US3513096A - Oil concentrate containing a compatible mixture of polyisobutylene and ethylene-alpha olefin copolymer - Google Patents

Oil concentrate containing a compatible mixture of polyisobutylene and ethylene-alpha olefin copolymer Download PDF

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US3513096A
US3513096A US781708A US3513096DA US3513096A US 3513096 A US3513096 A US 3513096A US 781708 A US781708 A US 781708A US 3513096D A US3513096D A US 3513096DA US 3513096 A US3513096 A US 3513096A
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ethylene
polyisobutylene
oil
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Darrell W Brownawell
Donald J Buckley
Norman Jacobson
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ExxonMobil Technology and Engineering Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/022—Well-defined aliphatic compounds saturated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/024—Well-defined aliphatic compounds unsaturated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/04—Well-defined cycloaliphatic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/10—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing cycloaliphatic monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/16—Dielectric; Insulating oil or insulators
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/17—Electric or magnetic purposes for electric contacts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • This invention relates to oil compositions that are useful primarily as engine lubricating oils and are characterized by a unique and most desirable low viscosity at low temperatures and high viscosity at higher temperatures.
  • the invention relates to an additive concentrate comprising a compatible mixture of polyisobutylene and ethylene-alpha olefin in mineral oil.
  • oils are generally oils or oil blends containing at least about 1% and as much as by volume of one or more high molecular weight polymers, which are well known in the industry as viscosity index improvers.
  • One such problem relates to means for accurately predieting the engine cold cranking characteristics (i.e., engine viscosity) of an oil.
  • cranking characteristics of the socalled straight mineral oils can, in general, be predicted adequately (i.e., without actual cranking) by using the viscosity at the temperature of interest, e.g., 0 to 20 F.
  • the straight mineral oil viscosity is obtained by extrapolating low-shear viscosities obtained at and 210 F. on the ASTM viscosity-temperature chart.
  • the method involves the use of an engine viscosity simulator of improved characteristics predicting the relative distribution of the viscous forces and the hydrodynamic forces in a liquid system particularly, a non-Newtonian liquid system.
  • the viscosity of a motor oil will thereby actually be measured at 0 and 210 F. This change will enhance the true contribution of the V.I. improver to the viscosity properties of the motor oil.
  • V.I. improvers e.g., polyisobutylene, polymers of methacrylic acid esters and higher fatty alcohols, copolymers of styrene and C -C olefins, etc. thicken motor oils to an undesirably large degree at 0 F.
  • V.I. improvers e.g., polyisobutylene, polymers of methacrylic acid esters and higher fatty alcohols, copolymers of styrene and C -C olefins, etc.
  • viscosity for the mixture of polyisobutylene plus ethylene-propylene copolymer or terpolymer may be lower than with either polymer alone. This may be referred to as the delta viscosity; that is, the viscosity difference between the viscosity measured for mixtures of polyisobutylene plus ethylene-propylene copolymer in mineral oil solvent, e.g., Solvent 150 Neutral, and the viscosity calculated from the measured viscosities of either polyisobutylene or ethylene-propylene copolymer or terpolymer alone in said Solvent 150 Neutral.
  • the delta viscosity that is, the viscosity difference between the viscosity measured for mixtures of polyisobutylene plus ethylene-propylene copolymer in mineral oil solvent, e.g., Solvent 150 Neutral, and the viscosity calculated from the measured viscosities of either polyisobutylene or ethylene-propylene copolymer or
  • the applicable isobutylene polymers generally have a viscosity average molecular weight of between about 20,000 and about 200,000 and preferably between about 100,000 and 150,000.
  • the polymerization reaction and the conditions utilized are well-known in the art and the polymerization reaction per se does not constitute a part of the present invention.
  • the polymerization of the isobutylene comprising monomer may be carried out in a wide variety of Ways.
  • the reaction process may be carried out as either a batch or a continuous operation and with or without the use of an inert organic diluent as a reaction medium. Usually a diluent is preferred for carrying out the process.
  • any inert organic solvent may be used as a diluent, as for example, aliphatic hydrocarbons such as hexane, heptane, isooctane, etc., cycloaliphatic hydrocarbons such as cyclohexane, aromatic hydrocarbons, such as benzene, toluene, xylene, etc., or any mixture of such hydrocarbons, or halogenated aromatic hydrocarbons such as chlorobenzenes, chloronaphthalenes, etc.
  • aliphatic hydrocarbons such as hexane, heptane, isooctane, etc.
