WO2005059066A1 - Lubricant including polyether- or polyester-modified polydialkylsiloxane - Google Patents

Lubricant including polyether- or polyester-modified polydialkylsiloxane Download PDF

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Publication number
WO2005059066A1
WO2005059066A1 PCT/IB2004/051682 IB2004051682W WO2005059066A1 WO 2005059066 A1 WO2005059066 A1 WO 2005059066A1 IB 2004051682 W IB2004051682 W IB 2004051682W WO 2005059066 A1 WO2005059066 A1 WO 2005059066A1
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Prior art keywords
polydialkylsiloxane
motor
oil
polyether
alkyl
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PCT/IB2004/051682
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French (fr)
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John A. Murray
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Motor Works Llc
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Publication of WO2005059066A1 publication Critical patent/WO2005059066A1/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M155/00Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/02Monomer containing silicon
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00Organic 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
    • C10M2229/04Siloxanes with specific structure
    • C10M2229/041Siloxanes with specific structure containing aliphatic substituents
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00Organic 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
    • C10M2229/04Siloxanes with specific structure
    • C10M2229/047Siloxanes with specific structure containing alkylene oxide groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00Organic 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
    • C10M2229/04Siloxanes with specific structure
    • C10M2229/048Siloxanes with specific structure containing carboxyl groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/055Particles related characteristics
    • C10N2020/06Particles of special shape or size
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/50Emission or smoke controlling properties
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54Fuel economy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/72Extended drain
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/255Gasoline engines
    • C10N2040/26Two-strokes or two-cycle engines

Definitions

  • the oxidized oil also coats and forms a glaze on the piston rings and piston walls.
  • the glazing of these surfaces compromises the proper sealing of the combustion chamber, which creates increased surface tension. Consequently, engine performance and efficiency are reduced, and harmful emissions increase.
  • Inadequate filming properties of conventional motor oils also result in a condition referred to as dry-start. Because the motor oil drains off of the engine parts when the engine is not running without leaving an adequate layer or film of lubricant, engine parts wear considerably each time the engine is started.
  • a number of additives have been developed to increase the lubricating properties of motor oil, and synthetic lubricants with enhanced lubricating properties have also been developed for use in lubricating engines.
  • SUMMARY Very fine particles of polyether- or polyester-modified polydialkylsiloxanes can be readily mixed with a lubricant (e.g., lubricating oil), fuel or other petroleum-based products, and the resulting mixture can be in the form of a stable dispersion or suspension having lubricating properties exceeding those of existing fuel-additive combinations and existing synthetic lubricants. More specifically, it has been discovered that a dispersion of the polyether- or polyester- modified polydialkylsiloxane in oil has enhanced filming properties, even at elevated temperatures within the engine. The enhanced filming properties provide for enhanced lubrication, providing an increased level of power while allowing engines to run more smoothly and cleanly.
  • a lubricant e.g., lubricating oil
  • fuel or other petroleum-based products e.g., lubricating oil
  • the resulting mixture can be in the form of a stable dispersion or suspension having lubricating properties exceeding those of existing fuel-additive combinations and existing
  • the polydialkylsiloxane can be added to a variety of fluid-conduits, such as the lubrication systems and fuel system, in a vehicle or in other types of motors.
  • the term, "siloxane” may be used as a shorthand version of polyether- or polyester-modified polydialkylsiloxane.
  • the concentration of polyether- or polyester-modified polydialkylsiloxane in the mixture can be between 0.5 percent to 2.5 percent by volume (all concentrations expressed herein are by volume unless otherwise indicated) and, in particular embodiments, the concentration of the siloxane is between 0.5 to 1.5 percent. Any other percentages depending on the particular use are possible as well.
  • Polyether- or polyester-modified polydialkylsiloxane of reduced particle size can be added directly to the engine oil in the oil pan of an automobile. However, the enhanced lubricating properties from use of the siloxane will not be realized until the siloxane is generally uniformly dispersed throughout the engine oil.
  • Other ways of adding the polydialkylsiloxane are to mix it directly with the fuel, in particular in case of a 2-stroke engine. In this case, adding can be effected either by premixing the polydialkylsiloxane with the fuel, or by injecting it from a separate chamber into the combustion chamber. If injected directly, a dispersion or suspension in water has an additional cleansing effect.
  • the siloxane can be premixed with a quantity of the lubricant, such as motor oil, to produce a premixture having a concentration of approximately 8 to 33 percent siloxane, or in a more-specific embodiment, at a ratio of one part siloxane to five parts oil to form a siloxane-and-oil additive.
  • the siloxane-and-oil additive is then added to the quantity or pool of lubricating oil in an oil pan or reservoir to obtain a siloxane concentration of, e.g., between approximately 0.5 to approximately 2.5 percent.
  • the polyether- or polyester-modified polydialkylsiloxane is mixed with oil to form the siloxane-and-oil additive using a sonic mixer, although other mixers including shear-producing mixers, such as a homogenizer or spray-nozzle-type mixer, can alternatively be utilized.
  • a sonic mixer although other mixers including shear-producing mixers, such as a homogenizer or spray-nozzle-type mixer, can alternatively be utilized.
  • the mixture is heated during mixing until the temperature of the mixture reaches approximately 200 degrees Fahrenheit (93 °C).
  • the mixture is mixed for sufficient time to reduce the average particle size of the siloxane to approximately 2 micrometers (microns) or less in any direction, e.g.
  • siloxane is generally uniformly distributed throughout the oil forming a suspension or dispersion of the polyether- modified polydimethylsiloxane in the oil. It is believed that improved lubricating properties will be achieved with the particle size of the siloxane being reduced to as small as 0.002 microns.
  • the resulting dispersion is filtered through a filter with a pore size of approximately 2 microns to filter out impurities or siloxane particles, droplets or agglomerates thereof exceeding 2 microns in diameter or related dimension.
  • a filter with a pore size of approximately 2 microns to filter out impurities or siloxane particles, droplets or agglomerates thereof exceeding 2 microns in diameter or related dimension.
  • Approximately 12 fluid ounces of the siloxane-and-oil additive or mixture, mixed in the manner described, is then added to enough oil to result in approximately five quarts of lubricant including the siloxane-and-oil additive which results, in this case, in a formulation of lubricant including approximately 1.25 percent-by-volume polyether- or polyester-modified polydialkylsiloxane.
  • a lubricant composition including the fine-particle polyether- or polyester-modified polydialkylsiloxane can offer filming properties that are substantially improved over those of existing motor oils that incorporate known additives and over existing synthetic lubricants. Moreover, these excellent filming properties can be maintained even at high temperatures and after the engine stops running. Consequently, the lubricant including the polyether- or polyester-modified polydialkylsiloxane, when used in an engine, can remain on engine parts longer after the engine stops running. Additionally, the small particle size of the polyether- or polyester-modified polydialkylsiloxane enables it to be mixed with an oil without separation and without settling of the siloxane from the oil.
  • siloxanes of this fine particle size can be used without abrading or with substantially reduced abrasion of engine parts.
  • Inclusion of the polydialkylsiloxane in the motor oil also reduces harmful vibrations in the engine due to the removal of dissolved gases.
  • inclusion of the polydialkylsiloxane increases the flashpoint of the motor oil, increases the service life of the motor oil, reduces pollutant emissions from the engine, and enables better sealing of the pistons in the engine by the motor oil.
  • the polydialkylsiloxane also helps to reduce engine rust by substantially eliminating moisture from the motor oil.
  • the polydialkylsiloxane when included in a fuel, the polydialkylsiloxane can increase the pumping capacity of the fuel system by lubricating the pump and the lines of the injection system.
  • the polydialkylsiloxane can also help to prevent vapor lock caused by vaporization in the fuel line.
  • FIG. 1 is a schematic diagram of a system and process for formulating a polyether- or polyester-modified polydialkylsiloxane-and-oil lubricating composition.
  • a particular embodiment of the invention includes a plurality of system elements or method steps
  • those elements or steps may be replaced with a single element or step; likewise, a single element or step may be replaced with a plurality of elements or steps that serve the same purpose.
  • this invention has been shown and described with references to particular embodiments thereof, those skilled in the art will understand that various other changes in form and details may be made therein without departing from the scope of the invention. It has been discovered that a polyether- or polyester-modified polydialkylsiloxane, when added to a selected quantity of a lubricating oil produces a lubricant having improved filming properties, particularly at elevated temperatures.
  • the method of the invention for lubricating a vehicle comprises: adding polyether- or polyester-modified polydialkylsiloxane particles to a fluid-conduit system in an engine-operated vehicle, wherein the polydialkylsiloxane particles form a mixture with oil in the fluid-conduit system; and operating the engine of the vehicle, wherein the mixture of polydialkylsiloxane particles and oil coats automobile parts accessed by the fluid-conduit system.
  • the polyether- or polyester-modified polydialkylsiloxanes of the present invention can generally be represented by the following chemical formula (1):
  • Ri and Rr are independently selected from Ci-C ⁇ alkyl and -Z-(C ⁇ -C6 alkyl)
  • R 2 and Rr are independently selected from Ci-Ce alkyl
  • R5 is selected from hydrogen, -0-(C ⁇ -C6-alkyl) and C1-C6 alkyl;
  • R , R 8 and R9 are independently selected from hydrogen and Ci-C ⁇ alkyl; n is an integer from 1 to 10; m is an integer from 0 to 5; v is an integer from 1 to 4; x is an integer from 1 to 150; and y is an integer from 1 to 500.
  • the -C ⁇ alkyl comprises methyl, ethyl, propyl, butyl, pentyl and isomers thereof.
  • the Ci-C ⁇ alkyl group comprises methyl, ethyl, propyl and isomers thereof.
  • Ri, Rr, R 2 and R 2 - are methyl so as to form a polyether- or polyester modified polydimethylsiloxane. All Ci-C ⁇ alkyl groups can be optionally substituted, i.e.
  • one or more of the hydrogen atoms of the alkyl groups can be replaced by a substituent selected from the group consisting of methyl, ethyl; propyl, -F and -CI.
  • the polydialkylsiloxanes used in the present invention can be in a solid form or in a liquid form, all being indicated as particles, dependent on their molecular weight and the alkyl groups used in particular for Ri, Rr, R 2 and R 2 . If the polydialkylsiloxane is in a solid form, particles with a diameter of less than 2 microns, preferably less than 1 micron are generally used in the present invention.
  • the polydialkylsiloxane is in a liquid form, then the polydialkylsiloxane will be present in droplet form within the same size range as mentioned above.
  • the physical properties of the polydialkylsiloxane will further be influenced by the respective type of polyether- or polyester group used in the polymer. If liquid siloxanes will be applied, said siloxanes usually have a viscosity from about 50 cs to about 1000 cs, preferably from about 100 cs to about 800 cs.
  • n is an integer from 1 to 10, preferably from 1 to 5.
  • m is an integer from 0 to 5, wherein m is preferably 1 or 2.
