WO1998030660A1 - Dithiocarbamyl carboxylic acids and their use as multifunctional additives for lubricating oils - Google Patents

Dithiocarbamyl carboxylic acids and their use as multifunctional additives for lubricating oils Download PDF

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Publication number
WO1998030660A1
WO1998030660A1 PCT/US1997/024233 US9724233W WO9830660A1 WO 1998030660 A1 WO1998030660 A1 WO 1998030660A1 US 9724233 W US9724233 W US 9724233W WO 9830660 A1 WO9830660 A1 WO 9830660A1
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Prior art keywords
lubricating oil
carboxylic acid
functional property
dithiocarbamyl
dithiocarbamyl carboxylic
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French (fr)
Inventor
John R. Baranski
Cyril A. Migdal
Robert G. Rowland
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Uniroyal Chemical Co Inc
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Uniroyal Chemical Co Inc
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Priority to EP97952691A priority Critical patent/EP0951526A1/en
Priority to CA002276740A priority patent/CA2276740A1/en
Priority to JP10530951A priority patent/JP2000507968A/en
Publication of WO1998030660A1 publication Critical patent/WO1998030660A1/en
Anticipated expiration legal-status Critical
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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
    • 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
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • C07C333/18—Esters of dithiocarbamic acids
    • C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/086—Imides [having hydrocarbon substituents containing less than thirty carbon atoms]
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/26—Amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • 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
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic acid salts
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol-fuelled engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • This invention relates to dithiocarbamyl carboxylic acids and their use as multifunctional additives for lubricating oils.
  • Zinc dialkyldithiophosphates have been used as anti-fatigue, anti-wear, extreme pressure and friction modifying additives for lubricating oils for many years. However, they are subject to several drawbacks owing to their zinc and phosphorus contents.
  • lubricating oil enters the combustion chambers by means such as clinging to cylinder walls as the piston makes its down stroke.
  • phosphorus-containing lubricating oil compositions enter the combustion reaction, phosphorus enters the exhaust stream where it acts as a catalyst poison thus shortening the useful life of the catalytic converter.
  • the presence of zinc contributes to the emission of particulates in the exhaust.
  • non-zinc (i.e., ashless) , non-phosphorus- containing lubricating oil additives are the reaction products of 2 , 5-dimercapto-l , 3 , 4-thiadiazole and unsaturated mono-, di- and tri-glycerides of U.S. Patent No. 5,512,190 and the dialkyl dithiocarbamate-derived organic ethers of U.S. Patent No. 5,514,189.
  • dithiocarbamyl carboxylic acids for lubricant additives having the general formula
  • R 1 and R 2 each independently is a hydrocarbyl group of from 1 to about 60 carbon atoms and R 3 is a divalent alkylene group of from 1 to about 20 carbon atoms .
  • dithiocarbamyl carboxylic acids are useful as ashless anti-fatigue, anti-wear and extreme pressure additives for lubricating oils where they can be employed in total or partial replacement of the ZDDPs currently in use.
  • dithiocarbamyl carboxylic acids of this invention can be prepared in accordance with the following sequence of reaction steps:
  • R 2 / SII R 2 / S In the foregoing sequence of reactions, R 1 , R 2 and R 3 are each as defined above, M is alkali metal and X is halogen.
  • dihydrocarbylamine R 1 R 2 NH is reacted with an equimolar amount of alkali metal hydroxide MOH and carbon disulfide, the latter preferably in slight molar excess, to provide an alkali metal di (hydrocarbyl) thiocarbamate intermediate R 1 R 2 NCSSM.
  • Useful dihydrocarbylamines are those in which hydrocarbyl groups R 1 and R 2 are selected from among alkyl , cycloalkyl, alkaryl and aralkyl groups of up to about 60 carbon atoms.
  • Preferred dihydrocarbylamine reactants are dialkylamines in which each alkyl group contains from about 2 to about 30, and more preferably from about 4 to about 24, carbon atoms.
