Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/14—Monomers containing five or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
  • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
• • 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
• • 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
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
• • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/08—Resistance to extreme temperature
• • 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
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
• • 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
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
  • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
• • 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
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
  • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
• • 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
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
  • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
• • 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
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
• • 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
  • C10N2040/12—Gas-turbines
• • 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
  • C10N2040/12—Gas-turbines
  • C10N2040/13—Aircraft turbines
• • 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

Definitions

• This invention relates to the preparation of synthetic lubricating oils. having unusually high viscosity indexes and low pour points by the polymerization of certain straight chain alpha olefins by means of a particular type of catalyst system.
• Lubricating oils there are. various special applications for lubricating oils in which it is highly desirable that the oil employed have an especially high viscosity index, for example, a V.I. above 130.
• the oil also should have a low pour point, e.g., below -30 F., a high oxidation stability and lubricating properties that provide good wear characteristics.
• One such application is in the lubrication of jet aircraft wherein conditions of both'low and'high temperature may be encountered.
• Other special applications in which lubricants having such characteristics are desirable are automatic transmission lubrication, high temperature hydraulic applications, brake fluids, instrument oils, gear lubricants, automatic power steering unit lubricants, electric motor bearing lubricants, greases and aerospace applications.
• Lubricating oils that can be derived from petroleum generally do not have the combination of properties desired for these special applications.
• the present invention constitutes an improvement over the process of aforesaid application Serial No. 251,724 for preparing high quality synthetic lubricating oils.
• the process of the present invention is particularly adapted for preparing lubricating oils of high viscosity index and low pour point which have kinematic viscosities at 210 F. below cs;
• the total lubricating oil product obtained from the polymerization that boils above 650 F. has a viscosity below 15 cs. at 210 F., it is more suitable for producing specialty oils of such types as mentioned above. than when such total oil product is above the 15 cs. level.
• the viscosity of the total lubricating oil product above 650 F. be in the range of 3-10 cs. at 210 F.
• the present process is capable of producing such oils while operating at high catalyst efhciencies.
• high quality synthetic lubricating oils are prepared by polymerizing C -C olefins in the subtantial absence of any added solvent as reaction medium.
• the starting reaction mixture is composed of the olefin monomer and the catalyst with little if any solvent.
• the catalyst is prepared from the same three types of components as the catalyst described in the afore-
• the catalyst is formed from the 3,259,067 Patented July 5, 1966 said application but in addition contains a fourth component, namely, a diene capable of chelating with a metal component of the catalyst.
• the diene is an essential component of the catalyst system, as otherwise in the substantial absence of any added solvent and of any diene in the catalyst system the oily polymer obtained has a viscosity considerably higher than is desirable for the intended uses.
• the process of the present invention is carried out by adding to one or more straight chain alpha olefins of the C -C range the following components which combine to form the catalyst system: (1) an aluminum alkyl sesquichloride, e.g., aluminum ethyl sesquichloride; (2) TiCl (3) an oxirane or a methyl alkyl ether; and (4) a diene capable of chelating with a metal component of the catalyst.
• the order of addition of these catalyst compo nents to the monomer preferably is as named above.
• the reaction mixture contains substantially no added solvent as reaction medium.