  • cycloaliphatic hydrocarbons such as cyclohexane
  • aromatic hydrocarbons such as benzene, toluene, xylene, etc.
  • halogenated aromatic hydrocarbons such as chlorobenzenes, chloronaphthalenes, etc.
  • the selection of the temperatures and the pressures utilized for the polymerization reaction will depend upon a number of factors, e.g., the purity of the monomer utilized, the activity of the catalyst system being used, the degree of polymerization desired, etc. In general, the polymerization will be carried out at temperatures within the range of from about C. to about 150 C. and preferably from about -20 C. to about C. Similarly, while atmospheric pressure or pressure of only a few pounds may be used, the polymerization reaction may be carried out at a wide range of pressures, as for example, through a partial vacuum to about 1,000 p.s.i. and preferably from about atmospheric to about 500 p.s.i. High pressures may, of course, be used, but generally do not appreciably alter the course of polymerization reaction.
  • Suitable catalysts systems include the Friedel-Crafts catalysts which are well-known in the art, e.g., Schildknecht, Vinyl and Related Polymers Wiley (1952), page 541. These materials include HgCl BeCl ZnCl ZnBr CdCl CaCl BF B01 BBr AlCl AlBr A113, TIBI4, ZI'C14, ZIBL ⁇ , SnCl SIIBI'4, SbCl SbCl MoCl BiCl FeCl UCl It is contemplated that the above Friedal-Crafts catalysts may be employed in a catalyst system consisting essentially of said Friedel-Crafts compound and an aluminum alkyl compound wherein the molar ratio of Friedel-Crafts compound to aluminum alkyl is a minimum of one.
  • the alkyl component of the alkyl aluminum compound preferably has from 1 to about 8 carbon atoms.
  • Specific examples of the preferred alkyl aluminum compounds include aluminum triethyl, aluminum triisobutyl, aluminum diethyl chloride, aluminum sesquichloride, aluminum ethyl dichloride, aluminurn ethyl dibromide, aluminum diethyl bromide, aluminum ethyl diiodide, aluminum diethyl iodide, aluminum methyl dichloride, aluminum dimethyl chloride, aluminum methyl dibromide, aluminum dimethyl bromide, aluminum methyl diiodidc, aluminum dimethyl iodide, aluminum trimethyl, and the like.
  • catalyst systems used in the preparation of the polyisobutylene component utilized herein include boron trifluoride, titanium tetrachloride, aluminum trichloride, and a combination of stannic chloride and aluminum triethyl.
  • catalysts may also be used in preparation of the isobutylene polymer such as natural earths of the type of fullers earth, bauxite, natural and artificial clays, active carbon and other similar well-known polymerizing agents.
  • the second component of the polymeric mixtures of the instant invention are oil-soluble polymers of ethylene and alpha-olefin, e.g., ethylene-propylene copolymers. These polymers will contain from about 40 to about 90 mole percent, preferably 50 to 88 mole percent, of ethylene; from about 60 to about 10 mole percent, preferably 50 to 12 mole percent, of a C3-C13 alpha-olefin and from about to about mole percent, e.g., 2 to 8 mole percent, of a third monomer selected from the group consisting of the hereinafter described C C alphaolefins and polyolefins.
  • ethylene-propylene copolymers will contain from about 40 to about 90 mole percent, preferably 50 to 88 mole percent, of ethylene; from about 60 to about 10 mole percent, preferably 50 to 12 mole percent, of a C3-C13 alpha-olefin and from about to about mole percent, e.g.
  • the ethylene-alpha olefin polymers useful in this invention exhibit a degree of crystallinity up to about 25%.
  • the ethylene-alpha olefin polymer of this invention may be further characterized as having a viscosity average molecular weight within the range between about 10,000 and 250,000, preferably 50,000 to 100,000.
  • the ethylene-alpha olefin polymer of this invention need only be oil-soluble and have the requisite crystallinity, molecular weight and monomer content.
  • the ethylene-alpha olefin copolymers of this invention may be prepared, for example, by reacting from about 2 to about 98 wt. percent ethylene with about 98 to about 2 Wt. percent of alpha-olefin, preferably propylene, in the presence of a soluble species of Ziegler catalyst, preferably a catalyst prepared by activating VCL; or VOCl with an alkyl aluminum chloride.
  • a conventional chain transfer agent such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, hydrogen, etc.
