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US2544376A - Lubricating oil containing a polymer of oleyl methacrylate - Google Patents

Lubricating oil containing a polymer of oleyl methacrylate Download PDF

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Publication number
US2544376A
US2544376A US45582A US4558248A US2544376A US 2544376 A US2544376 A US 2544376A US 45582 A US45582 A US 45582A US 4558248 A US4558248 A US 4558248A US 2544376 A US2544376 A US 2544376A
Authority
US
United States
Prior art keywords
polymer
oleyl methacrylate
lubricating oil
methacrylate
pour
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.)
Expired - Lifetime
Application number
US45582A
Inventor
Butler John Mann
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.)
Monsanto Chemicals Ltd
Monsanto Chemical Co
Original Assignee
Monsanto Chemicals Ltd
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
Application filed by Monsanto Chemicals Ltd filed Critical Monsanto Chemicals Ltd
Priority to US45582A priority Critical patent/US2544376A/en
Application granted granted Critical
Publication of US2544376A publication Critical patent/US2544376A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10Macromolecular 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
    • C10M145/12Macromolecular 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
    • C10M145/14Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular 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
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00Specific manufacturing methods for lubricant compositions
    • C10N2070/02Concentrating of additives

Definitions

  • This invention relates to the improvement of lubricating oils, and more particularly to the reduction of pour points of wax containing mineral oils. More specifically the invention relates to a method of altering the crystallization characteristics of the paraifin wax dissolved in lubricating oils, and avoiding the solidification of the lubricant upon cooling.
  • the purpose of this invention is to provide a convenient and readily available agent for depressing the pour points of lubricating oils.
  • a further purpose of this invention is to enable the selection of an effective pour point depressant for a wide variety of wax containing lubricating oils.
  • pour points of lubricating oils are measured by a standard A. S. T. M. procedure by which a sample of oil is heated and then gradually cooled while observing thefiuid characteristics of the sample at every 5 F. interval; the temperature being multiples of 5 F.
  • the pour point is the lowest recorded temperature at which the sample is fiuid.
  • the polymerized oleyl methacrylate is prepared by the polymerization of oleyl methacrylate, preferably by the well known thermal polymerization at temperatures between 50 and 150 C., in the pres- 2 ence of --a peroxide catalyst such as benzoyl peroxide, acetyl peroxide, or hydrogen peroxide, if desired.
  • a peroxide catalyst such as benzoyl peroxide, acetyl peroxide, or hydrogen peroxide, if desired.
  • the effectiveness of the polymer as a pour point depressant is not materially affected b the molecular weight of the polymer; the wide range of molecular weight achieved by conventional polymerization operations all appear to have the same or very similar pour point depression.
  • the polymerized oleyl methacrylate may be used in an amount varying from 0.01 to 5 percent by weight, but preferred practice involves the use of 0.05 to 2 percent.
  • the polymer is dissolved in the oil by adding it directly and stirring the mixture until a homogeneous mixture is effected. It is frequently desirable to prepare master batches by dispersing or dissolv ing large amounts of the polymerized oleyl methacrylate in a lubricating stock and thereafter mixing the concentrate with a suitable larger quantity of untreated oil, the proportions being chosen so as to achieve a small but effective proportion of the polymerized oleyl methacrylate in the final lubricant.
  • This invention may be practiced by using mixtures of polymeric methacrylates containing predominantly polymeric oleyl methacrylate, or copolymers of mixed methacrylic esters containing predominantly oleyl methacrylate, and substantial proportions of polymers of near homologues, for example, octadecyl methacrylate and linoleyl methacrylate.
  • copolymers are generally derived by the esterification of methacrylic acid with a mixed alcohol derived from animal or vegetable sources.
  • the pour depressants may be used in combination with other known depressants and with other modifying agents, such as antioxidants and detergents.
  • a lubricating composition which comprises a wax containing mineral lubricating oil of an A. S. T. M. pour point between 10 F. and +5 F., containing dissolved therein from 0.05 to 2 percent by weight of a polymer of oleyl methacrylate, said lubricating oil containing mineral oil as its major increment.

