WO2012104307A1 - Matériau fibreux solide pour utilisation dans la formation d'un lubrifiant épaissi, procédé pour former un lubrifiant épaissi et lubrifiant formé ainsi - Google Patents

Matériau fibreux solide pour utilisation dans la formation d'un lubrifiant épaissi, procédé pour former un lubrifiant épaissi et lubrifiant formé ainsi Download PDF

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Publication number
WO2012104307A1
WO2012104307A1 PCT/EP2012/051568 EP2012051568W WO2012104307A1 WO 2012104307 A1 WO2012104307 A1 WO 2012104307A1 EP 2012051568 W EP2012051568 W EP 2012051568W WO 2012104307 A1 WO2012104307 A1 WO 2012104307A1
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polymer
fibres
lubricating fluid
fibrous material
based material
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PCT/EP2012/051568
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English (en)
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Dick Meijer
Jeroen Bongaerts
Richard Schaake
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Aktiebolaget Skf
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Publication of WO2012104307A1 publication Critical patent/WO2012104307A1/fr

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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
    • C10M119/00—Lubricating compositions characterised by the thickener being a macromolecular compound
    • 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
    • C10M119/00—Lubricating compositions characterised by the thickener being a macromolecular compound
    • C10M119/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C10M2205/046—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene used as thickening agents
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/2805—Esters used as base material
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    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils used as base material
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C10M2209/046—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • C10M2209/0613—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid used as thickening agents
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    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/0813—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type used as thickening agents
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/102—Polyesters
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/102—Polyesters
    • C10M2209/1026—Polyesters use as thickening agent
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1036—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as thickening agents
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/12—Polysaccharides, e.g. cellulose, biopolymers
    • C10M2209/126—Polysaccharides, e.g. cellulose, biopolymers used as thickening agents
    • 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
    • C10M2213/062—Polytetrafluoroethylene [PTFE]
    • C10M2213/0626—Polytetrafluoroethylene [PTFE] used as thickening agents
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/0213—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds used as thickening agents
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/0406—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds used as thickening agents
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/044—Polyamides
    • C10M2217/0446—Polyamides used as thickening agents
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/045—Polyureas; Polyurethanes
    • C10M2217/0456—Polyureas; Polyurethanes used as thickening agents
    • 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/006—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions used as thickening agents
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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
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    • C10M2229/006—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions used as thickening agents
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/063—Fibrous forms
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10N2050/10—Semi-solids; greasy
    • C—CHEMISTRY; METALLURGY
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    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to solid fibrous materials for use in forming thickened lubricants, e.g., greases, thickened lubricants or greases containing the same and methods for making and using both.
  • thickened lubricants e.g., greases, thickened lubricants or greases containing the same and methods for making and using both.
  • US 6,482,780 discloses a grease composition for a roller bearing comprising a metal soap- based thickening agent containing a long fibre-like material having a major axis length of at least 3 microns incorporated in a base oil comprising a lubricant having a polar group in its molecular structure and a non-polar lubricant blended in combination.
  • US 5,415,791 discloses a lubricating composition for solid lubricant-embedded sliding members comprising 5 to 78% by weight of a solid lubricant powder material, 5 to 30% by weight of a lubricating oil which is in a liquid or paste form at ordinary temperatures, 1 to 15%) by weight of a carrier for absorbing and retaining said lubricating oil, and 15 to 50% by weight of a thermosetting synthetic resin binder.
  • the carrier may be an oleophilic fibre, such as cellulose fibre and polypropylene fibre.
  • US 4,370, 114 discloses a spinneret assembly for use in making "island-in-the-sea" materials, which comprise fibres (islands or cores) disposed or embedded in a polymer matrix (sea or sheath).
  • Polymeric non-woven mats or fabrics are typically produced from a hot polymer melt according to well-known melt-blowing or electro-spinning techniques.
  • the resulting fibres generally form a non-woven mat at relatively high temperatures, because the fibres partially melt to form bonds between them, thereby adhering the fibres.
  • solid fibrous materials also referred to herein interchangeably as "polymer-encapsulated fibrous materials"
  • polymeric fibres having a diameter less than 10 microns, and preferably greater than 50 nanometres are suspended, encapsulated or embedded in a second polymer composition.