  • the alkali metal hydroxide is conveniently aqueous sodium hydroxide and the reaction is advantageously conducted in a suitable solvent with water and/or a lower alkanol such as methanol, ethanol, propanol, 2-propanol, isopropanol, n-butanol, sec-butanol or t-butanol. Isopropanol being preferred for this purpose .
  • Step 2 an equimolar amount of haloalkanoic acid, e.g., 3 -chloropropionic acid, is added to the reaction medium of Step 1 where it reacts with alkali metal di (hydrocarbyl) thiocarbamate intermediate to provide product dithiocarbamyl carboxylic acid.
  • haloalkanoic acid e.g., 3 -chloropropionic acid
  • the dithiocarbamyl carboxylic acids of this invention can be utilized in lubricating oil compositions in amounts which impart significant anti -wear characteristics to the oils as well as reducing the friction of engines operating with the oils. Concentrations of from about 0.001 to about 10 weight percent based on the total weight of the lubricating oil composition can be used. Preferably, the concentration is from about 0.1 to about 3 weight percent.
  • mineral oils both paraffinic, naphthenic and mixtures thereof, including those oils defined as American Petroleum Institute Groups I, II, and III, can be employed as the lubricant vehicle, and can be of any suitable lubricating viscosity range, as for example, from about 2 cSt at 100°C to about 1,000 cSt at 100 °C and preferably from about 2 to about 100 cSt at
  • oils can have viscosity indexes preferably ranging to about 180.
  • the average molecular weights of these oils can range from about 250 to about 800.
  • synthetic oils can include, but are not limited to, polyisobutylene, polybutenes, hydrogenated polydecenes, polypropylene glycol , polyethylene glycol, trimethylpropane esters, neopentyl and pentaerythritol esters, di (2-ethylhexyl) sebacate, di (2-ethylhexyl) adipate, dibutyl phthalate, fluorocarbons , silicate esters, silanes, esters of phosphorus-containing acids, liquid ureas, ferocene derivatives, hydrogenated synthetic oils, chain-type polyphenyls, siloxanes and silicones (polysiloxanes) , alkyl -substituted diphenyl ethers typified by
  • the lubricating oil compositions herein can also contain other materials.
  • corrosion inhibitors, extreme pressure agents, detergents, dispersants, antiwear agents, antioxidants , antifoamants , friction modifiers, low temperature properties modifiers and the like can be used.
  • these materials include metallic phenates or sulfonates, alkylated diphenylamines , polymeric succinimides , non-metallic or metallic phosphorodithioates and the like. These materials do not detract from the value of the compositions of this invention, rather the materials serve to impart their customary properties to the particular compositions in which they are incorporated.
  • Step 1 Preparation of sodium diamyldithiocarbamate intermediate To a 250 mL 3 -neck round bottom reaction flask equipped with an overhead stirrer, a thermocouple probe, a reflux condenser, a Claisen adapter, and a 25 mL addition funnel, 30.0 g (0.19 mol) of diamyl amine, 15.3 g of a 50 weight percent ⁇ aOH solution (0.19 mol ⁇ aOH) and 100 mL reagent 2-propanol was added. 12.5 mL (0.21 mol) carbon disulfide was charged to the addition funnel. Carbon disulfide was added over a half -hour period. The reaction temperature was maintained at 25-30°C. The product was post-reacted at 25°C for 1 hour.
  • Step 2 Preparation of product 3 - (N, N- diamyldithiocarbamyl) -propionic acid
  • Step 2 Preparation of product 3 - (N, N-ditetradecyldithio- carbamyl) -propionic acid 21.7 g (0.20 mol) of 3 -chloropropionic acid was added to the reactor containing the Step 1 product .
  • the reactor was heated to reflux with the pot temperature maintained at 74 °C for 3 hours.
  • the reaction temperature was then reduced to 30 °C.
  • the product was transferred to a 1000 mL separatory funnel, combined with 100 mL reagant hexanes, and washed four times with 300 mL portions of 60 °C water.
