EP0340323A1 - Schmiermittel - Google Patents

Schmiermittel Download PDF

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Publication number
EP0340323A1
EP0340323A1 EP88107051A EP88107051A EP0340323A1 EP 0340323 A1 EP0340323 A1 EP 0340323A1 EP 88107051 A EP88107051 A EP 88107051A EP 88107051 A EP88107051 A EP 88107051A EP 0340323 A1 EP0340323 A1 EP 0340323A1
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EP
European Patent Office
Prior art keywords
oil
weight
agent
water
emulsion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP88107051A
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English (en)
French (fr)
Inventor
Haimi Nathan Singer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Singer and Hersch Industrial Development Pty Ltd
Original Assignee
Singer and Hersch Industrial Development Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Singer and Hersch Industrial Development Pty Ltd filed Critical Singer and Hersch Industrial Development Pty Ltd
Priority to EP88107051A priority Critical patent/EP0340323A1/de
Publication of EP0340323A1 publication Critical patent/EP0340323A1/de
Withdrawn legal-status Critical Current

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    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
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    • C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
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    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
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    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M135/02—Sulfurised compounds
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    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
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    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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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
    • C10M2229/00—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
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/045—Siloxanes with specific structure containing silicon-to-hydroxyl bonds
    • C10M2229/0455—Siloxanes with specific structure containing silicon-to-hydroxyl bonds 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
    • C10M2229/00—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
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/046—Siloxanes with specific structure containing silicon-oxygen-carbon bonds
    • C10M2229/0465—Siloxanes with specific structure containing silicon-oxygen-carbon bonds 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
    • C10M2229/00—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
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/047—Siloxanes with specific structure containing alkylene oxide groups
    • C10M2229/0475—Siloxanes with specific structure containing alkylene oxide groups 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
    • C10M2229/00—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
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/048—Siloxanes with specific structure containing carboxyl groups
    • C10M2229/0485—Siloxanes with specific structure containing carboxyl groups 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
    • C10M2229/00—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
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C10M2229/0505—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon 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
    • C10M2229/00—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
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C10M2229/051—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing halogen
    • C10M2229/0515—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing halogen 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
    • C10M2229/00—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
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C10M2229/052—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing nitrogen
    • C10M2229/0525—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing nitrogen 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
    • C10M2229/00—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
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C10M2229/053—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing sulfur
    • C10M2229/0535—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing sulfur 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
    • C10M2229/00—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
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C10M2229/054—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing phosphorus
    • C10M2229/0545—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing phosphorus used as base material

