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US20060100110A1 - Novel hydrogen-absorbing composition, process for its preparation and use as composition for filling optical fibre cables - Google Patents

Novel hydrogen-absorbing composition, process for its preparation and use as composition for filling optical fibre cables Download PDF

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Publication number
US20060100110A1
US20060100110A1 US11/298,658 US29865805A US2006100110A1 US 20060100110 A1 US20060100110 A1 US 20060100110A1 US 29865805 A US29865805 A US 29865805A US 2006100110 A1 US2006100110 A1 US 2006100110A1
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composition
hydrocarbonaceous
oil
vegetable oils
dispersing
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US11/298,658
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Gerard Trouve
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Societe dExploitation de Produits pour les Industries Chimiques SEPPIC SA
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Societe dExploitation de Produits pour les Industries Chimiques SEPPIC SA
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G02B6/4401Optical cables
    • G02B6/4429Means specially adapted for strengthening or protecting the cables
    • G02B6/44382Means specially adapted for strengthening or protecting the cables the means comprising hydrogen absorbing materials

Definitions

  • a subject-matter of the invention is novel hydrogen-absorbing compositions comprising dispersing agents and their use in the manufacture of optical fibre cables.
  • Optical fibres which make possible the transmission of increasingly large amounts of information, are laid in cables liable to be subjected to significant mechanical and chemical stresses, in particular when they are submarine cables.
  • the fibres are protected by metal or plastic sheathings and are “immersed” in greases which contribute to cushioning the impacts and to restricting the microcurves which result therefrom and which interfere with the transmission of the signals.
  • These microcurves are also caused by the appearance of hydrogen microbubbles which form inside the grease at the time of the manufacture of the cable, during welding operations or over time as an effect of ageing. This is why some greases currently sold comprise compounds which absorb hydrogen.
  • the French patent application published under the number 2 607 311 discloses a hydrophobic thixotropic composition intended for the manufacture of optical fibre cables comprising 100 parts by weight of a lubricating fluid composed of 30% to 100% by weight of polybutene, preferably hydrogenated polybutene, having a number-average molecular mass of between 280 and 800 and of 0% to 70% by weight of at least one liquid lubricant chosen from mineral oils, synthetic oils and silicones and 7 to 20 parts by weight of a hydrophobic thixotropic agent chosen from a hydrophobic silica and a hydrophobic bentonite.
  • a lubricating fluid composed of 30% to 100% by weight of polybutene, preferably hydrogenated polybutene, having a number-average molecular mass of between 280 and 800 and of 0% to 70% by weight of at least one liquid lubricant chosen from mineral oils, synthetic oils and silicones and 7 to 20 parts by weight of a hydrophobic thixotropic agent chosen from a hydrophobic si
  • 4,668,889 discloses hydrogen-absorbing compositions for the filling of optical fibre cables which comprise the mixture of an unsaturated silicone with a catalyst chosen from transition metals, organic salts of transition metals or organometallic compounds of the said metals and more specifically palladium powder, platinum powder, nickel powder, iron pentacarbonyl or chloroplatinic acid, the said metals optionally being supported on inert compounds, such as animal or vegetable carbon black.
  • a catalyst chosen from transition metals, organic salts of transition metals or organometallic compounds of the said metals and more specifically palladium powder, platinum powder, nickel powder, iron pentacarbonyl or chloroplatinic acid, the said metals optionally being supported on inert compounds, such as animal or vegetable carbon black.
  • 4,741,592 discloses hydrogen-absorbing compositions for the filling of optical fibre cables which comprise the mixture of an unsaturated polymer obtained by the polymerization of conjugated dienes with a catalyst chosen from transition metals, organic salts of transition metals or organometallic compounds of the said metals and more specifically palladium powder, platinum powder, nickel powder, iron pentacarbonyl or copper chromite, the said metals optionally being supported on inert compounds, such as animal or vegetable carbon black.
  • a catalyst chosen from transition metals, organic salts of transition metals or organometallic compounds of the said metals and more specifically palladium powder, platinum powder, nickel powder, iron pentacarbonyl or copper chromite, the said metals optionally being supported on inert compounds, such as animal or vegetable carbon black.
  • EP 0 632 301 discloses hydrogen-absorbing compositions for the filling of optical fibre cables which comprise the mixture of an unsaturated hydrocarbonaceous compound, for example polybutene or propylene-ethylene, propylene-butene and propylene-hexene copolymers, the propylene-butene-ethylene terpolymer, glyceryl ricin-oleate or resin oil, with a catalyst chosen from transition metals, organic salts of transition metals or organometallic compounds of the said metals and more specifically palladium powder, platinum powder, nickel powder or iron pentacarbonyl, the said metals optionally being supported on inert compounds.
  • an unsaturated hydrocarbonaceous compound for example polybutene or propylene-ethylene, propylene-butene and propylene-hexene copolymers, the propylene-butene-ethylene terpolymer, glyceryl ricin-oleate or resin oil
  • a catalyst chosen from transition metals,
  • the French patent application published under the number 2 763 955 discloses a composition for filling optical fibre cables which comprises from 75% to 95% by weight of a propoxylated bisphenol with a molecular weight of less than 3 000, from 5% to 25% by weight of a thixotropic agent and from 0.1% to 1% by weight of an antioxidizing agent.