  • v is an integer from 1 to 4, while x is an integer from 1 to 150, preferably from 5 to 120. Furthermore, y is an integer from 1 to 500, preferably from 10 to 350.
  • the polyether- or polyester-modified polydialkylsiloxane particles have an average diameter of less than 2 micrometers (microns), preferably less than 1 micron.
  • suitable polyether- or polyester-modified polydialkylsiloxanes can be obtained from BYK-Chemie USA, Inc. of Wallingford, Connecticut. Polyether-modified polydialkylsiloxanes can be used with a wide variety of petroleum-based lubricants, synthetic lubricants, or even with water, to form improved lubricating mixtures thereof for a wide variety of applications.
  • polyether- or polyester-modified polydialkylsiloxane in an automobile include its use as an additive for (1) manual and automatic transmission fluid; (2) power steering fluid; (3) gear oil for use in a differential; (4) all-purpose machine lubricant; and (5) fuel (e.g., in standard grades of gasoline and in a two-cycle engine in lieu of petroleum-based lubricants). Further still, the additive can be used as a rust and corrosion inhibitor and as a lubricant for plastic and rubber surfaces.
  • the polyether- or polyester modified polydialkylsiloxane is represented by the general formula (2):
  • Z is independently selected from O, or
  • R 3 is -(C(R6)(R7))-;
  • R4 is -(C(R 8 )(R 9 ))v-;
  • R 5 is selected from hydrogen, -0-(C ⁇ -C 6 -alkyl) and Ci-C ⁇ alkyl;
  • Re, R 7 , R 8 and R 9 are independently selected from hydrogen and C ⁇ -C 6 alkyl;
  • n is an integer from 1 to 10;
  • m is an integer from 0 to 5;
  • v is an integer from 1 to 4;
  • x is an integer from 1 to 150; and
  • y is an integer from 1 to 500.
  • C ⁇ -C 6 alkyl is the same as defined above.
  • Z is -O- in formula (2).
  • Polydialkylsiloxanes, in particular polydimethylsiloxane are inert and non-poisonous.
  • Motor oil is one example of a lubricating oil as mentioned above, with which the polyether- or polyester-modified polydialkylsiloxane is mixed.
  • Motor oil typically is either a processed crude oil (petroleum) composition or in the form of a "synthetic" motor oil.
  • the motor oil serves to lubricate engine components so that the components will pass across one another without significantly sacrificing power due to friction.
  • the motor oil creates a film between moving parts, wherein this film substantially reduces friction between the parts.
  • the motor oil also protects the parts from wear and against corrosion caused by acids that can form in the oil as a result of oxidation, condensation and combustion by-products.
  • Motor oil also helps to clean the engine by preventing formation of deposits that can compromise fuel efficiency and engine performance in addition to causing engine wear.
  • any solid particle larger than about 5-20 microns in size can seriously damage an engine if introduced directly into the combustion chamber without a chance to disintegrate into smaller particles.
  • the motor oil helps to hold any such particles in suspension until they can be removed by the oil filter.
  • motor oil serves to transport heat that is generated by combustion or by friction away from engine components such as the crankshaft, camshaft, timing gears, pistons, main and connecting rod bearings.
  • Motor oil includes a base fluid, known as a "basestock," and an additive package.
  • the basestock generally forms the majority of the motor oil and can either be petroleum or synthetic.
  • motor oils having petroleum basestocks include Chevron SUPREME motor oil, Pennzoil MULTIGRADE motor oil, Kendall GT-1 motor oil, Castrol GTX motor oil, Mobil DRIVE CLEAN motor oil and many others.
  • motor oils having synthetic basestocks include Mobil 1 SUPERSYN motor oil, Castrol SYNTEC motor oil, Valvoline SYNPOWER motor oil, Pennzoil SYNTHETIC motor oil, Kendall GT-1 SYNTHETIC motor oil and many others.
  • Petroleum basestocks are a purified form of crude oil and have been used since the earliest motor oils were developed. Petroleum basestocks include paraffins (wax), sulfur, nitrogen, oxygen, water, salts and a number of metals.
  • These contaminants are substantially (though not fully) removed from the basestock via a refining process via a procedure including many or all of the following steps.
  • the crude oil is then subject to partial vaporization; the components of the crude oil with the highest boiling points, except for asphaltic materials, are separated to form the petroleum basestock.
  • the basestock is then subject to vacuum distillation to separate it according to molecular weights and, accordingly, by viscosity. Solvents are extracted from the basestock. Waxes are also removed from the basestock to improve the basestock' s low-temperature fluidity, which is compromised by wax crystallization at low temperatures.
  • Hydro finishing can also be performed, whereby the basestock is passed through a catalyst bed (or via clay treatment) to remove components such as sulfur and nitrogen from the basestock, thereby improving its oxidation stability, thermal stability and its color.
  • hydrotreating can also be performed, wherein the basestock is subject to extremely high temperature and pressure in the presence of a catalyst to convert remaining aromatic hydrocarbon contaminants into usable nonaromatic hydrocarbon molecules .
  • Synthetic basestocks are chemically engineered specifically to meet the lubrication needs of an engine. Synthetic basestocks are engineered from pure, substantially contaminant-free compounds. Synthetic basestocks have been widely used in automobiles since the 1970's.
  • Synthetic basestocks typically are formed of one or more of the following: polyalphaolefins, diesters, and polyolesters.
  • Polyalphaolefin basestocks are the most common and are also referred to as "synthesized hydrocarbons.”
  • Polyalphaolefin basestocks include no wax, metals, sulfur or phosphorous and have a viscosity index around 150 and a pour point below about 40°F (4°C).
  • motor oils typically include an additive package to improve a variety of desirable properties in the motor oil. The additives, however, usually only form a small percentage of the oil, with the basestock forming the vast majority.
  • Additives that improve the viscosity characteristics of the motor oil include pour point depressants, which improve the flow of the basestock at low temperatures by absorbing into wax crystals and lowering their volume. Pour point depressants are routinely used in petroleum basestocks but are often not needed in synthetic basestocks.
  • Other additives relating to viscosity are viscosity index improvers, which are polymers that expand with increasing temperature; at high temperatures, the expanding polymers can compensate for high-temperature "thinning" of the basestock to help to provide a more-consistent viscosity in the motor oil across a broad temperature range.
  • Other classes of additives help to maintain lubricant stability in terms of helping to prevent breakdown and viscosity loss in the oil over time.
  • detergents and dispersants help to minimize and contain build up in the form of sludge and varnish in an oil.
  • Detergents and dispersants are attracted to the sludge and varnish contaminants and serve to contain and suspend those particles so that they do not agglomerate to form a deposit.
  • Anti-foaming agents are also included in the oil to control formation of air bubbles in the oil, which can otherwise form at room temperature, as a consequence of the detergents and dispersants.
  • oxidation inhibitors are included to reduce the tendency of oils to oxidize; the oxidation inhibitors either destroy free radicals or react with peroxides in the oil.
  • corrosion inhibitors are included; the corrosion inhibitors either neutralize acids that form in the oil or coat metal surfaces so that the surfaces do not contact the acids.
  • anti-wear agents such as zinc and phosphorus, can be included in the motor oil to coat metal surfaces with a protective barrier against physical wear.
  • One embodiment of a polyether- or polyester-modified polydialkylsiloxane additive for a lubricating oil is produced by mixing the selected polyether- or polyester-modified polydialkylsiloxane with the lubricating oil at a ratio of one part polyether- or polyester-modified polydialkylsiloxane to five parts lubricating oil (based on the volume) to form a pre-mixed siloxane-and-oil additive, wherein the polyether- or polyester-modified polydialkylsiloxane is uniformly distributed in the oil in the form of a dispersion or suspension.
  • the concentration of polyether- or polyester-modified polydialkylsiloxane is about 8 to about 33 percent-by-volume
  • the concentration of the lubricating oil is about 61 to about 92 percent-by-volume, i.e. the ratio is from about 1 :2 to about 1:12.
  • the siloxane and the oil can be mixed using a sonic mixer, such as a Branson 900-B mixer sold by Branson Ultrasonic Corp.
  • the mixing can be accomplished using a pump to circulate the polyether- or polyester- modified polydialkylsiloxane and lubricating oil through the sonic mixer for approximately three to four hours or until the temperature of the mixture reaches approximately 200 degrees Fahrenheit (93°C) due to the mixing. Although the temperature of the mixture rises due to the sonic mixing process, the mixture can also be heated using an external heater or other heating means.
  • the mixing process reduces the polyether- or polyester-modified polydialkylsiloxane to a generally spherical-shaped droplet or particle form, wherein the diameter of the particles can be less than approximately two micrometers (microns) and in particular mixtures is less than one micron.
  • the term, "diameter,” is generally intended to include the corresponding widest dimension of particles or droplets that are not spherical, such as a generally cube-shaped particle or droplet.
  • the benefits produced by the siloxane-and-oil additive when added to the lubricating oil will be realized for additive mixtures in which the particle size of the polyether- or polyester-modified polydialkylsiloxane is reduced to as small as 0.002 microns, preferably 0.001 microns in diameter.
  • the siloxane-and-oil additive is filtered through a filter having a pore size of approximately 2 microns to filter out any siloxane particles, droplets or agglomerates having a diameter of more than two microns. Further, filters having a pore size of approximately 1 micron or less can also be used.
  • the formulation process is shown schematically in the Figure.
  • Selected quantities of the selected polyether- or polyester-modified polydialkylsiloxane and oil e.g., 55 gallons oil and 11 gallons siloxane
  • Pump 7 then pumps the siloxane and oil through sonic mixer 9 and, optionally, through heater 11 to three-way valve 13.
  • Valve 13 can be set or positioned in a first or recirculating orientation to continuously direct the flow of siloxane and oil back to reservoir 5, where the flow is re-circulated through the sonic mixer 9 and optionally through heater 11.
  • valve 13 can be set or advanced to a second or filling orientation in which the siloxane and oil flows into the filtering station 15 and is allowed to drain by gravity through a filter 15 to a bottling station 17 where the mixture of siloxane and oil is bottled in selected quantities, such as 12 ounces.
  • the premixed siloxane-and-oil additive is then added to a sufficient quantity of lubricating oil to form a selected quantity of lubricant, such as the recommended amount of oil to be held in the lubricating system of an automobile engine, such that the resulting percentage of polyetlier- or polyester-modified polydialkylsiloxane in the resulting lubricant is approximately between 0.5 and 2.5 percent and, in a particular example, is approximately 1.25 percent of the total volume.
  • twelve ounces of the siloxane-and-oil additive formed at a ratio of one part siloxane to five parts oil, as explained above, can be added to enough oil to result in five quarts of a lubricant mixture.