  • the volatiles were removed using a rotary evaporator. 98.8 g of a light yellow product was obtained having a consistency of petroleum jelly at room temperature.
  • EXAMPLE 3 The anti-wear properties of the dithiocarbamyl carboxylic acids of Example 1, Example 2 and those of a conventional zinc dialkyldithiophosphate in two fully formulated lubricating oils were determined employing the Four-Ball Wear Test of ASTM D 4172.
  • Table 1 below sets forth the numerical value of the test results (Average Wear Scar Diameter, mm) . This value decreases with an increase in anti-wear effectiveness.
  • Anti-wear Additive 1 1.0
  • solvent neutral 150 was used m place of the additive at 1 . 0 weight percent

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Dithiocarbamyl carboxylic acids, useful as multifunctional additives for lubricating oils, possess general formula (I), wherein R?1 and R2¿ each independently is a hydrocarbyl group of from 1 to about 60 carbon atoms and R3 is a divalent alkylene group of from 1 to about 20 carbon atoms.

Description

DITHIOCARBA YL CARBOXYLIC ACIDS AND THEIR USE AS MULTIFUNCTIONAL ADDITIVES FOR LUBRICATING OILS
BACKGROUND OF THE INVENTION
This invention relates to dithiocarbamyl carboxylic acids and their use as multifunctional additives for lubricating oils.
Zinc dialkyldithiophosphates (ZDDPs) have been used as anti-fatigue, anti-wear, extreme pressure and friction modifying additives for lubricating oils for many years. However, they are subject to several drawbacks owing to their zinc and phosphorus contents. During operation of an internal combustion engine, lubricating oil enters the combustion chambers by means such as clinging to cylinder walls as the piston makes its down stroke. When phosphorus-containing lubricating oil compositions enter the combustion reaction, phosphorus enters the exhaust stream where it acts as a catalyst poison thus shortening the useful life of the catalytic converter. In addition, the presence of zinc contributes to the emission of particulates in the exhaust.
In view of the aforementioned shortcomings with the known zinc and phosphorus-containing additives, efforts have been made to provide lubricating oil additives which contain neither zinc nor phosphorus. Illustrative of non-zinc (i.e., ashless) , non-phosphorus- containing lubricating oil additives are the reaction products of 2 , 5-dimercapto-l , 3 , 4-thiadiazole and unsaturated mono-, di- and tri-glycerides of U.S. Patent No. 5,512,190 and the dialkyl dithiocarbamate-derived organic ethers of U.S. Patent No. 5,514,189. SUMMARY OF THE INVENTION
In accordance with the present invention, dithiocarbamyl carboxylic acids for lubricant additives are provided having the general formula
Figure imgf000004_0001
R2 S
wherein R1 and R2 each independently is a hydrocarbyl group of from 1 to about 60 carbon atoms and R3 is a divalent alkylene group of from 1 to about 20 carbon atoms .
The foregoing dithiocarbamyl carboxylic acids are useful as ashless anti-fatigue, anti-wear and extreme pressure additives for lubricating oils where they can be employed in total or partial replacement of the ZDDPs currently in use.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The dithiocarbamyl carboxylic acids of this invention can be prepared in accordance with the following sequence of reaction steps:
R3 R1
\ \
NH+CS2+MOH N — O — S — M + H20 (Step 1 )
/ / II
R2 R2 S
R1 R1 \
N C- -M + XR3 C—OH N—C—S— R1—C—OH + MX (Step 2)
R2 / SII R2 / S In the foregoing sequence of reactions, R1, R2 and R3 are each as defined above, M is alkali metal and X is halogen.
