US2544375A - Lubricating oil containing a polymer of tetradecyl vinyl ether - Google Patents

Lubricating oil containing a polymer of tetradecyl vinyl ether Download PDF

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Publication number
US2544375A
US2544375A US45580A US4558048A US2544375A US 2544375 A US2544375 A US 2544375A US 45580 A US45580 A US 45580A US 4558048 A US4558048 A US 4558048A US 2544375 A US2544375 A US 2544375A
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US
United States
Prior art keywords
vinyl ether
polymer
pour
polymerized
tetradecyl
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
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US45580A
Inventor
Butler John Mann
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Monsanto Chemicals Ltd
Monsanto Chemical Co
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Monsanto Chemicals Ltd
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Publication date
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Priority to US45580A priority Critical patent/US2544375A/en
Application granted granted Critical
Publication of US2544375A publication Critical patent/US2544375A/en
Anticipated expiration legal-status Critical
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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
    • C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • 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
    • C10M2209/04—Macromolecular 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
    • 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
    • C10M2209/06—Macromolecular 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
    • 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
    • C10M2209/06—Macromolecular 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
    • C10M2209/062—Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate
    • 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

  • This invention relatesto the improvement of lubricating oils, and more particularly to the reduction of pour points of wax containing mineral I oils. More specifically'the invention relates to a method of altering thecrystallization characteristics ofthe' paraffin wax dissolved in lubricating oils, and avoiding the solidification'of the lubricant upon cooling. j a
  • 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 eiiective 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 the fluid characteristics of the sample at every 5 F. interval, the temperature being multiples of 5 F.
  • the pour point is the lowest temperature at which the sample is fluid.
  • the polymerized tetradecyl vinyl ether is prepared preferably by'the well known low temperature poly merization technique, for example, at temperav tures between l0 F. and +20? F. in the presence of'catalysts, such as aluminum chloride or boron trifluoride.
  • the effectiveness of the polymer as a pour point depressant isnotmaterially affected by the molecular weight of the polymer; the wide range of molecular weights achieved by conventional polymerization operation all appear to have the same or very similar. pour point depression.
  • the polymerized tetradecyl vinyl ether may be used in an amount varying from 0.01 to 5 percent byweight, but preferred operation involves the use of from 0.05 to 2 percent.
  • the polymer is dis persed in the lubricating oil by adding it directly and stirring the mixture until a homogeneous dispersion, or solution, is effected; It is frequent 1y desirable to prepare master batches by dispersing large amounts of the polymerized tetradecyl vinyl ether in a lubricating stock and thereafter mixing the concentrate with a suitable large quantity of the untreated oil, the proportion being chosen so as to achieve a small but efiective proportion of the polymerized tetradecyl vinyl ether in the final lubricant.
  • This invention may be practiced by using a mixture of polymeric alkyl vinyl ethers containing predominantly the polymer of tetradecyl vinyl ethers, and copolymers of mixed alkyl vinyl ethers containing predominantly tetradecyl vinyl ethers and substantial portions of near homologues, for example, hexadecyl vinyl ether and dodecyl vinyl ether.
  • copolymers are generally derived from the mixed alcohols as obtained from animal and vegetable oils by saponification and reduction.
  • the pour point depressant may be used in combination with other known depressants and other modifying agents, such as antioxidant and detergents.
  • Example 1 The critical efiect of the dependent alkyl chain of various polymerized alkyl vinyl ethers was demonstrated by preparing one percent by weight solutions of polymerized octyl vinyl ether, polymerized decyl vinyl ether, polymerized dodecyl vinyl ether, polymerized tetradecyl vinyl ether, polymerized hexadecyl vinyl ether and polymerized octadecyl vinyl ether in wax containing lubricating oils having a 20 F. pour point in the unmodified condition. The six samples of modified oils were tested by means of the standard A. S. T. M. pour point measuring method, and the observed data is set forth in the following table.
  • a lubricating composition which comprises a wax containing mineral lubricating oil having an A. S. T. M. pour point of from 15 to F., containing intimately dissolved therein from 0.05 to 2 percent by weight of a polymer of tetradecyl vinyl ether.

