EP1394241A1 - Cyclische Thioharnstoffe als Zusatz für Schmieröle - Google Patents

Cyclische Thioharnstoffe als Zusatz für Schmieröle Download PDF

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Publication number
EP1394241A1
EP1394241A1 EP03254689A EP03254689A EP1394241A1 EP 1394241 A1 EP1394241 A1 EP 1394241A1 EP 03254689 A EP03254689 A EP 03254689A EP 03254689 A EP03254689 A EP 03254689A EP 1394241 A1 EP1394241 A1 EP 1394241A1
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EP
European Patent Office
Prior art keywords
alkyl
alkenyl
hydrogen
composition
independently
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.)
Withdrawn
Application number
EP03254689A
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English (en)
French (fr)
Inventor
Ravindranath Mukkamala
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.)
Rohm and Haas Co
Original Assignee
Rohm and Haas Co
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Filing date
Publication date
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Publication of EP1394241A1 publication Critical patent/EP1394241A1/de
Withdrawn legal-status Critical Current

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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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/22—Carboxylic acids or their salts
    • C10M105/24—Carboxylic acids or their salts having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/04—Polyethene
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/16—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiourea type, i.e. containing the group
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
    • C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/14—Synthetic waxes, e.g. polythene waxes
    • C10M2205/143—Synthetic waxes, e.g. polythene waxes used as base material
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/16—Paraffin waxes; Petrolatum, e.g. slack wax
    • C10M2205/163—Paraffin waxes; Petrolatum, e.g. slack wax used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/1253—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids used as base material
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/09—Heterocyclic compounds containing no sulfur, selenium or tellurium compounds in the ring
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
    • 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
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/023—Multi-layer lubricant coatings

Definitions

  • This invention relates generally to cyclic thioureas useful as additives for lubricating oils.
  • Zinc dialkyldithiophosphates are widely used as lubricant additives.
  • the principal disadvantages of these compounds are that an ash residue is produced by the zinc as the additive is consumed, and that phosphorus is known to affect the efficiency of catalytic converters in motor vehicles, thereby causing emissions problems.
  • Cyclic thiourea compounds useful as lubricant additives are disclosed in U.S. Patent No. 5,935,913. However, the compounds disclosed therein are not within the scope of the present invention.
  • the problem addressed by this invention is to find additional non-metallic, non-phosphorus-containing oil-soluble additives for lubricating oils.
  • the present invention is directed to a composition
  • a composition comprising:
  • the present invention is further directed to a method for improving the anti-wear characteristics of a lubricating oil by adding from 0.1% to 20% of a compound of formula I.
  • alkyl is a saturated hydrocarbyl group having from one to twenty-two carbon atoms in a linear, branched or cyclic arrangement, and having from 0 to 2 oxygen, nitrogen or sulfur atoms. Substitution on alkyl groups of one or more halo, hydroxy, alkoxy, alkanoyl or amido groups is permitted; alkoxy, alkanoyl and amido groups may in turn be substituted by one or more halo substituents.
  • alkyl groups contain from one to twelve carbon atoms and from 0 to 1 oxygen, nitrogen or sulfur atoms; in another preferred embodiment, alkyl groups contain from 12 to 22 carbon atoms, and more preferably, no heteroatoms.
  • An "alkenyl” group is an “alkyl” group in which at least one single bond has been replaced with a double bond.
  • An "aryl” group is a substituent derived from an aromatic compound, including heterocyclic aromatic compounds having heteroatoms chosen from among nitrogen, oxygen and sulfur.
  • An aryl group has a total of from five to twenty ring atoms, and has one or more rings which are separate or fused.
  • substitution on aryl groups of one or more halo, alkyl, alkenyl, hydroxy, alkoxy, alkanoyl or amido groups is permitted, with substitution by one or more halo groups being possible on alkyl, alkenyl, alkoxy, alkanoyl or amido groups.
  • An "aralkyl” group is an "alkyl” group substituted by an "aryl” group.
  • a “lubricating oil” is a natural or synthetic oil, or a mixture thereof, having suitable viscosity for use as a lubricant, e.g., as crankcase oil in an internal combustion engine, automatic transmission fluid, turbine lubricant, gear lubricant, compressor lubricant, metal-working lubricant, hydraulic fluid, etc.
  • formula (I) has R 1 , R 2 , R 3 and R 4 which independently are hydrogen, alkyl, alkenyl, aryl or aralkyl, i.e., the compound is not bicyclic.
  • R 1 , R 2 , R 3 and R 4 independently are hydrogen, alkyl or alkenyl, more preferably at least one of R 1 , R 2 , R 3 and R 4 is C 6 -C 22 alkyl or alkenyl, more preferably at least one of R 1 , R 2 , R 3 and R 4 is C 10 -C 22 alkyl, and most preferably at least one of R 1 , R 2 , R 3 and R 4 is C 16 -C 22 alkyl.
  • R 3 and R 4 groups in formula I combine with ring carbon atoms to which they are attached to form a five- to seven-membered heterocyclic ring.
  • R 3 and R 4 groups combine to form the following bicyclic system of formula (II): wherein R 5 and R 6 independently are hydrogen, alkyl, alkenyl, aryl or aralkyl.
  • W is O
  • R 1 and R 6 are the same
  • R 2 and R 5 are the same
  • the compound is a symmetric bicyclic compound of formula (III):
  • a compound of formula (I) is prepared from a 2-amino alkyl nitrile and carbon disulfide, as shown below:
  • R 2 is C 6 -C 22 alkyl or alkenyl, more preferably C 10 -C 22 alkyl, and most preferably C 16 -C 22 alkyl.
  • R 2 is derived from an unsubstituted C 16 -C 22 alkyl amine, R 2 NH 2 , preferably one which is an oil-soluble amine.
  • the alkyl amine is a tertiary alkyl primary amine., i.e., a primary amine in which the alkyl group is attached to the amino group through a tertiary carbon.
  • tertiary alkyl primary amines are the Primene TM amines available from Rohm and Haas Company, Philadelphia, PA.
  • a compound of formula (III) is prepared from a substituted thiourea and a di-ester of acetylenedicarboxylic acid, as shown below:
  • the R groups are alkyl, alkenyl, or aralkyl groups, preferably C 1 -C 4 alkyl groups.
  • R 1 and R 2 are hydrogen, alkyl or alkenyl, more preferably at least one of R 1 and R 2 is C 6 -C 22 alkyl or alkenyl, more preferably at least one of R 1 and R 2 is C 10 -C 22 alkyl, and most preferably at least one of R 1 and R 2 is C 16 -C 22 alkyl.
  • a compound of formula (I) is prepared from a substituted thiourea and an ester of a ⁇ , ⁇ -unsaturated carboxylic acid, as shown below:
  • R 3 and R 4 are hydrogen or C 1 -C 4 alkyl.
  • R 1 and R 2 are hydrogen, alkyl or alkenyl, more preferably at least one of R 1 and R 2 is C 6 -C 22 alkyl or alkenyl, more preferably at least one of R 1 and R 2 is C 10 -C 22 alkyl, and most preferably at least one of R 1 and R 2 is C 16 -C 22 alkyl.
  • the compound(s) of formula (I) is present in a lubricating oil in a total amount of at least 0.2%, more preferably at least 0.3%, and most preferably at least 0.4%.
  • the compound(s) of formula (I) is present in a lubricating oil in a total amount no greater than 10%, more preferably no greater than 5%, and most preferably no greater than 2%.
  • the compounds are soluble at the aforementioned levels.
  • additives typically used in lubricating oils are present in the composition.
  • additives include, but are not limited to, other anti-wear additives, anti-corrosion additives, dispersants, detergents, antioxidants, antifoamants, friction modifiers, seal swell agents, demulsifiers, viscosity index improvers and pour point depressants.
  • anti-wear additives that can be used in combination with the compound of formula (I) include the commercial products known as ZDDP, which are zinc dialkyldithiophosphates.
  • ZDDP zinc dialkyldithiophosphates.
  • the compound of formula (I) typically also improves anti-corrosion characteristics and functions as an anti-oxidant.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
EP03254689A 2002-08-07 2003-07-28 Cyclische Thioharnstoffe als Zusatz für Schmieröle Withdrawn EP1394241A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US40154002P 2002-08-07 2002-08-07
US401540P 2002-08-07