  • the ethylene-alpha olefin polymer of this invention may be prepared by chemically, thermally, or mechanically degrading high molecular weight polymer in accordance with well-known techniques to produce a polymer having the requisite molecular weight and oilsolubility characteristics.
  • Other methods of preparing the ethylene-alpha olefin polymer of the instant invention are given in copending application Ser. No. 657,064, filed July 31, 1967, which disclosure is incorporated herein in its entirety by express reference.
  • the resultant product which finds utility in the present invention has a viscosity average molecular weight (Mv.) of about 10,000 to 250,000 preferably from about 40,000 to 150,000 and most preferably from about 50,000 to 100,000.
  • Mv. viscosity average molecular weight
  • the term molecular weight as used herein means molecular weight based on viscosity measurement. The molecular weights indicated herein and in the claims hereof were estimated on the basis of viscosity measurement at 135 F. of solutions which contained 0.5 milligram of polymer per milliliter of decalin.
  • the soluble catalysts which may be used in polymerizing the monomers of this invention can be formed by mixing an organo-aluminum halide with various vanadium compounds. These vanadium compounds may then be reacted with an aluminum alkyl compound in order to produce the final catalyst composition.
  • the vanadium compounds which may be used include the vanadium oxyhalides, the vanadium tetrahalides, the vanadium oxyacetylacetonates, the alkyl vanadates, and the like.
  • the copolymers may also be prepared with certain titanium compounds.
  • the titanium compounds suitably employed are those that can be reacted with a selected vanadium compound to produce a reaction product which is a complex.
  • the alkyl aluminum compounds most conveniently used include those having the formula R AlX wherein R is a C to C preferably C to C monovalent hydrocarbon radical, X is a halogen having an atomic number above 17, preferably chlorine or a C to C preferably C to C monovalent hydrocarbon radical or hydrogen, in is an integer between 1 and 3 and the sum of in plus it is equal to 3.
  • R groups include methyl, ethyl, propyl, n-butyl, n-amyl, isoamyl, phenyl, tolyl, and cyclopentyl radicals.
  • Ethylene and a C to C alpha-olefin can be copolymerized to prepare the additives of this invention.
  • the alpha-olefin may be linear or branched where the branching occurs three or more carbon atoms from the double bond, and, while a single olefin is preferably, mixtures of these C to C olefins may be employed.
  • C to C alpha-olefins include: propylene, 1- butene, l-pentene, l-hexene, l-he'ptane, l-octene, 1- nonene, l-decene, 4-methyl-l-pentene, 4-methyl-1-hexene, S-methyl-l-hexen, 4,4-dimethyl 1 pentene, 4-methyl-1- heptene, S-methyl-l-heptene, 6-methyl- 1 -heptene, 4,4- dimethyl-l-hexene, 5,6,5-trimethyl-l-heptene and mixtures thereof.
  • the present invention also contemplates the use of a C to C alpha-olefin and/or diolefin, polyolefin and the like which is copolymerized with ethylene and propylene to produce terpolymers.
  • These unsaturated monomers are also preferably linear, but may be branched where' the branching occurs three or more carbon atoms from the double bond, and, while a single olefinic monomer is preferable, mixtures of these C to C olefinic monomers may be employed.
  • the diolefins which are useful for copolymerization with ethylene and propylene include the bicyclic, alicyclic or aliphatic nonconjugated diolefins containing from about 6 to about 28 carbon atoms, preferably from about 6 to 12 carbon atoms.
  • suitable' monomers include 1,5-cyclooctadiene, 1,5-hexadiene, dicyclopentadiene, vinyl 2 norbornene, 1,5-cyclodecadiene, 2,4-dimethyl-2,7-octadiene, 3(2-methyl-1-propenyl) cyclopentene, 1,5-octadecadiene, and the like.
  • methylene-norborene that is:
  • a preferred embodiment of the instant invention is an ethylenepropylene-methylene norbornene terpolymer.
  • the polymer mixture of this invention is employed as an additive concentrate, i.e., a polymer blend in an inert solvent or neutral oil, in concentrations of about 0.1 to about wt. percent, preferably between about 0.5 and about 5.0 wt. percent based on the oleaginous composition being treated, so as to accomplish the desired objects. It is to be understood that such ranges are flexible and will be determined by the particular character of the oleaginous composition to which the additive concentrate is added. However, no more polymer mixture will be added than will be in solution in the oleaginous composition.
  • the additives are sold as concentrates wherein the polymeric blend is present in amounts of from about 5 to 50 wt. percent, preferably 8 to 40 wt.