  • the resulting mixture includes approximately two ounces of polyether- or polyester-modified polydialkylsiloxane in 160 ounces of lubricant, such that the volume of siloxane is 1.25 percent of the total volume, hi an automobile engine, where the polydialkylsiloxane has been added to the lubrication system, the polydialkylsiloxane will generally be well mixed in the oil after the automobile is driven about 10 miles (16 km). Without being bound to any particular theory it is believed that the superior effect of the polyether- or polyester-modified polydialkylsiloxane is due to several different properties of the siloxanes.
  • the polydialkylsiloxanes will decompose when coming into contact with the hot surfaces of the motor, e.g. the cylinder walls, piston rings and piston walls.
  • a SiO/Si0 2 -film is built on said surfaces which coats and protects the respective parts of the motor.
  • the polyether- or polyester-modified polydialkylsiloxane serves to de-gas the motor oil and to displace moisture from the motor oil.
  • the polydialkylsiloxane also prevents re-introduction of dissolved gases and water into the motor oil.
  • motor oil typically comprises 10 to 15% infiltrated air, which is dissolved in the oil.
  • the polyether- or polyester-modified polydialkylsiloxane serves a function far beyond traditional uses of "anti-foamants" in motor oil, wherein an anti-foamant is used to remove large gas bubbles, formed, e.g., by detergents. Rather, the polyether- or polyester-modified polydialkylsiloxane removes substantially all of the dissolved gas (e.g., at least 99.9% removal) and water from the oil. By substantially eliminating this source of gas bubbles when the motor oil approaches its maximum operating temperature, the motor oil flows more fluidly and smoothly around hot parts and better coats those parts. The flashpoint and oxidation temperature of the motor oil can also be raised substantially by the addition of the polydialkylsiloxane.
  • the flashpoint of a PENNZOIL 10/30 motor oil was raised from 228°F (109°C) to greater then 500°F (>260°C) by adding the polydialkylsiloxane.
  • the improved flow of the oil and the substantial removal of gas bubbles from around the hot parts enables the oil to form a film around piston cylinders, thereby sealing the pistons properly and cooling the pistons to thereby help to prevent pre-ignition due to contact of the fuel with overheated pistons.
  • the polydialkylsiloxane displaces moisture from the motor oil. The presence of moisture (i.e., water) in the motor oil can cause lubricated cast-iron parts to rust.
  • Rust generates acid, which can destroy the oil and bearings lubricated therewith. Accordingly, inclusion of the polydialkylsiloxane helps to promote longer oil life [e.g., an oil life of 12,500 miles (20,000 km) or more] and also to lengthen the life of engine parts by displacing water (and gases) from the oil.
  • One reason for the improved filming properties and lengthened life of the oil is the displacement of air and water by polydialkylsiloxane from the oil, but also other phenomena may contribute.
  • Additional additives can be added to the siloxane-and-oil mixture to enhance properties of the mixture. Potential additional additives include rust inhibitors and anti-oxidants.
  • Selected strippers or solvents such as mineral spirits or lacquer thinner can also be added to strip off any glazing on engine parts formed during previous operation of the engine before introduction of the siloxane-and-oil additive.
  • the stripper or solvent would function to deglaze the affected engine parts and to then volatilize at elevated engine-operating temperatures. It is believed that the material deglazed from the engine parts by the stripper is then filtered out of the lubricant as it passes through the oil filter.
  • additives that can be included in the siloxane-and-oil mixture include viscosity index improvers or dimethylsulfoxide at a concentration of approximately one tenth of one percent (0.1%) for use as a blending agent, sodium hydroxide (0.0001%) as a blending and binding agent, and glycerol to help maintain the siloxane in suspension.
  • the polyether- or polyester-modified polydialkylsiloxane of reduced particle size can be added directly to a quantity of lubricant, such as the motor oil in an oil pan of an automobile, without premixing the siloxane with a portion of the lubricating oil to be used, while still achieving the enhanced lubricating properties.
  • polyether- or polyester-modified polydialkylsiloxane can be used as an additive to a motor oil, wherein said polyether- or polyester-modified polydialkylsiloxane is represented by general formula (1) or (2) as mentioned above.
  • Example 1 - Coating Tests Various tests demonstrated the improved lubricating and emission-reducing properties of the siloxane-and-oil additive. In one test, the coating capability of lubricant including the polydialkylsiloxane-and-oil additive at approximately 1.25 percent of the total volume was compared to the coating capability of a mixture of SLICK 50 Advanced Formula Engine Treatment in 10W-30 motor oil and to the coating capability of MOBIL 1 SYNTHETIC motor oil.
  • Oils that were used for mixing with the polydialkylsiloxane are Penzoil 10/30, Castroil 10/30, Napa Premium 10/30, Union 76 10/30, Castrol Semi Synthetic 10/30 and Castroil Full Synthetic 10/30, all by weight. Equal quantities of each lubricant were applied to a hot plate heated to 350 degrees Fahrenheit (177°C) and angled downward at a 45-degree angle. The hot plate comprised a TEFLON-coated aluminum plate. Through visual inspection, it was observed that the SLICK 50 engine treatment in 10W-30 motor oil and the MOBIL 1 SYNTHETIC motor oil did not adhere to or coat the surface of the hot plate to any appreciable degree and essentially just ran off the hot plate.
  • the test was performed as follows: All the oils tested were tested without the added polydialkylsiloxane. The test was completed with standard oil and runoff was noted. All the test oils were then mixed with the polydialkylsiloxane mix and retested as before. The results showed marked improvement as to coating properties on the hot plate.
  • An oxidation test was performed in the same manner, where as a spoon shaped receptacle was used to hold 2 cc's of oil above a heat source of 800 °F for 2 min. observation of the samples showed that regular oils oxidized and evaporated within 10 to 30 sec. The same test was performed with the same base oils with a proportional addition of siloxane. Observations showed a significant reduction in oxidation and evaporation of the mixture.
  • Example 2 Comparative Horsepower Tests: The improved lubricating properties of lubricants including the siloxane-and-oil additive were further demonstrated by comparing the horsepower generated by an automobile engine operating without the siloxane-and-oil additive added to the lubricant versus the horsepower generated by the same automobile engine with the siloxane-and-oil additive added to the engine lubricant.
  • the horsepower generated by a 1998 Jeep GRAND CHEROKEE LAREDO automobile having a 4.0-liter, six-cylinder engine was measured using a Dynajet Model 248C Dynamometer.
  • the horsepower of the Jeep GRAND CHEROKEE automobile was initially measured without the siloxane-and-oil additive added to the engine lubricant.
  • the lubricant utilized in the engine lubricating system was 5 quarts of 10W-30 petroleum based motor oil.
  • the engine of the automobile was accelerated from 0 to 5200 RPM (revolutions per minute), and measurements were taken at increasing increments of 250 RPM.
  • the absolute barometric pressure was recorded as 29.92 in. Hg (about 100 kPa) with a vapor pressure of 0.61 in. Hg (about 2 kPa).
  • the intake air temperature was measured at 86 degrees Fahrenheit (30°C), and the gear ratio was recorded as 49 RPM/MPH.
  • SAE Society of Automotive Engineers
  • a second test was performed on the same automobile by adding 12 ounces of the siloxane-and-oil additive to the engine-lubricating oil.
  • the ratio of siloxane to oil in the additive was 1 ounce siloxane to 11 ounces oil. Adding the twelve ounces of additive to the existing 5 quarts of oil in the automobile resulted in a concentration of siloxane in the lubricant of approximately 0.58%).
  • the automobile was again accelerated from 0 to 5200 RPM with measurements again taken at increasing 250 RPM intervals.
  • the absolute barometric pressure was recorded as 29.92 in. Hg (about 100 kPa) with a vapor pressure of 0.61 in. Hg (about 2 kPa).
  • the intake air temperature was measured at 88.8 degrees Fahrenheit (31.6°C), and the gear ratio was recorded as 48 RPM/MPH.
  • An SAE correction factor of 1.01 was used to convert the measured horsepower to a corrected horsepower.
  • the measured and corrected horsepower of the automobile operating with lubricant only versus with the siloxane-and-oil additive added to the lubricant at various engine speeds is provided, below, in Table 1.
  • Example 3 - ASM Emission Tests A comparison of the emissions of automobiles with and without the siloxane-and-oil additive added to the engine lubricant Penzoil 10/30 was preformed using the acceleration simulation mode (ASM) emission test for the State of California. The test results, below, provide the measured exhaust concentrations of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxide (NO x ) gases, which are generally considered harmful.
  • ASM acceleration simulation mode
  • the data in the column entitled, "Concentration without additive,” comprise the results for a first test in which no additive was added to the engine lubricant (5 quarts of motor oil), and the data in the column entitled, “Concentration with additive,” comprises the results of a second test in which 12 ounces of the siloxane-and-oil additive (at a ratio of 2 ounces siloxane per 10 ounces oil) were added to the engine lubricant to result in an overall concentration of siloxane in the lubricant of approximately 1.16% by volume .
  • Example 4 Siloxane Alone in Automobile Engine Lubrication System
  • the polyether-modified polydimethylsiloxane of reduced particle or droplet size at a viscosity of approx 10/30 wt. was the sole lubricant utilized in an automobile engine lubricating system.
  • the polyether-modified polydimethylsiloxane was processed in the same manner as the siloxane-and-oil mixture described above with reference to the Figure, except that no oil was added.
  • polyether-modified polydimethylsiloxane without oil, was circulated by pump 7 through sonic mixer 9 until the particle or droplet size was reduced to approximately one micron in diameter and then passed through the filter 15 to remove any particles having a diameter exceeding the pore size of approximately two microns.
  • Approximately five quarts of the processed polyether-modified polydimethylsiloxane was then added to the engine lubricating system of an automobile to replace the recommended five quarts of motor oil, which was previously drained from the lubricating system.
  • the automobile using the siloxane only lubricant was then run for approximately two thousand miles without any adverse affects identified. This test showed improved fuel use as compared to regular oils.
  • Example 5 Use of Siloxane and Gasoline Mixutre in a Two-Cycle Engine:
  • the polyether-modified polydimethylsiloxane processed in the manner described in Example 4, above, was added to gasoline to replace the two-cycle engine oil normally included in an oil-and-gas mixture used with a two-cycle engine.
  • the ratio of gasoline to polyether-modified polydimethylsiloxane was fifty to one, and no adverse engine effects were observed. Passing through of particulate (oil) through the engine was reduced if not completely eliminated.
  • the temperature readings were taken using a digital, infrared thermometer.
  • the reduced-temperature readings indicate improved lubricating properties of the siloxane versus two-cycle engine oil.
  • the polyether-modified polydimethylsiloxane can be premixed with a quantity of two- cycle engine oil before adding the resulting lubricant to the gasoline at the recommended fuel-to- lubricant ratio.
  • processed polyether-modified polydimethylsiloxane of reduced particle size can be added to the gasoline separate from the two-cycle engine oil to achieve the desired fuel-to-lubricant ratio. While certain formulations of the present invention have been illustrated and described herein, the invention is not limited to the specific formulations described and shown.