  • the palladium-based compounds are provided in the form of very fine powders with a diameter of approximately ten microns and with a high specific surface area. In point of fact, these powders are difficult to disperse homogeneously and have a tendency to form agglomerates in the greases, which reduces the overall specific surface area of the catalyst and thus the effectiveness of the grease in absorbing hydrogen. On the other hand, at equal effectiveness, a good dispersion of the catalyst in the grease makes it possible to use smaller amounts of catalyst and thus to decrease the cost price of these greases. This is why the Applicant Company has sought to develop novel compositions in which the catalyst powders are dispersed more homogeneously than in those of the state of the art.
  • a subject-matter of the invention is a composition, characterized in that it comprises a hydrocarbonaceous and/or silicone compound or a mixture of hydrocarbonaceous and/or silicone compounds, a nonzero proportion of one or more transition metals and a nonzero proportion of at least one slightly polar dispersing liquid fatty phase, having one or more hydrocarbonaceous chains, with an HLB of between 0.5 and 9, preferably between 4 and 9.
  • hydrocarbonaceous and/or silicone compound or mixture of hydrocarbonaceous and/or silicone compounds denotes in particular hydrocarbons, hydrocarbonaceous polymers, silicone oils and/or polyol derivatives.
  • composition which is a subject-matter of the present invention generally comprises from 50% to 90% by weight of hydrocarbonaceous and/or silicone compound or of mixture of hydrocarbonaceous and/or silicone compounds.
  • Hydrocarbons or hydrocarbonaceous polymers include, for example, poly-alpha-olefins (PAO) or copolymers of alpha-olefins comprising from 8 to 12 carbon atoms, polyisobutene (PIB) or polybutene, obtained by polymerization of isobutene, of 1-butene and/or of 2-butene, propylene-ethylene, propylene-butene and propylene-hexene copolymers, propylene-butene-ethylene terpolymers or polybutadienes.
  • PAO poly-alpha-olefins
  • PIB polyisobutene
  • the silicone oils can be chosen from poly(alkylsiloxanes), in particular poly(dimethylsiloxanes), with high molecular weights having a viscosity of the order of 10 000 to 30 000 cSt at ambient temperature.
  • the polyol derivatives are obtained by etherification or esterification of a compound having several hydroxyl functional groups, such as, for example, glycerol, TMP or bisphenol, by means of hydrocarbonaceous fatty chains or alkoxide chains, such as polyethylene glycol, polypropylene glycol or polybutylene glycol.
  • the composition which is a subject-matter of the present invention also comprises one or more metal catalysts in a proportion by weight ranging up to 5% by weight of the said composition.
  • metal compounds appropriate to the present invention include, for example, transition metals, organic salts of transition metals or organometallic compounds of the said metals and more specifically palladium powder, platinum powder, nickel powder, iron pentacarbonyl, chloroplatinic acid, copper chromite, Raney nickel, palladium supported on active charcoal, palladium supported on alumina, platinum supported on alumina or platinum supported on active charcoal.
  • the composition comprises up to 1% by weight of palladium supported on alumina or on active charcoal.
  • composition which is a subject-matter of the present invention also comprises up to 15% by weight of silica.
  • Hydrophobic treated silica such as, for example, AerosilTM R974
  • the preferred silica is hydrophilic silica, for example hydrophilic pyrogenic silica, such as that sold under the name of AerosilTM 200, or hydrophilic colloidal silica, such as that sold under the name of Cab-O-SilTM TS 720.
  • composition which is a subject-matter of the present invention optionally comprises up to approximately 5% of a viscosifying polymer.
  • viscosifying polymer include styrene, ethylene, propylene, butylene or butadiene polymers or diblock copolymers of these monomers, such as polystyrene-polyethylene, polystyrene-[polyethylene+polypropylene], polystyrene-polyisoprene or polystyrene-polybutene, or triblock polymers, such as polystyrene-polyethylene-polystyrene, polystyrene-[polyethylene+polypropylene]-polystyrene, polystyrene-polyisoprene-polystyrene or polystyrene-polybutadiene-polystyrene. Polymers of this type are sold under the trade names KratonTM G or Kraton
  • composition which is a subject-matter of the present invention optionally comprises up to approximately 2% of an antioxidizing agent chosen, for example, from compounds with a sterically hindered phenolic structure, such as polymeric 2,2,4-trimethyl-1,2-dihydroquinoline, phenothiazine, octyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, hydroquinone monomethyl ether or triethylene glycol bis[3-(3′-tert-butyl-4′-hydroxy-5′-methylphenyl)propionate], sold under the name of IrganoxTM 245, or ethylenebis-(oxyethylene) bis(3-tert-butyl-4-hydroxy-5-methylhydro-cinnamate), IrganoxTM 1076, or IrganoxTM 1010.
