EP0329756A1 - Additifs et compositions a base de methacrylate abaissant le point d'ecoulement - Google Patents

Additifs et compositions a base de methacrylate abaissant le point d'ecoulement

Info

Publication number
EP0329756A1
EP0329756A1 EP88907922A EP88907922A EP0329756A1 EP 0329756 A1 EP0329756 A1 EP 0329756A1 EP 88907922 A EP88907922 A EP 88907922A EP 88907922 A EP88907922 A EP 88907922A EP 0329756 A1 EP0329756 A1 EP 0329756A1
Authority
EP
European Patent Office
Prior art keywords
polymer
pour point
lubricating oil
point depressant
oil composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88907922A
Other languages
German (de)
English (en)
Other versions
EP0329756A4 (fr
EP0329756B1 (fr
Inventor
Bruce E. Wilburn
William J. Heilman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pennzoil Quaker State Co
Original Assignee
Pennzoil Products Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=22202743&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0329756(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Pennzoil Products Co filed Critical Pennzoil Products Co
Priority to AT8888907922T priority Critical patent/ATE105581T1/de
Publication of EP0329756A1 publication Critical patent/EP0329756A1/fr
Publication of EP0329756A4 publication Critical patent/EP0329756A4/fr
Application granted granted Critical
Publication of EP0329756B1 publication Critical patent/EP0329756B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56—Amides; Imides
    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
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    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • C—CHEMISTRY; METALLURGY
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    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/02—Polyethene
    • C—CHEMISTRY; METALLURGY
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    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/04—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing propene
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
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    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
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    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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    • 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
    • C10M2205/022—Ethene
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    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
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    • C10M2227/065—Organic compounds derived from inorganic acids or metal salts derived from Ti or Zr
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12