  • polyether-modified polydimethylsiloxane is described primarily with reference to its use in forming an additive for motor oil
  • polyether-modified polydimethylsiloxane has also been formulated and tested as an additive for power steering fluid, transmission fluid or oil and gear grease. Testing on these various formulations all showed improvement in the lubricating properties of the formulations. Such testing has also been performed on water-based Lubricants as well as petroleum-based lubricants. In addition, testing was done on a wide range of weights of oil, from 5 to 120 weight oil The tests included although were not limited to motor oils from 20 wt to 140 wt oils as well as 10/20, 10/30, 10/40, 20/50.

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Abstract

Polyether- or polyester-modified polydimethylsiloxane is mixed with a lubricant, such as motor oil. Preferably, the polydialkylsiloxane can form at least about 0.5 percent by volume of the mixture. And the mixture can be used in a fluid-conduit system (e.g., a lubrication system) of a motor or a vehicle (e.g., an automobile), wherein the mixture offers excellent filming properties on, e.g., engine parts and helps to improve engine efficiency, to lengthen the service life of the lubricant, and to reduce harmful emissions from the vehicle.

Description

LUBRICANT INCLUDING POLYETHER- OR POLYESTER MODIFIED POLYDIALKYLSTLOXANE
RELATED APPLICATION A priority claim is made to a provisional patent application, filed on December 12, 2003, entitled, "Emission Reducing Lubrication Mixture and Additive Including Polyether Modified Poly-Dimethyl-Siloxane," and naming John A. Muαay as inventor, the entire teachings of which are incorporated herein by reference.
BACKGROUND Conventional motor oil is used to lubricate moving parts in an engine or in other mechanical devices. Proper lubrication of engine parts is essential to preserving the life of the engine. However, there are many well-recognized limitations affecting the lubricating efficiency of motor oil. In particular, the filming properties of petroleum-based and synthetic motor oils are often inadequate, particularly in high heat areas of the motor such as the pistons, rods and cylinder walls. Without proper filming of motor oil in these areas, these parts become extremely hot [i.e., approximately 300 to 370 degrees Fahrenheit (~149-188°C)], which compounds the problems associated with inadequate lubrication. For example, at elevated temperatures, the oil oxidizes and forms a glaze on the surface of the cylinder walls. The oxidized oil also coats and forms a glaze on the piston rings and piston walls. The glazing of these surfaces compromises the proper sealing of the combustion chamber, which creates increased surface tension. Consequently, engine performance and efficiency are reduced, and harmful emissions increase. Inadequate filming properties of conventional motor oils also result in a condition referred to as dry-start. Because the motor oil drains off of the engine parts when the engine is not running without leaving an adequate layer or film of lubricant, engine parts wear considerably each time the engine is started. A number of additives have been developed to increase the lubricating properties of motor oil, and synthetic lubricants with enhanced lubricating properties have also been developed for use in lubricating engines. SUMMARY Very fine particles of polyether- or polyester-modified polydialkylsiloxanes can be readily mixed with a lubricant (e.g., lubricating oil), fuel or other petroleum-based products, and the resulting mixture can be in the form of a stable dispersion or suspension having lubricating properties exceeding those of existing fuel-additive combinations and existing synthetic lubricants. More specifically, it has been discovered that a dispersion of the polyether- or polyester- modified polydialkylsiloxane in oil has enhanced filming properties, even at elevated temperatures within the engine. The enhanced filming properties provide for enhanced lubrication, providing an increased level of power while allowing engines to run more smoothly and cleanly. The polydialkylsiloxane can be added to a variety of fluid-conduits, such as the lubrication systems and fuel system, in a vehicle or in other types of motors. As used herein, the term, "siloxane," may be used as a shorthand version of polyether- or polyester-modified polydialkylsiloxane. The concentration of polyether- or polyester-modified polydialkylsiloxane in the mixture can be between 0.5 percent to 2.5 percent by volume (all concentrations expressed herein are by volume unless otherwise indicated) and, in particular embodiments, the concentration of the siloxane is between 0.5 to 1.5 percent. Any other percentages depending on the particular use are possible as well. Polyether- or polyester-modified polydialkylsiloxane of reduced particle size can be added directly to the engine oil in the oil pan of an automobile. However, the enhanced lubricating properties from use of the siloxane will not be realized until the siloxane is generally uniformly dispersed throughout the engine oil. Other ways of adding the polydialkylsiloxane are to mix it directly with the fuel, in particular in case of a 2-stroke engine. In this case, adding can be effected either by premixing the polydialkylsiloxane with the fuel, or by injecting it from a separate chamber into the combustion chamber. If injected directly, a dispersion or suspension in water has an additional cleansing effect. Since the water is evaporated and at least partially split into oxygen and hydrogen in the combustion chamber a further reduction of the C, CO and NOx emission is achieved. Other possible carriers/solvents are alcohol based or mineral based. Moreover, direct injection allows a high concentration of the polydialkylsiloxane dispersion or suspension up to the pure product, called a 100% product by a manufacturer named BYK Chemie USA, Inc. of Wallingford, Connecticut. One of the useful products is for instance labeled BYK-333. To reduce the time it takes to uniformly disperse the polyether- or polyester-modified polydialkylsiloxane throughout the lubricant, the siloxane can be premixed with a quantity of the lubricant, such as motor oil, to produce a premixture having a concentration of approximately 8 to 33 percent siloxane, or in a more-specific embodiment, at a ratio of one part siloxane to five parts oil to form a siloxane-and-oil additive. The siloxane-and-oil additive is then added to the quantity or pool of lubricating oil in an oil pan or reservoir to obtain a siloxane concentration of, e.g., between approximately 0.5 to approximately 2.5 percent. Depending on the use, also other concentrations are possible. In one embodiment, the polyether- or polyester-modified polydialkylsiloxane is mixed with oil to form the siloxane-and-oil additive using a sonic mixer, although other mixers including shear-producing mixers, such as a homogenizer or spray-nozzle-type mixer, can alternatively be utilized. The mixture is heated during mixing until the temperature of the mixture reaches approximately 200 degrees Fahrenheit (93 °C). The mixture is mixed for sufficient time to reduce the average particle size of the siloxane to approximately 2 micrometers (microns) or less in any direction, e.g. less than 1 micron, and until the siloxane is generally uniformly distributed throughout the oil forming a suspension or dispersion of the polyether- modified polydimethylsiloxane in the oil. It is believed that improved lubricating properties will be achieved with the particle size of the siloxane being reduced to as small as 0.002 microns.
The resulting dispersion is filtered through a filter with a pore size of approximately 2 microns to filter out impurities or siloxane particles, droplets or agglomerates thereof exceeding 2 microns in diameter or related dimension. Approximately 12 fluid ounces of the siloxane-and-oil additive or mixture, mixed in the manner described, is then added to enough oil to result in approximately five quarts of lubricant including the siloxane-and-oil additive which results, in this case, in a formulation of lubricant including approximately 1.25 percent-by-volume polyether- or polyester-modified polydialkylsiloxane. Numerous advantages are offered by various methods and compositions, described in greater detail below. First, a lubricant composition including the fine-particle polyether- or polyester-modified polydialkylsiloxane can offer filming properties that are substantially improved over those of existing motor oils that incorporate known additives and over existing synthetic lubricants. Moreover, these excellent filming properties can be maintained even at high temperatures and after the engine stops running. Consequently, the lubricant including the polyether- or polyester-modified polydialkylsiloxane, when used in an engine, can remain on engine parts longer after the engine stops running. Additionally, the small particle size of the polyether- or polyester-modified polydialkylsiloxane enables it to be mixed with an oil without separation and without settling of the siloxane from the oil. Further, unlike, naturally occurring siloxanes, which may be formed in an engine as a byproduct of the combustion cycle and as a byproduct of infiltration of dirt into the engine, siloxanes of this fine particle size can be used without abrading or with substantially reduced abrasion of engine parts. Inclusion of the polydialkylsiloxane in the motor oil also reduces harmful vibrations in the engine due to the removal of dissolved gases. Further still, inclusion of the polydialkylsiloxane increases the flashpoint of the motor oil, increases the service life of the motor oil, reduces pollutant emissions from the engine, and enables better sealing of the pistons in the engine by the motor oil. The polydialkylsiloxane also helps to reduce engine rust by substantially eliminating moisture from the motor oil. Further still, when the polyether- or polyester-modified polydialkylsiloxane is included in a fuel, the polydialkylsiloxane can increase the pumping capacity of the fuel system by lubricating the pump and the lines of the injection system. The polydialkylsiloxane can also help to prevent vapor lock caused by vaporization in the fuel line.
BRIEF DESCRIPTION OF THE DRAWINGS The Figure is a schematic diagram of a system and process for formulating a polyether- or polyester-modified polydialkylsiloxane-and-oil lubricating composition.
DETAILED DESCRIPTION Particular embodiments of the present invention are included in the following discussion; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Consequently, specific details disclosed herein are not to be interpreted as limiting, but merely serve as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in a broad range of alternative formulations and processes. In describing embodiments of the invention, specific terminology is used for the sake of clarity. For purposes of description, each specific term is intended to at least include all technical and functional equivalents that operate in a similar manner to accomplish a similar purpose. Additionally, in some instances where a particular embodiment of the invention includes a plurality of system elements or method steps, those elements or steps may be replaced with a single element or step; likewise, a single element or step may be replaced with a plurality of elements or steps that serve the same purpose. Moreover, while this invention has been shown and described with references to particular embodiments thereof, those skilled in the art will understand that various other changes in form and details may be made therein without departing from the scope of the invention. It has been discovered that a polyether- or polyester-modified polydialkylsiloxane, when added to a selected quantity of a lubricating oil produces a lubricant having improved filming properties, particularly at elevated temperatures. In particular, the method of the invention for lubricating a vehicle comprises: adding polyether- or polyester-modified polydialkylsiloxane particles to a fluid-conduit system in an engine-operated vehicle, wherein the polydialkylsiloxane particles form a mixture with oil in the fluid-conduit system; and operating the engine of the vehicle, wherein the mixture of polydialkylsiloxane particles and oil coats automobile parts accessed by the fluid-conduit system. The polyether- or polyester-modified polydialkylsiloxanes of the present invention can generally be represented by the following chemical formula (1):
Figure imgf000006_0001
z I RΛ Rc wherein Z is independently selected from O,
Figure imgf000007_0001
or ;
Ri and Rr are independently selected from Ci-Cβ alkyl and -Z-(Cι-C6 alkyl)
R2 and Rr are independently selected from Ci-Ce alkyl;
Figure imgf000007_0002
R5 is selected from hydrogen, -0-(Cι-C6-alkyl) and C1-C6 alkyl;
Re, R , R8 and R9 are independently selected from hydrogen and Ci-Cβ alkyl; n is an integer from 1 to 10; m is an integer from 0 to 5; v is an integer from 1 to 4; x is an integer from 1 to 150; and y is an integer from 1 to 500.