  • an antioxidizing agent chosen, for example, from compounds with a sterically hindered phenolic structure, such as polymeric 2,2,4-trimethyl-1,2-
  • liquid fatty phase having one or more hydrocarbonaceous chains with an HLB of between 0.5 and 9, preferably between 4 and 9′′ is preferably understood to mean fatty phases which are liquid at ambient temperature.
  • HLB hydrophilic-lipophilic balance
  • HLB 20 ⁇ ( M h /M ) in which M h is the mass of the hydrophilic part of the molecule and M is its overall molecular mass.
  • composition which is a subject-matter of the present invention comprises from 1% to 20% and preferably between 5% and 10% by weight of dispersing fatty phase.
  • the ratio by weight of the metal catalyst or catalysts to the dispersing fatty phase in the composition is between approximately 0.01 and 0.20.
  • Slightly polar dispersing fatty phase appropriate to the present invention includes vegetable oils, such as, for example, sunflower oil, rapeseed oil, maize oil, soybean oil, castor oil, linseed oil, coconut oil, groundnut oil, olive oil, palm oil or hydrogenated palm oil, or modified vegetable oils, such as methyl esters of vegetable oils, monoglycerides or diglycerides obtained by controlled hydrolysis of vegetable oils, weakly alkoxylated vegetable oils, in particular weakly ethoxylated and/or propoxylated vegetable oils, more particularly ethoxylated vegetable oils comprising from 1 to 10 ethylene oxide units, or weakly alkoxylated methyl esters of vegetable oils, in particular weakly ethoxylated and/or propoxylated methyl esters of vegetable oils and more particularly methyl esters of vegetable oils ethoxylated with 1 to 4 ethylene oxides.
  • modified vegetable oils such as, for example, sunflower oil, rapeseed oil, maize oil, soybean oil, castor oil,
  • slightly polar liquid dispersing fatty phase appropriate to the present invention includes surface-active agents having an HLB number of between 1 and 9, preferably between 4 and 9, which are miscible with the oils which participate in the composition of the greases.
  • surface-active agents having an HLB number of between 1 and 9, preferably between 4 and 9, which are miscible with the oils which participate in the composition of the greases.
  • examples include linear or branched fatty alcohols or fatty acids comprising from 5 to 30 carbon atoms and more particularly from 12 to 22 carbon atoms or the esters of the said acids, the said alcohols, acids or esters optionally being weakly alkoxylated.
  • a subject-matter of the latter is a process for producing the composition as defined above comprising a stage of dispersing the catalyst in the dispersing agent as defined above, followed by mixing the dispersion in the other constituents of the composition which is a subject-matter of the present invention.
  • the process as defined above is a preferred route but it is possible to mix the dispersing phase with the oils of the grease, to add the palladium powder and then to add the other components.
  • a subject-matter of the latter is the use of the composition as defined above as composition for filling optical fibre cables.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition, characterized in that it comprises a hydrocarbonaceous compound or a mixture of hydrocarbonaceous compounds, a nonzero proportion of one or more transition metals and a nonzero proportion of at least one slightly polar dispersing liquid fatty phase, having one or more hydrocarbonaceous chains, with an HLB of between 0.5 and 9, preferably between 4 and 9. Its process of preparation and its use as composition for filling optical fibre cables.

Description

  • A subject-matter of the invention is novel hydrogen-absorbing compositions comprising dispersing agents and their use in the manufacture of optical fibre cables.
  • Optical fibres, which make possible the transmission of increasingly large amounts of information, are laid in cables liable to be subjected to significant mechanical and chemical stresses, in particular when they are submarine cables. To restrict the effects of these stresses, the fibres are protected by metal or plastic sheathings and are “immersed” in greases which contribute to cushioning the impacts and to restricting the microcurves which result therefrom and which interfere with the transmission of the signals. These microcurves are also caused by the appearance of hydrogen microbubbles which form inside the grease at the time of the manufacture of the cable, during welding operations or over time as an effect of ageing. This is why some greases currently sold comprise compounds which absorb hydrogen.
