalized phenol.
  • the reaction takes place under ambient pressures, although pressure is not critical and subatmospheric or superatmospheric pressures may be employed.
  • “Functionalized phenols” may be reacted successively or simultaneously with a cyclic phosphazene.
  • such functionalized phenols are chosen from the group consisting of molecules of formula CF 3 (C 6 H 4 )OH, F(C 6 H 4 )OH, CH 3 C(O)HN(C 6 H 4 )OH, PhC(O)O(C 6 H 4 )OH, CH 3 OC(O)CH 2 (C 6 H 4 )OH, HOCH 2 CH 2 O(C 6 H 4 )OH and CN(C 6 H 4 )OH which are called trifluoromethylphenol, fluorophenol, hydroxyphenyl acetamide, benzoyloxy resorcinol, methyl-hydroxyphenyl acetate, 2-hydroxyethoxy phenol and 4-cyanophenol, respectively.
  • the order of addition of the reactants is not critical. However, agitation, such as stirring, is useful in ensuring uniformity of reactant concentrations in the reaction mix.
  • the preferred reactant hexachloro-l,3,5-triaza-2,4,6-triphosphorine is also called phosphonitrilic chloride trimer and hexachlorocylclotriphosphazene.
  • Other cyclic phosphazenes, such as tetra and penta, can be reacted in the same manner described above.
  • the reactant phosphazene should have six or eight atoms in the ring structure depending on the number of atoms in the ring structure of the desired final product.
  • the phosphazene starting material is preferably fully substituted with halogen atoms.
  • such halogen is chloro or fluoro.
  • the halogen is chloro.
  • a fully chloro- substituted phosphazene ring is a suitable phosphazene reactant.
  • the minimum molar ratio of functionalized phenol to cyclic phosphazene starting material is dependent upon the halide content of the latter. Generally, a slight molar excess, one to ten mole percent, of functionalized phenol ensures complete halide substitution. Mixes of partially halide substituted and completely halide substituted product may provide the properties sought. In these cases, using a smaller molar ratio of phenol to phosphazene may be preferred economically.
  • the solvent need only be inert in the reaction system and be capable of solubilizing the reactions under reaction conditions.
  • solvents such as diglyme, tetraglyme, toluene, xylenes, mesitylene, dimethyl formamide, and dimethyl sulfoxide and mixtures thereof may be suitable.
  • the process of the present invention is preferably run at reflux conditions, and thus, in these preferred cases, the solvent used is one which will provide reflux at the chosen process temperature.
  • a preferred solvent is a mixture of xylenes and diglyme in a ratio of from 5: 1 to 10: 1.
  • the reaction occurs at a temperature that will vary depending on the starting materials and solvent.
  • the subject process is generally run within the temperature range of from 50 to 140 degrees Celsius and is more typically the reflux temperature. High yields are generally obtained when the process temperature is within the temperature range of from 100 to 140 degrees Celsius. Temperatures substantially lower than 50 degrees Celsius may produce the product sought; however, the yield is predicted to be low and reaction times long. While the subject process is preferably run under reflux conditions, it is to be understood that reflux conditions need not be used. Other temperature control techniques can be used such as reactor immersion in a controlled temperature bath.
  • reaction time for the process of this invention should be sufficiently long to achieve the desired substitution of the halo substituents initially present in the chlorocyclophosphazene reactant.
  • the rate of substitution is interrelated with process temperature. After initiation, the higher the temperature used, the shorter the reaction period will be. Generally speaking, for the temperature range of 100 to 140 degrees Celsius, the reaction period will be 8 hours to 4 hours depending in part on the amount and type of starting materials used.
  • Some functionalized-phenoxy phosphazenes may require a second process step to prepare, for example, those products having the following X substituents: -SH, -OH, -(CH 2 ) n NH 2 , -(CH 2 ) n CO 2 H.
  • the two step process is characterized by a substitution reaction followed by a deprotection reaction.
  • the following, respectively, are examples of functionalized phenols which may be used in the two step process to derive desired X substituents listed immediately above: PhC(O)O(C 6 H 4 )OH, CH 3 C(O)HN(C 6 H 4 )OH, HO(C 6 H 4 )(CH 2 )CO 2 CH 3 .
  • These functionalized phenols are known in the literature or are commercially available.
  • step two of the process entails deprotecting the product of step one to produce a functionalized-phenoxy phosphazene having desired functional groups.
  • the product may be deprotected or converted to the final product by processes such as hydrolysis or hydrogenolysis.
  • the deprotection step two for esters and amides, may be carried out in the presence of an acid catalyst such as concentrated HC1 of from 5N to 12N or concentrated H 2 SO of from 18N to 36N.