  • Suitable solvents and/or oils are' well-lenown to the art and nonlimiting examples include mineral oils, hexane, heptane and the like.
  • Example I The following example is presented in order to illustrate a typical method of preparing the polyisobutylene component employed in the blends of this invention.
  • the polymeric blend of the present invention can be employed alone in oleaginous compositions or, if desired, can be employed in combination with other viscosity index improvers in order to affect that characteristic of the base oleaginous composition. If desired, said blend may be employed in combination with other additives, for example, pour point depressants, detergent type additives corrosion inhibitors, anti-oxidants, sludge inhibitors, metal deactivators, etc.
  • oleaginous composition comprised of a lubricating oil
  • present invention also contemplates that the additives defined herein may, if desired be employed with various other oleaginous compositions such as, for example, gasoline, middle distillate fuels, transformer oils, greases, etc.
  • the above-described polymers of isobutylene and ethylene-alpha-olefin copolymers represent mutually soluble polymeric components and that mixtures of these two polymers in oil have highly unusual viscosity properties. It must be noted, however, that, in addition to using the polymers in the manner hereinbefore described, to achieve the desired properties, said polymers must be employed in certain relative weight ratios. Accordingly, the additive products which attain the objectives described above are derived exclusively from the foregoing polymers and used in such Weight proportions so that the solvated individual polymeric components are miscible with each other.
  • compositions of said mixture lie approximately within the area similar to the ternary phase diagram of FIG. 1 which is incorporated herein by reference.
  • FIG. 1 represents an embodiment of the present invention wherein various blends of polyisobutyleneethylene-propylene, in Solvent Neutral oil are represented.
  • the temperature of the blend concentrate is a factor of miscibility, however, it is well within the bounds of facile experimentation to complete ternary phase diagrams for other temperatures, as Well as for different polymeric components, e.g., components of different monomeric origin, molecular weight, etc.
  • the curves of the figure represent compositional threshold values at which phase separation just begins to occur.
  • a blend of about 10.5 weight percent ethylene/propylene copolymer with 5.5 wt. percent polyisobutylene in 84 wt. percent Solvent 150 Neutral oil would be miscible at temperatures of about 20 C. and above.
  • a 10-10 wt. percent blend of ethylene/propylene copolymer with polyisobutylene in 80 wt. percent solvent would not be miscible at 25 C. and lower and would separate into phases.
  • FIG. 1 is in keeping with the spirit of phase separation occurrence and that other factors, e.g., pressure, polymer purity, other blend components will affect the ternary phase behaviors but, as mentioned, the actual phase behaviors are easily ascertainable for each specific composition mixture.
  • the blends of the instant invention will range from about 3.0 to about 20.0 wt. percent of polyisobutylene and from about 2.0 to about 25.0 wt. percent of ethylene-alpha-olefin polymer, the remainder of the blend comprising neutral solvent for the components.
  • the resulting treated composition will usually contain from about 0.3 to about 2.0 wt. percent of polyisobutylene and about 0.2 to about 2.5 wt. percent of ethylenealpha-olefin polymer.
  • the relative amounts of polymeric constituents, without solvent, etc. will generally be from about 10 to about 90 wt.
  • a sleeve is fixed within said cavity with a spindle adapted to rotate within said sleeve.
  • the spindle comprises, in combination, a shaft, an insulator and a drum.
  • the drum is provided with a pair of substantially symmetrical flats which create a continuously varying shear weight which simulates, to a degree heretofore unattainable, engine viscosity.
  • the spindle is driven by means of a gear train responsive to a motor which gear train and motor also drive a tachometer for measuring rate of evolution of said spindle.
  • the method of simulating the engine viscosity of a test oil comprises (a) cranking, at a substantially constant voltage, first oil sample of known viscosity (b) recording the thus-known viscosity and the corresponding cranking speed (c) repeating steps (a) and (b) using a second oil sample of known viscosity, thereby generating a positive viscosity versus speed (d) repeating step (a) using an oil of unknown viscosity (e) noting the cranking speed resulting from step (d) and reading the engine viscosity of said oil of unknown viscosity from said plot.
  • Example 3 In this example the efiicacy of the polyisobutylene-
  • the foregoing data illustrate that a mixture of polyisobutylene and ethylene-propylene copolymer prepared using hydrogen halide exhibits a synergistic improvement when compared with either polyisobutylene or the ethylene-propylene copolymer per se or the numerical average thereof.