  • the resulting solid fibrous materials eliminate the need to utilize dry (loose) polymeric fibrous materials to prepare thickened lubricants or greases and hence provide a safer material to work with.
  • a thickened lubricant such as a grease or a solid oil
  • a thickened lubricant may be prepared by dispersing such fibres or fibrous network, which have been suspended, embedded or encapsulated in another polymer composition, in an oil or other lubricating fluid so that the resulting lubricant will have a structured three-dimensional network, which is able to retain and also release the lubricating fluid, e.g., an oil.
  • This structure can be created by using nano- and/or micro-polymeric fibres that are produced prior to the formation of the lubricant or grease.
  • the polymeric encapsulating material is selected so that it dissolves in the oil or other lubricating fluid, thereby suspending the fibres or three-dimensional fibrous network(s) in the oil or other lubricating fluid.
  • the polymeric fibres generally maintain their shape when contacting the oil or other lubricating fluid, i.e. at least a portion of the polymeric fibres do not dissolve or melt into the oil or other lubricating fluid during operation or usage.
  • the polymeric fibres thicken the oil or lubricating fluid, and/or increase the viscosity thereof, and form advantageous three-dimensional networks within the oil or lubricating fluid.
  • the present teachings advantageously enable a wide flexibility or choice in the selection of the structuring (fibre or fibrous) material.
  • the material can be selected to satisfy very specific operating conditions and/or to impart the lubricant or grease with advantageous properties, such as temperature stability, particular oil bleeding characteristics, etc.
  • refinements are possible in the physics and chemical tuning of the performance (lubrication, bleeding, fibre reinforcing, etc) as well as the particular processes for making and delivering this lubricant into the systems in need of lubrication.
  • the polymeric fibres according to the present teachings are preferably "oleophilic".
  • oleophilic means that the surface of a flat piece of the material (i.e. the material that will be used to form the oleophilic fibres or fibrous material) will be readily covered (wetted) by oil or another lubricating fluid, because that will reduce the total surface energy of the system.
  • a porous structure of an oleophilic material will absorb oil, like a sponge, through capillary action.
  • the contact angle a suitable measure of the degree of oleophilicity in accordance with the present teachings.
  • a small drop of oil exhibits an inner contact angle that is less 90 degrees when dropped onto a material, such material can be considered oleophilic.
  • a higher degree of oleophilicity of the fibrous materials according to the present teachings may be more advantageous in certain embodiments.
  • Polymeric and/or oleophilic fibres may be manufactured from one or more of the following polymer materials: polypropylene (PP), polyamide (PA), nylon 6,6, polyamide-6,6 (PA-6,6), polyamide-4,6 (PA-4,6), polyurethanes (PU), polybenzimidazole (PBI), polycarbonate (PC), polyacrylinitrile (PAN), acrylonitrile rubber (NBR), polyvinylalcohol (PVA), polylactic acid (PLA), polyethylene-co-vinyl-acetate (PEVA), PEVA, polymethacryate (PMMA), tetrahydroperfluorooctylacrylate (TAN), polyethylene oxide (PEO), collagen-PEO, polyaniline (PANI), polystyrene (PS), silk-like polymer with fibronectin functionality, polyninylcarbazole, polyethylene terephtalate (PET), polyacrylic acid (PAA), polypyrene m
  • suitable polymer materials include biopolymers, especially for the production of biodegradable greases.
  • suitable biopolymers are polysaccharides, such as cellulose, starch, chitin, chitosan, proteins, (poly)peptides, and gelatin.
  • Suitable diameters of the fibres are between 50 nanometres and 10 microns. More preferably, the fibres have diameters between 100 nanometres and 1 micron, which is the range of diameters usually found in metallic-soap thickened greases.
  • the fibres preferably have a length that is at least 5-10 times the diameter thereof. That is, the fibres preferably have an aspect ratio of at least 5 to 10.
  • the length of the fibres can be suitably modified to effect desirable changes to the structural properties of the grease, its mechanical stability, and its bulk rheological properties.
  • the fibre length can be optimized for particular application (usage) conditions.
  • the base material for the fibres can be formulated, tuned or adapted for a specific application.
  • the fibres may be provided in a loose form or in a non-woven mat form, as will be further described below.