Definitions

  • This invention relates to pour point depressants for use in lubricating oils and more particularly to a new and novel class of poly(methacrylate) polymeric pour point depressants which provide substantial advantages when used in lubricating oils.
  • Wax-bearing lubricating oils are known to set to a semi-plastic mass on cooling below the temperature of the crystallization point of the wax contained in the lubricating oil. This change is measured in terms of pour point which may be defined as the temperature at which the oil sample is no longer considered to flow when subjected to the standardized schedule of quiescent cooling prescribed by ASTM D97-47. This problem presents a substantial disadvantage in the use of lubricating oils by the petroleum industry.
  • the problem with lubricating oils which contain any amount of waxes is that the wax contained in the oil, which is a paraffinic oil, will crystallize when the oil is cooled, and networks of wax crystals will then form on further cooling which will prevent the oil from flowing.
  • the point at which the oil stops flowing is defined as the pour point temperature. Dewaxing of an oil improves the pour point, but this is an expensive procedure. Usually, the procedure is to dewax an oil to a certain temperature and then add pour point depressants to improve the low temperature properties. However, at the lower temperature, the same amount of wax will still separate. The pour point depressants do not make the wax more soluble in oil; they function rather by disrupting or preventing the formation of the waxy network. As little as 0.2 wt. % of a good pour point depressant can lower the pour point of the paraffinic oil or lubricating composition by 30-35oC.
  • the wax networks will also lead to an increase in oil viscosity.
  • the increase in viscosity is genarally temporary as a "normal" internal combustion engine can generate sufficient shear to disrupt the wax networks and allow the oil to flow.
  • the temporary disruption in the oil flow can lead to an increase in bearing wear.
  • Studies have indicated that the amount of wax needed to prevent flow or gel for an oil is quite small. Approximately 2% precipitated wax will gel middle distillates, and a similar amount is needed for lubricating oils. Many different types of pour point depressants have been used in the prior art.
  • Previously used pour point depressants are predominantly oligomers having molecular weights of 1,000 to 10,000, or polymers which have molecular weights greater than 10,000.
  • the early point depressants were either alkylated aromatic polymers or comb polymers. Comb polymers characteristically have long alkyl chains attached to the backbone of the polymer, with the alkyl groups being of different carbon chain lengths. The mechanism of action for pour point depressants has been the subject of much interest. Early indications were that alkylated aromatic compounds function as pour point depressants by coating the surface of the wax crystals and preventing further growth.
  • the pour point depressants are either absorbed into the face of the wax crystal if the pour point depressant is an alkyl aromatic or co-crystallize with the wax crystal if it is comb polymer. Thus, crystal growth is not prohibited, it is simply directed or channeled along different routes. Light microscopy suggests that wax crystals are typically thin plates or blades, and when a pour point depressant is added to the system, those crystals are smaller and more branched, and thus the pour point depressant may disrupt or redirect crystal growth from different directions into a single direction, and bulkier crystals will be formed. These crystals then can form networks only at much lower temperatures which results in a lower pour point.
  • Patent No. 3,598,736 discloses the addition of small amounts of oil soluble polymethacrylates to lubricating oils to reduce the pour point.
  • the polyalkylmethacrylates are described as copolymers wherein the alkyl side chain contains from 10 to 20 carbon atoms with an average of between 13.8 and 14.8 carbon atoms.
  • Patent No. 3,679,644 is a division of 3,598,736 and contains the same disclosure.
  • Patent No. 4,073,738 discloses the use of a pour point depressant which comprises an alkyl acrylate or alkyl methacrylate wherein the alkyl group side chain can have from 8 to 30 carbon atoms and preferably from
  • U. S. Patent No. 4,088,589 discloses a combination of pour point depressants of which one can be an oil soluble polymer of an alkyl acrylate or methacrylate which contains a side chain comprising 10 to 18 carbon atoms in the alkyl group.
  • U. S. Patent No. 2,655,479 of Munday et al is directed to polyester pour depressants and is particularly concerned with average side chain length of acrylate polymer pour depressants.
  • this patentee uses a combination of only two polymers to obtain this side chain length and the results are unsatisfactory.
  • U. S. Patent 3,598,737 discloses lubricant compositions which contain copolymers of acrylate esters which are said to improve various characteristics including pour point. This patent states that the average number of carbon atoms should be at least 12.5 to 14.3. These compounds do not appear to be acrylate esters wherein the side chain is this value, but rather this patent shows the use of hydr ⁇ xyalkyl esters in a poly(methacrylate).
  • U. S. Patent No. 3,897,353 discloses oil compositions comprising lubricating oil and a pour depressant which can be an alkylmethacrylate. These acrylates may be made from monomers wherein the alkyl portion of the ester or the side chain has from 12 to 18 carbon atoms and includes mixtures. However, the polymers of this patent are made from nitrogen- containing monomers.