• the catalyst components may be convenient to add one or more of the catalyst components as a solution in a solvent such as hexane; but the amount of solvent thus included in the reaction mixture will not be substantial, being for example only 2-10% by volume of the olefin monomer charged.
• the reaction is carried out by stirring the reaction mixture at a temperature in the range of 0-50 C., more preferably 15-35. C., until no further polymerization occurs or until an undesirably slow rate of polymerizationis reached.
• the catalyst is then fully deactivated and removed from the hydrocarbons and the latter can be distilled to recover any unreacted monomer and to separate the polymeric product into fractions as desired. In view of the fact that substantially no solvent is used in the reaction system, recovery of solvent for reuse is avoided or minimized.
• the components of the catalyst system be present in certain proportions.
• the aluminum alkyl sesquichloride and the titanium tetrachloride should be used in amounts such that the atomic ratio of A1 to Ti is in the range of 0.8-2.5 and more preferably 1.0-1.6.
• the amount of oxirane or methyl alkyl ether employed in the catalyst system be such that the atomic ratio of O to Al is withina certain narrow range. This range is 0.421 to 0.821, and a preferred range is 0.50-0.75. Reduction of the O to Al ratio below 0.4
• the amount of chelating diene used should be in the range of 0.1-3.0 moles per atom of titanium.
• the effect of the incorporation of diene in the catalyst system is to reduce the viscosity of the oil product. Enough of the diene is employed to reduce the viscosity of the total oil product that boils above 650 F. to below 15 cs. at 210 F. and more preferably below 10 cs. at 210 F;
• the amount of diene is increased above 3 moles per atom of titanium, the catalyst efiiciency drops and the degree of conversion of the monomer is reduced to an undesirably low value.
• the amount of diene be in the range of 0.1-1.0 mole .per atom of titanium.
• the proportion of diene incorporated in the catalyst usually is less than 0.5% by weight and preferably is of the order of 0.02-0.2%.
• the diene becomes combined with the other catalyst components through chelation and does not partake in the reaction as a monomer.
• oxygen-containing organic compound used in preparing the catalyst is an oxirane
• R is either hydrogen or an alkyl group of 1-20 carbon atoms.
• the oxiranes preferred for use in practicing the invention are ethylene oxide and propylene oxide.
• other oxiranes conforming to the foregoing formula can be used, such as the 1,2-epoxy derivatives of butane, n-pentane, isopentane, n-hexane, isohexanes, octanes, decanes, dodecanes, .cetane, octadecanes, etc.
• the alkyl group can be any of those specified above for the oxirane compounds. Examples are dimethyl ether, methyl ethyl ether, methyl propyl ether, methyl isbutyl ether, methyl hexyl ethers, methyl decyl ethers, etc.
• the aluminum-containing component of the catalyst system must be a sequichloride, as the desired results cannot be obtained with either an aluminum dialkyl monochloride or an aluminum alkyl dichloride.
• the alkyl group in the sesquichloride can contain from one to ten carbon atoms and preferably is a straight chain alkyl group.
• the sesquichloride can contain branched chain alkyl groups such as isobutyl or isopentyl, although this is not preferred. Examples of suitable alkyl groups in the sesquichloride are methyl, ethyl, propyl, n-butyl, n-hexyl, n-octyl and n-decyl.
• the diene used in preparing the catalyst system is one which is capable of chelating with a metal component of the catalyst system. Chelation is believed to occur with the titanium atoms rather than the aluminum atoms.
• the capacity for chelation depends upon the diene having a structure such that the spacing between the double bonds in the molecule is within certain limits so that the metal atom (titanium) can become coordinated at each double bond position.
• dienes that Will provide such structure and hence are capable of chelating into the catalyst system. These are listed in Table I as Types A, B and C and are defined therein with several subtypes for each. Type A constitutes conjugated dienes, any of which are capable of chelating regardless of Whether the double bonds occur in rings or chains.
• Type B consists of dienes in which the bonds have 1,4-spacing and at least one double bond occurs in a ring.
• 1,4- spacing means that one carbon atom occurs between a carbon atom adjacent one of the double bonds and a carbon atom adjacent the other regardless of where the latter two carbon atoms are situated in the molecule.
• Type C consists of dienes wherein the double bonds have 1,5-spacing, at least one of the double bonds is in a ring and the two double bonds have a cis relationship to each other.