In the above formula (1), the -Cβ alkyl comprises methyl, ethyl, propyl, butyl, pentyl and isomers thereof. In a preferred embodiment the Ci-Cβ alkyl group comprises methyl, ethyl, propyl and isomers thereof. In one particular preferred embodiment of the present invention Ri, Rr, R2 and R2- are methyl so as to form a polyether- or polyester modified polydimethylsiloxane. All Ci-Cδ alkyl groups can be optionally substituted, i.e. one or more of the hydrogen atoms of the alkyl groups can be replaced by a substituent selected from the group consisting of methyl, ethyl; propyl, -F and -CI. The polydialkylsiloxanes used in the present invention can be in a solid form or in a liquid form, all being indicated as particles, dependent on their molecular weight and the alkyl groups used in particular for Ri, Rr, R2 and R2. If the polydialkylsiloxane is in a solid form, particles with a diameter of less than 2 microns, preferably less than 1 micron are generally used in the present invention. If the polydialkylsiloxane is in a liquid form, then the polydialkylsiloxane will be present in droplet form within the same size range as mentioned above. The physical properties of the polydialkylsiloxane will further be influenced by the respective type of polyether- or polyester group used in the polymer. If liquid siloxanes will be applied, said siloxanes usually have a viscosity from about 50 cs to about 1000 cs, preferably from about 100 cs to about 800 cs. In the above formula (1), n is an integer from 1 to 10, preferably from 1 to 5. m is an integer from 0 to 5, wherein m is preferably 1 or 2. v is an integer from 1 to 4, while x is an integer from 1 to 150, preferably from 5 to 120. Furthermore, y is an integer from 1 to 500, preferably from 10 to 350. The polyether- or polyester-modified polydialkylsiloxane particles have an average diameter of less than 2 micrometers (microns), preferably less than 1 micron. For example, suitable polyether- or polyester-modified polydialkylsiloxanes can be obtained from BYK-Chemie USA, Inc. of Wallingford, Connecticut. Polyether-modified polydialkylsiloxanes can be used with a wide variety of petroleum-based lubricants, synthetic lubricants, or even with water, to form improved lubricating mixtures thereof for a wide variety of applications. Other uses of a polyether- or polyester-modified polydialkylsiloxane in an automobile include its use as an additive for (1) manual and automatic transmission fluid; (2) power steering fluid; (3) gear oil for use in a differential; (4) all-purpose machine lubricant; and (5) fuel (e.g., in standard grades of gasoline and in a two-cycle engine in lieu of petroleum-based lubricants). Further still, the additive can be used as a rust and corrosion inhibitor and as a lubricant for plastic and rubber surfaces. In one embodiment of the present invention, the polyether- or polyester modified polydialkylsiloxane is represented by the general formula (2):
( 2 )
Figure imgf000008_0001
wherein Z is independently selected from O,
Figure imgf000009_0001
or
R3 is -(C(R6)(R7))-; R4 is -(C(R8)(R9))v-;
R5 is selected from hydrogen, -0-(Cι-C6-alkyl) and Ci-Cβ alkyl; Re, R7, R8 and R9 are independently selected from hydrogen and Cι-C6 alkyl; n is an integer from 1 to 10; m is an integer from 0 to 5; v is an integer from 1 to 4; x is an integer from 1 to 150; and y is an integer from 1 to 500. In formula (2), Cι-C6 alkyl is the same as defined above. In a further preferred embodiment of the present invention, Z is -O- in formula (2). Polydialkylsiloxanes, in particular polydimethylsiloxane are inert and non-poisonous. Motor oil is one example of a lubricating oil as mentioned above, with which the polyether- or polyester-modified polydialkylsiloxane is mixed. Motor oil typically is either a processed crude oil (petroleum) composition or in the form of a "synthetic" motor oil. hi either, the motor oil serves to lubricate engine components so that the components will pass across one another without significantly sacrificing power due to friction. When the engine is running, the motor oil creates a film between moving parts, wherein this film substantially reduces friction between the parts. By coating parts, the motor oil also protects the parts from wear and against corrosion caused by acids that can form in the oil as a result of oxidation, condensation and combustion by-products. Motor oil also helps to clean the engine by preventing formation of deposits that can compromise fuel efficiency and engine performance in addition to causing engine wear. In particular, any solid particle larger than about 5-20 microns in size can seriously damage an engine if introduced directly into the combustion chamber without a chance to disintegrate into smaller particles. The motor oil helps to hold any such particles in suspension until they can be removed by the oil filter. Further still, motor oil serves to transport heat that is generated by combustion or by friction away from engine components such as the crankshaft, camshaft, timing gears, pistons, main and connecting rod bearings. Motor oil includes a base fluid, known as a "basestock," and an additive package. The basestock generally forms the majority of the motor oil and can either be petroleum or synthetic. Examples of motor oils having petroleum basestocks include Chevron SUPREME motor oil, Pennzoil MULTIGRADE motor oil, Kendall GT-1 motor oil, Castrol GTX motor oil, Mobil DRIVE CLEAN motor oil and many others. Examples of motor oils having synthetic basestocks include Mobil 1 SUPERSYN motor oil, Castrol SYNTEC motor oil, Valvoline SYNPOWER motor oil, Pennzoil SYNTHETIC motor oil, Kendall GT-1 SYNTHETIC motor oil and many others. Petroleum basestocks are a purified form of crude oil and have been used since the earliest motor oils were developed. Petroleum basestocks include paraffins (wax), sulfur, nitrogen, oxygen, water, salts and a number of metals. These contaminants are substantially (though not fully) removed from the basestock via a refining process via a procedure including many or all of the following steps. First, the crude oil is distilled to remove salt contaminants. The crude oil is then subject to partial vaporization; the components of the crude oil with the highest boiling points, except for asphaltic materials, are separated to form the petroleum basestock. The basestock is then subject to vacuum distillation to separate it according to molecular weights and, accordingly, by viscosity. Solvents are extracted from the basestock. Waxes are also removed from the basestock to improve the basestock' s low-temperature fluidity, which is compromised by wax crystallization at low temperatures. Hydro finishing can also be performed, whereby the basestock is passed through a catalyst bed (or via clay treatment) to remove components such as sulfur and nitrogen from the basestock, thereby improving its oxidation stability, thermal stability and its color. Finally, hydrotreating can also be performed, wherein the basestock is subject to extremely high temperature and pressure in the presence of a catalyst to convert remaining aromatic hydrocarbon contaminants into usable nonaromatic hydrocarbon molecules . Synthetic basestocks are chemically engineered specifically to meet the lubrication needs of an engine. Synthetic basestocks are engineered from pure, substantially contaminant-free compounds. Synthetic basestocks have been widely used in automobiles since the 1970's. Synthetic basestocks typically are formed of one or more of the following: polyalphaolefins, diesters, and polyolesters. Polyalphaolefin basestocks are the most common and are also referred to as "synthesized hydrocarbons." Polyalphaolefin basestocks include no wax, metals, sulfur or phosphorous and have a viscosity index around 150 and a pour point below about 40°F (4°C). In addition to the basestock, motor oils typically include an additive package to improve a variety of desirable properties in the motor oil. The additives, however, usually only form a small percentage of the oil, with the basestock forming the vast majority. Additives that improve the viscosity characteristics of the motor oil include pour point depressants, which improve the flow of the basestock at low temperatures by absorbing into wax crystals and lowering their volume. Pour point depressants are routinely used in petroleum basestocks but are often not needed in synthetic basestocks. Other additives relating to viscosity are viscosity index improvers, which are polymers that expand with increasing temperature; at high temperatures, the expanding polymers can compensate for high-temperature "thinning" of the basestock to help to provide a more-consistent viscosity in the motor oil across a broad temperature range. Other classes of additives help to maintain lubricant stability in terms of helping to prevent breakdown and viscosity loss in the oil over time. First, detergents and dispersants help to minimize and contain build up in the form of sludge and varnish in an oil. Detergents and dispersants are attracted to the sludge and varnish contaminants and serve to contain and suspend those particles so that they do not agglomerate to form a deposit. Anti-foaming agents are also included in the oil to control formation of air bubbles in the oil, which can otherwise form at room temperature, as a consequence of the detergents and dispersants. Additionally, oxidation inhibitors are included to reduce the tendency of oils to oxidize; the oxidation inhibitors either destroy free radicals or react with peroxides in the oil. Further still, corrosion inhibitors are included; the corrosion inhibitors either neutralize acids that form in the oil or coat metal surfaces so that the surfaces do not contact the acids. Finally, anti-wear agents, such as zinc and phosphorus, can be included in the motor oil to coat metal surfaces with a protective barrier against physical wear. One embodiment of a polyether- or polyester-modified polydialkylsiloxane additive for a lubricating oil is produced by mixing the selected polyether- or polyester-modified polydialkylsiloxane with the lubricating oil at a ratio of one part polyether- or polyester-modified polydialkylsiloxane to five parts lubricating oil (based on the volume) to form a pre-mixed siloxane-and-oil additive, wherein the polyether- or polyester-modified polydialkylsiloxane is uniformly distributed in the oil in the form of a dispersion or suspension. For example, 55 gallons of standard 10W-30 motor oil maybe mixed with 11 gallons with the aforementioned commercial product BYK-333 of the suspended or dispersed polyether- or polyester-modified polydialkylsiloxane to form the siloxane-and-oil additive. In various embodiments of the mixture, the concentration of polyether- or polyester-modified polydialkylsiloxane is about 8 to about 33 percent-by-volume, and the concentration of the lubricating oil is about 61 to about 92 percent-by-volume, i.e. the ratio is from about 1 :2 to about 1:12. The siloxane and the oil can be mixed using a sonic mixer, such as a Branson 900-B mixer sold by Branson Ultrasonic Corp. (Danbury, Connecticut, USA). Where a sonic mixer is used, the mixing can be accomplished using a pump to circulate the polyether- or polyester- modified polydialkylsiloxane and lubricating oil through the sonic mixer for approximately three to four hours or until the temperature of the mixture reaches approximately 200 degrees Fahrenheit (93°C) due to the mixing. Although the temperature of the mixture rises due to the sonic mixing process, the mixture can also be heated using an external heater or other heating means. The mixing process reduces the polyether- or polyester-modified polydialkylsiloxane to a generally spherical-shaped droplet or particle form, wherein the diameter of the particles can be less than approximately two micrometers (microns) and in particular mixtures is less than one micron. As used herein, the term, "diameter," is generally intended to include the corresponding widest dimension of particles or droplets that are not spherical, such as a generally cube-shaped particle or droplet. It is believed that the benefits produced by the siloxane-and-oil additive when added to the lubricating oil will be realized for additive mixtures in which the particle size of the polyether- or polyester-modified polydialkylsiloxane is reduced to as small as 0.002 microns, preferably 0.001 microns in diameter. Before adding the siloxane-and-oil additive or mixture to a selected quantity of the lubricating oil, the siloxane-and-oil additive is filtered through a filter having a pore size of approximately 2 microns to filter out any siloxane particles, droplets or agglomerates having a diameter of more than two microns. Further, filters having a pore size of approximately 1 micron or less can also be used. The formulation process is shown schematically in