  • Thus, the French patent application published under the number 2 607 311 discloses a hydrophobic thixotropic composition intended for the manufacture of optical fibre cables comprising 100 parts by weight of a lubricating fluid composed of 30% to 100% by weight of polybutene, preferably hydrogenated polybutene, having a number-average molecular mass of between 280 and 800 and of 0% to 70% by weight of at least one liquid lubricant chosen from mineral oils, synthetic oils and silicones and 7 to 20 parts by weight of a hydrophobic thixotropic agent chosen from a hydrophobic silica and a hydrophobic bentonite. The use of a polar agent, such as propylene carbonate, for improving the dispersion of the silicas or bentonites is disclosed in the patent application. The British patent application published under the number 2 144 559 discloses hydrogen-absorbing compositions for optical fibre cables which comprise polybutene, aromatic hydrocarbons, palladium or active charcoal. The United States patent published under the U.S. Pat. No. 4,668,889 discloses hydrogen-absorbing compositions for the filling of optical fibre cables which comprise the mixture of an unsaturated silicone with a catalyst chosen from transition metals, organic salts of transition metals or organometallic compounds of the said metals and more specifically palladium powder, platinum powder, nickel powder, iron pentacarbonyl or chloroplatinic acid, the said metals optionally being supported on inert compounds, such as animal or vegetable carbon black. The United States patent published under the U.S. Pat. No. 4,741,592 discloses hydrogen-absorbing compositions for the filling of optical fibre cables which comprise the mixture of an unsaturated polymer obtained by the polymerization of conjugated dienes with a catalyst chosen from transition metals, organic salts of transition metals or organometallic compounds of the said metals and more specifically palladium powder, platinum powder, nickel powder, iron pentacarbonyl or copper chromite, the said metals optionally being supported on inert compounds, such as animal or vegetable carbon black. The European patent application published under the number EP 0 632 301 discloses hydrogen-absorbing compositions for the filling of optical fibre cables which comprise the mixture of an unsaturated hydrocarbonaceous compound, for example polybutene or propylene-ethylene, propylene-butene and propylene-hexene copolymers, the propylene-butene-ethylene terpolymer, glyceryl ricin-oleate or resin oil, with a catalyst chosen from transition metals, organic salts of transition metals or organometallic compounds of the said metals and more specifically palladium powder, platinum powder, nickel powder or iron pentacarbonyl, the said metals optionally being supported on inert compounds. The French patent application published under the number 2 763 955 discloses a composition for filling optical fibre cables which comprises from 75% to 95% by weight of a propoxylated bisphenol with a molecular weight of less than 3 000, from 5% to 25% by weight of a thixotropic agent and from 0.1% to 1% by weight of an antioxidizing agent.
  • The palladium-based compounds are provided in the form of very fine powders with a diameter of approximately ten microns and with a high specific surface area. In point of fact, these powders are difficult to disperse homogeneously and have a tendency to form agglomerates in the greases, which reduces the overall specific surface area of the catalyst and thus the effectiveness of the grease in absorbing hydrogen. On the other hand, at equal effectiveness, a good dispersion of the catalyst in the grease makes it possible to use smaller amounts of catalyst and thus to decrease the cost price of these greases. This is why the Applicant Company has sought to develop novel compositions in which the catalyst powders are dispersed more homogeneously than in those of the state of the art.
  • A subject-matter of the invention is a composition, characterized in that it comprises a hydrocarbonaceous and/or silicone compound or a mixture of hydrocarbonaceous and/or silicone compounds, a nonzero proportion of one or more transition metals and a nonzero proportion of at least one slightly polar dispersing liquid fatty phase, having one or more hydrocarbonaceous chains, with an HLB of between 0.5 and 9, preferably between 4 and 9.
  • The term “hydrocarbonaceous and/or silicone compound or mixture of hydrocarbonaceous and/or silicone compounds” denotes in particular hydrocarbons, hydrocarbonaceous polymers, silicone oils and/or polyol derivatives.
  • The composition which is a subject-matter of the present invention generally comprises from 50% to 90% by weight of hydrocarbonaceous and/or silicone compound or of mixture of hydrocarbonaceous and/or silicone compounds.
  • Hydrocarbons or hydrocarbonaceous polymers include, for example, poly-alpha-olefins (PAO) or copolymers of alpha-olefins comprising from 8 to 12 carbon atoms, polyisobutene (PIB) or polybutene, obtained by polymerization of isobutene, of 1-butene and/or of 2-butene, propylene-ethylene, propylene-butene and propylene-hexene copolymers, propylene-butene-ethylene terpolymers or polybutadienes. The silicone oils can be chosen from poly(alkylsiloxanes), in particular poly(dimethylsiloxanes), with high molecular weights having a viscosity of the order of 10 000 to 30 000 cSt at ambient temperature. The polyol derivatives are obtained by etherification or esterification of a compound having several hydroxyl functional groups, such as, for example, glycerol, TMP or bisphenol, by means of hydrocarbonaceous fatty chains or alkoxide chains, such as polyethylene glycol, polypropylene glycol or polybutylene glycol.
  • The composition which is a subject-matter of the present invention also comprises one or more metal catalysts in a proportion by weight ranging up to 5% by weight of the said composition. Examples of metal compounds appropriate to the present invention include, for example, transition metals, organic salts of transition metals or organometallic compounds of the said metals and more specifically palladium powder, platinum powder, nickel powder, iron pentacarbonyl, chloroplatinic acid, copper chromite, Raney nickel, palladium supported on active charcoal, palladium supported on alumina, platinum supported on alumina or platinum supported on active charcoal.
  • According to a specific alternative form of the present invention, the composition comprises up to 1% by weight of palladium supported on alumina or on active charcoal.
  • The composition which is a subject-matter of the present invention also comprises up to 15% by weight of silica. Hydrophobic treated silica, such as, for example, Aerosil™ R974, can be used but the preferred silica is hydrophilic silica, for example hydrophilic pyrogenic silica, such as that sold under the name of Aerosil™ 200, or hydrophilic colloidal silica, such as that sold under the name of Cab-O-Sil™ TS 720.