  • the present invention provides a pour point depressant based on poly(methacrylate) polymeric compositions which represent a narrow class of such compositions and which have advantageous properties in improving the low temperature properties of lubricating compositions while maintaining a good viscosity index.
  • a further object of the invention is to provide a unique and advantageous poly(methacrylate) polymer useful as a pour point depressant in lubricating oils.
  • a still further object of the present invention is to provide a lubricating oil composition which contains a pour point depressant comprising a poly(methacrylate) polymeric material having an alkyl side chain of critical carbon chain length.
  • a pour point depressant for lubricating oils which comprises a poly(methacrylate) polymer having the repeating unit
  • R is an alkyl group having an average chain length in the polymer of 12.6 to 13.50, preferably 12.6 to 13.0
  • n is an integer indicating the number of repeating units, the value of n being sufficient to provide a molecular weight of 30,000 to 220,000 for the polymer, said polymer being a polymer formed from at least three but less than five methacrylate monomers with no individual monomer present in an amount less than 10-15 wt. %.
  • a lubricating oil which contains an effective amount of the novel poly(methacrylate) polymer, the effective amount being sufficient to provide an oil which meets the Federal Stable Pour for a 5W-30 lubricating oil.
  • Figure 1 is a graph showing the pour point effectiveness of a polymer of the invention
  • Figure 2 is a graph comparing a pour point polymer of the invention with commercial products; and Figure 3 is a graph similar to Figure 2 but with correction of a concentration of a commercial product .
  • Figure 4 is a graph showing the pour point effectiveness of a polymer of the invention in different base stocks .
  • pour point depressants of the present invention comprise a selective group of poly(methacrylate) polymers which have the following repeating units
  • R is an alkyl group having an average carbon chain length in the polymer of 12.6 to 13.50, preferably 12.6 to 13.30 and more preferably 12.6 to 13.0
  • n is an integer indicating the number of repeating units, the value of n being sufficient to provide a molecular weight of 10,000 to 300,000, preferably 30,000 to 220,000 for the polymer, the polymer having been prepared from at least three but less than five methacrylate monomers in the C 10 to C 15 range with no individual monomer present in an amount less than 10-15 wt. %.
  • a polymethacrylate for a polymethacrylate to be effective as a pour point depressant in a lubricating oil, it must have an average side carbon chain length of 12.6 to 13.30 carbon atoms, and preferably 12.6 to 13.0 carbon atoms.
  • a polymethacrylate pour point depressant of this type is used in conjunction with a compatible viscosity index improver, a lubricating oil of the 5W-30, 10W-30, 10W-40 and 15W-40 qualities can be produced to provide a formulation which will pass the required low temperature tests for such oils.
  • a successful formulation is defined as one with a Federal Stable Pour of ⁇ -35oC, a viscosity of ⁇ 3,500 cP at -25oC in the Cold Cranking Simulator (CCS), and a MRV (mini- rotary viscometer) viscosity of ⁇ 30,000 cP at -30o in both the 18 hour (D-3829) and TP-1 cooling cycles.
  • CCS Cold Cranking Simulator
  • MRV mini- rotary viscometer
  • the reference to average side carbon chain length refers to the length of the carbon chain (R in the formula) in the alkyl group on the ester moiety.
  • the carbon chain length is determined by the alcohol used to esterify the methacrylic acid in preparation of the methacrylate monomer.
  • the identity and number of the ester side chains present in the pour point depressant determines the effectiveness of the formulation as measured by the above tests. According to this invention, it has been found that only certain specific combinations of average side chain alkyl length provide acceptable results.
  • the average side chain length (R) of a poly(methacrylate) pour point depressant must be in the range of 12.6 to 13.50, preferably 12.6 to 13.30, and more preferably 12.6 to 13.0.
  • This average side chain length of the polymer has been found to depress the pour point of a suitable lubricating oil from 0o to -35°F. Alkyl side chain averages lower than this do not provide acceptable results, and polymers with side chain averages larger than 13.50 lower the pour point a lesser amount.
  • a poly(methacrylate) polymer which is an effective pour point depressant and, when used with a suitable viscosity index improver, provides a pour point depressant combination and engine oil which meets the required standards of the Federal Stable Pour.
  • the poly(methacrylate) pour point depressants of this invention are described as having an average side chain carbon length of 12.6 to 13.50, preferably 12.6 to 13.30, and more preferably 12.6 to 13.0. This value is obtained by using the correct mix of monomers in preparation of the polymer.
  • the polymer is prepared by preparation of the monomers, mixing and blending properly and then subjecting to polymerization.
  • the appropriate mix to obtain an average side chain in the range of 12.6 to 13.50 carbon atoms requires a mixture of at least three monomers of a mixture of C 10 to C 16 monomers but less than five such monomers.
  • These references to side chains refer to the esterified portion of the methacrylate or R in Formula I as the carbon chain is supplied by the alcohol used for esterification.
  • a formulation of monomers which includes 35-38% of C 10 monomers, 31-34% C 14 monomers and 28-34% C 16 monomers will provide a polymer having an average chain length of 12.68 to 13.0. It is within the scope of the present invention, however, to select any combination of at least three but less than five methacrylate monomers in the C 10 to C 16 range, with no monomer present in less than 10-15 wt. % which will provide the final polymethacrylate polymer with an average side chain length, or value of R, of 12.6 to 13.50.
