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
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
  • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
  • C10M145/14—Acrylate; Methacrylate
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
  • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/084—Acrylate; Methacrylate
• • 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

• ABSTRACT Pour points of lubricating oils are depressed by adding thereto small amounts of oil-soluble copolymer of polyalkyl methacrylates having (a) a molar percentage of alkyl methacrylates with branched alkyl chains from 5 to 25 percent, (b) at least six alkyl chains with a different number of carbon atoms, and (c) a number average molecular weight of 2,000 to 2,000,000, wherein the alkyl groups in said alkyl methacrylates contain 9 to 18 carbon atoms with an average of from 12.4 to l3.7 carbon atoms.
• lubricating oil as used in this specification also includes lubricating oil compositions which comprise, besides a lubricating oil proper, additives which render improved properties to that lubricating oil) at different temperatures is considered a measure of the suitability for application of that lubricating oil.
• lubricating oils were, until recently with relation to their viscosity properties, valued and classified according to their viscosity at 210F (99C) and 100F (38C).
• the viscosity at F (18C) is determined with a standardized method (ASTM method D 2602) and in general the requirement set is that the viscosity determined in that way be for, e.g., a W oil at most 24 Stokes.
• Base oils for the preparation of lubricating oils can be prepared from vacuum distillation fractions or residues of the vacuum distillation of crude mineral oils.
• the vacuum distillation fractions and the deasphalted residue (or mixtures of one or more of the vacuum distillation fractions and/or the residue) are treated with a solvent, e.g., sulphur dioxide, furfural and phenol, for the removal of aromatic compounds.
• a solvent e.g., sulphur dioxide, furfural and phenol
• Base oils for the preparation of lubricating oils can also be prepared by hydrocracking, which is understood to be a treatment of a mineral oil-based material with hydrogen at elevated temperature and pressure in the presence of a bifunctional catalyst comprising a metal-containing hydrogenating component on a carrier possessing cracking activity, with the object of, inter alia, increasing the viscosity index (as determined according to ASTM method D-2270) of the mineraloil-based material; deasphalted residual fractions of the vacuum distillation of a crude mineral oil are very suitable to be hydrocracked.
• hydrocracking is understood to be a treatment of a mineral oil-based material with hydrogen at elevated temperature and pressure in the presence of a bifunctional catalyst comprising a metal-containing hydrogenating component on a carrier possessing cracking activity, with the object of, inter alia, increasing the viscosity index (as determined according to ASTM method D-2270) of the mineraloil-based material; deasphalted residual fractions of the vacuum distillation of a crude mineral oil are very
• the base oils for the preparation of lubricating oils may contain considerable quantities of wax. This wax separates if the base oil for the preparation of a lubricating oil is cooled below a certain temperature. As cooling proceeds, more wax is separated until the mixture of wax and oil almost or entirely ceases to flow. The lowest temperature observed in a standard laboratory test at which the waxy mixture still flows is called the pour point. The pour point of a lubricating oil is of great practical importance. To prevent difficulties in the use of the lubricating oils their pour points should lie below the minimum temperature at which the oil is stored, transported and used.
• Dewaxing may be carried out with the aid of urea; in most cases dewaxing comprises diluting the waxy base oil for the preparation of a lubricating oil with a suitable solvent, cooling the mixture and filtering off the wax precipitated.
• the mixture is cooled to such a temperature that the dewaxed lubricating oil obtained after removal of the solvent has a pour point of about 16F (9C).
• pour-point depressants such as viscosity-index improvers, detergent additives, antioxidants, extreme-pressure additives
• a class of novel compounds of particular structure and composition has now been found which effect a great reduction in pour point not only of lubricating oils the base oil of which has been dewaxed to a pour point of that lubricating oil of about 16F, but also of lubricating oils in the preparation of which the dewaxing of the waxy base oil has been carried out in such a way that the pour point of the lubricating oil obtained is about 0F.
• These compounds are oil-soluble po1yalkyl methacrylates wherein the alkyl group has from 9-18 carbon atoms and meets the following requirements (a) the average number of carbon atoms of the alkyl chains in the methacrylates is from 12.4 to 13.7, (b) the molar percentage of the alkyl methacrylates with branched alkyl chains is from 5 to 25 percent, and (c) there are present among the alkyl chains in the methacrylates at least six alkyl chains with a different number of carbon atoms.