• LS-spacing means that two carbon atoms occur between a carbon atom adjacent one of the double bonds and a carbon atom adjacent the other double bond regardless of where the latter two carbon atoms are situated in the molecule.
• Type C.-1,5-dienes with at least one double bond in a ring and the double bonds having cz's-relationship to each other:
• dienes of Types A, B and C and the various sub-types thereunder are given in Table II along with the structural formulas for the dienes named.
• Table II there are many other dienes which are capable of chelating with a metal component of the catalyst provided that they conform to the classification of operative dienes set forth in Table I.
• halogen-substituted dienes of the structures specified in Table I are equally capable of chelating with the catalyst and can be considered as equivalent to the diene hydrocarbons for purposes of the present invention.
• Type Specific Dlene Structure 5 A4 2,3,4,5,9,10,1l,13-octahydro- C2 l,4,7,8,9,l0-hexahydrobenzonaphthene. naphthalene. l
• the present catalyst system which includes a chelating diene as a B-3 1-methyl-2,5-cyclohexadiene fourth component, when used in the absence of a solvent will result in total oil products having viscosities in the desired range of 3l5 cs. at 210 F.
• dienes normally would be considered as poisons for Ziegler type catalysts, their incorporation in the catalyst of the presl4'cyclooctadmne O ent process in the small proportions herein specified permits the production of oils having the desired viscosity 3 5 6 7 g h ah d without substantial loss in catalyst efliciency.
• the omisnaphthalene is included in the catalyst of the presl4'cyclooctadmne O ent process in the small proportions herein specified permits the production of oils having the desired viscosity 3 5 6 7 g h ah d without substantial loss in catalyst efliciency.
• the atomic ratio of AlzTi was 1.25 and C the OzAl ratio was 0.5 in all runs.
• the weight ratio of Limonene 06 starting monomer to TiCl was 300:1.
• Each reaction was carried out at 30 C. for a total time of 20 hours
• the catalyst was then deactivated by adding to the reaction C2 v r y mixture 4 g. of Na CO adding 5 ml. of water with thorough mixing and then filtering.
• the filtrate was topped to remove unpolymerized octene, and the ol mer splmu'mdeca'lg'dlene product was vacuum distilled to remove the din ier a'nd obtain trimer and higher polymers as residuum.
• This residuum constitutes the total oil product boiling above 650 F. at atmospheric pressure. Results for six runs, including one run in which no diene was used, are shown in Table III.
• the column entitled Percent Conversion represents the total weight percent of octene-l which was converted to higher molecular weight compounds including the dimers.
• the column entitled Percent Dimer represents the weight percent of dimer in the total polymer solvent and at a temperature in the range of 0-50 C. with a catalyst system formed from (1) an aluminum alkyl sesquichloride, (2) titanium tetrachloride, (3) an oxygencontaining organic compound selected from the group consisting of oxiranes having the formula product consisting of dimer plus higher polymers.
• R1111 1 Shows that the Catalyst Without a chelating wherein R is selected from the group consisting of hydiene will effect a good conversion of the starting monodrogen and alkyl groups having 1-20 carbon atoms and mer but that the viscosity of the total oil product above ethyl alkyl ethers, in whi h the alkyl groups has 1-20 650' F. is considerably higher than is desirable for making arbon ato nd (4) a dien capable of chelating with the types of specialty oil products contemplated within a metal com onent of the catalyst system, the amounts the scope of the invention.
• the results are sub- 7 (4) a diene capable of chelating with a metal component of the catalyst system, the amounts of the aluminum alkyl sesquichloride and titanium tetrachloride being such that the atomic ratio of A1 to Ti is in the range of 1.0-1.6, the amount of oxirane being such that the atomic ratio of O to A1 is in the range of 0.5-0.7 and the amount of said diene being in the range of 0.1-3.0 moles per atom of titanium, and thereafter separating from the reaction mixture olefin polymer of lubricating oil boiling range.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Lubricants (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (6)

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Citations (2)

• 1963
  • 1963-10-21 US US317775A patent/US3259667A/en not_active Expired - Lifetime
• 1964
  • 1964-06-26 GB GB26597/64A patent/GB1077302A/en not_active Expired
  • 1964-07-22 NL NL6408358A patent/NL6408358A/xx unknown
  • 1964-08-14 BE BE651862A patent/BE651862A/xx unknown
  • 1964-08-18 DE DE1520885A patent/DE1520885C3/de not_active Expired

Patent Citations (2)

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