  • the variations in the chain length are provided by the alcohol which is used to form the ester monomer of methacrylic acid.
  • the value of R in the monomer may range from C 8 to C 20 , but more preferably from about C 10 to C 16.
  • a preferred group of monomers will have the value of R ranging from C 10 to C 16 .
  • the resulting product is therefore a polymer in which the value of R may range from C 8 to C 20 , but wherein the average value or average carbon chain length for R is 12.6 to 13.30 provided that the average is obtained with at least three but less than five monomers in the C 10 to C 16 range where the minimum concentration of each monomer is at least 10-15% by weight.
  • CN 1 is the number of chain carbons in the first chain
  • CN 2 is the number of chain carbons in the second chain
  • CN n is the number of chain carbons in the nth chain
  • MP 1 is the mole percent of first component
  • MP 2 is the mole percent of the second component
  • MP n is the mole percent of the nth component.
  • Mole percent is equal to the mole fraction times 100%.
  • the pour point of the base oil alone can be depressed with any combination of chains that will yield a 12.6-13.50 chain average; however, with formulated oils the 3 to 5 monomers in the C 10 to C 16 range must be carefully chosen as not all combinations will work with ethylene-propylene viscosity index (VI) improvers.
  • VI ethylene-propylene viscosity index
  • any synergistic mixture of monomers to produce a polymer having this average side chain length or value of R is considered to be within the scope of the invention.
  • the monomers and resulting terpolymers may be produced by methods well known to the art described, for example, in United States Patents 3,598,736, and 4,088,589, the disclosures of which are incorporated herein by reference.
  • a pour point depressant is used in a lubricating oil or engine oil in order to provide a resulting formulation which will pass the low temperature tests required for such fluids, such as the Federal Stable Pour test.
  • the pour point depressant is often used in combination with a viscosity index improver, VI, of which many different types are available.
  • ethylene/propylene viscosity index improvers are particularly available from Amoco.
  • Other viscosity index improvers sold under the name TLA which are ethylene-propylene copolymers to which a vinyl pyrrolidone has been grafted to provide dispersing characteristics, may also be used with such formulations.
  • Certain chain combinations of the pour point depressant will function with one or the other VI improvers even though the pour point depressant has the requisite 12.6-13.50 side chain average.
  • the pour point improvers are normally used with a suitable lubricating fluid or engine oil.
  • a preferred lubricating oil of this type is sold by Pennzoil Company under the tradename Atlas, and particularly Atlas 100N.
  • Other base stocks such as, but not limited to, Ashland 100N or Exxon 100 LP are also suitable for use.
  • the lubricating oil may be a 5W-30, 10W-30, 10W- 40 or 15W-40 grade.
  • an effective pour point depressant will have an average side chain length of 12.6 to 13.50, preferably 12.6 to 13.30, more preferably 12.6 to 13.0 and this will depress the pour point of a lubricating fluid such as Atlas 100N from 0° down to -35°F.
  • a pour point depressant is provided, which is not effective to meet industry standards.
  • Polymers with side chain averages higher than 13.50 will lower the pour point only to about -20°F.
  • the polymers are formed from a group of indicated monomer components to provide the best results.
  • the molecular weight of the polymer of the invention have a lower limit of about 30,000 dalton and an upper limit in the range of 220,000 dalton.
  • the degree of polymerization is also important.
  • the amount of pour point depressant of this invention to be added to the lubricating oil will range from 0.001 to 1.0 wt.% and preferably range from about 0.01 to 0.50 wt. % when the pour point depressant is a concentrate.
  • the amount of viscosity index improver added is preferably about 5 to 20 wt.% depressant.
  • the lubricating oil composition will also preferably contain a detergent composition such as the commercially available detergent packages.
  • a detergent composition such as the commercially available detergent packages.
  • the pour point depressant compositions of this invention are compatible with all such detergent packages.
  • Formulated oils that met this classification level offered more protection against corrosion, oil oxidation, rust and engine deposits than earlier oils.
  • the SF category was introduced in 1980.
  • Formulated oils that met this classification level had better oxidative stability and anti-wear performance than SE oils.
  • the SG level was introduced in 1988.
  • Formulated oils that met this classification level had better sludge control and anti-wear performance than SF oils.
  • the improvement in anti-wear performance is needed because of the extended warranties that are currently available. The trend has been for formulated oils to meet more exciting performance requirements dictated by today's smaller more demanding engines.
  • Detergent package F uses polyisobutylene dispersant chemistry.
  • Detergent package G is a spike composed of calcium phenates and sulf ⁇ nates to give additional performance.
  • Detergent package I uses Mannich dispersant chemistry. Detergent package I is approximately 23 wt% dispersant. Detergent package J employs polyisobutylene succinimide dispersant chemistry. The above description is merely qualitative as these packages are composed of other additives that serve different purposes.