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  • 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 Mar. 6, 1951 LUBRICATING OIL CONTAINING A POLYMER 1 OF T-ETRADEGYL VINYL ETHER John Mann Butler, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo.,
a corporation of Delaware No Drawing. Application August 21, 1948,
Serial No. 45,580
1 Claim. (01. 252-:s2)
'This invention relatesto the improvement of lubricating oils, and more particularly to the reduction of pour points of wax containing mineral I oils. More specifically'the invention relates to a method of altering thecrystallization characteristics ofthe' paraffin wax dissolved in lubricating oils, and avoiding the solidification'of the lubricant upon cooling. j a
Many of the commercially available petroleum stocks contain high molecular weight hydrocarbon waxes, and the lubricating 'oil'iractions, 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 issolidifled, It is known that some substances afiec't the crystallization of the 'waxa'ndpermit the lu'bri cants 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 eiiective 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 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 Bulletin, on petroleum prodnets and lubricants D-9'7-39.
It has been discovered that there is a critical relationship between the length of the alkyl group of an alkyl vinyl ether, and the pour point of a wax containing oil in which the polymer is an efiective pour point depressant. Polymers of alkyl vinyl ethers having alkyl groups longer or shorter than the critical length may be less efiective, or entirely ineffective, in depressing the pour point of the same oil. In accordance with this invention the polymer of tetradecyl vinyl ether is used as a pour depressant for wax containing oils having pour points between and 50 F. Other polymeric alkyl vinyl ethers are not effective pour point depressants for 15 to 50 F. pour oils, and the polymer of tetradecyl vinyl ether is not effective in higher or lower pour oils.
In the practice of this invention, the polymerized tetradecyl vinyl ether is prepared preferably by'the well known low temperature poly merization technique, for example, at temperav tures between l0 F. and +20? F. in the presence of'catalysts, such as aluminum chloride or boron trifluoride. The effectiveness of the polymer as a pour point depressant isnotmaterially affected by the molecular weight of the polymer; the wide range of molecular weights achieved by conventional polymerization operation all appear to have the same or very similar. pour point depression. The polymerized tetradecyl vinyl ether may be used in an amount varying from 0.01 to 5 percent byweight, but preferred operation involves the use of from 0.05 to 2 percent. The polymer is dis persed in the lubricating oil by adding it directly and stirring the mixture until a homogeneous dispersion, or solution, is effected; It is frequent 1y desirable to prepare master batches by dispersing large amounts of the polymerized tetradecyl vinyl ether in a lubricating stock and thereafter mixing the concentrate with a suitable large quantity of the untreated oil, the proportion being chosen so as to achieve a small but efiective proportion of the polymerized tetradecyl vinyl ether in the final lubricant.
This invention may be practiced by using a mixture of polymeric alkyl vinyl ethers containing predominantly the polymer of tetradecyl vinyl ethers, and copolymers of mixed alkyl vinyl ethers containing predominantly tetradecyl vinyl ethers and substantial portions of near homologues, for example, hexadecyl vinyl ether and dodecyl vinyl ether. These copolymers are generally derived from the mixed alcohols as obtained from animal and vegetable oils by saponification and reduction.
The pour point depressant may be used in combination with other known depressants and other modifying agents, such as antioxidant and detergents.
The critical characteristics of pour point depression of lubricating oils with polymerized vinyl ethers are demonstrated by the following specific examples.
Example 1 The critical efiect of the dependent alkyl chain of various polymerized alkyl vinyl ethers was demonstrated by preparing one percent by weight solutions of polymerized octyl vinyl ether, polymerized decyl vinyl ether, polymerized dodecyl vinyl ether, polymerized tetradecyl vinyl ether, polymerized hexadecyl vinyl ether and polymerized octadecyl vinyl ether in wax containing lubricating oils having a 20 F. pour point in the unmodified condition. The six samples of modified oils were tested by means of the standard A. S. T. M. pour point measuring method, and the observed data is set forth in the following table.
Pour Depres- Polymerized agent Pgliint, 55in,
Octyl vinyl ether 20 Decyl vinyl ether 20 0 Dodecyl vinyl ether- 15 5 Tetradecyl vinyl ether 0 20 Hexadecyl vinyl ether--- 20 0 Octadecyl vinyl ether 20 0 This demonstrates that the polymerized alkyl Example 2 For the purpose of demonstrating the criticality of the original pour point of the oil upon the degree of pour point depression achieved by means of the polymerized tetradecyl vinyl ether, a series of samples were prepared by dissolving one percent by weight of polymerized tetradecyl vinyl ether in samples of oils having pour points varying from 0 to 60 F. The following table sets forth the original and final pour point as well as the degree of pour point depression achieved.
This data clearly demonstrates that tetradecyl vinyl ether is a good pour point depressant for 20 F. pour oil and unusually good depressant for F. pour oil, but that its effect on 60 F. pour oil is almost negligible. On the other hand, in 0 F'. pour oil, the polymerized tetradecyl vinyl ether has a deleterious effect in increasing the pour point of the oil.
The invention is defined by the following claim:
A lubricating composition which comprises a wax containing mineral lubricating oil having an A. S. T. M. pour point of from 15 to F., containing intimately dissolved therein from 0.05 to 2 percent by weight of a polymer of tetradecyl vinyl ether.
JOHN MANN BUTLER.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,020,703 Schumann et a1. Nov. 12, 1935 2,020,714 Wulfi et a1 Nov. 12, 1935 2,091,627 Bruson Aug. 31, 1937 2,389,227 Wright Nov. 20, 1945
US45580A 1948-08-21 1948-08-21 Lubricating oil containing a polymer of tetradecyl vinyl ether Expired - Lifetime US2544375A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2782167A (en) * 1950-11-30 1957-02-19 Exxon Research Engineering Co Viscosity index improvers
US2994663A (en) * 1959-08-10 1961-08-01 California Research Corp Lubricant containing copolymer viscosity index improver
US3382055A (en) * 1965-02-24 1968-05-07 Exxon Research Engineering Co Polyalkylethyleneoxide pour point depressant additive
US8980810B2 (en) 2011-12-21 2015-03-17 Exxonmobil Research And Engineering Company Vinyl ether polymer fluids made using controlled living cationic polymerization and their use as synthetic lubricant basestocks