  • the concentration of the acid can vary depending on reaction conditions.
  • the mixture is typically refluxed at 50 to 100 degrees Celsius for 4 to 8 hours. More preferably, the temperature is 80 to 100 degrees Celsius.
  • An alternate method of preparation involves the use of phase transfer catalysis.
  • the starting phenols may be converted to their corresponding phenoxides by dissolving in an aqueous solution of base (equimolar), such as Na 2 CO 3 , NaOH, or tetramethyl ammonium hydroxide, as well as a catalytic amount (1-5 mol percent) of a tetraalkyl ammonium salt, such as tetrabutyl ammonium bromide.
  • base equimolar
  • a tetraalkyl ammonium salt such as tetrabutyl ammonium bromide.
  • a solution of the phosphonitrilic chloride in an organic solvent such as chlorobenzene or toluene.
  • the reaction mixture may be stirred vigorously and heated (25 °C to reflux), if necessary.
  • the layers are separated, and the organic layer is washed (for example, three times with dilute aqueous NaOH or Na 2 CO 3 , and then with water).
  • the organic layer is then dried over MgSO 4 , filtered and then concentrated.
  • the resulting crude product can be purified by chromatography or distillation.
  • the product phosphazenes can be recovered and purified by standard techniques such as by filtration, recrystallization, distillation, and chromatography. Various specific examples of preparing these phosphazenes are provided, below, in the "Examples" section.
  • Product recovery on a commercial scale may be achieved by passing the product through a column of adsorbent, such as carbon, silica gel, alumina, or ion exchange resin rather than via distillation.
  • any number of functionalized-phenoxy phosphazenes can be prepared using the processes described. These phosphazene materials may be used with other multifunctional compounds to produce new polymers. Alternatively, the phosphazenes could be used as intermediates to produce oils useful as lubricants and also may be used in conjunction with various additives. The phosphazenes of this invention may themselves be used as additives with other lubricant fluids to form lubricant mixtures. In addition, the phosphazenes of this invention may be used alone as a lubricating fluid.
  • the phosphazenes of the present invention When used as an additive to a lubricant fluid, the phosphazenes of the present invention should be compatible with the lubricant fluid; in other words, the compounds of the present invention should be readily dispensable or soluble in the lubricant fluid to form a homogeneous or non-homogeneous blend, either with or without the addition of an appropriate surfactant; and preferably should not be antagonistic to the lubricity of the present compounds.
  • An example of lubricant fluids useful in conjunction with the phosphazenes of this invention include perfluoropolyether oils as described, for example, in WO 96/01303, page 5, lines 13-31.
  • the phosphazenes When used as an additive in combination with another lubricant fluid, the phosphazenes are employed in an amount sufficient to increase the lubricity (or antifriction effect) of the lubrication mixture.
  • the phosphazenes are employed in a concentration, based on the weight of the lubricating fluid component, of at least 0.001 weight percent, more preferably greater than 0.01 percent, and most preferably greater that 0.1 percent.
  • the phosphazenes are employed in a concentration of less than 10 weight percent, more preferably less than 5 percent, and most preferably less than 2 percent.
  • Another embodiment of the invention is a magnetic recording medium with a 5 substrate having a magnetic recording lamina deposited thereon wherein the lamina comprises magnetic particles and at least one phosphazene of the present invention.
  • the substrate generally comprises a non-magnetic metal or a plastic such as polyester (for example, polyethylene terephthalate).
  • the lamina may comprise a thin film having an average thickness of 1 to 2000 Angstroms (10 "10 to 2 x 10 "7 meters).
  • the magnetic recording o lamina may also comprise a metal evaporated tape. Examples of magnetic recording media include high density rigid disks, ultra high density floppy disks, digital audio tapes and video tapes which can be read by a magnetic recording head.
  • the lubricant may 5 be applied, for example, as follows.
  • the tape may be passed through a bath containing the lubricant and taken up onto a reel.
  • the amount of lubricant may be controlled, for example, by dragging the tape over a knife edge to remove excess lubricant.
  • the lubricated tape may then be passed through a hot air drier to evaporate the solvent used in the bath.
  • the present invention is also a process for lubricating a surface by applying the phosphazene of this invention to the surface, which preferably comprises a magnetic medium.