  • Figure 1 is a graph illustrating the pour point of the lubricating fluid Atlas 100N as the pour point changes depending on the average side chain length or the number of carbons for the value of R.
  • Figure 3 illustrates the pour point of the lubricant Atlas 100N containing Polymer 12.6 in comparison with Acryloid 154-70 with respect to pour point depression versus weight percent concentration of the depressant but wherein the Acryloid 154-70 has had its concentration corrected to account for the diluent oil.
  • Figure 4 displays the activity of polymer 12.6 in different base stocks. At 0.25 wt. %, the base stocks have pour points of -30 to -35'F, indicating the pour point depressant activity is not limited solely to Atlas 100N.
  • the following examples are presented to illustrate the invention, but the invention is not to be considered as limited thereto. In the examples and throughout the specification, parts are by weight unless otherwise indicated.
  • the polymethacrylate polymer compositions set forth in Experiments 1-13 were prepared using the monomers indicated as C 4 , C 10 , C 1 1 , C 12 , C 14 and C 16 .
  • the polymers were produced using a combination of methacrylic acid esters wherein the alcohol used to esterify the methacrylic acid had the indicated C value.
  • the polymer was prepared from a mixture of three monomers , 45. 1% C 10 , 43 . 1% C 12 and 11 . 8% C 14 for a chain length average of 11.2.
  • the chain length distribution (normalized weight distribution) was determined by gas chromatography on an SE-30 column of the methacrylate monomer mixture prior to polymerization.
  • the monomer mixtures was isolated after polymerization, and the composition was nearly the same as the initial charge.
  • Polymerizations were conducted in xylene under a nitrogen atmosphere with benzoyl peroxide as the free radical initiator. Reactions were conducted at 85-95oC for a period of several hours. Molecular weights were measured by gel permeation chromatography, relative to polystyrene.
  • Polymers with two components work as well as polymers with 3 components (polymer 8).
  • a variety of 3 component chains work, (e.g., Polymers 4, 5 or 10).
  • Polymer 13 has an Mw of 4300 but does not work while polymer 6 functions with a Mw of 34,000.
  • a Mw of about 30,000 is considered a reasonable lower limit.
  • Example 2 These pour point depressants also compare favorably with commercially available products such as EGA 7955 or Acryloid 154-70.
  • Atlas 100N was blended with several different concentrations of Polymer 4 (Table 1), EGA 7955 or Acryloid 154-70.
  • the pour points are depicted graphically in Figure 2 with Polymer 4 being referred to as Polymer 12.6.
  • the graph is somewhat misleading because the commercial pour point depressants are sold as concentrates so that the actual polymer concentration is less than what is displayed.
  • the MS-DS for Acryloid 154-70 states that the concentrate is 40-45 wt. % polymer.
  • Figure 3 shows the Atlas 100N pour points with the corrected concentration shown for Acryloid 154-70. Polymer 4 depresses the pour better and to a lower overall level than does Acryloid 154-70.
  • formulations are prepared to represent a motor oil having the proper components to meet the Federal Stable Pour, the MRV test, the CCS, the TP-1 cooling cycles.
  • the heading for PPD Polymer refers to the numbered polymer prepared in Tables 1 and/or 2.
  • the VI improver A is an olefin copolymer of ethylene-propylene to which vinyl pyrrolidone has been grafted to give dispersing characteristics. It has a molecular weight of about 180,000. Atlas 100N is the base oil to which these components are added in the amounts indicated.
  • VI improver A has a Mw of 189,000 and Mn of 43,000.
  • VI improver B has a bimodel molecular weight distribution. The lower fraction has an Mw of 189,000 and Mn of 76,750. The higher fraction has an Mw > of 1,000,000.
  • Polymers 19 and 20 were prepared in Atlas 100N and used as concentrates with an effective polymer concentration of 25-35% wt.
  • the Viscosity Index Improver A with their D-97 pour points, Federal Stable Pour, -25°C CCS viscosities, the CCS, the -30°C viscosity as measured in the MRV with an.18 hour (D 3829) and TP-1 cooling cycles, and 100oC viscosities are displayed in Table 3.
  • the results of the Viscosity Index Improver B formulations are shown in Table 4.
  • Detergent package A consists of a borated succinate ester dispersant with a mixture of calcium and magnesium phenates used as detergents. Other detergent packages were used (see below); detergent package B was composed of a polyisobutylene succinimide dispersant with a magnesium sulfonate detergent; detergent package C contained a polyisobutylene succinimide dispersant with a calcium sulfonate detergent; detergent package D contained only a calcium sulfonate detergent and detergent package E, which has similar constituents as detergent package A but with less calcium phenate. Detergent packages C and D were used together. All detergent packages contained zinc dialkyldithiophosphates. Detergent packages are items of commerce with varied ingredients and methods of preparation, some of which are trade secrets, such that the exact nature or number of components cannot be readily determined. Consequently the above description of the detergent packages is qualitative and is not exhaustive.
  • Formulations 4A, SB, 10A, 10B, 12A and 12B met the following low temperature standards for a 5W-30 oil; a CCS viscosity of ⁇ 3,500 cP at -25oC, a Federal Stable Pour of ⁇ -35°C, and a MRV viscosity of ⁇ 30,000 cP at -30°C with the D-3829 and TP-1 cooling cycles.
  • Formulations 4A, 5B, 10A, 10B, 12A and 12B used polymers with chain compositions that were 35-38% C 10 , 31-34% C 14 , and 28-34% C 16 with a side chain average of 12.68-13.0.
