US2456496A - Lubricants - Google Patents

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Publication number
US2456496A
US2456496A US439066A US43906642A US2456496A US 2456496 A US2456496 A US 2456496A US 439066 A US439066 A US 439066A US 43906642 A US43906642 A US 43906642A US 2456496 A US2456496 A US 2456496A
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US
United States
Prior art keywords
lubricant
dimethyl
lubricants
viscosity
silicones
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.)
Expired - Lifetime
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US439066A
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English (en)
Inventor
James G Ford
Robert N Wenzel
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Westinghouse Electric Corp
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Westinghouse Electric Corp
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Publication date
Application filed by Westinghouse Electric Corp filed Critical Westinghouse Electric Corp
Priority to US439066A priority Critical patent/US2456496A/en
Priority to CH265201D priority patent/CH265201A/de
Application granted granted Critical
Publication of US2456496A publication Critical patent/US2456496A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B31/00—Bearings; Point suspensions or counter-point suspensions; Pivot bearings; Single parts therefor
    • G04B31/08—Lubrication
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • 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
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties

Definitions

  • This invention relates to lubricants, and more particularly to synthetic compositions characterized by a relatively fiat viscosity-temperature curve.
  • the object of this invention is to provide a lubricant composed essentially of liquid polymers of dimethyl silicone.
  • a further object of this invention is to provide for polymerizing essentially dimethyl silicols in producing lubricants characterized by an extremely flat temperature viscosity curve.
  • lubricating substance In the application of lubricating substances to bearings or surfaces to be separated during relative movement, it is desirable that the lubricating substance remain present at the applied surfaces without evaporating or creeping away therefrom. Changes in the lubricating substance due to the presence of atmospheric gases in combination with the temperatures to which it is subjected should not cause sludging or gumming of the lubricant. In addition, a satisfactory lubricant is characterized by relative non-reactivity with the surfaces to which itis applied. Usually lubrication fails when any one of these three changes takes place in an applied lubricant.
  • a further unsatisfactory characteristic of prior art lubricants is the rapid change in viscosity with temperature change.
  • a lubricant which has been selected because it is satisfactory in viscosity at a mean temperature in a given mechanism may become thin and considerably less effective as a lubricant at high temperature conditions.
  • the mechanism when the mechanism is at its lowest temperature, the lubricant may become extremely thick and viscous. In this state the lubricant not only causes an increased power loss, but frequently surfaces may run bare for a period of time before the lubricant penetrates to all parts of the bearing surfaces and is eliective.
  • the problem of a satisfactory lubricant for many types of apparatus therefore, is not successfully met by employing the usual types of materials, with or without the addition of inhibitors and other additives.
  • a lubricant meeting all of the above seven requirements as well as or better than any known lubricant may be prepared from silicones.
  • dimethyl silicone polymers which have been treated to remove low boiling constituents meet the above requirements for a lubricant more successfully than any material heretofore known.
  • - silicon tetrachloride in cold ether solution may be casacca Cl SiCliCH: l Cl-gl-Cl CHsMgBr BiClz(CHs)z MSBrCl l SiCl(CHx)
  • the individual components of this mixture have different boiling points and can be separated by fractional distillation. Dimethyi silicon dichloride may thus be isolated. Its subsequent reaction with water yields dimethyl silicol and the silicol then polymerizes, spontaneously or through the agency of applied heat or catalysts which may be employed to control, within limits. the degree of polymerization and the physical properties of the resulting polymeric product.
  • the methyl ethoxysilanes are readily separable by distillation into monomethyl, dimethyl and trimethyl ethoxysilanes. As mentioned previously, it is desirable to work with only the dimethyl compound.
  • the isolated dimethyl diproduct is unsatisfactory as a lubricant, since the monomethyl silicones present permit the formation of solids and thermosetting types of compounds due to cross linkages between chains of polymer. If liquid polymers from such mixtures are subjected to heat when exposed to oxygen and moisture, they are not stable and will poiymerize further to form more viscous liquids and plastic or rigid solid bodies.
  • the product is a liquid characterized by extreme stability. It is believed that chains or closed rings having the following general form occur:
  • Polymeric dimethyl silicones which may be produced by practicing any of the processes above disclosed, or other possible methods, so as to isolate essentially the dimethyl fraction consist of a mixture of polymers of different molecular weight.