the Figure. Selected quantities of the selected polyether- or polyester-modified polydialkylsiloxane and oil (e.g., 55 gallons oil and 11 gallons siloxane) are added to a container or reservoir 5. Pump 7 then pumps the siloxane and oil through sonic mixer 9 and, optionally, through heater 11 to three-way valve 13. Valve 13 can be set or positioned in a first or recirculating orientation to continuously direct the flow of siloxane and oil back to reservoir 5, where the flow is re-circulated through the sonic mixer 9 and optionally through heater 11. Once the desired degree of mixing is obtained, the valve 13 can be set or advanced to a second or filling orientation in which the siloxane and oil flows into the filtering station 15 and is allowed to drain by gravity through a filter 15 to a bottling station 17 where the mixture of siloxane and oil is bottled in selected quantities, such as 12 ounces. The premixed siloxane-and-oil additive is then added to a sufficient quantity of lubricating oil to form a selected quantity of lubricant, such as the recommended amount of oil to be held in the lubricating system of an automobile engine, such that the resulting percentage of polyetlier- or polyester-modified polydialkylsiloxane in the resulting lubricant is approximately between 0.5 and 2.5 percent and, in a particular example, is approximately 1.25 percent of the total volume. For example, twelve ounces of the siloxane-and-oil additive, formed at a ratio of one part siloxane to five parts oil, as explained above, can be added to enough oil to result in five quarts of a lubricant mixture. The resulting mixture includes approximately two ounces of polyether- or polyester-modified polydialkylsiloxane in 160 ounces of lubricant, such that the volume of siloxane is 1.25 percent of the total volume, hi an automobile engine, where the polydialkylsiloxane has been added to the lubrication system, the polydialkylsiloxane will generally be well mixed in the oil after the automobile is driven about 10 miles (16 km). Without being bound to any particular theory it is believed that the superior effect of the polyether- or polyester-modified polydialkylsiloxane is due to several different properties of the siloxanes. First, it is believed that the polydialkylsiloxanes will decompose when coming into contact with the hot surfaces of the motor, e.g. the cylinder walls, piston rings and piston walls. As a consequence of this decomposition, a SiO/Si02-film is built on said surfaces which coats and protects the respective parts of the motor. Furthermore, the polyether- or polyester-modified polydialkylsiloxane serves to de-gas the motor oil and to displace moisture from the motor oil. The polydialkylsiloxane also prevents re-introduction of dissolved gases and water into the motor oil. Without the polydialkylsiloxane, motor oil typically comprises 10 to 15% infiltrated air, which is dissolved in the oil. As the typical motor oil approaches hot engine parts, the temperature of the motor oil rises, which causes the dissolved gas to vaporize, thereby forming air bubbles in the motor oil. Those air bubbles then grow larger and larger as the oil approaches the hot engine parts and temperature increases. The air bubbles displace oil and produce turbulance in the flow of the oil around the engine parts, thereby compromising the ability of the motor oil to coat the engine parts and producing potentially destructive harmonic vibrations in the engine due to implosion of the gas bubbles. In this scenario, the polyether- or polyester-modified polydialkylsiloxane serves a function far beyond traditional uses of "anti-foamants" in motor oil, wherein an anti-foamant is used to remove large gas bubbles, formed, e.g., by detergents. Rather, the polyether- or polyester-modified polydialkylsiloxane removes substantially all of the dissolved gas (e.g., at least 99.9% removal) and water from the oil. By substantially eliminating this source of gas bubbles when the motor oil approaches its maximum operating temperature, the motor oil flows more fluidly and smoothly around hot parts and better coats those parts. The flashpoint and oxidation temperature of the motor oil can also be raised substantially by the addition of the polydialkylsiloxane. For example, the flashpoint of a PENNZOIL 10/30 motor oilwas raised from 228°F (109°C) to greater then 500°F (>260°C) by adding the polydialkylsiloxane. Further, in an engine, the improved flow of the oil and the substantial removal of gas bubbles from around the hot parts enables the oil to form a film around piston cylinders, thereby sealing the pistons properly and cooling the pistons to thereby help to prevent pre-ignition due to contact of the fuel with overheated pistons. Further still, the polydialkylsiloxane displaces moisture from the motor oil. The presence of moisture (i.e., water) in the motor oil can cause lubricated cast-iron parts to rust. Rust generates acid, which can destroy the oil and bearings lubricated therewith. Accordingly, inclusion of the polydialkylsiloxane helps to promote longer oil life [e.g., an oil life of 12,500 miles (20,000 km) or more] and also to lengthen the life of engine parts by displacing water (and gases) from the oil. One reason for the improved filming properties and lengthened life of the oil is the displacement of air and water by polydialkylsiloxane from the oil, but also other phenomena may contribute. Additional additives can be added to the siloxane-and-oil mixture to enhance properties of the mixture. Potential additional additives include rust inhibitors and anti-oxidants. Selected strippers or solvents such as mineral spirits or lacquer thinner can also be added to strip off any glazing on engine parts formed during previous operation of the engine before introduction of the siloxane-and-oil additive. The stripper or solvent would function to deglaze the affected engine parts and to then volatilize at elevated engine-operating temperatures. It is believed that the material deglazed from the engine parts by the stripper is then filtered out of the lubricant as it passes through the oil filter. Other additives that can be included in the siloxane-and-oil mixture include viscosity index improvers or dimethylsulfoxide at a concentration of approximately one tenth of one percent (0.1%) for use as a blending agent, sodium hydroxide (0.0001%) as a blending and binding agent, and glycerol to help maintain the siloxane in suspension. The polyether- or polyester-modified polydialkylsiloxane of reduced particle size can be added directly to a quantity of lubricant, such as the motor oil in an oil pan of an automobile, without premixing the siloxane with a portion of the lubricating oil to be used, while still achieving the enhanced lubricating properties. Additional engine operational time is needed, however, for the siloxane to become generally uniformly dispersed throughout the engine oil when the polyether- or polyester-modified polydialkylsiloxane is added directly to the automobile engine oil, thereby extending the operational time before the maximum benefits of enhanced lubrication occur. Finally, the polyether- or polyester-modified polydialkylsiloxane can be used as an additive to a motor oil, wherein said polyether- or polyester-modified polydialkylsiloxane is represented by general formula (1) or (2) as mentioned above.
EXPERIMENTAL EXEMPLIFICATIONS Example 1 - Coating Tests: Various tests demonstrated the improved lubricating and emission-reducing properties of the siloxane-and-oil additive. In one test, the coating capability of lubricant including the polydialkylsiloxane-and-oil additive at approximately 1.25 percent of the total volume was compared to the coating capability of a mixture of SLICK 50 Advanced Formula Engine Treatment in 10W-30 motor oil and to the coating capability of MOBIL 1 SYNTHETIC motor oil. Oils that were used for mixing with the polydialkylsiloxane are Penzoil 10/30, Castroil 10/30, Napa Premium 10/30, Union 76 10/30, Castrol Semi Synthetic 10/30 and Castroil Full Synthetic 10/30, all by weight. Equal quantities of each lubricant were applied to a hot plate heated to 350 degrees Fahrenheit (177°C) and angled downward at a 45-degree angle. The hot plate comprised a TEFLON-coated aluminum plate. Through visual inspection, it was observed that the SLICK 50 engine treatment in 10W-30 motor oil and the MOBIL 1 SYNTHETIC motor oil did not adhere to or coat the surface of the hot plate to any appreciable degree and essentially just ran off the hot plate. The test was performed as follows: All the oils tested were tested without the added polydialkylsiloxane. The test was completed with standard oil and runoff was noted. All the test oils were then mixed with the polydialkylsiloxane mix and retested as before. The results showed marked improvement as to coating properties on the hot plate. An oxidation test was performed in the same manner, where as a spoon shaped receptacle was used to hold 2 cc's of oil above a heat source of 800 °F for 2 min. observation of the samples showed that regular oils oxidized and evaporated within 10 to 30 sec. The same test was performed with the same base oils with a proportional addition of siloxane. Observations showed a significant reduction in oxidation and evaporation of the mixture. In 90% of the tests there was no noticeable change of the sample being tested. The remaining 10%) of the samples that were tested showed a change 2 min into the testing and was found to be a result of wax/paraffin separating from the mixture, although it should be noted that the remaining oil remained stable and did not oxidize. In contrast, visual observation of the surface onto which the polydialkylsiloxane-and-oil additive was poured revealed formation of a lasting and even lubricant coating thereon. The test was repeated with similar results for hot-plate temperatures ranging from 250 to 500 degrees Fahrenheit (121-260°C). The tests demonstrated that the siloxane-and-oil additive adheres to and coats hot surfaces to a greater degree than does the non-treated SLICK 50 treated motor oil or the MOBIL 1 synthetic, Napa premium 10/30, Penzoil 10/30 and 30 wt, Union 76 10/30 and 30 wt. oil. Napa premium 10/30 did show slight coating prior to being treated with siloxane, although with the siloxane added it showed a marked improvement in coating at temp.
Example 2 - Comparative Horsepower Tests: The improved lubricating properties of lubricants including the siloxane-and-oil additive were further demonstrated by comparing the horsepower generated by an automobile engine operating without the siloxane-and-oil additive added to the lubricant versus the horsepower generated by the same automobile engine with the siloxane-and-oil additive added to the engine lubricant. In each case, the horsepower generated by a 1998 Jeep GRAND CHEROKEE LAREDO automobile having a 4.0-liter, six-cylinder engine was measured using a Dynajet Model 248C Dynamometer. In a first test, the horsepower of the Jeep GRAND CHEROKEE automobile was initially measured without the siloxane-and-oil additive added to the engine lubricant. The lubricant utilized in the engine lubricating system was 5 quarts of 10W-30 petroleum based motor oil. In the first test, the engine of the automobile was accelerated from 0 to 5200 RPM (revolutions per minute), and measurements were taken at increasing increments of 250 RPM. During the first test, the absolute barometric pressure was recorded as 29.92 in. Hg (about 100 kPa) with a vapor pressure of 0.61 in. Hg (about 2 kPa). The intake air temperature was measured at 86 degrees Fahrenheit (30°C), and the gear ratio was recorded as 49 RPM/MPH. A Society of Automotive Engineers (SAE) correction factor of 1.01 was used to convert the measured horsepower to a corrected horsepower. A second test was performed on the same automobile by adding 12 ounces of the siloxane-and-oil additive to the engine-lubricating oil. The ratio of siloxane to oil in the additive was 1 ounce siloxane to 11 ounces oil. Adding the twelve ounces of additive to the existing 5 quarts of oil in the automobile resulted in a concentration of siloxane in the lubricant of approximately 0.58%). The automobile was again accelerated from 0 to 5200 RPM with measurements again taken at increasing 250 RPM intervals. During the second test, the absolute barometric pressure was recorded as 29.92 in. Hg (about 100 kPa) with a vapor pressure of 0.61 in. Hg (about 2 kPa). The intake air temperature was measured at 88.8 degrees Fahrenheit (31.6°C), and the gear ratio was recorded as 48 RPM/MPH. An SAE correction factor of 1.01 was used to convert the measured horsepower to a corrected horsepower. The measured and corrected horsepower of the automobile operating with lubricant only versus with the siloxane-and-oil additive added to the lubricant at various engine speeds is provided, below, in Table 1.