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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)

Description

Patented Mar. 6, 1951 LUBRICATING OIL CONTAINING A POLYMER OF OLEYL METHACRYLATE John Mann Butler, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, M0,, a corporation of Delaware No Drawing. Application August 21, 1948,
Serial No. 45,582
1 Claim.
This invention relates to the improvement of lubricating oils, and more particularly to the reduction of pour points of wax containing mineral oils. More specifically the invention relates to a method of altering the crystallization characteristics of the paraifin wax dissolved in lubricating oils, and avoiding the solidification of the lubricant upon cooling.
Many of the commerciall available petroleum stocks contain high molecular weight hydrocarbon waxes, and the lubricating oil fractions separated by various refining procedures, contain a substantial proportion dissolved therein. Upon cooling these lubricants, the dissolved waxes crystallize in such form that the mass is solidified. It is known that some substances affect the crystallization of the wax and permit the lubricants to retain their fluidity after cooling to temperatures below the normal pour points of the oils.
The purpose of this invention is to provide a convenient and readily available agent for depressing the pour points of lubricating oils. .A further purpose of this invention is to enable the selection of an effective pour point depressant for a wide variety of wax containing lubricating oils.
The pour points of lubricating oils are measured by a standard A. S. T. M. procedure by whicha sample of oil is heated and then gradually cooled while observing thefiuid characteristics of the sample at every 5 F. interval; the temperature being multiples of 5 F. The pour point is the lowest recorded temperature at which the sample is fiuid. The details of the method of determining pour points are set forth in the American Society for Testing Materials Bulletin on petroleum products and lubricants D-9'739.
It has been found that there is a critical rela tionship between the structure of a methacrylic acid ester and the pour point of a wax containing petroleum fraction if effective depression of pour point is to be achieved. In accordance with this invention, a polymer of oleyl methacrylate is used as a pour point depressant for wax containing mineral oils having pour points between 10 F. and +5 F., inclusive. Comparable polymers of saturated esters are not effective and the polymer of oleyl methacrylate will not depress the pour point of oils having pour points higher than +5 F. and lower than 10 F.
In the practice of this invention, the polymerized oleyl methacrylate is prepared by the polymerization of oleyl methacrylate, preferably by the well known thermal polymerization at temperatures between 50 and 150 C., in the pres- 2 ence of --a peroxide catalyst such as benzoyl peroxide, acetyl peroxide, or hydrogen peroxide, if desired. The effectiveness of the polymer as a pour point depressant is not materially affected b the molecular weight of the polymer; the wide range of molecular weight achieved by conventional polymerization operations all appear to have the same or very similar pour point depression. The polymerized oleyl methacrylate may be used in an amount varying from 0.01 to 5 percent by weight, but preferred practice involves the use of 0.05 to 2 percent. The polymer is dissolved in the oil by adding it directly and stirring the mixture until a homogeneous mixture is effected. It is frequently desirable to prepare master batches by dispersing or dissolv ing large amounts of the polymerized oleyl methacrylate in a lubricating stock and thereafter mixing the concentrate with a suitable larger quantity of untreated oil, the proportions being chosen so as to achieve a small but effective proportion of the polymerized oleyl methacrylate in the final lubricant. I
This invention may be practiced by using mixtures of polymeric methacrylates containing predominantly polymeric oleyl methacrylate, or copolymers of mixed methacrylic esters containing predominantly oleyl methacrylate, and substantial proportions of polymers of near homologues, for example, octadecyl methacrylate and linoleyl methacrylate. These copolymers are generally derived by the esterification of methacrylic acid with a mixed alcohol derived from animal or vegetable sources.
The pour depressants may be used in combination with other known depressants and with other modifying agents, such as antioxidants and detergents.
The critical characteristics of the pour point depression of lubricating oils with polymerized oleyl methacrylate are demonstrated by the following examples.
Ezample I These data demonstrate that no pour point depression efiect is achieved in 20 F. pour oil and that an unusually desirable depression is achieved in F. pour oil. A depression efiect is also noticed for pour points below zero, but these are of little commercial value except in special low temperature oils.
Example I! Pour Depres- Polymerized Agent Point, sion,
Oieyl methacrylate -25 25 Octadccyl mcthacrylatc l0 These data demonstrate that a very desirable eifect is achieved by using oleyl methacrylate, but
when the saturated homologue, octadecyl methacrylate, is used, an increase in pour point is produced instead of a. decided depression.
The invention is defined by the following claim:
A lubricating composition which comprises a wax containing mineral lubricating oil of an A. S. T. M. pour point between 10 F. and +5 F., containing dissolved therein from 0.05 to 2 percent by weight of a polymer of oleyl methacrylate, said lubricating oil containing mineral oil as its major increment.
JOHN MANN BUTLER.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,091,627 Bruson Aug. 31, 1937 2,129,665 Barrett Sept. 13, 1938 2,407,954 Fenske Sept. 17, 1946
US45582A 1948-08-21 1948-08-21 Lubricating oil containing a polymer of oleyl methacrylate Expired - Lifetime US2544376A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US45582A US2544376A (en) 1948-08-21 1948-08-21 Lubricating oil containing a polymer of oleyl methacrylate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US45582A US2544376A (en) 1948-08-21 1948-08-21 Lubricating oil containing a polymer of oleyl methacrylate