  • Loose fibres and non-woven fibre mats can be made by melt blowing the polymer material according to well-known techniques in the art, in order to form micron or sub-micron diameter fibres. In the alternative, other techniques can be used as well, such as electro-spinning or nanotubing.
  • the fibre material may also be obtained in the form of non-woven mats or cloths or "island-in-the-sea" materials from commercially available sources, as will be further discussed below.
  • the solid fibrous material can also be sent to a final user as is, i.e. as a polymer-encapsulated fibrous network or as a fibre-embedded polymer material.
  • the final user would only need to add oil or other lubricating fluid (and perform a simple mixing procedure) to produce the thickened lubricant or grease.
  • This aspect of the present teachings provides a great degree of flexibility, because the solid fibrous material can be shipped worldwide relatively inexpensively due to its low weight (i.e. unlike oil or greases, which are relatively heavy).
  • a small fraction (e.g., 0.1-5%) of fibres of one type can be added to grease that primarily contains a second type of fibre so as to impart special properties to the grease.
  • the fibres can be designed to melt at elevated temperatures to form a lubricant.
  • the fibres can provide a structural function in the lubricant or grease. Mixtures of two types of fibres A and B in a ratio A:B between 10:90 and 50:50 can be utilized to impart unique properties to the lubricant or grease.
  • more than two types of different fibres also may be combined into a single solid fibrous material and/or used to thicken a lubricating fluid, and the present teachings are not particularly limited in this regard.
  • the present fibres may be utilized with a wide variety of fluids having lubricating properties at the operating temperatures appropriate for various applications.
  • Particularly suitable lubricants include, but are not limited to, mineral oils obtained from crude oil, group I, II and III lubricants, group IV lubricants (polyalphaolefins "PAO") and group V lubricants (all others).
  • group IV lubricants polyalphaolefins "PAO"
  • group V lubricants all others.
  • groups are lubricant groups as designated by the American Petroleum Institute.
  • a more particular, but non-limiting, list of lubricating oils includes mineral oils, synthetic esters, and plant-based oils and their derivatives, such as oils derived from rapeseed, canola, sunflower, canola and palm.
  • Animal-based oils, their derivatives and synthetic lubricants also may be suitably used in certain aspects of the present teachings, including but not limited to polyglycols (PG), polyalkylene glycol (PAG), white oils, silicone oils, very-high viscosity index oils (VHVI), water, glycerol and waxes.
  • PG polyglycols
  • PAG polyalkylene glycol
  • VHVI very-high viscosity index oils
  • water glycerol and waxes.
  • Particularly preferred oils are mineral oils, synthetic esters, PAOs and synthetic hydrocarbons.
  • the viscosity of the lubricant can range from very low (below lcSt at 40°C) to very high (several 1000 cSt at 40°C).
  • the most suitable viscosity depends on the application temperature, speed, etc., and the present teachings provide for a wide variety of possible lubricating properties.
  • oil types as mentioned above
  • having a viscosity between 10 and 300 cSt at 40 degrees C are particularly preferred.
  • the optimal fibre density in the oil or other lubricating fluid (as described above) will depend on the required viscosity and consistency of the lubricant or grease for the particular application, as well as on the length and diameters of the fibres.
  • Preferred fibre weight densities (based on the total lubricant weight) for a fibre-thickened lubricant according to the present teachings are between 0.1 and 20%.
  • Preferred fibre densities for a fibre-thickened 'grease' are 2-15%, more preferably between 5 and 12%.
  • the fibre content may be reduced accordingly.
  • the polymer fibres, the solid fibrous material (or polymer-encapsulated fibrous networks), the lubricating fluid/oil and/or the thickened lubricant (e.g., grease) according to the present teachings may include one or more known additives that are commonly used in the lubricant field.
  • Suitable additives include additives that are typically used in the lubrication field to impart additional properties to the lubricant. These additives may give the lubricant special functionality with regard to aging of the lubricant (anti -oxidants), friction reducers, anti-wear, extreme pressure properties, etc.
  • additives can be added to give the grease a stronger structure by linking the fibres, such as by connecting the fibres using suitable polymers, waxes or the like.
  • Other fibres can be used as additives as well.
  • additives are ceramic particulates (silica, alumina, zirconia, etc), metallic particles, etc.