  • Polymers are identical except for the molecular weight.
  • Polymer 10, used in formulations 4A- C has Mw of 39,900 and Mn of 11,700.
  • Polymer 14, used in formulations 5A-B has a Mw of 68,000 and Mn of 13,300.
  • Polymer 19, used in formulations 10A and 10B has a Mw of 139,000 and Mn of 30,000.
  • Polymer 20 had a Mw of 195,700 and a Mn of 65,300.
  • Formulations l and 3 fail miserably.
  • Formulations 2A, 2B and 6 have unacceptably high MRV (D-3829) viscosities.
  • Formulation 6 also suffers from a high Federal Stable Pour.
  • Formulation 9 has a high Federal Stable Pour although its MRV (D-3829) and TP-1 viscosities are acceptable.
  • Formulations 2A-2B and 7A-7B demonstrate that increasing the pour point depressant concentration can cause a deterioration in the properties of the formulations.
  • the MRV viscosity, with the D-3829 cooling cycle, increases for Polymer 5 in formulations 2A and 2B.
  • the stable pour increased in formulations 7A and 7B when the concentration and Polymer 16 was increased.
  • Formulations 11A-C use Acryloid 154-70 as the pour point depressant. Formulations 11A and 11B have stable pour problems. The MRV viscosities also increase to unacceptably high levels when the Acryloid 154-70 concentration is increased to 1.0 wt.% (Formulation 11C).
  • the three component pour point depressant that has a C 10 , C 14 , and C 16 chain distribution and the four component pour point depressant with the C 10 , C 11 , C 14 and C 16 chain length distributions are the best pour point depressants tested. They produce formulations with better low temperature properties than either Acryloid 154-70 or any of the other experimental pour point depressants. For the latter polymers, it is not clear why certain three or four components function in the presence of DOCP VI improvers and other three or four chain combinations do not. It is also not clear why a three component pour point depressant should work better than-almost all of the four component pour point depressants and the five component pour point depressants.
  • Formulations 2A, 2B, 3, 8 and 12 have acceptable stable pours, CCS viscosities and MRV (D-3829) viscosities.
  • Formulations 2-3 contain Polymers 5 or 6; these polymers contain the same chain distribution, and they differ only in molecular weight. There does not seem to be any difference in overall performance of the formulation due to molecular weight for Polymers 5 or 6. Only Polymer 19 or Polymer 20 (see Table 5) functions effectively with both VI Improver A or VI Improver B. The other polymers work successfully with only one of the VI improvers. Polymer 5 fails with VI Improver A, formulation 2A-B in Table 3, but works effectively with VI Improver B, formulations 2A-B in Table 4.
  • Polymer 17 functions with VI Improver A, formulation 8 in Table 3, but fails with VI Improver B, formulation 10 in Table 4.
  • Polymer 15 functions effectively with VI Improver B, formulation 8, in Table 4, but is not effective with VI Improver A, formulation 6, Table 3.
  • the other formulations have high MRV viscosities in the standard cooling cycle (formulation 7) or with the TP-1 cycle (Formulations 7, 9-11).
  • Formulation 13 contains Acryloid 154-70. While it has acceptable MRV viscosities in both the D-3829 and TP-1 cooling cycles, the stable pour is too high.
  • the experimental pour point depressants described in Tables 1 and 2 produce better 5W-30 formulations.
  • Polymer 7 in formulation 4 is an interesting contrast to the success of Polymer 6 in Formulation 3.
  • the only difference between the two pour point depressant polymers is that Polymer 7 contains butyl groups.
  • the butyl groups may be interfering with the success of the formulation.
  • the 10W series is required to have ⁇ -30°C Federal Stable Pour, a CCS viscosity of ⁇ 3500 cP at -20°C, and a viscosity of ⁇ 30,000 cP at -25°C in both the 18-hour and TP-1 cooling cycles.
  • the formulations with Polymer 20 quite easily surpassed these requirements.
  • the fact that the pour point depressant functions in 5W-30s, 10W-30s, and 10W-40s makes it an attractive, versatile additive.
  • the pour point depressant Polymer 19, was tested in Ashland 100N with very good results shown in Table 7.
  • the 5W-30 formulations had very good low- temperature properties, indicating that the pour point depressant is not limited to only one base stock.
  • Example A shows the calculation of the Cav for one 200 gram alcohol mixture mentioned in column 6 of the U. S. Patent 3,897,353 composed of 150 g of Neodol 25L and 50 g of Alfol 1620 SP.
  • the relative weight distribution shown was calculated by multiplying each alcohol mixture by its respective weight distribution, as described above, adding together the components that overlapped, and then normalizing the new distribution.
  • Example B shows the methacrylate distribution for polymer 19, Table 2 of this application.
  • the Cav was calculated to be 12.83.
  • the tables for these calculations are as follows:
  • the pour point depressants of this invention were evaluated with various detergent packages used in lubricating oils. In this work, additional pour point depressants were prepared. Compositions and molecular weight distributions, (MWDs), of three pour point depressants that share the same components decyl methacrylate (C 10 meth), tetradecyl methacrylate (C 14 meth), and hexadecyl methacrylate (C 16 meth), but in different proportions, to give three different side chain averages, Cav, are shown in Table 9.
  • the polymers in concentrates 21, 22 and 23 have very similar MWDS as well as polymer loads. It should be pointed out the polymers 19 and 20 in Table 2 of the application are really concentrates containing those polymers.