  • The composition which is a subject-matter of the present invention optionally comprises up to approximately 5% of a viscosifying polymer. Examples of viscosifying polymer include styrene, ethylene, propylene, butylene or butadiene polymers or diblock copolymers of these monomers, such as polystyrene-polyethylene, polystyrene-[polyethylene+polypropylene], polystyrene-polyisoprene or polystyrene-polybutene, or triblock polymers, such as polystyrene-polyethylene-polystyrene, polystyrene-[polyethylene+polypropylene]-polystyrene, polystyrene-polyisoprene-polystyrene or polystyrene-polybutadiene-polystyrene. Polymers of this type are sold under the trade names Kraton™ G or Kraton D, Septon™ or Shellvis™.
  • The composition which is a subject-matter of the present invention optionally comprises up to approximately 2% of an antioxidizing agent chosen, for example, from compounds with a sterically hindered phenolic structure, such as polymeric 2,2,4-trimethyl-1,2-dihydroquinoline, phenothiazine, octyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, hydroquinone monomethyl ether or triethylene glycol bis[3-(3′-tert-butyl-4′-hydroxy-5′-methylphenyl)propionate], sold under the name of Irganox™ 245, or ethylenebis-(oxyethylene) bis(3-tert-butyl-4-hydroxy-5-methylhydro-cinnamate), Irganox™ 1076, or Irganox™ 1010.
  • The term “slightly polar dispersing liquid fatty phase having one or more hydrocarbonaceous chains, with an HLB of between 0.5 and 9, preferably between 4 and 9″ is preferably understood to mean fatty phases which are liquid at ambient temperature.
  • The HLB number, or hydrophilic-lipophilic balance, and its method of determination are known to a person skilled in the art. This parameter makes it possible to assess the hydrophobic and hydrophilic natures of a given surface-active agent. In the context of the present invention, for surface-active agents comprising an ester functional group, it is determined by the following formula:
    HLB=20×[1−(SN/AN)
    in which SN represents the saponification number of the product, measured according to NFT Standard 60206, and AN represents the acid number of the precursor acids, measured according to NFT Standard 60204.
  • In the case of surface-active agents comprising an ether functional group, the HLB is calculated by the equation:
    HLB=20×(M h /M)
    in which Mh is the mass of the hydrophilic part of the molecule and M is its overall molecular mass.
  • The composition which is a subject-matter of the present invention comprises from 1% to 20% and preferably between 5% and 10% by weight of dispersing fatty phase.
  • According to another specific aspect of the present invention, the ratio by weight of the metal catalyst or catalysts to the dispersing fatty phase in the composition is between approximately 0.01 and 0.20.
  • Slightly polar dispersing fatty phase appropriate to the present invention includes vegetable oils, such as, for example, sunflower oil, rapeseed oil, maize oil, soybean oil, castor oil, linseed oil, coconut oil, groundnut oil, olive oil, palm oil or hydrogenated palm oil, or modified vegetable oils, such as methyl esters of vegetable oils, monoglycerides or diglycerides obtained by controlled hydrolysis of vegetable oils, weakly alkoxylated vegetable oils, in particular weakly ethoxylated and/or propoxylated vegetable oils, more particularly ethoxylated vegetable oils comprising from 1 to 10 ethylene oxide units, or weakly alkoxylated methyl esters of vegetable oils, in particular weakly ethoxylated and/or propoxylated methyl esters of vegetable oils and more particularly methyl esters of vegetable oils ethoxylated with 1 to 4 ethylene oxides. The preparation of these modified vegetable oils is disclosed in the international patent applications published under the numbers WO 96/22109 and WO 00/01233.
  • The term “weakly alkoxylated” indicates, in the preceding and in the following, that the alkoxylation number and in particular the ethoxylation and propoxylation numbers, which represent respectively the number of ethoxyl units (EO number) and the number of propoxyl units (PO number) per molecule, is less than or equal to approximately 15 [EO number=15 or PO number=15 or (EO number+PO number)=approximately 15].
  • Other slightly polar liquid dispersing fatty phase appropriate to the present invention includes surface-active agents having an HLB number of between 1 and 9, preferably between 4 and 9, which are miscible with the oils which participate in the composition of the greases. Examples include linear or branched fatty alcohols or fatty acids comprising from 5 to 30 carbon atoms and more particularly from 12 to 22 carbon atoms or the esters of the said acids, the said alcohols, acids or esters optionally being weakly alkoxylated. Preference is given, among these, to surface-active agents which are liquid at ambient temperature, such as those comprising an oleyl, oleyl/cetyl, linoleyl or behenyl chain. These compounds are optionally weakly alkoxylated. Examples of surface-active agents of this nature include sorbitan oleic esters, oleyl alcohols comprising from 1 to 5 ethylene oxide units (EO=5), polyethylene glycol (PEG) oleates comprising from 1 to 5 ethylene oxide units (1≦EO≦5), liquid glucose ethers or oleic acid comprising from 1 to 5 ethylene oxide units.