Publications (1)

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EP1394241A1 true EP1394241A1 (de) 2004-03-03

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US (1) US20040029743A1 (de)
EP (1) EP1394241A1 (de)
JP (1) JP2004162027A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1457585A1 (de) * 2003-03-14 2004-09-15 T R Oil Services Limited Verfahren und Verbindungen zur Korrosionsinhibierung

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1394242A3 (de) * 2002-08-07 2004-04-21 Rohm And Haas Company Zyclische Thioharnstoffverbindungen und ihre Verwendung als Schmierölzusatzstoffe
WO2013068875A1 (en) 2011-11-11 2013-05-16 Pfizer Inc. 2-thiopyrimidinones
CR20170498A (es) 2015-05-05 2018-01-26 Pfizer 2-tiopirimidinonas

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901815A (en) * 1974-06-05 1975-08-26 Texaco Inc Synthetic aircraft turbine oil
US3939084A (en) * 1966-04-06 1976-02-17 Monsanto Company Functional fluid compositions containing substituted pyrimidines
US4189587A (en) * 1977-04-05 1980-02-19 Ciba-Geigy Corporation 1,3-Diaminomethyl-hydantoin additives for lubricating oils
WO2000053703A1 (en) * 1998-10-16 2000-09-14 Uniroyal Chemical Company, Inc. Cyclic thiourea additives for lubricants

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1441998A (en) * 1974-01-12 1976-07-07 Ciba Geigy Ag N-carbamoyl imidazolidinones and imidazolidinethiones and their use as stabilisers for organic material
JPS513223A (en) * 1974-06-26 1976-01-12 Fuji Photo Film Co Ltd Netsugenzokankozairyo
DE2609361C3 (de) * 1976-03-06 1980-12-18 Hoechst Ag, 6000 Frankfurt Schnellhärtende Pulvermischungen
US5106975A (en) * 1989-11-20 1992-04-21 Ethyl Petroleum Additives, Inc. Hexahydropyrimidine derivatives

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3939084A (en) * 1966-04-06 1976-02-17 Monsanto Company Functional fluid compositions containing substituted pyrimidines
US3901815A (en) * 1974-06-05 1975-08-26 Texaco Inc Synthetic aircraft turbine oil
US4189587A (en) * 1977-04-05 1980-02-19 Ciba-Geigy Corporation 1,3-Diaminomethyl-hydantoin additives for lubricating oils
WO2000053703A1 (en) * 1998-10-16 2000-09-14 Uniroyal Chemical Company, Inc. Cyclic thiourea additives for lubricants

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1457585A1 (de) * 2003-03-14 2004-09-15 T R Oil Services Limited Verfahren und Verbindungen zur Korrosionsinhibierung

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US20040029743A1 (en) 2004-02-12
JP2004162027A (ja) 2004-06-10

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