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US2541686A - Lubricating oil - Google Patents

Lubricating oil Download PDF

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Publication number
US2541686A
US2541686A US56267A US5626748A US2541686A US 2541686 A US2541686 A US 2541686A US 56267 A US56267 A US 56267A US 5626748 A US5626748 A US 5626748A US 2541686 A US2541686 A US 2541686A
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US
United States
Prior art keywords
allyl
pour
myristate
pour point
oils
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
US56267A
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 US56267A priority Critical patent/US2541686A/en
Application granted granted Critical
Publication of US2541686A publication Critical patent/US2541686A/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
    • C10M1/00Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • 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
    • C10M2209/04Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • 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
    • C10M2209/06Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • 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
    • C10M2209/06Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • C10M2209/062Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate

Definitions

  • 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 which a sample of oil is heated and then gradually cooled while observing the fluid 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 fluid.
  • the details of the method of determining pour points are set forth in the American Society for Testing Materials Publication, A. S. T. M. Standards on Petroleum Products and Lubricants (1946), p. 93, A. S. T. M. designation: D-97-39'.
  • the polymers of allyl myristate are used as pour point depressants for wax containing oils having pour points between 30 F. and 65 F.
  • Other polymeric allyl carboxylates are not efiective pour point depressants for 30 F. to 65 F. pour oils, and polyallyl z myristate is not effective in higher: or-lowerrpour oils.
  • the polymerized allyl myristate. may be used in an amount varying frombi'Ol to' 5.
  • Thegpolymer is dissolved or dispersed in the lubricating oil by adding it directly or stirring sthesmixturexuntil a homogeneous mixture or solutionisefiected. ltisirequently desirable to prepare master batches by dispersing or dissolving large amounts of the polyallyl myristate in a lubricating stock, and thereafter mixing the concentrate with a suitable larger quantity of untreated oil, the proportions being achieved so as to have a small but effective proportion of the polyallyl myristate in the final lubricant.
  • This invention may be practiced by using mixtures of polymeric allyl carboxylates containing predominantly polymeric allyl myristate, and copolymers of mixed allyl carboxylates containing predominantly allyl myristate and substantial proportions of near homologues, for example allyl caprate, allyl laurate and allyl palmitate.
  • copolymers are generally derived from the allyl esters of the mixed fatty acids as obtained from animal and vegetable oils by saponification.
  • pour point depressants described in this specification may be used in combination with other known depressants and with other modifying agents, such as viscosity index improvers, anti-oxidants and detergents.
  • Example 1 The critical efiect of the length of the carboxylate chain of various polymerized allyl carboxylates was demonstrated by preparing one percent by weight of polymerized allyl laurate, polymerized myristate, polymerized allyl palmitate and polymerized allyl stearate in a wax containing lubricating oil having a 45 F. pour point.
  • polyallyl myristate has no pour point depression action in 20 pour oil, but that it has an efiective pour point depression action in and F. pour oils.
  • the polyallyl myristate also has a pour point depression effect on oils having pour points in excess of 60 F., for example F. pour oils, but these are'of little commercial importance. Effective pour points depressions of 30 F. pour oils are also achieved by using polyallyl myristate.
  • a lubricating composition which comprises a paraffin wax containing hydrocarbon lubricating oil having a pour point of 30 to 65 F., containing intimately dispersed therein from 0.05 to 2 percent by weight of polyallyl myristate.