• Alkyl chains are considered to be present in the oilsoluble polyalkyl methacrylates if the number of those alkyl chains is at least 1 percent of the total number of alkyl chains of 9-18 carbon atoms present in the polyalkyl methacrylates. Preference is given to polyalkyl methacrylates in which the average number of carbon atoms in the alkyl chains is from 12.8 to 13.5. Oilsoluble polyalkyl methacrylates in which some of the alkyl chains contain nine carbon atoms are very suitable; polyalkyl methacrylates wherein the number of alkyl chains of nine carbon atoms is from 2 to 10 percent of the total number of alkyl chains are in particular preferred.
• the polyalkyl methacrylates according to the invention must have at least six, and preferably at least eight, alkyl chains with a different number of carbon atoms present among the alkyl chains containing 9-18 carbon atoms.
• polyalkyl methacrylates may have some alkyl chains which contain fewer than nine (e.g., l, 2 or 4) carbon atoms and/or more than 18 (e.g., 20,22) carbon atoms, it is preferred that all alkyl chains present in the polyalkyl methacrylates of the invention contain from 9-18 carbon atoms.
• polyalkyl methacrylates of the invention containing alkyl chains of 9-18 carbon atoms, at least 5 to 25 percent of which alkyl chains are branched alkyl chains.
• branched alkyl chains denotes alkyl chains which contain at least one tertiary or quaternary carbon atom.
• Polyalkyl methacrylates in which 5-15 percent of the alkyl chains are branched are particularly preferred.
• the novel polyalkyl methacrylates are obtained by polymerization, e.g., radical polymerization, of a mixture of alkyl methacrylates at least part of which consists of alkyl methacrylates with 9-18 carbon atoms in the alkyl group.
• polymerization e.g., radical polymerization
• a simple process yields polymers meeting the three aforementioned criteria.
• Very suitable polyalkyl methacrylates are prepared by polymerization of a mixture of alkyl methacrylates part of which are derived from unbranched natural and/or synthetic alcohols with 16 and/or 18 carbon atoms and the remaining part from a mixture of branched and unbranched synthetic alcohols with 9-15 carbon atoms.
• the latter alcohol mixture can be obtained, for example, by the 0x0 process or by reacting a mixture of olefins with 8-14 carbon atoms (or several mixtures of olefins in this range, e.g., a mixture of olefins with 8-10 carbon atoms and a mixture of olefins with 1 1-14 carbon atoms), with carbon monoxide and hydrogen in the presence of a complex catalyst consisting of cobalt, carbon monoxide and a phosphorus compound.
• a complex catalyst consisting of cobalt, carbon monoxide and a phosphorus compound.
• the molecular weight of the polymers of the invention can vary within wide limits. Polymers used as lubricating oil additives should have a number average molecular weight of between 2,000 and 2,000,000, in particular between 5,000 and 500,000. The molecular weight was determined by an ebullioscopic method.
• polyalkyl methacrylates When used as additives for lubricating oils they can be added directly to the oil or in the form of a concentrate obtained by mixing the polymers with a small quantity of oil.
• the concentration in which the polyalkyl methacrylates can be used may also vary within wide limits, dependent on the structure and the molecular weight of the polymer to be used, the nature and the quantity of the waxes present in the lubricating oil and the pourpoint depressing effect to be achieved. In some cases a quantity of0.01 percent w calculated on the lubricating oil composition is sufficient to reach the desired pour point. In most cases a quantity of 2.0 percent w is ample. One preferably incorporates 0.05 to 0.5 percent w of the polymers in the lubricating oil. If the application of the polymers in question is directed to V1 improvement as well as to pour-point depression it may be desirable to incorporate quantities of the polymers greater than the afore-mentioned 2.0 percent w.
• the lubricating oil compositions so obtained may also comprise other additives such as antioxidants, additives with a detergent action, viscosityincreasing compounds, anti-corrosives, anti-foaming agents, agents to improve the lubricating effect and other compounds which are usually added to lubricating oils.
• additives such as antioxidants, additives with a detergent action, viscosityincreasing compounds, anti-corrosives, anti-foaming agents, agents to improve the lubricating effect and other compounds which are usually added to lubricating oils.
• Base Oils Oil A A lubricating oil with a viscosity of 4.87 cS at 99C (210F) and 29.6 cS at 38C (100F) obtained from a Middle East crude by distillation and extraction of aromatic compounds, followed by solvent dewaxing to a pour point of 18C (0F).
• Oil B A lubricating oil with a viscosity of 4.36 cS at 99C (210F) and 23.7 cS at 38C (100F) obtained from a Middle East crude as described for oil A, dewaxed to a pour point of 24C (1 1F).