  • concentrates 20 and 21 are essentially the same; both have the same methacrylate compositions that yield basically identical Cavs and very similar MWDS.
  • the only difference between the two concentrates is that concentrate 20 is approximately 25 wt% polymer while concentrate 21 is approximately 40-45 wt% polymer.
  • Table 9 Composition of pour point depressants. Normalized weight distribution of starting methacrylate monomer mixture, side chain average, Cav, molecular weight distribution of resulting polymer and polymer content of concentrate.
  • Olefin copolymer viscosity index improver concentrate C was used in the formulations. It is similar in nature to olefin copolymer concentrate A discussed in Example 4 of the application. However, it has a lower molecular weight than A. The lower molecular weight is believed to make the polymer less likely to shear in the engine. Viscosity Index (VI) improvers with this property have only recently been introduced in the industry; they are called shear stable VI improvers.
  • VI Viscosity Index
  • Detergent package F at SG performance levels, is used in formulations displayed in Tables 10 and 11. It uses polyisobutylene dispersant chemistry.
  • Detergent package F is 25 wt% dispersant while H is 19 wt% dispersant.
  • Detergent package G is a spike composed of calcium phenates and sulfonates to give additional calcium phenates and sulfonates to give additional performance.
  • Detergent package I uses Mannich dispersant chemistry. Detergent package I is approximately 23 wt% dispersant.
  • Detergent package J employs polyisobutylene succinimide dispersant chemistry. The above description is merely qualitative as these packages are composed of other additives that serve different purposes.
  • the low temperature properties of the 5W30 formulations with the various PPD concentrates are displayed in Table 10.
  • the 18 hr and TP-1 MRV viscosities are essentially the same. In the 5W30 formulations, the viscosities are independent of treat level and Cav.
  • the stable pour data does show a trend toward higher stable pours with increasing treat rates of the concentrates. Compare entries 1-3 for concentrate 21 where the stable pour increases from ⁇ -41 to -36°C as the treat rates increases from 0.06 wt% to 0.31 wt%. Within the limits of experimental error, there is an increase in the stable pour as the Cav increases (at low treat rates).
  • D-S7 pour points discussed earlier, see figure 1. It is pointed out that the D-97 pour point and the stable pour are similar in name only; they are completely different tests.
  • a D-97 pour point test is conducted over a few hours and is basically a straight cooling test. Refiners use it as a quality control test for base stocks. While it was originally used in formulation work, it has been rendered obsolete by a battery of other tests, including the stable pour. At least one company has renamed their pour point depressants lube oil flow improvers to reflect this change.
  • the stable pour test is conducted over a period of 7 days with heating and cooling cycles. It is used for formulations because there is some relationship between the test and the performance of the formulation in the real world. Its major flaw is that it takes 7 days to complete and is therefore not a good quality control tool for production work.
  • the PPD concentrates were also tested in 10W30 formulations.
  • the results of one 10W30 series is displayed in Table 11.
  • the detergent package H of SF quality, is used in entry 1.
  • Concentrate 21 with a Cav of 12.78 is fairly effective in the formulation.
  • the concentrate does not function when the detergent package is switched to the SG detergent package F.
  • the formulation freezes solid in the TP-1 MRV, entry 2.
  • the situation improves when the treat rate is increased, but the results are still not acceptable, entry 3.
  • the situation dramatically improves when the concentrates with the higher Cavs are used.
  • the yield stress disappears when concentrate 22 with a Cav of 13.6, entry 4, or concentrate 23 with a Cav of 13.38, entry 5, are employed.
  • Concentrate 21 was tested in 10W30s and 10W40s composed of Chevron basestocks. The concentrates and low temperature results are displayed in Table 13. The results are excellent.
  • Table 11 Pour point depressant performance in 10W-30.
  • the stock formulation was composed of 6.39 wt % Olefin Copolymer Concentrate C. 11.90% Detergent Package F, 28.0% Atlas 325 and 54.3% Atlas 100N. Entry 1 used detergent package H at 11.28 wt%, Olefin Copolymer Concentrate C at 6.38%, Atlas 100N at 54.33% and 28.0% Atlas 325N.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Un additif abaissant le point d'écoulement d'huiles de lubrification comprend un polymère de poly(méthacrylate) ayant l'unité de répétition (I) dans laquelle R est un groupe alkyle ayant une longueur de chaîne moyenne dans le polymère comprise entre 12,6 et 13,50, et n est un nombre entier indiquant le nombre d'unités répétitrices, la valeur de n étant suffisante pour donner au polymère un poids moléculaire compris entre 10,000 et 300,000, l'additif d'abaissement du point d'écoulement ayant la capacité de réduire le point d'écoulement stable jusqu'à -35°C, tout en étant compatible avec d'autres additifs tels que des agents d'amélioration de l'indice de viscosité et des détergents.
EP88907922A 1987-08-19 1988-08-18 Additifs et compositions a base de methacrylate abaissant le point d'ecoulement Revoked EP0329756B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT8888907922T ATE105581T1 (de) 1987-08-19 1988-08-18 Giesspunkterniedrigende methacrylatadditive und - zusammensetzungen.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US8703587A 1987-08-19 1987-08-19
US87035 1987-08-19
PCT/US1988/002730 WO1989001507A1 (fr) 1987-08-19 1988-08-18 Additifs et compositions a base de methacrylate abaissant le point d'ecoulement