  • the additive(s) can be added to the polymer bulk base before the fibres are produced, but can be added also to the dry fibres or to the solid fibrous network (e.g., to the polymer material that coats, suspends, embeds and/or encapsulates the fibres).
  • the additive(s) can also be added to the oil which is then mixed and homogenized with the fibres or solid fibrous material.
  • Another aspect of the present teachings relates to improved lubrication systems, e.g., for bearings, linear actuators, gears and any other mechanical raceway, track or sliding surface, which are lubricated using any of the thickened lubricants or greases disclosed herein.
  • lubricants are provided in the form thickened oils and/or greases. More specifically, lubricating fluids or oils are thickened with fibres according to the present teachings. While the most appropriate consistency is often determined by the application or usage of the thickened lubricant, the LGI grade or consistency (the standard set or determined by the National Lubricating Grease Institute) is preferably equal to or greater than 00. More preferably, lubricants according to the present teachings have a consistency or NLGI grade between 1 and 3, e.g., 2. Such thickened greases are particularly suitable for usage in bearings.
  • polymer fibres are preferably disposed, embedded and/or encapsulated in a "sea" of supporting polymeric material having a different composition and/or physical properties (e.g., different melting temperature and/or solubility) than the composition and/or physical properties of the polymer fibre material.
  • INS islands-in-the-sea
  • Such INS bi-component materials are available, e.g., from Hills Inc. of W. Melbourne, Florida, U.S.A. and include, e.g., sub-micron polypropylene fibres disposed in a polyvinyl acetate sea.
  • the fibre 'island' material has a higher melting temperature than the sea material, it is possible to melt the sea material off or to dissolve it when added to a heated solvent, for example, a lubricating oil.
  • a heated solvent for example, a lubricating oil.
  • the fibres or fibrous network which were/was encapsulated in the polymer sea material, will become suspended in the lubricating fluid and will form advantageous three-dimensional structures, thereby imparting advantageous properties to the lubricating fluid, as was discussed above.
  • the sea material need not necessarily have a lower melting temperature than the island (fibre) material.
  • the sea material may be a material that dissolves naturally in the lubricating fluid (i.e.
  • the sea material can be dissolved or melted in oil, optionally by heating, to release the fibres or fibrous networks into the oil.
  • polypropylene (PP) having a relatively high melting temperature may be spun into fibres having a diameter less than 10 microns, but greater than 50 nanometres.
  • the loose fibres may be utilized as is in the following steps, or may first be heated to form a non -woven mat material (i.e. a fibrous network), thereby bonding or adhering individual fibres together.
  • a non -woven mat material i.e. a fibrous network
  • These fibres or fibrous networks are then coated, suspended, embedded and/or encapsulated in a sea material, which preferably has a lower melting temperature than the PP fibres and/or is highly soluble in the lubricating fluid, in which the solid fibrous material will be dispersed.
  • Various known techniques may be utilized to suspend, embed or encapsulate the fibres or fibrous networks in the polymer sea material, including filament melt extrusion.
  • the polymer encapsulating (sea) material may be comprised at least substantially of:
  • a lower molecular weight PP for isotactic PP, MW ⁇ 30,000, more preferably MW ⁇ 10,000
  • Waxes in particular, provide the advantage that they can impart supplemental lubricating properties to the lubricating fluid.
  • Preferred waxes include polymers having a molecular weight less than lx the molecular weight of the polymer with the same monomer unit between polymer entanglements, and include waxes, such as e.g., natural waxes, such as bees wax, or high molecular weight hydrocarbons, such as paraffin waxes.
  • a low molecular weight polymer is defined as less than 3x molecular weight between entanglements.
  • a high molecular weight polymer is defined as having at least 3x molecular weight between entanglements.
  • the fibres having a diameter less than 10 microns are comprised at least substantially of polypropylene (PP) having a relatively high melting temperature, e.g., between 160 and 175 °C.
  • PP polypropylene
  • the sea material is a 'wax' having a melting temperature of 90 - 100 °C, e.g., PP Licocene PP 1302 GR TP obtainable from Clariant International Ltd. of Muttenz Switzerland (hereinafter simply "Clariant").
  • the sea material is a 'wax' having a melting temperature of 120 - 130 °C, e.g., TP Licocene PP 4202 or Licowax PE 520 obtainable from Clariant.