• Oil C A lubricating oil with a viscosity of 7.03 cS at 99C (210F) and 44.30 cS at 38C (100F) prepared from a deasphalted distillation residue of a Middle East crude by hydrocracking. The oil was dewaxed to a pour point of 18C (0F).
• Oil D A lubricating oil with a viscosity of 9.41 05 at 99C (210F) and 26.7 cS'at 38C (100F) pre pared from a deasphalted distillation residue of a Middle East crude by hydrocracking. The oil was dewaxed to a pour point of 18C (0F).
• Oil E A lubricating oil with a viscosity of 1 1.87 cS at 99C (210F) and 113.5 cS at 38C (100F) obtained from a Middle East crude by blending of solvent-extracted distillate fractions and a solventextracted deasphalted residue. The oil was dewaxed to a pour point of 9C (16F).
• Oil F A lubricating oil with a viscosity of 10.18 cS at 99C (210F) and 78.92 cS at 38C (100F) obtained by hydrocracking of a deasphalted distillation residue of a Middle East crude. The oil was de waxed to a pour point of 21C (-6F).
• Oil G A lubricating oil with a viscosity of 5.37 08 at 99C (210F) and 33.9 cS at 38C (100F) obtained from a Middle East crude by distillation and extraction of aromatic compounds, followed by solvent dewaxing to a pour point of 9C (16F).
• the alcohols l and II had been obtained by reaction of a mixture of olefins with 8-10 and 11-14 carbon atoms, respectively, with carbon monoxide and hydrogen in the presence of a complex catalyst consisting of cobalt, carbon monoxide and a phosphorus compound.
• composition of alcohols l and II determined with the aid of gas chromatographyand their apparent molecular weight according to their hydroxyl number are given in Tables I and II.
• n-undecyl alcohol 26.0 iso-undecyl alcohol 5.3 alcohols with 11 carbon atoms 0.3 r I I I' l wmge cm a Wash 16 Polymers l and 2 are more actlve than the comparative polymers 3, 4 and 5 in oils which have a viscosity Table II of less than about 10 c5 at 99C (210F) which have been dewaxed to a pour point of about -18C (0F), Composition i.e., oils A-D.
• a lubricating oil composition consisting essentially of a wax-containing hydrocarbon lubricating oil having a viscosity of less than about l0 08 at 210F and dewaxed to a pour point of about 0F or less and from about 0.01 to 2 percent by weight of oil-soluble copoly- Monomer concentration: 42.5%w, leadingto the formation mer of polyalkyl methacrylates having (a) a molar pergs g g z' g z r g f g gi centage of alkyl methacrylates with branched alkyl b jo gmy g chains from 5 to 25 percent, (b) at least eight alkyl Q Y t n hains with a different number of carbon atoms in figlj gfi ggaz Peron e which the number of alkyl chains of 9 carbon atom
• composition of claim 1 in which the percentage of oil-soluble copolymer of polyalkyl methacylates Polymers 1 and 2 come within the scope of the inveni bo t 0,05 to 0.5 percent by weight. tion. Polymer 3 is not according to the invention since 3, Th composition of claim 1 in which the molar the average number of carbon atoms in the side chains is 14, and polymer 4 is not according to the invention percentage of alkyl methacrylates with branched alkyl chains is 5 to 15 percent.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Lubricants (AREA)

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Cited By (25)

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• 1971
  • 1971-05-05 GB GB1321171*[A patent/GB1347713A/en not_active Expired
• 1972
  • 1972-04-25 BE BE782598A patent/BE782598A/xx not_active IP Right Cessation
  • 1972-04-27 US US248261A patent/US3869396A/en not_active Expired - Lifetime
  • 1972-04-28 IT IT23697/72A patent/IT955181B/it active
  • 1972-05-02 JP JP47043399A patent/JPS5911638B1/ja active Pending
  • 1972-05-03 SE SE7205849A patent/SE383895B/sv unknown
  • 1972-05-03 AU AU41853/72A patent/AU464362B2/en not_active Expired
  • 1972-05-03 ZA ZA722994A patent/ZA722994B/xx unknown
  • 1972-05-03 CA CA141,226A patent/CA970100A/en not_active Expired
  • 1972-05-03 AT AT383372A patent/AT323994B/de not_active IP Right Cessation
  • 1972-05-03 FR FR7215689A patent/FR2135252B1/fr not_active Expired
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  • 1972-05-03 DE DE19722221662 patent/DE2221662A1/de active Granted

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