Table 1:
Figure imgf000017_0001
Figure imgf000018_0001
In comparing the data in Table 1 , it can be seen that the corrected horsepower increased by an average of 8.4 horsepower when the siloxane-and-oil additive was added to the engine lubricant compared with the corresponding tests performed without the additive. In addition, the maximum horsepower achieved in the tests using the siloxane-and-oil additive exceeded the maximum horsepower in the tests without the additive by 4.3 horsepower. The test measurements of increased horsepower resulting from use of the siloxane-and-oil additive supports the conclusion that use of the siloxane-and-oil additive provides better lubrication of the engine parts.
Example 3 - ASM Emission Tests: A comparison of the emissions of automobiles with and without the siloxane-and-oil additive added to the engine lubricant Penzoil 10/30 was preformed using the acceleration simulation mode (ASM) emission test for the State of California. The test results, below, provide the measured exhaust concentrations of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxide (NOx) gases, which are generally considered harmful. The data in the column entitled, "Concentration without additive," comprise the results for a first test in which no additive was added to the engine lubricant (5 quarts of motor oil), and the data in the column entitled, "Concentration with additive," comprises the results of a second test in which 12 ounces of the siloxane-and-oil additive (at a ratio of 2 ounces siloxane per 10 ounces oil) were added to the engine lubricant to result in an overall concentration of siloxane in the lubricant of approximately 1.16% by volume .
Table 2: Vehicle Model: GMC YUKON Year: 1996 Mileage: 133,321 (214,559 km)
Figure imgf000019_0001
Table 3:
Vehicle Model: BMW 325i Year: 1995 Mileage: 70,329 (113,184 km)
Figure imgf000019_0002
Table 4: Vehicle Model: Jeep Grand Cherokee Laredo Year: 2000 Mileage: 27,845 (44,812 km)
Figure imgf000019_0003
Table 5: Vehicle Model: Dodge CARAVAN Year: 1988 Mileage: 123,767 (199,184 km)
Figure imgf000020_0001
These test results demonstrate that use of the siloxane-and-oil additive significantly reduced the concentration of hydrocarbons and carbon monoxide in each case, and significantly reduced the NOx emissions in all but one of the applications. These results support the conclusion that use of the siloxane-and-oil additive improves engine efficiency (i.e., provides more-thorough combustion of the fuel in the engine), which thereby reduces emissions of hydrocarbons, carbon monoxide and NOx gases.
Example 4 - Siloxane Alone in Automobile Engine Lubrication System In one test, the polyether-modified polydimethylsiloxane of reduced particle or droplet size at a viscosity of approx 10/30 wt. was the sole lubricant utilized in an automobile engine lubricating system. The polyether-modified polydimethylsiloxane was processed in the same manner as the siloxane-and-oil mixture described above with reference to the Figure, except that no oil was added. More specifically, polyether-modified polydimethylsiloxane, without oil, was circulated by pump 7 through sonic mixer 9 until the particle or droplet size was reduced to approximately one micron in diameter and then passed through the filter 15 to remove any particles having a diameter exceeding the pore size of approximately two microns. Approximately five quarts of the processed polyether-modified polydimethylsiloxane was then added to the engine lubricating system of an automobile to replace the recommended five quarts of motor oil, which was previously drained from the lubricating system. The automobile using the siloxane only lubricant was then run for approximately two thousand miles without any adverse affects identified. This test showed improved fuel use as compared to regular oils. Data collected prior to and after adding siloxane 100% showed a 3 mile per gallon savings after adding siloxane. Example 5 - Use of Siloxane and Gasoline Mixutre in a Two-Cycle Engine: In another test, the polyether-modified polydimethylsiloxane, processed in the manner described in Example 4, above, was added to gasoline to replace the two-cycle engine oil normally included in an oil-and-gas mixture used with a two-cycle engine. The ratio of gasoline to polyether-modified polydimethylsiloxane was fifty to one, and no adverse engine effects were observed. Passing through of particulate (oil) through the engine was reduced if not completely eliminated. No oil residue was noted when using siloxane in place of regular 2 cycle oil as compared to regular 2 cycle oils that were observed to pass through the engine as unburned solids, causing detrimental environmental damage to both land and water, as well as killing any plant life that the solids came into contact with. When using polydialkylsiloxane as a 100%) product or in aqueous dispersion, suspension or solution in place of oil this was not to be considered a problem as any of the base lubricant that passed through the engine is not harmful to nature or humans. The test was performed for approximately 200 hours and temperature readings taken on the engine using the mixture of gasoline and polyether-modified polydimethylsiloxane were lower than simultaneous temperature readings taken on another two- cycle engine using the recommended gasoline and oil mixture. The temperature readings were taken using a digital, infrared thermometer. The reduced-temperature readings indicate improved lubricating properties of the siloxane versus two-cycle engine oil. The polyether-modified polydimethylsiloxane can be premixed with a quantity of two- cycle engine oil before adding the resulting lubricant to the gasoline at the recommended fuel-to- lubricant ratio. Alternatively, processed polyether-modified polydimethylsiloxane of reduced particle size can be added to the gasoline separate from the two-cycle engine oil to achieve the desired fuel-to-lubricant ratio. While certain formulations of the present invention have been illustrated and described herein, the invention is not limited to the specific formulations described and shown. For example, although polyether-modified polydimethylsiloxane is described primarily with reference to its use in forming an additive for motor oil, polyether-modified polydimethylsiloxane has also been formulated and tested as an additive for power steering fluid, transmission fluid or oil and gear grease. Testing on these various formulations all showed improvement in the lubricating properties of the formulations. Such testing has also been performed on water-based Lubricants as well as petroleum-based lubricants. In addition, testing was done on a wide range of weights of oil, from 5 to 120 weight oil The tests included although were not limited to motor oils from 20 wt to 140 wt oils as well as 10/20, 10/30, 10/40, 20/50. Also, tests included bearing grease, power steering fluids, axle lubricants from 50 to 160 wt in range. The tests were preformed on spray lubricants WD-40, and alike. It was noted that in all testing the addition of siloxane improved the lubricating features of the products being tested. When added to WD-40 it was noted that the lubrication features of this product was marked when tests of a mixture of siloxane and water were preformed and tested head to head with WD-40 spray lube. Test included lubricity, staining, water resistance, longevity. It was noted that the use of WD-40 applied to test hinge mounted to metal door plate.
WD-40 applied as directions required, coated the hinge with an oily coating that reduced sqeaking. Further, the use of this product caused permanent staining on the metal plate. When flushed with water (with water hose) the product repelled the water and staining remained. The test repeated with a 25% siloxane mixed with 75%> water by vol. revealed that the siloxane mixture also coated the hinge and metal although the water evaporated and no noticeable staining occurred. After the mixture was dry and water was applied the lubrication of the mixture continued. During all testing there was a marked improvement with each and every test and base lubricant used, so the addition of siloxane when mixed and used without the addition of a base lubricant worked equally across the tests performed.

Claims

1. A method for lubricating a vehicle comprising: adding polyether- or polyester-modified polydialkylsiloxane particles to a fluid- conduit system in an engine-operated vehicle, wherein the polydialkylsiloxane particles form a mixture with oil in the fluid-conduit system; and operating the engine of the vehicle, wherein the mixture of polydialkylsiloxane particles and oil coats automobile parts accessed by the fluid-conduit system.
2. The method of claim 1 wherein the polyether- or polyester-modified polydialkylsiloxane is represented by the general formula (1)
Figure imgf000023_0001
Z I R, wherein
Z is independently selected from O,
Figure imgf000023_0002
or Ri and Rr are independently selected from Cι-C6 alkyl and -Z-(Cι-C6 alkyl) R2 and Rr are independently selected from Ci-Cβ alkyl; R3 is -(C(R6)(R7))-; R4 is -(C(R8)(R9))v-; R5 is selected from hydrogen, -0-(Cι-C6-alkyl) and Ci-Cβ alkyl; Re, R7, R8 and R9 are independently selected from hydrogen and Ci-Cβ alkyl; n is an integer from 1 to 10; m is an integer from 0 to 5; v is an integer from 1 to 4; x is an integer from 1 to 150; and y is an integer from 1 to 500.
3. The method of claim 2, wherein said Ci-Cβ alkyl comprises methyl, ethyl, propyl, butyl, pentyl and isomers thereof.
4. The method of claim 2, wherein Ri, Rr, R2 and R2- are methyl.
5. The method of claim 1, wherein the polydialkylsiloxane particles have an average diameter of less than 2 microns.
6. The method of claim 5 wherein the polydialkylsiloxane particles have an average diameter of less than 1 micron.
7. The method of claim 5, wherein the size of the polydialkylsiloxane particles is reduced and the particles are filtered such that substantially all of the polydialkylsiloxane particles have an average diameter of less than 2 microns.
8. The method of claim 1 , wherein the polydialkylsiloxane is at least about 0.5 percent by volume of the polydialkylsiloxane-and-oil mixture in the fluid-conduit system.
9. The method of claim 1 , wherein the polydialkylsiloxane is at least about 1 percent by volume of the polydialkylsiloxane-and-oil mixture in the fluid-conduit system.
10. The method of claim 1 , wherein the fluid-conduit system is an engine lubrication system.
11. The method of claim 1 , wherein the oil is a motor oil.
12. The method of claim 11, wherein the motor oil is a petroleum-based motor oil.
13. The method of claim 11 , wherein the motor oil is a synthetic motor oil.
14. The method of claim 1 , wherein the fluid-conduit system is a power-steering lubrication system.
15. The method of claim 1 , wherein the fluid-conduit system is a fuel system.
16. The method of claim 15, wherein the the fuel system belongs to a 2-stroke engine and the polyether- or polyester-modified polydialkylsiloxane is either premixed with the fuel or injected directly into the combustion chamber of the engine.
17. The method of claim 1 , wherein the polyether- or polyester-modified polydialkylsiloxane is added to the fluid-conduit system as a mixture of the polyether- or polyester modified polydialkylsiloxane and oil.
18. The method of claim 17, wherein the polyether- or polyester-modified polydialkylsiloxane is dispersed substantially uniformly in the oil when added to the fluid-conduit system.