  • the phosphazene is applied to the surface to provide a lubricant film having an average thickness of 1 to 2000 Angstroms (10 ⁇ 10 to 2 x 10 "7 meters) on the surface.
  • the phosphazene is typically applied to magnetic media using a volatile solvent. 5
  • the reactants useful for the process of the present invention may be obtained from commercial sources, such as Aldrich Chemical, and the solvents used are of commercial grade.
  • the products are either o flash distilled using a Kugelrohr apparatus under reduced pressure or an adsorbent bed.
  • the structures of the titled compounds are confirmed by IR, NMR, and MS spectra.
  • Example 1 Preparation of mono(3-aminophenoxy)2,2,4,4,6,6-hexahydro-2,2,4,4,6- pentakis(3-trifluoromethyl)phenoxy)-l,3,5-triaza-2,4,6-triphosphorine:
  • the mixture was stirred for two hours and washed twice with 500 mL portions of water.
  • the product phase was separated and passed through sodium sulfate.
  • Low boilers were distilled off at 100 degrees Celsius (°C) under reduced pressure of 20 mrnHg.
  • the product was further distilled at 210 °C and 0.5 mmHg to produce 158 g of oil.
  • 2,2,4,4,6,6 hexahydro-bis(3-hydroxyphenoxy)tetrakis(3- 5 trifluoromethyl)phenoxy)-l,3,5-triaza-2,4,6-triphosphorine was prepared by using more benzoylexy resorcinol and less 3-trifluoromethylphenol than stated above resulting in a 4:2 molar ratio of trifluoromethylphenol to benzoyloxy resorcinol.
  • Example 4 Preparation of a mixture of 4-fluorophenoxy-, 3-(trifluoromethyl) phenoxy and 2-(hydroxyethoxy)phenoxy-substituted derivatives of 2,2,4,4,6,6-hexahydro-l,3,5-triaza-2,4,6-triphosphorine with the major derivative being bis(4-fluorophenoxy)-2,2,4,4,6,6-hexahydro-mono- (2-hydroxyethoxy)phenoxy)-tris(3-trifluoromethyl)phenoxy- 1 ,3,5-triaza-
  • a phosphazene having exclusively -F and -CF substituents might be prepared as described in U.S. Patent No. 5,230,964 to Kar, column 7, lines 5-55.
  • the phosphazene lubricant used in the following examples was a mixture of 4-fluorophenoxy- and 3-(trifluoromethyl) phenoxy-substituted derivatives of 2,2,4,4,6,6- hexahydro-l,3,5-triaza-2,4,6-triphosphorine with the major derivative being bis(4-fluorophenoxy)2,2,4,4,6,6-hexahydro-2,2,4,6-tetrakis (3-trifluoromethyl)phenoxy)- 1 ,3,5-triaza-2,4,6-triphosphorine.
  • Unlubricated carbon-overcoated 3.75 inch (9.5cm) magnetic hard disks were cleaned for 10 minutes in hexane using an ultra-sonic bath and allowed to air dry in a clean air hood (Class 100) for at least one hour.
  • the disks were then submerged for five minutes in a 5 inch (12 cm) x 8 inch (20 cm) x 6 inch (15 cm) stainless steel container containing a 0.1 weight percent solution of the lubricant to be tested.
  • the solution was then drained from the container at a rate of 1.0 inch (2.54 cm) per minute.
  • the lubricants adsorbed/absorbed onto the disks during the residence time in the bath.
  • the disks were dried at room temperature in a clean air hood for at least 1 hour to evaporate solvent.
  • the average lubricant film thickness on the carbon-overcoat magnetic hard disks was 5 to 20 angstroms.
  • the lubricated disks were tested to determine coefficients of friction and stiction after various stages of use according to the following procedure.
  • the head wear test system measured the static and dynamic friction between the hard magnetic disk and slider, and was controlled by a host computer equipped with MEGASISS software.
  • the lubricated hard magnetic disks were loaded into the head wear test system and spun such that the surface velocity of the disk was 3.4 x 10 4 inches per minute at a radial distance of 1.5 inch (3600 ram, 8.6 x 10 4 cm per minute) with a 5 gram head load.
  • the slider was suspended over the disk due to the flow of air between the slider and the disk surface.
  • the disk speed was periodically slowed until the slider touches the disk. After every 1000 cycles, the coefficient of friction was measured and recorded at 5 rotations per minute.
  • Example 4 The lubricants described in Example 4 (Lube 1), Example 5 (Lube 2), and the Comparative Example (Lube 3) were evaluated for their adsorption/abso ⁇ tion ability on the magnetic disk carbon overcoat by measuring the reduction in lubricant film thickness on the magnetic disk after high speed spinning.
  • a layer of phosphazene A layer of phosphazene
  • Example A IR absorbance at 1330 cm “1 was used to monitor relative film thickness changes.
  • the disk was then rotated at ambient temperature at 10,000 rotations per minute (rpm) and the thickness of the lubricant layer relative to the initial thickness was measured after 24 and 72 hours of spinning.
  • the average data from 2 test runs each of the lubricants corresponding to those described in Examples 4, 5 and the Comparative Example above are shown in Table 3.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
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  • Lubricants (AREA)