  • According to another aspect of the present invention, a subject-matter of the latter is a process for producing the composition as defined above comprising a stage of dispersing the catalyst in the dispersing agent as defined above, followed by mixing the dispersion in the other constituents of the composition which is a subject-matter of the present invention.
  • The process as defined above is a preferred route but it is possible to mix the dispersing phase with the oils of the grease, to add the palladium powder and then to add the other components.
  • According to a final aspect of the present invention, a subject-matter of the latter is the use of the composition as defined above as composition for filling optical fibre cables.
  • The following examples illustrate the invention without, however, limiting it.
  • A) Demonstration of the Influence of the Dispersing Fatty Phase on the Amount of Hydrogen Absorbed by the Composition
  • The examples in Tables 1 a to 1e are obtained from a model grease composed of:
      • 5 or 10% by weight of a dispersing fatty phase (referred to as DFP)
      • 3.8% by weight of a viscosifying polymer (Shellvis™ 40),
      • 6.5% by weight of hydrophilic silica (Cab-O-Sil™ TS 720),
      • 0.4% of an antioxidant (Irganox™ 1076),
      • 0.6% of palladium supported on alumina catalyst,
      • q.s. for 100% of poly-alpha-olefin (PAO).
  • The measured characteristics of the compositions are as follows:
      • the volatility, after residence in an oven at 150° C. for 24 h,
      • the release of oil (exsudation) , after residence in an oven at 150° C. for 24 hours,
      • the viscosity at a high shear gradient (approximately 2 500 Pa·s), measured on a Carrimed viscometer with a cone with a diameter of 2 cm and an angle of 2°,
      • the hydrogen absorption per gram of grease at 24 hours and at 48 hours, in a cell under an initial hydrogen pressure of 400 mm of mercury at ambient temperature.
  • The results reveal that all the greases formulated with 5 to 10% of a polar fatty phase have viscosities, exsudations and volatilities close to those of the control formula but that the hydrogen absorption is, on the other hand, markedly improved, in particular when the dispersing fatty phase has an HLB number in the region of 4 or greater than 4. Additives not possessing a long hydrocarbonaceous fatty chain, such as oxypropylated bisphenol A (comparative example), give results which are only slightly better than those of the control.
    TABLE 1a
    Examples Control Ex. 1
    DFP (nature; amount as %; HLB) None Methyl ester of
    rapeseed oil; 5%
    HLB = 0.5
    Volatility 1.17% 4.16%
    Exsudation 0% 0%
    Plastic viscosity 0.90 Pa · s at 0.78 Pa · s at
    2534 Pa 2445 Pa
    H2 pressure at T = 0 h 405 mmHg (0) 401 mmHg (0)
    in mmHg, at T = 24 h 322 mmHg (1.08) 204 mmHg (3.27)
    H2 absorption at T = 48 h 321 mmHg (1.39) 174 mmHg (3.76)
    in ml/g
  • TABLE 1b
    Examples Ex. 2 Ex. 3
    DFP (nature; amount as %; HLB) Ethoxylated (2 Rapeseed oil;
    EO) oleyl/cetyl 5%;
    alcohol; 5%; HLB = 0.5
    HLB = 6
    Volatility 2.67% 1.81%
    Exsudation 0% 0%
    Plastic viscosity 0.81 Pa · s at 0.83 Pa · s at
    2093 Pa 2394 Pa
    H2 pressure at T = 0 h 406 mmHg (0) 400 mmHg
    in mmHg, at T = 24 h 277 mmHg (2.14) 304 mmHg (1.59)
    H2 absorption at T = 48 h 246 mmHg (2.65) 277 mmHg (2.04)
    in ml/g
  • TABLE 1c
    Examples Ex. 4 Ex. 5
    DFP (nature; amount as Ethoxylated (4 Alkoxylated (5
    %; HLB) EO) maize oil; 5%; EO 4 PO 5 EO)
    HLB = 5 oleic acid; 5%;
    HLB = 3
    Volatility 1.6% 2.01%
    Exsudation 0% 0%