Landscapes

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

Description

Patented Feb. 13, 1 951 TED PATENT OFFICE fiIiUBRICATIN G OIL John "Mann 'Butler, Dayton, Ohio, (assignor Lto Monsanto Chemical Company, .St.-.L'ouis, -.Mo., "a corporation ofiDelaware :.'No;.Drawing. Application october' 23, 1948, Serial No. 56.267
.rmethod of:altering the: crystallization character- :istics of the paraffin wax dissolved in lubricating oils, and :avoiding the solidification of the lubricant upon cooling.
Many of the commercially available petroleum stocks contain high molecular weight hydrocarbon vwaxes,""and the lubrica-tingoil fractions-separated by various refining procedures, contain a substantial proportion dissolved'therein. Upon coolin'g-theselub'ricantsthe dissolved waxescerys- 'tallize' in sueh form that the ma ss'is -fs'olidifi'ed.
It is known that some substances afiect thewrystallization 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 which a sample of oil is heated and then gradually cooled while observing the fluid 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 fluid. The details of the method of determining pour points are set forth in the American Society for Testing Materials Publication, A. S. T. M. Standards on Petroleum Products and Lubricants (1946), p. 93, A. S. T. M. designation: D-97-39'.
It has now been discovered that there is a critical relationship between the length of the carboxylic acid group of allyl carboxylates and the pour point of a wax containing oil in which a polymer of the allyl carboxylate is an effective pour point depressant. Polymers of the allyl carboxylates, having alkyl chains longer or shorter than the critical length, may be less effective, or entirely ineffective in depressing the pour points of the same oil.
In accordance with the invention the polymers of allyl myristate are used as pour point depressants for wax containing oils having pour points between 30 F. and 65 F. Other polymeric allyl carboxylates are not efiective pour point depressants for 30 F. to 65 F. pour oils, and polyallyl z myristate is not effective in higher: or-lowerrpour oils.
In the practice of 'this'invention the polyallyl myristate is prepared by the' polymer-ization of auyi: myris'tate by. heating in the presence 'of peroxy catalysts, such'as benzoyl peroxide. Ihe:.'effectiveness of the polymer asa pour point-de- 'pressant 1 is not materially affected by -'-the molecular weight o'f the polymer; the wide range= of molecular weightsachieved 'by conventionaLpolymerization operations allappearto have thezsame or very similarpounpoint depression. The polymerized allyl myristate. may be used in an amount varying frombi'Ol to' 5. percent byweight, but the preferred operation involvesthe useof from 0.05 to 2 percent. Thegpolymer is dissolved or dispersed in the lubricating oil by adding it directly or stirring sthesmixturexuntil a homogeneous mixture or solutionisefiected. ltisirequently desirable to prepare master batches by dispersing or dissolving large amounts of the polyallyl myristate in a lubricating stock, and thereafter mixing the concentrate with a suitable larger quantity of untreated oil, the proportions being achieved so as to have a small but effective proportion of the polyallyl myristate in the final lubricant.
This invention may be practiced by using mixtures of polymeric allyl carboxylates containing predominantly polymeric allyl myristate, and copolymers of mixed allyl carboxylates containing predominantly allyl myristate and substantial proportions of near homologues, for example allyl caprate, allyl laurate and allyl palmitate. These copolymers are generally derived from the allyl esters of the mixed fatty acids as obtained from animal and vegetable oils by saponification.
The pour point depressants described in this specification may be used in combination with other known depressants and with other modifying agents, such as viscosity index improvers, anti-oxidants and detergents.
The critical characteristics of the pour point depression of lubricating oils with polyallyl myristate are demonstrated by the following specific examples.
Example 1 The critical efiect of the length of the carboxylate chain of various polymerized allyl carboxylates was demonstrated by preparing one percent by weight of polymerized allyl laurate, polymerized myristate, polymerized allyl palmitate and polymerized allyl stearate in a wax containing lubricating oil having a 45 F. pour point.
3 The four samples were tested by means of the standard A. S. T. M. measuring method and the observed data is set forth in the following table.
Pour Depres- Polymer of Point, sion, F. F.
Allyl Laurate 45 Allyl Myn'state 35 Allyl Palmitate 25 I 20 Allyl Stearate 60 Example 2 The critical effect of the original pour point of the oil upon the degree of pour point depression achieved was effectively demonstrated by dissolving one percent by weight of polyallyl myristate in samples of oil having 20, 45 and 60 F. pour points. The following table sets forth the original and final pour points of the oils tested as well as the pour point depression achieved.
Original 53 Depres- Pour Point, Point S1011, r F. g a F F.
This table of measurements demonstrates that polyallyl myristate has no pour point depression action in 20 pour oil, but that it has an efiective pour point depression action in and F. pour oils. ,The polyallyl myristate also has a pour point depression effect on oils having pour points in excess of 60 F., for example F. pour oils, but these are'of little commercial importance. Effective pour points depressions of 30 F. pour oils are also achieved by using polyallyl myristate.
The invention is defined by the following claim.
I claim:
A lubricating composition which comprises a paraffin wax containing hydrocarbon lubricating oil having a pour point of 30 to 65 F., containing intimately dispersed therein from 0.05 to 2 percent by weight of polyallyl myristate.
JOHN MANN BUTLER.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS by Kalichevsky, Reinhold Publishing Co., 1938, page 183.
US56267A 1948-10-23 1948-10-23 Lubricating oil Expired - Lifetime US2541686A (en)

Priority Applications (1)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2020714A (en) * 1932-10-12 1935-11-12 Ig Farbenindustrie Ag Lubricating hydrocarbon product
GB484964A (en) * 1936-10-01 1938-05-12 Bataafsche Petroleum A process for manufacturing viscous products suitable for lubrication
US2374081A (en) * 1941-09-30 1945-04-17 American Cyanamid Co Polymerized allyl esters
US2441023A (en) * 1945-01-26 1948-05-04 Shell Dev Lubricating oil compositions containing polymerized allyl esters of carboxylic acids

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2020714A (en) * 1932-10-12 1935-11-12 Ig Farbenindustrie Ag Lubricating hydrocarbon product
GB484964A (en) * 1936-10-01 1938-05-12 Bataafsche Petroleum A process for manufacturing viscous products suitable for lubrication
US2374081A (en) * 1941-09-30 1945-04-17 American Cyanamid Co Polymerized allyl esters
US2441023A (en) * 1945-01-26 1948-05-04 Shell Dev Lubricating oil compositions containing polymerized allyl esters of carboxylic acids

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