  • the viscosity depends to a great extent upon the nature of the polymers present. The followingtable is indicative of the range of physical properties obtainable when mixtures prepared under diiferent conditicas were fractionated,
  • Example 3 Stock and Somieski, Ber, Deuts. Chem. Ges. 52, 695 (1919), disclose that silane may be reacted with hydrogen chloride to produce monochlorosilane and dichlorosilane. Exhaustive methylation of the dichlorosilane with zinc methyl vapor produced dimethylsilane.
  • dialkylsilane produced is hydrolyzed with sodium hydroxide to produce a soiution'which when acidered precipitates silicones.
  • Stock and Somieski have shown that dimethyl silicone is conveniently prepared by this method. They further disclose that polymers obtained by this process are of a nature similar to those secured by the practice of the Kipping process.
  • Silicone polymers are built up through chains of alternating silicon and oxygen atoms. It an unseparated mixture of mono. di, and trimethyl silicon derivatives is hydrolyzed, the polymerized u
  • the column headed fraction refers to the volatile and non-volatile fractions which separate on distilling at 200 C. at an absolute pressure of 5 millimeters of mercury. The volatile fraction in the table in each instance 'is liquid at room temperature.
  • a satisfactory lubricant can be secured only if essentially dimethyl silicol molecules are condensed and polymerized.
  • the product produced by condensing essentially dimethyl siliool will be radically different from the polymerized product resulting when a mixture of mono, diand trimethyl silicols having an average of 2 methyl groups .physical or chemical characteristics.
  • the product consisting of substantially two methyl groups per silicon atom but containing monoand trimethyl silicols in addition to dimethyl silicols.
  • This product is stated to be essentially an oily liquid which. when heated for four hours at 120 C., sets to a soft, somewhat robbery gel. Obviously a gel is an unsatisfactory lubricant.
  • Other properties of these mixtures have been described by those working in the art as forming solids upon being polymerized by exposure to temperatures of 200 C. These solids are not stable at elevated temperatures, since heating for several days at 200 C. causes any increasing embrittlement. They have been described further as oxidizing in air at 300 C. with disintegration taking place when this heating is prolonged for 24 hours.
  • the product produced from essentially dimethyl silicol polymerized at any temperature with or without a catalyst is a liquid. No solid products have been encountered when this material has been polymerized in numerous ways. When heated at 200 C. for prolonged periods of time, there is no observable chemical change. By heating at this temperature in vacuo light fractions may be removed as a vapor, but the major portion of the liquid does not distill even at 5 mm. of Hg and 200 C.
  • dimethyl silicone polymer has been heated at 200 C. while agitated by a stream of pure oxygen for 17 hours and longer Without any observable change in The liquid was as mobile and as clear after the test as be-4 fore. No sludging or gumming occurred.
  • the slope m in the table is calculated from the viscosities at 210 F. and 100 F. according to the following formula:
  • the dimethyl silicone polymer lubricant appears to meet all of the seven requirements herein set forth for an exceptionally satisfactory lubricant. Every test to which the material has been subjected has been successfully met.
  • a lubricant having the extremely :dat viscosity temperature curve exhibited by the dimethyl silicone polymers is highly advantageous for use in apparatus subjected to a wide lrange of temperatures.
  • Precision instruments such. as Watches, clocks me I ters, scientific apparatus and the like willoperate with less power being required at temperatures below 0 l1'. with the silicone lubricant retaining-sumcient body and film forming characteristics to lubricate the bearings adequately at temperatures as high as the boilins point of wa. ter and even higher.
  • the lubricant has been found not to freeze or harden until considerably below -70 E'.
  • Dimethyl silicones have been found to be satisfactory lubricante since they are stable at high temperatures even when exposed to engen.
  • other dia'lkyl silicones such. for exampie. as diethyl silicone, may be utilized asilibricants dependina on the conditions met.
  • a lubricant composed of a mixture of liqi uid polymers of diallwl silicones in which the al.
  • kyl groups each have at least two carbon atoms u substantially free of the monoalkyl and trialkyi silicone derivatives, the iubricantbeing characterized by resistance to deterioration at high temperatures.
  • a lubricant composed of a mixture of liquid polymers of dialkyl silicones, the dialkyl silicones each having a substantial number of alkyl groups with at least two carbon atoms to provide an average of more than two carbon atoms per silicon atom, the silicones being substantially free of the monoalkyl and trialkyl silicone derivatives, the lubricant being characterized by resistance to deterioration at high temperatures.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Lubricants (AREA)
US439066A 1942-04-15 1942-04-15 Lubricants Expired - Lifetime US2456496A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US439066A US2456496A (en) 1942-04-15 1942-04-15 Lubricants
CH265201D CH265201A (de) 1942-04-15 1946-02-12 Verfahren zur Schmierung von Lagern und beweglichen Teilen.