Publications (1)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3278500A (en) * 1960-12-07 1966-10-11 Union Carbide Corp Sulfur-containing polymers
US3462249A (en) * 1967-03-31 1969-08-19 Exxon Research Engineering Co Fuel oil compositions containing grafted polymers
US4761241A (en) * 1986-04-14 1988-08-02 Nihon Kousakuyu Co., Ltd. Oily lubricant for cold plastic processing of metallic material
US4844829A (en) * 1987-08-19 1989-07-04 Pennzoil Products Company Methacrylate pour point depressants and compositions
US4956111A (en) * 1987-08-19 1990-09-11 Pennzoil Products Company Methacrylate pour point depressants and compositions
EP0435418A1 (en) * 1989-12-01 1991-07-03 Texaco Development Corporation A dispersant/antioxidant viscosity index improving lubricant additive

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2091627A (en) * 1934-06-08 1937-08-31 Rohm & Haas Composition of matter and process
US2129665A (en) * 1934-07-14 1938-09-13 Du Pont Esters of methacrylic acid
US2407954A (en) * 1942-05-23 1946-09-17 Rohm & Haas Lubricating composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2091627A (en) * 1934-06-08 1937-08-31 Rohm & Haas Composition of matter and process
US2129665A (en) * 1934-07-14 1938-09-13 Du Pont Esters of methacrylic acid
US2407954A (en) * 1942-05-23 1946-09-17 Rohm & Haas Lubricating composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3278500A (en) * 1960-12-07 1966-10-11 Union Carbide Corp Sulfur-containing polymers
US3462249A (en) * 1967-03-31 1969-08-19 Exxon Research Engineering Co Fuel oil compositions containing grafted polymers
US4761241A (en) * 1986-04-14 1988-08-02 Nihon Kousakuyu Co., Ltd. Oily lubricant for cold plastic processing of metallic material
US4844829A (en) * 1987-08-19 1989-07-04 Pennzoil Products Company Methacrylate pour point depressants and compositions
US4956111A (en) * 1987-08-19 1990-09-11 Pennzoil Products Company Methacrylate pour point depressants and compositions
EP0435418A1 (en) * 1989-12-01 1991-07-03 Texaco Development Corporation A dispersant/antioxidant viscosity index improving lubricant additive

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