Definitions

  • This invention relates to lubricants.
  • a water-based lubricant which comprises a substantially oil-free, aqueous, emulsion-free composition of matter comprising a major amount of water including up to as much as 99,9 percent of weight of water, a minor but effective amount of at least one substantially water-insoluble, oil-soluble functional additive stably dispersed therein, and a minor but effective amount of at least one substantially water-­soluble, liquid organic dispersing agent which is capable of dissolving the functional additive and of stably dispersing the functional additive in the composition.
  • the composition is formed by premixing the functional additive and the dispersing agent followed by adding this mixture of the water.
  • the preferred functional additive is an extreme pressure (EP) agent such as a sulphur- or chlorosulphur- extreme pressure agent, a chlorinated hydrocarbon or phosphorus extreme pressure agent or a mixture of two or more of these agents.
  • EP extreme pressure
  • the composition can optionally contain at least one water-soluble polymeric thickener.
  • a lubricant comprising an oil-in-water emulsion having a viscosity of at least 68 mm2/sec. measured on a Brookfield Viscometer with a No. 1 spindle at 25 rpm and 25°C and comprising:
  • a method of producing such a lubricant including the steps of providing an aqueous composition as described above, thickening the composition with a thickener which is also capable of stabilising the emulsion and adding an oil to the thickened water-based composition under conditions suitable to produce an emulsion.
  • the lubricant of the invention is one which has a relatively high viscosity. This means that the lubricant has a viscosity of at least 68 mm2/sec. measured on a Brookfield viscometer with a No. 1 spindle at 25 rpm and 25°C or measured on a Canon Fenske tube at 40°C.
  • the lubricant has a grease-like consistency and can be applied by spraying, brushing, trowelling or like manner to an area to be lubricated.
  • the grease-like consistency of the composition enables it to stick, and be retained on a surface to which it is applied without readily running off. This is one characteristic which distinguishes the lubricant from the water-based lubricant of British Patent No. 1,571,652 which is liquid and free flowing.
  • the lubricant of the invention can thus be used in applications where the water-based lubricant of this British patent cannot be used.
  • the emulsion is of the oil-in-water type, i.e. the aqueous composition forms the continuous phase while the oil forms the discontinuous phase dispersed in the continuous phase.
  • the aqueous composition constitutes 99 to 60% by weight of the emulsion and the oil constitutes from 1 to 40% by weight of the emulsion.
  • the aqueous composition constitutes 92 to 80% by weight of the emulsion and the oil constitutes 8 to 20% of the emulsion.
  • the oil is preferably a synthetic oil.
  • suitable synthetic oils are di-esters, neopentyl polyol esters, phosphate esters, methyl silicones, phenyl methyl silicones, chlorinated phenyl methyl silicones, polyalkylene glycols, typically polypropylene glycols, chlorinated di-phenyls, silicate esters, polyphenyl ethers and fluorocarbons.
  • the oil preferably has dissolved therein an extreme pressure (EP) agent which is soluble in the oil and which is water-insoluble.
  • EP agent is preferably a sulphur or chlorosulphur EP agent, a chlorinated hydrocarbon EP agent, or a phosphorous EP agent.
  • EP agents are chlorinated wax, organic sulfides and polysulfides, such as benzyldisulfide, bis-(chlorobenzyl) disulfide, dubutyl tetrasulfide, sulfurized sperm oil, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons, such as the reaction product of phosphorus sulfide with turpentine or methyl oleate, phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, i.e.
  • organic sulfides and polysulfides such as benzyldisulfide, bis-(chlorobenzyl) disulfide, dubutyl tetrasulfide, sulfurized sperm oil, sulfurized methyl ester of ole
  • the EP agent is the oil is preferably present in an amount of 1 to 10% by weight of the oil.
  • the emulsifier will be one capable of producing an oil-in-water emulsion from the oil used and the water.
  • suitable emulsifiers are alkylaryl sulfonates, lignosulfonate salts, starch and the like.
  • the emulsifier will be chosen to suit the characteristics of the oil used in the emulsion.
  • the emulsifier will typically be present in an amount of 1 to 50%, preferably 2 to 10% by weight of the oil.
  • the emulsion may be made by methods known in the art.
  • the aqueous composition will be agitated, for example by vigorous stirring, with the oil in the presence of an emulsifier or emulsion stabiliser.
  • the emulsifier may be dissolved in the aqueous composition or in the oil depending on its solubility characteristics.
  • the emulsion may be thickened to the required viscosity by adding a suitable thickener.
  • This thickener will typically be added to the aqueous composition before the emulsion is produced, but it can also be added after the emulsion has been produced. Examples of suitable thickeners are described in British Patent No. 1,571,652. More than one thickener may be used.
  • a preferred method of producing the emulsion comprises providing the water-based composition, thickening the composition by adding thereof a thickener which is also capable of stabilising an emulsion, and adding the oil to the thickened aqueous composition under conditions, e.g. vigorous agitation, suitable to produce an emulsion.
  • the thickener is preferably added in an amount of up to 3% by weight of the aqueous composition.
  • the thickener which also functions as an emulsion stabiliser is preferably a water-soluble acrylic acid polymer which has recurring units of the general structure:
  • Such polymers are sold under the name Carbopol® by the B.F. Goodridge Company.
  • the preferred polymers are Carbopol 910 and Carbopol 941.
  • aqueous composition will be of the type and having the characteristics of those described in British patent No. 1,591,652, the contents of which are incorporated herein by reference.
  • the lubricant of the invention may also include minor amounts by weight of other materials such as solid lubricants, corrosion inhibitors, friction modifiers, film formers and the like.
  • a solid lubricant it may, for example, be selected from a graphite, molybdenum disulfide, and powdered PTFE (polytetrafluoroethylene).
  • the lubricant of the invention contains an aqueous composition and an oil, each of which is a lubricant. It has surprisingly been found that, particularly when the oil is a synthetic oil, the lubricant of the invention has lubricating properties which are better than the lubricating properties of either of the individual components. It is believed that a synergistic action operates. Further, the compositions are water-resistant in the sense that they are not adversely affected by the presence of water. This distinguishes them from known and commonly used oils and greases which are adversely affected by the presence of water. The water-­resistant properties of the lubricant of the invention renders it ideally suitable for applications such as in bearings where water is present.
  • the higher viscosity and grease-like consistency of the composition enables it to be used in applications such as open gear dressings, chain saw lubrication, and in bearings.
  • Other applications for the lubricant are in rock drilling, diamond prospecting drilling, oil well drilling, and tapping.
  • aqueous composition of the type described in British Patent 1,571,652 was prepared by assembling the following ingredients in the indicated amount: Ingredient Amount (a) Hydroxy ethyl cellulose (Natrosol LR) 40 g (b) Zinc dithiophosphate 2 g (c) A first portion of polypropylene glycol (Pluriol P900) 1 g (d) Anglamol 32 1 g (e) A second portion of polypropylene glycol (Pluriol P900) 2 g (f) Diethanolamine 5 g (g) Emulan SH 10 g (h) Ethylene glycol 50 g (i) Dye 1 g
  • Ingredient (a) was dispersed in 600ml of water and allowed to hydrate. Ingredients (a) and (c) were mixed and dispersed well into a portion of the thickened water. Ingredients (d) and (e) were mixed and dispersed well into the remainder of the thickened water. The two portions of the thickened water were recombined and agitated to form a homogeneous dispersion. The remaining ingredients were added individually to the thickened mixture which was agitated after each addition.
  • the thus produced water-based composition was thickened by adding to it 8 gms of Carbopol 910.
  • the composition was neutralised by the addition of diethanolamine.
  • 2g of molybdenum dithiophosphate and 10g of zinc dithiophosphate were added to 80g of a polypropylene glycol sold under the trade name Pluriol P2000.
  • the pre-mix was then added to the thickened water-based composition with agitation to produce a stable emulsion.
  • the emulsion has a viscosity of exceeding 12000 mm2/sec. measured on a Brookfield viscometer with a No. 1 spindle at 25 rpm and 25°C.
  • a lubricant was produced in the manner described in Example 1 save the the molybdenum dithiophosphate and zinc dithiophosphate were not added to the polypropylene glycol.
  • the polypropylene glycol was used on its own without any such addition of an EP agent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
EP88107051A 1988-05-03 1988-05-03 Schmiermittel Withdrawn EP0340323A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP88107051A EP0340323A1 (de) 1988-05-03 1988-05-03 Schmiermittel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP88107051A EP0340323A1 (de) 1988-05-03 1988-05-03 Schmiermittel