    Plastic viscosity 0.90 Pa · s at 0.88 Pa · s at
    2125 Pa 2494 Pa
    H2 pressure at T = 0 h 400 mmHg 405 mmHg
    in mmHg, at T = 24 h 304 mmHg (1.7) 299 mmHg (1.76)
    H2 absorption at T = 48 h 277 mmHg (2.24) 291 mmHg (1.89)
    in ml/g
  • TABLE 1d
    Examples Ex. 6 Comparative
    DFP (nature; amount as Ethoxylated (5 Oxypropylated
    %; HLB) EO) oleic acid; 5%; bisphenol A 10%;
    HLB = 8.7 HLB = 1
    Volatility 1.43% 1.71%
    Exsudation 0% 0.06%
    Plastic viscosity 0.90 Pa · s at 0.91 Pa · s at
    2344 Pa 2394 Pa
    H2 pressure at T = 0 h 402 mmHg 403 mmHg
    in mmHg, at T = 24 h 279 mmHg (2.03) 315 mmHg (1.45)
    H2 absorption at T = 48 h 249 mmHg (2.53) 309 mmHg (1.55)
    in ml/g
  • TABLE 1e
    Examples Ex. 7 Ex. 8
    DFP (nature; amount as %; HLB) Sorbitan Ethoxylated (10
    oleate; 10%; EO) oleic acid;
    HLB = 4.3 HLB = 8.7
    Volatility 2.22% 2.0%
    Exsudation 1.94% 0%
    Plastic viscosity 0.85 Pa · s at 0.89 Pa · s
    1994 Pa
    H2 pressure at T = 0 h 403 mmHg 401 mmHg
    in mmHg, at T = 24 h 284 mmHg (1.97) 255 mmHg (2.4)
    H2 absorption at T = 48 h 249 mmHg (2.54) 221 mmHg (2.97)
    in ml/g

    B) Demonstration of the Influence of the Catalyst/Dispersing Fatty Phase Ratio by Weight on the Amount of Hydrogen Absorbed by the Composition
  • The examples in Tables 2a to 2c are obtained from a model grease composed of:
      • 5% by weight of ethoxylated (5 EO) oleic acid with an HLB of 8.7,
      • 3.8% by weight of a viscosifying polymer (Shellvis™ 40),
      • 6.5% by weight of hydrophilic silica (Cab-O-Sil™ TS720),
      • 0% to 0.6% of palladium supported on alumina catalyst,
      • q.s. for 100% of poly-alpha-olefin (PAO).
  • In all cases, the amounts of hydrogen absorbed in 48 h are greater than those absorbed by the control not comprising dispersing phase while comprising 0.6% of catalyst.
    TABLE 2a
    Examples Control Ex. 9
    Catalyst/DFP ratio by weight 0 0.04
    Catalyst (% by weight) 0% Pd/Al2O3; 0.20%
    Volatility 1.3% 1.3%
    Exsudation 0% 0%
    Plastic viscosity 0.90 Pa · s at 0.90 Pa · s at
    2344 Pa 2344 Pa
    H2 pressure at T = 0 h 403 mmHg (0) 402 mmHg (0)
    in mmHg, at T = 48 h 402 mmHg (0) 295 mmHg (1.78)
    H2 absorption
    in ml/g
  • TABLE 2b
    Examples Ex. 10 Ex. 11
    Catalyst/DFP ratio by weight 0.08 0.12
    Catalyst (% by weight) Pd/Al2O3; 0.40% Pd/Al2O3; 0.60%
    Volatility 1.9% 1.9%
    Exsudation 0% 0%
    Plastic viscosity 0.90 Pa · s at 0.90 Pa · s at
    2344 Pa 2344 Pa
    H2 pressure at T = 0 h 403 mmHg (0) 402 mmHg (0)
    in mmHg, at T = 48 h 244 mmHg (2.59) 173 mmHg (3.78)
    H2 absorption
    in ml/g
  • TABLE 2c
    DFP-free
    Examples Ex. 12 control
    Catalyst/DFP ratio by weight 0.06% 8
    Catalyst (% by weight) Pd/Al2O3; 0.30% Pd/Al2O3; 0.60%
    Volatility 1.43% 1.17%
    Exsudation 0% 0%
    Plastic viscosity 0.90 Pa · s · at 0.90 Pa · s at
    2344 Pa 2344 Pa
    H2 pressure at T = 0 h 401 mmHg (0) 405 mmHg (0)
    in mmHg, at T = 48 h 221 mmHg (2.97) 321 mmHg (1.39)
    H2 absorption
    in ml/g
  • The examples in Tables 3a to 3c are obtained from a model grease composed of:
      • 10% by weight of vegetable oil (HLB 0.5),
      • 3.8% by weight of a viscosifying polymer (Shellvis™ 40),
      • 6.5% by weight of hydrophilic silica (Cab-O-Sil™ TS720),
      • 0% to 0.3% of palladium supported on alumina catalyst,
      • q.s. for 100% of poly-alpha-olefin (PAO).
  • In all cases where the catalyst/DFP ratio by weight is greater than 0.01, the amounts of hydrogen absorbed in 48 h are greater than those absorbed by the control not comprising dispersing phase while comprising 0.6% of catalyst.