  • the sea material is a polyether (PE), e.g., Licowax PE 190P obtainable from Clariant.
  • PE polyether
  • the sea material is a wax consisting of a copolymer having polar and non-polar properties, e.g., Licowax OMFL obtainable from Clariant.
  • Example E Licowax OMFL obtainable from Clariant.
  • the sea material is an oil, e.g., a polyalphaolefin (PAO) having a base viscosity of 48 cSt.
  • PAO polyalphaolefin
  • the sea material is obtained by degrading the same polymer as used for the fibres by subjecting the material to flash heating.
  • the island-in-the-sea solid fibrous material i.e. the polymer-encapsulated fibrous network
  • it can be dispersed in, and the sea material can be directly dissolved into, the oil or lubricating fluid at a temperature that melts and dissolves the sea material.
  • heating may be applied to the dispersion (mixture) to expedite the dissolving of the sea material.
  • Continuous stirring also should be applied to the dispersion in order to ensure proper entanglement of the fibres and the creation of a continuous three- dimensional network within the oil or lubricant fluid. Cooling of the mixture, if necessary, then finalises the lubricant-thickening (e.g., grease-forming) process.
  • the lubricant-thickening e.g., grease-forming
  • the INS fibres may be cut to an appropriate length before melting and/or dissolving the INS fibres in the oil or lubricating fluid, as will be discussed below. If pre-cut, the fibres may dissolve into the oil more quickly, but whilst still producing a suitable three-dimensional structure.
  • polymeric fibres having a diameter less than 10 microns into the oil or lubricating fluid.
  • any of the above-described known fibre-producing methods e.g., melt- blowing, electro-spinning, force spinning, nanotubing or any similar method, may be utilized to make the fibres.
  • such methods are modified by immediately depositing the just-formed fibres in the oil or lubricating fluid.
  • Such an embodiment enables fast cooling and/or quenching of the fibres, because the fibres are contacted and covered or coated by the oil or lubricating fluid before the fibres form a mat. This ensures that the fibres can be separated by the oil again and prevents the formation of 'non-continuous' networks, which would occur if a non-woven mat is broken into pieces.
  • Embodiment 3 is a modification of Embodiment 2, wherein polymeric fibres having a diameter less than 10 microns are produced from a molten polymer base, such as by melt- blowing, electro-spinning or another known fibre-forming technique as described above or below, but the fibres are first cooled to well below their melting point before suspending in oil or lubricating fluid. This ensures the formation of a loosely structured fibrous network that can be easily dissolved into oil. It further enables the formation of a continuous three-dimensional network, which can be achieved by setting the air flow applied to the fibres at an appropriate temperature and flow rate.
  • polymeric fibrous networks e.g., non- woven mats
  • the fibrous networks are processed (cut) to a suitable length, e.g., in the form of a solid fibrous material.
  • the method of the fourth embodiment enables fine control over the determination of the fibre length(s).
  • this method for processing the fibres or fibrous networks has the advantageous effect of significantly reducing the amount of loose (dry) fibres that may be inhaled during handling to prepare the thickened lubricant and/or grease, thereby reducing potential health concerns of dangerous airborne materials.
  • a dry fibrous network or non-woven fibre mat (formed according to any above-described method) is preferably soaked in a wax or wax-like material at a temperature above the melting temperature of the wax, but at a temperature below the melting temperature of the fibres contained in the dry fibrous network or non- woven fibre mat.
  • any material having a melting temperature lower than the polymer composition of the polymer fibres can be used as the encapsulating material in the present embodiment.
  • Such a relatively low-melting temperature encapsulating material enables the fibres or fibrous networks to soak and embed into the encapsulating material when in a melted or liquid state. After the fibres or fibrous networks have been soaked in the encapsulating material for a sufficient amount of time, the mixture may be cooled and thus solidified, thereby embedding the fibres in a solid matrix.
  • the solidified matrix can be cut, e.g., at room temperature or lower.
  • the matrix can be processed using a variety methods known in the art to produce fibres cut to different length distributions that are suitable for the desired thickening properties.
  • a preferred cutting method is to use a sharp cutting tool to slice clearly defined pieces of the solidified matrix under fine control and thus produce a narrow range of length distributions of the fibres.