  • Example 4 This example serves to illustrate the fact that conventional polymeric V.I. improvers, other than those of the present invention, are not compatible for blending.
  • Table IV illustrates systems in which two conventional V.I. improvers were employed and the amounts utilized thereof. In each instance it is noteworthy that the components used were not compatible.
  • Example An ethylene-propylene-methylene-norbornene copolymer is prepared in accordance with conventional procedures.
  • the resulting terpolymer is blended with an isobutylene polymer prepared in accordance with Example 1.
  • the resultant blend evidences utility as a viscosity improver for lubricating oils.
  • Example 6 Ethylene and propylene were continuously polymerized in the'presence of n-heptane solvent, VOCl -Al Et Cl and hydrogen.
  • the polymerization reaction was carried out in a two-liter glass reactor equipped with a monomer inlet tube, catalyst inlet, co-catalyst inlet, solvent inlet, reflux condenser, stirrer, product recovery outlet and a temperature control jacket. Provision was made to continuously control the rate of addition of monomer, hydrogen, solvent, catalyst and co-catalyst.
  • the reaction was carried out continuously under conditions of constant volume and pressure (i.e., 1 atm.) by controlling the rate of fed introduction and product removal.
  • the ethylene and propylene monomers were purified by contact with hot (e.g., 150 C.) copper oxide and molecular sieves. Purification of the solvent, i.e., n-heptane, was effected by passage through a bed of alumina and silica gel. Similarly, the hydrogen gas was dried by passage through a silica gel bed. The entire system was maintained oxygen and moisture-free by blanketing with bonedry nitrogen.
  • VOCl in n-heptane corresponding to a 0.03 molar solution A solution of vanadium oxychloride (VOCl in n-heptane corresponding to a 0.03 molar solution was introduced through the catalyst inlet while a solution of ethyl aluminum sesquichloride (Al Et Cl in n-heptane corresponding to a 0.12 molar solution was introduced through the co-catalyst inlet.
  • Al Et Cl in n-heptane corresponding to a 0.12 molar solution A solution of vanadium oxychloride (VOCl in n-heptane corresponding to a 0.03 molar solution was introduced through the catalyst inlet while a solution of ethyl aluminum sesquichloride (Al Et Cl in n-heptane corresponding to a 0.12 molar solution was introduced through the co-catalyst inlet.
  • the reactor operating conditions were as shown in Table V.
  • Viscosity Index as determined by ASTM D-567 in Reference 011 1150 which is a solvent extracted, neutral, paraflimctype oil of about 46.53 SUS at 210 F. and 189.9 SUS at 100 F
  • Thickening etficiency is the ratio of wt. percent polyisob'utylene (20,000 Staudinger mol. wt.) required to thicken Reference 011 150 to a viscosity of 12:5 cs. at 210 F./ ⁇ vt. percent ethylenepropylene copolymer required to thicken Reterence Oil 150 to the same viscosity.
  • the ethylenepropylene copolymer prepared in this example was blended with various amounts of the polyisobutylene of Example 12' 3 in Solvent 150 Neutral Oil. A'ternary phase diagram essentially similar to FIG. 1 was obtained.
  • a compatible composition which comprises a major proportion of a hydrocarbon solvent and from about 3.0 to about 20.0 wt. percent of polyisobutylene having a molecular weight within the range between about 20,000 and 200,000 and from about 2.0 to about 25.0 wt. percent of a second polymer comprised of 40 to 90 mole percent ethylene and 10 to 60 mole percent C -C alphaolefin; said second polymer being further characterized as having a viscosity average molecular weight within the range between about 10,000 and 250,000 and a crystallinity ofless than 25% 2.
  • said hydrocarbon solvent is a mineral oil.
  • composition of claim 2 wherein said alphaolefin is propylene.
  • composition of claim 3 wherein said second polymer contains 0-10 mole percent of a third monomer selected from the group consisting of C C alpha-olefins, C -C nonconjugated diolefins and combinations thereof.
  • composition of claim 4 wherein said third monomer is methylene-norbornene.
  • composition of claim 3 wherein said second polymer comprises 50 to 88 mole percent ethylene and 12 to 50 mole percent propylene.
  • composition of claim 6 wherein said second polymer has a viscosity average molecular weight Within the range between about 50,000 and 100,000.
  • composition of claim 7 wherein said second polymer comprises to 88 mole percent ethylene and 12 to 20 mole percent propylene.