In step 1, dihydrocarbylamine R1R2NH is reacted with an equimolar amount of alkali metal hydroxide MOH and carbon disulfide, the latter preferably in slight molar excess, to provide an alkali metal di (hydrocarbyl) thiocarbamate intermediate R1R2NCSSM. Useful dihydrocarbylamines are those in which hydrocarbyl groups R1 and R2 are selected from among alkyl , cycloalkyl, alkaryl and aralkyl groups of up to about 60 carbon atoms. Preferred dihydrocarbylamine reactants are dialkylamines in which each alkyl group contains from about 2 to about 30, and more preferably from about 4 to about 24, carbon atoms. The alkali metal hydroxide is conveniently aqueous sodium hydroxide and the reaction is advantageously conducted in a suitable solvent with water and/or a lower alkanol such as methanol, ethanol, propanol, 2-propanol, isopropanol, n-butanol, sec-butanol or t-butanol. Isopropanol being preferred for this purpose .
In Step 2 , an equimolar amount of haloalkanoic acid, e.g., 3 -chloropropionic acid, is added to the reaction medium of Step 1 where it reacts with alkali metal di (hydrocarbyl) thiocarbamate intermediate to provide product dithiocarbamyl carboxylic acid.
The dithiocarbamyl carboxylic acids of this invention can be utilized in lubricating oil compositions in amounts which impart significant anti -wear characteristics to the oils as well as reducing the friction of engines operating with the oils. Concentrations of from about 0.001 to about 10 weight percent based on the total weight of the lubricating oil composition can be used. Preferably, the concentration is from about 0.1 to about 3 weight percent.
In general, mineral oils, both paraffinic, naphthenic and mixtures thereof, including those oils defined as American Petroleum Institute Groups I, II, and III, can be employed as the lubricant vehicle, and can be of any suitable lubricating viscosity range, as for example, from about 2 cSt at 100°C to about 1,000 cSt at 100 °C and preferably from about 2 to about 100 cSt at
100°C. These oils can have viscosity indexes preferably ranging to about 180. The average molecular weights of these oils can range from about 250 to about 800. Where synthetic oils are employed, they can include, but are not limited to, polyisobutylene, polybutenes, hydrogenated polydecenes, polypropylene glycol , polyethylene glycol, trimethylpropane esters, neopentyl and pentaerythritol esters, di (2-ethylhexyl) sebacate, di (2-ethylhexyl) adipate, dibutyl phthalate, fluorocarbons , silicate esters, silanes, esters of phosphorus-containing acids, liquid ureas, ferocene derivatives, hydrogenated synthetic oils, chain-type polyphenyls, siloxanes and silicones (polysiloxanes) , alkyl -substituted diphenyl ethers typified by a butyl - substituted bis (p-phenoxy phenyl) ether, and phenoxy phenylethers .
It is to be understood, however, that the lubricating oil compositions herein can also contain other materials. For example, corrosion inhibitors, extreme pressure agents, detergents, dispersants, antiwear agents, antioxidants , antifoamants , friction modifiers, low temperature properties modifiers and the like can be used. Examples of these materials include metallic phenates or sulfonates, alkylated diphenylamines , polymeric succinimides , non-metallic or metallic phosphorodithioates and the like. These materials do not detract from the value of the compositions of this invention, rather the materials serve to impart their customary properties to the particular compositions in which they are incorporated.
The following examples are illustrative of the preparation of the dithiocarbamyl carboxylic acids of this invention and their use as anti-fatigue, anti-wear and extreme pressure additives for lubricating oils.
EXAMPLE 1 This example illustrates the preparation of 3-
(N, N-diamyldithiocarbamyl ) -propionic acid.
Step 1: Preparation of sodium diamyldithiocarbamate intermediate To a 250 mL 3 -neck round bottom reaction flask equipped with an overhead stirrer, a thermocouple probe, a reflux condenser, a Claisen adapter, and a 25 mL addition funnel, 30.0 g (0.19 mol) of diamyl amine, 15.3 g of a 50 weight percent ΝaOH solution (0.19 mol ΝaOH) and 100 mL reagent 2-propanol was added. 12.5 mL (0.21 mol) carbon disulfide was charged to the addition funnel. Carbon disulfide was added over a half -hour period. The reaction temperature was maintained at 25-30°C. The product was post-reacted at 25°C for 1 hour.