Publications (3)

Publication Number Publication Date
EP0329756A1 true EP0329756A1 (fr) 1989-08-30
EP0329756A4 EP0329756A4 (fr) 1989-12-28
EP0329756B1 EP0329756B1 (fr) 1994-05-11

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EP88907922A Revoked EP0329756B1 (fr) 1987-08-19 1988-08-18 Additifs et compositions a base de methacrylate abaissant le point d'ecoulement

Country Status (5)

Country Link
EP (1) EP0329756B1 (fr)
JP (1) JPH078990B2 (fr)
CA (1) CA1339677C (fr)
DE (1) DE3889533T2 (fr)
WO (1) WO1989001507A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992014807A1 (fr) * 1991-02-22 1992-09-03 Massachusetts Institute Of Technology Procede pour ameliorer l'efficacite d'un lubrifiant
FR2701036B1 (fr) * 1993-02-04 1995-04-21 Great Lakes Chemical France Additif de viscosité stable au cisaillement pour huiles lubrifiantes.
US5312884A (en) * 1993-04-30 1994-05-17 Rohm And Haas Company Copolymer useful as a pour point depressant for a lubricating oil
HUT69323A (en) * 1993-07-23 1995-09-28 Rohm & Haas Copolymer useful as viskosity index improving additive for hydraulic fluid
ZA97222B (en) * 1996-01-16 1998-02-18 Lubrizol Corp Lubricating compositions.
US5939365A (en) * 1996-12-20 1999-08-17 Exxon Chemical Patents Inc. Lubricant with a higher molecular weight copolymer lube oil flow improver
US5955405A (en) * 1998-08-10 1999-09-21 Ethyl Corporation (Meth) acrylate copolymers having excellent low temperature properties
CN100369946C (zh) * 2005-12-12 2008-02-20 中国海洋石油总公司 一种扩链剂及其制备方法与应用
WO2008055797A1 (fr) * 2006-11-07 2008-05-15 Ciba Holding Inc. Additifs à base de copolymère de méthacrylate abaissant le point d'écoulement
JP5528693B2 (ja) * 2008-12-17 2014-06-25 コスモ石油ルブリカンツ株式会社 エンジン油組成物
US20100160196A1 (en) * 2008-12-23 2010-06-24 Clarke Dean B Power Transmission Fluids with Improved Viscometric Properties
ATE547472T1 (de) * 2009-09-25 2012-03-15 Evonik Rohmax Additives Gmbh Zusammensetzung zur verbesserung der kaltflusseigenschaften von brennstoffölen
US9783757B2 (en) 2012-07-24 2017-10-10 Jx Nippon Oil & Energy Corporation Poly(meth)acrylate-based viscosity index improver, lubricant additive and lubricant composition containing viscosity index improver
JP6125503B2 (ja) * 2012-07-24 2017-05-10 Ｊｘｔｇエネルギー株式会社 潤滑油組成物
JP6228742B2 (ja) * 2013-03-29 2017-11-08 Ｊｘｔｇエネルギー株式会社 潤滑油組成物
JP6420964B2 (ja) * 2014-03-31 2018-11-07 出光興産株式会社 内燃機関用潤滑油組成物

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US2655479A (en) * 1949-01-03 1953-10-13 Standard Oil Dev Co Polyester pour depressants
DE1920971A1 (de) * 1968-04-26 1969-11-06 Shell Int Research OElloesliche Mischpolymere,Verfahren zu ihrer Herstellung und ihre Verwendung als OElzusatzstoffe
FR2135252A1 (fr) * 1971-05-05 1972-12-15 Shell Int Research
FR2346380A1 (fr) * 1976-04-02 1977-10-28 Texaco Development Corp Nouveaux poly(acrylates d'alkyle)
EP0225598A2 (fr) * 1985-12-13 1987-06-16 Röhm Gmbh Huile lubrifiante multifonctionnelle stable au cisaillement ayant un indice de viscosité

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US4203854A (en) * 1974-02-20 1980-05-20 The Ore-Lube Corporation Stable lubricant composition containing molybdenum disulfide and method of preparing same
US4045376A (en) * 1976-04-23 1977-08-30 Texaco Inc. Synthetic turbine oils
US4088589A (en) * 1976-05-20 1978-05-09 Exxon Research & Engineering Co. Dual pour depressant combination for viscosity index improved waxy multigrade lubricants
DE2905954C2 (de) * 1979-02-16 1982-10-28 Röhm GmbH, 6100 Darmstadt Konzentrierte Polymerisatemulsionen als Viskositätsindexverbesserer für Mineralöle
DE3339103A1 (de) * 1983-10-28 1985-05-09 Röhm GmbH, 6100 Darmstadt Additive fuer schmieroele

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Publication number Priority date Publication date Assignee Title
US2655479A (en) * 1949-01-03 1953-10-13 Standard Oil Dev Co Polyester pour depressants
DE1920971A1 (de) * 1968-04-26 1969-11-06 Shell Int Research OElloesliche Mischpolymere,Verfahren zu ihrer Herstellung und ihre Verwendung als OElzusatzstoffe
FR2135252A1 (fr) * 1971-05-05 1972-12-15 Shell Int Research
US3869396A (en) * 1971-05-05 1975-03-04 Shell Oil Co Lubricating oil compositions
FR2346380A1 (fr) * 1976-04-02 1977-10-28 Texaco Development Corp Nouveaux poly(acrylates d'alkyle)
EP0225598A2 (fr) * 1985-12-13 1987-06-16 Röhm Gmbh Huile lubrifiante multifonctionnelle stable au cisaillement ayant un indice de viscosité

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See also references of WO8901507A1 *
Ullmanns Encyklopädie der technischen Chemie, 4th edition, vol. 20, pp. 548-549, Verlag Chemie 1981 *

Also Published As

Publication number Publication date
DE3889533T2 (de) 1994-12-01
JPH078990B2 (ja) 1995-02-01
EP0329756A4 (fr) 1989-12-28
JPH02500528A (ja) 1990-02-22
EP0329756B1 (fr) 1994-05-11
WO1989001507A1 (fr) 1989-02-23
DE3889533D1 (de) 1994-06-16
CA1339677C (fr) 1998-02-17

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