    TABLE 3a
    Examples Control Ex. 13
    Catalyst/DFP ratio by weight 0 0.01
    Catalyst (% by weight) 0% Pd/Al2O3; 0.10%
    Volatility 1.8% 1.8%
    Exsudation 0% 0%
    Plastic viscosity 0.87 Pa · s at 0.89 Pa · s at
    2550 Pa 2556 Pa
    H2 absorption at T = 0 h 0 0
    in ml/g at T = 48 h 0.05 0.98
  • TABLE 3b
    Examples Ex. 14 Ex. 15
    Catalyst/DFP ratio by weight 0.02 0.03
    Catalyst (% by weight) Pd/Al2O3; 0.20% Pd/Al2O3; 0.30%
    Volatility 1.8% 1.8%
    Exsudation 0% 0%
    Plastic viscosity 0.88 Pa · s at 0.87 Pa · s at
    2550 Pa 2560 Pa
    H2 absorption at T = 0 h 0 0
    in ml/g at T = 48 h 1.9 2.3
  • TABLE 3c
    DFP-free
    Examples Ex. 16 control
    Catalyst/DFP ratio by weight 0.06% 8
    Catalyst (% by weight) Pd/Al2O3; 0.60% Pd/Al2O3; 0.60%
    Volatility 1.8% 1.17%
    Exsudation 0% 0%
    Plastic viscosity 0.83 Pa · s at 0.90 Pa · s at
    2394 Pa 2344 Pa
    H2 absorption at T = 0 h 0 0
    in ml/g at T = 48 h 2 1.4

Claims (15)

1. A composition, comprising a hydrocarbonaceous and/or silicone compound or a mixture of hydrocarbonaceous and/or silicone compounds, a nonzero proportion of one or more transition metals and a nonzero proportion of at least one slightly polar dispersing liquid fatty-phase, having one or more hydrocarbonaceous chains, with an HLB of between 0.5 and 9, wherein one or more metal catalysts are present in an amount up to 5% by weight of said composition, and wherein the metal catalyst is selected from the group consisting of palladium powder, platinum powder, nickel powder, iron pentacarbonyl, chloroplatinic acid, copper chromite, Raney nickel, palladium supported on active charcoal, palladium supported on alumina, platinum supported on alumina, and platinum supported on active charcoal, and
wherein a silicone compound is present and said silicone compound is a silicone oil selected from the group consisting of poly(alkylsiloxanes) and poly(dimethyl-siloxanes) with high molecular weights.
2. The composition as defined in claim 1, wherein said composition comprises from 50% to 90% by weight of hydrocarbonaceous and/or silicone compound or of mixture of hydrocarbonaceous and/or silicone compounds.
3. The composition as defined in claim 1, wherein a hydrocarbonaceous compound is present and the hydrocarbonaceous compound is a polymer selected from the group consisting of poly-alpha-olefins, polyisobutene, propylene-ethylene, propylene-butene and propylene-hexene copolymers, propylene-butene-ethylene terpolymers and polybutadienes.
4. The composition as defined in claim 1, wherein said composition comprises up to approximately 5% of a viscosifying polymer.
5. The composition as defined in claim 1, wherein said composition comprises up to approximately 2% of an antioxidizing agent.
6. The composition as defined in claim 1, wherein the slightly polar dispersing liquid fatty phase, having one or more hydrocarbonaceous chains, with an HLB of between 0.5 and 9, is liquid at ambient temperature.
7. The composition as defined in claim 1, wherein said composition comprises from 1% to 20% by weight of dispersing fatty phase.
8. The composition as defined in claim 7, wherein the ratio by weight of the metal catalyst or catalysts to the dispersing fatty phase in the composition is between approximately 0.01 and 0.20.
9. The composition as defined in claim 1, wherein the dispersing fatty phase is chosen from vegetable oils.
10. A composition, comprising a hydrocarbonaceous and/or silicone compound or a mixture of hydrocarbonaceous and/or silicone compounds, a nonzero proportion of one or more transition metals and a nonzero proportion of at least one slightly polar dispersing liquid fatty phase, having one or more hydrocarbonaceous chains, with an HLB of between 0.5 and 9, wherein the dispersing fatty phase is selected from the group consisting of methyl esters of vegetable oils, monoglycerides or diglycerides obtained by controlled hydrolysis of vegetable oils, weakly alkoxylated vegetable oils, weakly ethoxylated vegetable oils, propoxylated vegetable oils, ethoxylated vegetable oils comprising from 1 to 10 ethylene oxide units, weakly alkoxylated methyl esters of vegetable oils, weakly ethoxylated and/or propoxylated methyl esters of vegetable oils, and methyl esters of vegetable oils ethoxylated with 1 to 4 ethylene oxides.
11. The composition as defined in claim 9, wherein the vegetable oil is selected from the group consisting of sunflower oil, rapeseed oil, maize oil, soybean oil, castor oil, linseed oil, coconut oil, groundnut oil, olive oil, palm oil and hydrogenated palm oil.
12. The composition as defined in claim 7, wherein the dispersing fatty phase is chosen from surface-active agents having an HLB number of between 1 and 9.
13. The composition as defined in claim 12, wherein the dispersing fatty phase is chosen from linear or branched fatty alcohols or fatty acids comprising from 5 to 30 carbon atoms.
14. The composition as defined in claim 7, wherein the dispersing fatty phase is chosen from surface-active agents which are liquid at ambient temperature.
15. The composition as defined in claim 7, wherein the dispersing fatty phase is chosen from optionally weakly alkoxylated surface-active agents comprising an oleyl, oleyl/cetyl, linoleyl or behenyl chain.
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US20130324447A1 (en) * 2012-06-01 2013-12-05 Exxonmobil Research And Engineering Company Lubricant compositions and processes for preparing same
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