Step 2: Preparation of product 3 - (N, N- diamyldithiocarbamyl) -propionic acid
20.6 g (0.19 mol) of 3 -chloropropionic acid was added to the reactor containing the Step 1 product . The reactor was heated to reflux with the pot temperature maintained at 70°C for 3 hours. The reaction temperature was then reduced to 30°C. The product was transferred to a 500 mL separatory funnel combined with 100 mL reagant hexanes and washed four times with 500 mL portions of 60°C water. The volatiles were removed using a rotary evaporator. 33.1 g of a light yellow low viscosity clear liquid product was obtained.
EXAMPLE 2 This example illustrates the preparation of 3-
(N, N-ditetradecyldithiocarbamyl ) -propionic acid. Step 1: Preparation of sodium di (tetradecyl) dithiocarbamate intermediate
To a 500 mL 3 -neck round bottom reaction flask equipped with an overhead stirrer, a thermocouple probe, a reflux condenser, a Claisen adapter, and a 25 mL addition funnel, 82.0 g (0.20 mol) of dicoco amine (Armeen 2C, AKZO) , 16.2 g of a 50 weight percent NaOH solution (0.20 mol NaOH) and 100 mL reagent 2-propanol was added. 13.0 mL (0.22 mol) carbon disulfide was charged to the addition funnel. The reactor was heated to 50°C. Once the amine was dissolved, the reaction temperature was reduced to 40°C. Carbon disulfide was added over a half-hour period. The reaction temperature was lowered over the course of the carbon disulfide addition from 40°C to 30°C. The product was post-reacted at 30°C for 1 hour.
Step 2: Preparation of product 3 - (N, N-ditetradecyldithio- carbamyl) -propionic acid 21.7 g (0.20 mol) of 3 -chloropropionic acid was added to the reactor containing the Step 1 product . The reactor was heated to reflux with the pot temperature maintained at 74 °C for 3 hours. The reaction temperature was then reduced to 30 °C. The product was transferred to a 1000 mL separatory funnel, combined with 100 mL reagant hexanes, and washed four times with 300 mL portions of 60 °C water. The volatiles were removed using a rotary evaporator. 98.8 g of a light yellow product was obtained having a consistency of petroleum jelly at room temperature.
EXAMPLE 3 The anti-wear properties of the dithiocarbamyl carboxylic acids of Example 1, Example 2 and those of a conventional zinc dialkyldithiophosphate in two fully formulated lubricating oils were determined employing the Four-Ball Wear Test of ASTM D 4172. The two lubricating oils, Formulations A and B of Table 2 below, also contained 1 wt . % cumene hydroperoxide . Table 1 below sets forth the numerical value of the test results (Average Wear Scar Diameter, mm) . This value decreases with an increase in anti-wear effectiveness.
Table 1: Four-Ball Wear Results
Average
Wear
Motor Oil Scar
Anti-wear Additive Formulation Diametei , mm
3- (N, N-dιamyldιthιocarbamyl) -propionic acid A 0 . 54
3- (N, N-dιtetradecyldιthιocarbamyl) -propionic a icciidd A 0.54
No anti-wear additive A 0 . 93
Zinc dialkyldithiophosphate A 0 . 46
3- (N, JV-diamyldithiocarbamyl) -propionic acid B 0 . 64
3- (N, IV-ditetradecyldith ocarbamyl) -propionic a icciidd B 0.64
No anti-wear additive B 0 . 98
Zinc dialkyldithiophosphate B 0 . 53
Table 2: SAE 10W-30 Motor Oil Formulations
Formulation A wt . % Formulation B wt
Solvent Neutral 100 22.8 Solvent Neutral 100 22 .