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
US2020703A (en) * 1932-10-11 1935-11-12 Ig Farbenindustrie Ag Improved hydrocarbon products, especially lubricating oils
US2091627A (en) * 1934-06-08 1937-08-31 Rohm & Haas Composition of matter and process
US2389227A (en) * 1943-09-15 1945-11-20 Standard Oil Dev Co Pneumatic tool lubricant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2020703A (en) * 1932-10-11 1935-11-12 Ig Farbenindustrie Ag Improved hydrocarbon products, especially lubricating oils
US2020714A (en) * 1932-10-12 1935-11-12 Ig Farbenindustrie Ag Lubricating hydrocarbon product
US2091627A (en) * 1934-06-08 1937-08-31 Rohm & Haas Composition of matter and process
US2389227A (en) * 1943-09-15 1945-11-20 Standard Oil Dev Co Pneumatic tool lubricant

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2782167A (en) * 1950-11-30 1957-02-19 Exxon Research Engineering Co Viscosity index improvers
US2994663A (en) * 1959-08-10 1961-08-01 California Research Corp Lubricant containing copolymer viscosity index improver
US3382055A (en) * 1965-02-24 1968-05-07 Exxon Research Engineering Co Polyalkylethyleneoxide pour point depressant additive
US8980810B2 (en) 2011-12-21 2015-03-17 Exxonmobil Research And Engineering Company Vinyl ether polymer fluids made using controlled living cationic polymerization and their use as synthetic lubricant basestocks

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