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US439066A US2456496A (en) 1942-04-15 1942-04-15 Lubricants

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2467976A (en) * 1943-03-30 1949-04-19 Corning Glass Works Method for increasing the viscosity of liquid polymeric dimethyl silicone
US2626434A (en) * 1950-05-01 1953-01-27 Leslie C Ike Window construction
US2660559A (en) * 1949-08-31 1953-11-24 Maryland Lab Inc Method and apparatus for the purification of liquids
DE945283C (de) * 1951-03-23 1956-07-05 Union Carbide & Carbon Corp UEberzugsmasse fuer die Kaltverformung von Metallen
US2760925A (en) * 1952-03-14 1956-08-28 Grove Valve & Regulator Co Method for surfacing aluminum
US2825609A (en) * 1956-07-20 1958-03-04 Edward C Jeffers Journal lubricator
US3330162A (en) * 1964-09-28 1967-07-11 Stewart Warner Corp Speedometer bearing structure
US4019591A (en) * 1975-06-09 1977-04-26 Engineering Enterprises, Inc. Well drilling tool
USRE30257E (en) * 1975-01-31 1980-04-22 Engineering Enterprises, Inc. Well drilling tool
US4830520A (en) * 1983-06-27 1989-05-16 Alsthom-Atlantique Method of protecting a limited-displacement mechanical system against an agressive medium

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2129281A (en) * 1936-03-23 1938-09-06 Continental Oil Co Lubricating oils
US2181914A (en) * 1935-03-19 1939-12-05 Standard Oil Dev Co Oil composition containing arylated metallo-organic inhibitors
US2242400A (en) * 1937-09-13 1941-05-20 Standard Oil Co Extreme pressure lubricant
US2258219A (en) * 1939-09-27 1941-10-07 Gen Electric Halogenated aryl silicones
US2286763A (en) * 1940-12-26 1942-06-16 Gen Electric Methyl silicon halides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2181914A (en) * 1935-03-19 1939-12-05 Standard Oil Dev Co Oil composition containing arylated metallo-organic inhibitors
US2129281A (en) * 1936-03-23 1938-09-06 Continental Oil Co Lubricating oils
US2242400A (en) * 1937-09-13 1941-05-20 Standard Oil Co Extreme pressure lubricant
US2258219A (en) * 1939-09-27 1941-10-07 Gen Electric Halogenated aryl silicones
US2286763A (en) * 1940-12-26 1942-06-16 Gen Electric Methyl silicon halides

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2467976A (en) * 1943-03-30 1949-04-19 Corning Glass Works Method for increasing the viscosity of liquid polymeric dimethyl silicone
US2660559A (en) * 1949-08-31 1953-11-24 Maryland Lab Inc Method and apparatus for the purification of liquids
US2626434A (en) * 1950-05-01 1953-01-27 Leslie C Ike Window construction
DE945283C (de) * 1951-03-23 1956-07-05 Union Carbide & Carbon Corp UEberzugsmasse fuer die Kaltverformung von Metallen
US2760925A (en) * 1952-03-14 1956-08-28 Grove Valve & Regulator Co Method for surfacing aluminum
US2825609A (en) * 1956-07-20 1958-03-04 Edward C Jeffers Journal lubricator
US3330162A (en) * 1964-09-28 1967-07-11 Stewart Warner Corp Speedometer bearing structure
USRE30257E (en) * 1975-01-31 1980-04-22 Engineering Enterprises, Inc. Well drilling tool
US4019591A (en) * 1975-06-09 1977-04-26 Engineering Enterprises, Inc. Well drilling tool
US4830520A (en) * 1983-06-27 1989-05-16 Alsthom-Atlantique Method of protecting a limited-displacement mechanical system against an agressive medium

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Publication number Publication date
CH265201A (de) 1949-11-30

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