Solvent Neutral 150 60 Solvent Neutral 150 60 Succmimide Dispersant 7.5 Succmimide Dispersant 7 , Overbased Calcium Overbased Calcium
Phenate Detergent 2.0 Sulfonate Detergent 2 . 0 Neutral Calcium Neutral Calcium
Sulfonate Detergent 0.5 Sulfonate Detergent Antioxidant 0.5 Antioxidant
Rust Inhibitor 0.1 Rust Inhibitor
Pour Point Depressant 0.1 Pour Point Depressant 0 . 1 OCP VI Improver 5.5 OCP VI Improver 5 . 5
Anti-wear Additive1 1.0 Anti-wear Additive 1 . 0
1In the case where no anti -wear additive was employed , solvent neutral 150 was used m place of the additive at 1 . 0 weight percent
As the data m Table 1 show , the dithiocarbamyl carboxylic acids of this invention performed nearly as well as the known zmc dialkyldithiophosphate additive m both motor oil formulations .

Claims

WHAT IS CLAIMED IS:
1. A dithiocarbamyl carboxylic acid lubricant additive composition of the general formula
Figure imgf000010_0001
wherein R1 and R2 each independently is a hydrocarbyl group of from 1 to about 60 carbon atoms and R3 is a divalent alkylene group of from 1 to about 20 carbon atoms.
2. The dithiocarbamyl carboxylic acid of Claim 1 wherein R1 and R2 each is an alkyl group of from about 2 to about 30 carbon atoms.
3. The dithiocarbamyl carboxylic acid of Claim 1 wherein R1 and R2 each is an alkyl group of from about 4 to about 24 carbon atoms .
4. The dithiocarbamyl carboxylic acid of Claim 1 wherein R3 contains from 2 to about 12 carbon atoms .
5. The dithiocarbamyl carboxylic acid of
Claim 1 wherein R1 and R2 each is an alkyl group of from about 4 to about 24 carbon atoms and R3 contains from 2 to about 12 carbon atoms.
6. The dithiocarbamyl carboxylic acid of Claim 1 which is 3 - (N, N-diamyldithiocarbamyl ) -propionic acid.
7. The dithiocarbamyl carboxylic acid of Claim 1 which is 3- (N, N-ditetradecyldithiocarbamyl ) - propionic acid.
8. A lubricating oil composition comprising a lubricating oil and a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 1.
9. A lubricating oil composition comprising a lubricating oil and a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 2.
10. A lubricating oil composition comprising a lubricating oil and a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 3.
11. A lubricating oil composition comprising a lubricating oil and a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 4.
12. A lubricating oil composition comprising a lubricating oil and a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 5.
13. A lubricating oil composition comprising a lubricating oil and a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 6.
14. A lubricating oil composition comprising a lubricating oil and a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 7.
15. A method for improving at least one functional property of a lubricating oil which comprises adding to the lubricating oil a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 1.
16. A method for improving at least one functional property of a lubricating oil which comprises adding to the lubricating oil a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 2.
17. A method for improving at least one functional property of a lubricating oil which comprises adding to the lubricating oil a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 3.
18. A method for improving at least one functional property of a lubricating oil which comprises adding to the lubricating oil a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 4.
19. A method for improving at least one functional property of a lubricating oil which comprises adding to the lubricating oil a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 5.
20. A method for improving at least one functional property of a lubricating oil which comprises adding to the lubricating oil a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 6.
21. A method for improving at least one functional property of a lubricating oil which comprises adding to the lubricating oil a functional property- improving amount of at least one dithiocarbamyl carboxylic acid of Claim 7.
22. A dithiocarbamyl carboxylic acid of the general formula
R1 0
\ ||
N ΓÇö C S- -R3 ΓÇö C- -OH
/ II
R2 S
wherein R1 and R2 each independently is a hydrocarbyl group of from 1 to about 60 carbon atoms and R3 is a divalent alkylene group of from 3 to about 20 carbon atoms .
PCT/US1997/024233 1997-01-10 1997-12-18 Dithiocarbamyl carboxylic acids and their use as multifunctional additives for lubricating oils Ceased WO1998030660A1 (en)

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