  • microtome adapted to cut slices of the solid fibrous material into a thickness between 1 and 100s of microns, e.g. between about 1-400 microns, more preferably 1-50 microns.
  • a sled microtome may be utilized by the placing a sample of the solid matrix (solid fibrous material) into a shuttle. The shuttle is then moved back and forth across a knife to form micron-thin slices.
  • a cutting device in size of cutting length as well as number of cutters may be utilized with the present teachings.
  • Waxes are particularly well suited for use as the encapsulating or embedding material in this embodiment, because they are generally solid at room temperature. Any of the above- described waxes may be utilized in this embodiment of the present teachings.
  • the encapsulating (e.g., wax or wax-like) material By embedding the fibres in the encapsulating (e.g., wax or wax-like) material, there is significantly reduced chance that the fibres will become airborne during post-processing (e.g., during formation of the thickened-lubricant and/or grease) and form a fine dust. This will significantly improve the working environment for making the thickened-lubricants and/or grease.
  • the encapsulating e.g., wax or wax-like
  • the length distribution can be extremely narrow.
  • the wax (having the fibres or fibrous networks embedded therein) of the sliced solidified matrix can be dissolved in an oil or lubricating fluid, which may be heated if necessary, thereby immediately forming a fibre-thickened lubricant or grease that can be used as a lubricant.
  • suitable lubricant additives can be added at any points in the manufacturing process. Any of the above-noted lubricant additives may be utilized, as necessary and/or desired.
  • the wax is suitably selected based upon the lubricating properties that it will impart to the oil or lubricating fluid after being dissolved therein. Non-limiting examples are natural waxes and commercially-available waxes marketed as having lubricating properties, such as the ones described above.
  • the wax may exhibit structure-enhancing properties, e.g., by depositing itself or precipitating onto the three-dimensional fibre structure upon cooling of the oil-wax -fibre mixture. Suitable ratios, by weight or by volume, of wax to fibres are between l-to-10 and 10-to-l, more suitable are between 3 : 1 and 1 :3. Most suitable is around 1-to-l .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne un matériau fibreux solide dans l'épaississement d'un fluide lubrifiant qui comprend une pluralité de fibres lâches et/ou un mat non-tissé de fibres, qui comprennent un premier matériau à base de polymère et sont enrobées, suspendues, incluses ou encapsulées dans un deuxième matériau à base de polymère. Le premier matériau à base de polymère est hydrophobe, est au moins substantiellement insoluble dans le fluide lubrifiant à une température de service normale du fluide lubrifiant et est capable d'augmenter la viscosité du fluide lubrifiant. Le deuxième matériau à base de polymère est au moins substantiellement soluble dans le fluide lubrifiant et/ou a une température de fusion au-dessous de la température de fusion du premier matériau à base de polymère. La présente invention concerne en outre un procédé pour former un lubrifiant épaissi qui comprend la dispersion du matériau fibreux solide dans le fluide lubrifiant et la dissolution et/ou fusion du deuxième matériau à base de polymère. La présente invention concerne en outre un lubrifiant épaissi formé selon ce procédé.
PCT/EP2012/051568 2011-02-01 2012-01-31 Matériau fibreux solide pour utilisation dans la formation d'un lubrifiant épaissi, procédé pour former un lubrifiant épaissi et lubrifiant formé ainsi WO2012104307A1 (fr)

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PCT/EP2012/051587 WO2012104313A1 (fr) 2011-02-01 2012-01-31 Procédé pour former un lubrifiant épaissi et lubrifiant épaissi formé par celui-ci

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CN113491791A (zh) * 2020-04-01 2021-10-12 苏州合祥纺织科技有限公司 一种负载肝素的微纳复合纤维膜及其制备方法
CN112680269B (zh) * 2020-12-28 2022-08-30 中铁十局集团有限公司 一种环保型盾尾密封油脂及其制备方法
WO2022241683A1 (fr) * 2021-05-19 2022-11-24 安美科技股份有限公司 Lubrifiant fibreux et procédé de préparation associé
CN113956913B (zh) * 2021-10-29 2022-07-26 中铁建华南建设(广州)高科技产业有限公司 水基盾尾密封脂及其制备方法和应用

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