Abstract

Cette invention concerne des phénoxy phosphazènes fonctionnalisés ainsi que leur utilisation en tant que lubrifiants pour des supports d'enregistrement magnétiques. Elle concerne notamment des phosphazènes cycliques comportant six ou huit atomes dans leur structure cyclique et ayant au moins un groupe trifluorométhylphénoxy; ainsi que des groupes hydroxyphénoxy, aminophénoxy, carboxyméthylphénoxy, cyanophénoxy et 2-hydroxyéthoxyphénoxy ou une combinaison de ces derniers; et éventuellement des groupes fluorophénoxy.
PCT/US1997/016651 1996-10-28 1997-09-17 Phenoxy phosphazenes fonctionnalises et leur utilisation en tant que lubrifiant WO1998018804A1 (fr)

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US08/740,355 1996-10-28

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001021630A1 (fr) * 1999-09-21 2001-03-29 Matsumura Oil Research Corp. Composes phosphazene et lubrifiants renfermant ces composes
US10843355B2 (en) 2011-10-06 2020-11-24 Bic-Violex Sa Razor blade, razor head, and method of manufacture
US11985841B2 (en) 2020-12-07 2024-05-14 Oti Lumionics Inc. Patterning a conductive deposited layer using a nucleation inhibiting coating and an underlying metallic coating
US12069938B2 (en) 2019-05-08 2024-08-20 Oti Lumionics Inc. Materials for forming a nucleation-inhibiting coating and devices incorporating same
US12101987B2 (en) 2019-04-18 2024-09-24 Oti Lumionics Inc. Materials for forming a nucleation-inhibiting coating and devices incorporating same
US12113279B2 (en) 2020-09-22 2024-10-08 Oti Lumionics Inc. Device incorporating an IR signal transmissive region
US12150374B2 (en) 2015-10-26 2024-11-19 Oti Lumionics Inc. Method for patterning a coating on a surface and device including a patterned coating
US12178064B2 (en) 2018-02-02 2024-12-24 Oti Lumionics Inc. Materials for forming a nucleation-inhibiting coating and devices incorporating same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4745206A (en) * 1986-05-30 1988-05-17 The Dow Chemical Company Aminophenoxyphosphazenes and a process for producing same
EP0287892A2 (fr) * 1987-04-16 1988-10-26 Hitachi Metals, Ltd. Lubrifiant synthétique pour la lubrification en film fin et support d'enregistrement magnétique
US5230964A (en) * 1989-10-05 1993-07-27 The Dow Chemical Company Magnetic recording media a comprising magnetic particles binder and (fluorinated phenoxy)(3-perfluoroalkylphenoxy)-cyclic phosphazene lubricant
WO1996001303A1 (fr) * 1994-07-01 1996-01-18 Hmt Technology Corporation Composition de lubrifiant et procede

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4745206A (en) * 1986-05-30 1988-05-17 The Dow Chemical Company Aminophenoxyphosphazenes and a process for producing same
EP0287892A2 (fr) * 1987-04-16 1988-10-26 Hitachi Metals, Ltd. Lubrifiant synthétique pour la lubrification en film fin et support d'enregistrement magnétique
US5230964A (en) * 1989-10-05 1993-07-27 The Dow Chemical Company Magnetic recording media a comprising magnetic particles binder and (fluorinated phenoxy)(3-perfluoroalkylphenoxy)-cyclic phosphazene lubricant
WO1996001303A1 (fr) * 1994-07-01 1996-01-18 Hmt Technology Corporation Composition de lubrifiant et procede

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001021630A1 (fr) * 1999-09-21 2001-03-29 Matsumura Oil Research Corp. Composes phosphazene et lubrifiants renfermant ces composes
US6608009B2 (en) 1999-09-21 2003-08-19 Matsumura Oil Research Corp. Phosphazene compounds and lubricants containing the same
US10843355B2 (en) 2011-10-06 2020-11-24 Bic-Violex Sa Razor blade, razor head, and method of manufacture
US12150374B2 (en) 2015-10-26 2024-11-19 Oti Lumionics Inc. Method for patterning a coating on a surface and device including a patterned coating
US12178064B2 (en) 2018-02-02 2024-12-24 Oti Lumionics Inc. Materials for forming a nucleation-inhibiting coating and devices incorporating same
US12101987B2 (en) 2019-04-18 2024-09-24 Oti Lumionics Inc. Materials for forming a nucleation-inhibiting coating and devices incorporating same
US12069938B2 (en) 2019-05-08 2024-08-20 Oti Lumionics Inc. Materials for forming a nucleation-inhibiting coating and devices incorporating same
US12113279B2 (en) 2020-09-22 2024-10-08 Oti Lumionics Inc. Device incorporating an IR signal transmissive region
US11985841B2 (en) 2020-12-07 2024-05-14 Oti Lumionics Inc. Patterning a conductive deposited layer using a nucleation inhibiting coating and an underlying metallic coating

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