Publications (1)

Publication Number Publication Date
EP0340323A1 true EP0340323A1 (de) 1989-11-08

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Application Number Title Priority Date Filing Date
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Country Link
EP (1) EP0340323A1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6933263B2 (en) 2002-05-23 2005-08-23 The Lubrizol Corporation Emulsified based lubricants
US7435707B2 (en) 2002-05-23 2008-10-14 The Lubrizol Corporation Oil-in-water emulsions and a method of producing
WO2010071784A1 (en) * 2008-12-16 2010-06-24 Pq Corporation Friction modifier for drilling fluids
CN102863946A (zh) * 2011-07-08 2013-01-09 长江大学 一种抗高温钻井液润滑剂

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2926513A1 (de) * 1979-06-30 1981-01-15 Dynamit Nobel Ag Schmierstoffsystem fuer die warmverformung von metallen
GB1591652A (en) * 1976-08-04 1981-06-24 Singer & Hersch Industrial Dev Water-based industrial fluids
US4313836A (en) * 1980-12-01 1982-02-02 Basf Wyandotte Corporation Water-based hydraulic fluid and metalworking lubricant
EP0024848B1 (de) * 1979-08-27 1983-02-23 Mobil Oil Corporation Dithiophosphate enthaltende wässrige Schmiermittel
EP0102212A2 (de) * 1982-08-20 1984-03-07 Castrol Limited Hydraulikflüssigkeiten auf Wasserbasis

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1591652A (en) * 1976-08-04 1981-06-24 Singer & Hersch Industrial Dev Water-based industrial fluids
DE2926513A1 (de) * 1979-06-30 1981-01-15 Dynamit Nobel Ag Schmierstoffsystem fuer die warmverformung von metallen
EP0024848B1 (de) * 1979-08-27 1983-02-23 Mobil Oil Corporation Dithiophosphate enthaltende wässrige Schmiermittel
US4313836A (en) * 1980-12-01 1982-02-02 Basf Wyandotte Corporation Water-based hydraulic fluid and metalworking lubricant
EP0102212A2 (de) * 1982-08-20 1984-03-07 Castrol Limited Hydraulikflüssigkeiten auf Wasserbasis

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6933263B2 (en) 2002-05-23 2005-08-23 The Lubrizol Corporation Emulsified based lubricants
US7435707B2 (en) 2002-05-23 2008-10-14 The Lubrizol Corporation Oil-in-water emulsions and a method of producing
WO2010071784A1 (en) * 2008-12-16 2010-06-24 Pq Corporation Friction modifier for drilling fluids
US8003576B2 (en) 2008-12-16 2011-08-23 The Lubrizol Corporation Friction modifier for drilling fluids
CN102863946A (zh) * 2011-07-08 2013-01-09 长江大学 一种抗高温钻井液润滑剂

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