19. A method for forming a mixture comprising mixing together a polyether- or polyester- modified polydialkylsiloxane and a liquid lubricant to produce a mixture wherein the polyether- or polyester-modified polydialkylsiloxane forms at least 0.5% of the mixture.
20. The method of claim 19 wherein the polyether- or polyester-modified polydialkylsiloxane is represented by the general formula (1)
- R-, - ( 1 )
Figure imgf000025_0001
wherein Z is independently selected from O,
Figure imgf000026_0001
or ; Ri and Rr are independently selected from Ci-Cβ alkyl and -Z-(Cι-Cβ alkyl) R2 and R2- are independently selected from Ci-Cβ alkyl; R3 is -(C(R6)(R7) ; R4 is -(C(R8)(R9))v-; Rs is selected from hydrogen, -0-(Cι-C6-alkyl) and Ci-Cβ alkyl; Re, R7, R8 and R9 are independently selected from hydrogen and Ci-Cβ alkyl; n is an integer from 1 to 10; m is an integer from 0 to 5; v is an integer from 1 to 4; x is an integer from 1 to 150; and y is an integer from 1 to 500.
21. The method of claim 20, wherein said Ci-Cβ alkyl comprises methyl, ethyl, propyl, butyl, pentyl and isomers thereof.
22. The method of claim 20, wherein Ri, Rr, R2 and R2- are methyl.
23. The method of claim 19, wherein the polydialkylsiloxane particles have an average diameter of less than 2 microns.
24. The method of claim 23, wherein the polydialkylsiloxane particles have an average diameter of less than 1 micron.
25. The method of claim 23, wherein the polydialkylsiloxane is in the form of particles, the method further comprising reducing the particle size of the polydialkylsiloxane particles and filtering the particles so that substantially all of the polydialkylsiloxane particles in the mixture have an average diameter of less than 2 microns after mixing.
26. The method of claim 19, wherein the lubricant is motor oil.
27. The method of claim 26, wherein the motor oil is a petroleum-based motor oil.
28. The method of claim 26, wherein the motor oil is a synthetic motor oil.
29. The method of claim 26, wherein the polyether- or polyester-modified polydialkylsiloxane is about 8 to about 33 percent by volume of the mixture.
30. The method of claim 26, wherein the polyether- or polyester-modified polydialkylsiloxane is about 15 to about 20 percent by volume of the mixture.
31. The method of claim 26, wherein the polyether- or polyester-modified polydialkylsiloxane and the motor oil are mixed by sonic mixing.
32. The method of claim 26, wherein the polyether- or polyester-modified polydialkylsiloxane and the motor oil is heated to at least about 200°F (about 93 °C) during mixing.
33. The method of claim 26, further comprising adding the oil-and-polydialkylsiloxane mixture to additional motor oil to form a secondary mixture.
34. The method of claim 33, wherein the polyether- or polyester-modified polydialkylsiloxane is less than about 2.5 percent by volume of the secondary mixture.
35. The method of claim 34, wherein the polyether- or polyester-modified polydialkylsiloxane comprises about 1 to about 1.5 percent by volume of the secondary mixture.
36. The method of claim 19, wherein the polydialkylsiloxane particles are dispersed substantially uniformly in the mixture.
37. A motor oil mixture comprising: a petroleum-derived or synthetic motor oil; and polyether- or polyester-modified polydialkylsiloxane dispersed in the motor oil.
38. The motor oil mixture of claim 37 wherein the polyether- or polyester-modified polydialkylsiloxane is represented by the general formula (1)
R, I R, -Si-O- -Si-O- -Si-O- -Si-Rx- I I (1 ) R2- (R ""3, ' ra R,- R,
Figure imgf000028_0001
R. wherein
Z is independently selected from O,
Figure imgf000028_0002
or ; Ri and Rr are independently selected from Ci-Cβ alkyl and -Z-(Cι-Cβ alkyl) R2 and R2- are independently selected from Ci-Cβ alkyl; R3 is -(C(R6)(R7) ;
Figure imgf000028_0003
R5 is selected from hydrogen, -O-(Cι-Ce-alkyl) and Ci-Cβ alkyl; Re, R7, R8 and R9 are independently selected from hydrogen and Cι-C6 alkyl; n is an integer from 1 to 10; m is an integer from 0 to 5; v is an integer from 1 to 4; x is an integer from 1 to 150; and y is an integer from 1 to 500.
39. The motor oil mixture of claim 38, wherein said Ct-Cβ alkyl comprises methyl, ethyl, propyl, butyl, pentyl and isomers thereof.
40. The motor oil mixture of claim 38, wherein Ri, Rr, R2 and R2- are methyl.
41. The motor oil mixture of claim 37, wherein the polydialkylsiloxane particles have an average diameter of less than 2 microns.
42. The motor oil mixture of claim 41, wherein the polydialkylsiloxane particles have an average diameter of less than 1 micron.
43. The motor oil mixture of claim 37, wherein the motor oil is a synthetic motor oil that mostly comprises a basestock selected from the group consisting of polyalphaolefins, diesters, and polyolesters.
44. The motor oil mixture of claim 37, wherein the motor oil mostly comprises a purified form of crude oil.
45. The motor oil mixture of claim 37 , wherein the polyether- or polyester-modified polydialkylsiloxane particles are dispersed substantially uniformly in the motor oil.
46. The motor oil mixture of claim 37, wherein the polyether- or polyester-modified polydialkylsiloxane particles form at least about 0.5 percent by volume of the motor oil dispersion.
47. The motor oil mixture of claim 37, wherein the polyether- or polyester-modified polydialkylsiloxane particles form at least about 1 percent by volume of the motor oil dispersion.
48. The motor oil mixture of claim 37, wherein the polyether- or polyester-modified polydialkylsiloxane particles form about 8 to about 33 percent by volume of the motor oil dispersion.
49. The motor oil mixture of claim 37, wherein the polyether- or polyester-modified polydialkylsiloxane particles form about 15 to about 20 percent by volume of the motor oil dispersion.
50. A motor comprising: a mechanism for converting energy from an energy source into mechanical displacement of motor parts; a lubrication system including a conduit that passes through the motor and offers access to the displaceable motor parts; and polyether- or polyester-modified polydialkylsiloxane particles in the conduit of the lubrication system.
51. The motor of claim 50 wherein the polyether- or polyester-modified polydialkylsiloxane is represented by the general formula (1)
R, R2 R, I 2 — Si-O- -Si-O- -Si-O- -Si— R, - I I ( 1 ) I R,- ( R3 > m R, -
Figure imgf000030_0001
wherein O O
Z is independently selected from O, " or ~ ; Ri and Rr are independently selected from Ci-Cβ alkyl and -Z-(Cι-Cβ alkyl) R2 and R2- are independently selected from Ci-Cβ alkyl; R3 is -(C(R6)(R7))-; R4 is -(C(R8)(R9))V-; R5 is selected from hydrogen, -0-(Cι-C6-alkyl) and Ci-Cβ alkyl; Re, R7, R8 and R are independently selected from hydrogen and Ci-Cβ alkyl; n is an integer from 1 to 10; m is an integer from 0 to 5; v is an integer from 1 to 4; x is an integer from 1 to 150; and y is an integer from 1 to 500.
52. The motor of claim 51, wherein said Ci-Cβ alkyl comprises methyl, ethyl, propyl, butyl, pentyl and isomers thereof.
53. The motor of claim 51 , wherein Ri, Rr, R2 and R2- are methyl.
54. The motor of claim 50, wherein the polydialkylsiloxane particles have an average diameter of less than 2 microns.
55. The motor of claim 54, wherein the polydialkylsiloxane particles have an average diameter of less than 1 micron.
56. The motor of claim 50, wherein the motor is an internal combustion engine .
57. The motor of claim 50, wherein the polyether- or polyester-modified polydialkylsiloxane particles are dispersed in motor oil.
58. The motor of claim 57, wherein the polyether- or polyester-modified polydialkylsiloxane particles form at least about 0.5 percent by volume of the motor oil dispersion.
59. The motor of claim 50, wherein the motor is a 4-stroke engine.
60. The motor of claim 51 , wherein the motor is a 4-stroke engine .
61. The motor of claim 50, wherein the motor is a 2-stroke engine .
62. The motor of claim 51 , wherein the motor is a 2-stroke engine .
63. Use of a polyether- or polyester-modified polydialkylsiloxane as an additive to a motor oil, wherein said polyether- or polyester-modified polydialkylsiloxane is represented by the general formula 1
R R2 R, I i — Si-O- -Si-O- -Si-O- -Si-Ri- ( 1 ) I I R2- ( R3 ) m R,- R, z I R„ Rc wherein
Z is independently selected from O,
Figure imgf000032_0001
or ; Ri and Rr are independently selected from Ci-Cβ alkyl and -Z-(Cι-C6 alkyl) R2 and R2- are independently selected from Ci-Cδ alkyl; R3 is -(C(R6)(R7))-; R4 is -(C(R8)(R9))V-; R5 is selected from hydrogen, -0-(Cι-C6-alkyl) and Ci-Cβ alkyl; Re, R7, R8 and R9 are independently selected from hydrogen and -Ce alkyl; n is an integer from 1 to 10; m is an integer from 0 to 5; v is an integer from 1 to 4; x is an integer from 1 to 150; and y is an integer from 1 to 500.
64. The use of claim 63, wherein said Ci-Cδ alkyl comprises methyl, ethyl, propyl, butyl, pentyl and isomers thereof
65. The use of claim 63, wherein Ri, Rr, R2 and R2- are methyl.
10
66. The use of claim 63, wherein the polydialkylsiloxane particles have an average diameter of less than 2 microns.
67. The use of claim 63, wherein the polydialkylsiloxane particles have an average diameter of less than 1 micron.
11
PCT/IB2004/051682 2003-12-12 2004-09-03 Lubricant including polyether- or polyester-modified polydialkylsiloxane WO2005059066A1 (en)

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WO2006028536A1 (en) * 2004-09-03 2006-03-16 Motor Works Llc Engine part coating created from polysiloxane and coating method
WO2009111099A1 (en) * 2008-03-07 2009-09-11 Exxonmobil Chemical Patents Inc. Silicone functionalized fluids with low traction characteristics

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US3371104A (en) * 1961-11-10 1968-02-27 Goldschmidt Ag Th Process of preparing acyloxyalkyl group containing polysiloxanes
US4378459A (en) * 1980-09-05 1983-03-29 General Electric Company Ester functional organopolysiloxane lubricants and process
US4652386A (en) * 1984-10-03 1987-03-24 Bayer Aktiengesellschaft Lubricating oil preparations
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WO2006028536A1 (en) * 2004-09-03 2006-03-16 Motor Works Llc Engine part coating created from polysiloxane and coating method
WO2009111099A1 (en) * 2008-03-07 2009-09-11 Exxonmobil Chemical Patents Inc. Silicone functionalized fluids with low traction characteristics
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