  • said alphaolefin is propylene.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US781708A 1968-12-03 1968-12-03 Oil concentrate containing a compatible mixture of polyisobutylene and ethylene-alpha olefin copolymer Expired - Lifetime US3513096A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2126952A1 (de) * 1970-06-02 1971-12-16 Esso Research And Engineering Co., Linden, N.J. (V.St.A.) Schmierölmischung
US3668111A (en) * 1970-07-16 1972-06-06 Union Oil Co Fouling rate reduction in heated hydrocarbon streams with degraded polyisobutylene
US4290925A (en) * 1979-02-16 1981-09-22 Rohm Gmbh Lubricating oil additives
EP0262977A2 (de) * 1986-10-03 1988-04-06 World Oil Kabushiki Kaisha Flüssiges Schmiermittelgemisch
US4968444A (en) * 1983-10-28 1990-11-06 Rohm Gmbh Lubricating oil additives
US5116795A (en) * 1985-08-02 1992-05-26 Quantum Chemical Corporation Alpha olefin oligomerization catalyst
US5122581A (en) * 1985-08-02 1992-06-16 Quantum Chemical Corporation Polymerization method

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1088446A (en) * 1976-05-25 1980-10-28 Polysar Limited Mineral oil compositions
GB1592553A (en) * 1976-12-20 1981-07-08 Orobis Ltd Viscosity index improver additive composition
NO145408C (no) * 1977-05-19 1982-03-17 Orobis Ltd Smoeremiddeltilsetning.
US4507515A (en) * 1983-12-21 1985-03-26 Exxon Research & Engineering Co. Lubricating oil compositions containing ethylene-alpha-olefin polymers of controlled sequence distribution and molecular heterogeneity
DE102009015911A1 (de) 2009-04-03 2010-10-07 Carl Zeiss Meditec Ag Vorrichtung und Verfahren zur Entfernung eines Lentikels aus der Hornhaut

Citations (2)

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Publication number Priority date Publication date Assignee Title
US2779753A (en) * 1952-12-29 1957-01-29 Exxon Research Engineering Co Process for preparing high molecular polymers from isobutylene
US2791576A (en) * 1956-01-12 1957-05-07 Standard Oil Co Process of polymerizing olefins with group 6a oxide

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2462360A (en) * 1949-02-22 Method of preparing lubricating
BE560366A (de) * 1956-08-28
US2980744A (en) * 1959-12-18 1961-04-18 Sun Oil Co Preparation of viscous polymers
NL230196A (de) * 1960-06-24
CH488003A (de) * 1967-03-08 1970-03-31 Geigy Ag J R Zusatz zur Verbesserung der Eigenschaften von Schmierölen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2779753A (en) * 1952-12-29 1957-01-29 Exxon Research Engineering Co Process for preparing high molecular polymers from isobutylene
US2791576A (en) * 1956-01-12 1957-05-07 Standard Oil Co Process of polymerizing olefins with group 6a oxide

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2126952A1 (de) * 1970-06-02 1971-12-16 Esso Research And Engineering Co., Linden, N.J. (V.St.A.) Schmierölmischung
US3668111A (en) * 1970-07-16 1972-06-06 Union Oil Co Fouling rate reduction in heated hydrocarbon streams with degraded polyisobutylene
US4290925A (en) * 1979-02-16 1981-09-22 Rohm Gmbh Lubricating oil additives
US4968444A (en) * 1983-10-28 1990-11-06 Rohm Gmbh Lubricating oil additives
US5116795A (en) * 1985-08-02 1992-05-26 Quantum Chemical Corporation Alpha olefin oligomerization catalyst
US5122581A (en) * 1985-08-02 1992-06-16 Quantum Chemical Corporation Polymerization method
EP0262977A2 (de) * 1986-10-03 1988-04-06 World Oil Kabushiki Kaisha Flüssiges Schmiermittelgemisch
EP0262977A3 (de) * 1986-10-03 1988-10-12 World Oil Kabushiki Kaisha Flüssiges Schmiermittelgemisch

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GB1230714A (de) 1971-05-05
AU1128270A (en) 1971-08-12
DE1952574A1 (de) 1971-04-29
NL6915687A (de) 1971-04-20
FR2063976A1 (de) 1971-07-16
AU447999B2 (en) 1974-04-19
DE1952574C2 (de) 1983-08-04
FR2063976B1 (de) 1974-05-03

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