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
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/02—Sulfurised compounds
  • C10M135/06—Esters, e.g. fats
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
  • C07G99/00—Subject matter not provided for in other groups of this subclass
  • C07G99/002—Compounds of unknown constitution containing sulfur
• • 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
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/68—Esters
  • C10M129/78—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids, hydroxy carboxylic acids
• • 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
  • C10M2207/28—Esters
  • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
• • 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
  • C10M2207/28—Esters
  • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
• • 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
  • C10M2207/28—Esters
  • C10M2207/283—Esters of polyhydroxy 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/286—Esters of polymerised unsaturated acids
• • 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
  • C10M2207/28—Esters
  • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
• • 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
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
  • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
• • 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
  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2221/043—Polyoxyalkylene ethers with a thioether 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
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
• • 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
  • C10N2040/02—Bearings
• • 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
  • C10N2040/20—Metal working
• • 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
  • C10N2040/20—Metal working
  • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling

Definitions

• R is a monovalent aliphatic remainder of a monocarboxylic acid having a monoethylenic aliphatic chain
• R is a divalent aliphatic remainder of a die] or a divalent group of the formula +ROm+R-, R being a divalent saturated aliphatic radical, m an integer of small value, and R is a divalent aliphatic remainder of dicarboxylic acid.
• the best solution consists in improving the lubricity of the oil, i.e., the resistance of the oil film, particularly by addition of a small amount of sulfurized spermaceti oil.
• the natural spermaceti oil will no longer be available.
• compositions of unsaturated esters from which it is possible to manufacture additives for lubricants which are capable of imparting to the lubricating oils, as well the mineral as the synthetic oils, lubricity, anti-wear and extreme-pressure properties which, in most cases, are higher than those obtained with a sulfurized spermaceti oil.
• compositions of unsaturated esters used as starting compounds in this invention comprise fi'om 10 to I by mole of at least one unsaturated complex ester of the general formula:
• Radicals R may, for example, contain from to 23 carbon atoms and,
• the radicals R which are identical to or different from each other, are saturated or unsaturated, linear or branched divalent aliphatic hydrocarbon remainders of diols or divalent groups of the formula 4 R O ,,,R in which R is a saturated divalent aliphatic hydrocarbon radical containing 2 or 3 carbon atoms and m is a low integer, for example 1 or 2; the radicals R contain for example 2 to 6 carbon atoms.
• R is a saturated or unsaturated, linear or branched divalent aliphatic hydrocarbon remainder of a dicarboxylic acid. It contains for example, from 1 to 20 carbon atoms.
• composition of unsaturated esters used according to the invention are prepared by total esterification of at least one diol of the formula HO R OH by a mixture of at least one monocarboxylic acid of the formula and at least one dicarboxylic acid of the formula in which the radicals R R and R are as defined herein above, the proportion of dicarboxylic acid being preferably from 0.05 to 0.5 mole per mole of monocarboxylic acid and the amount of the mixture of said carboxylic acids being such that all the hydroxy functions of the one or more diols are esterified.
• diols there can be mentioned ethylene glycol, propylene glycol, butenediol, neopentylglycol, hexanediol, diethyleneglycol, triethyleneglycol, dipropyleneglycol and tripropyleneglycol.
• unsaturated monocarboxylic acids there can be mentioned fatty acids such as undecenoic acid and oleic acid.
• unsaturated mixtures of monocarboxylic acids there can be mentioned certain mixtures of fatty acids such as soja oil, colza oil or Tall Oil, which are particularly advantageous since they are easily available.
• dicarboxylic acids there can be mentioned maleic acid, fumaric acid, succinic acid, adipic acid, azelaic acid, trimethyl adipic acid, sebacic acid, dodecanedioic acid, and the alkenylsuccinic acids such as tetrapropenylsuccinic acid.
• the complete esterification of the diol by means of the mixture of monoand di-carboxylic acids may be carried out according to any convenient method.
• the process may include a reflux of a solvent such for example as benzene, toluene or xylene with an azeotropic removal of the formed water and the reaction may be catalyzed with from 0.1 to 2 by weight of an acid such for example as paratoluene sulfonic acid.
• the esterification product may be purified for example by treatment with active earth.
• compositions of unsaturated esters used according to the invention it is possible to make use, instead of the mono and dicarboxylic acids themselves, of certain of their functional derivatives such as chlorides, anhydrides or lower alkyl esters.
• compositions of unsaturated esters used in this invention have, according to the nature and the proportions of their constituents, a degree of unsaturation which may vary from about 0.20 to about 0.60 ethylenic bonds for 100 grams.
• a degree of unsaturation which may vary from about 0.20 to about 0.60 ethylenic bonds for 100 grams.
• the degree of unsaturation of the composition may be more particularly from about 0.24 to 0.42 ethylenic bonds for 100 grams and, in the case of the use of a mixture of monocarboxylic acids of the type of fatty acids of Tall Oil, the unsaturation degree of the composition is more particularly from about 0.35 to 0.61.
• the invention especially relates to sulfur-products from the compositions of unsaturated esters defined hereinabove and more particularly the products whose sulfur content is from 6 to 12 by weight.
• the sulfur content may be higher than 12 and for example as high as 15 by weight.
• compositions of unsaturated esters may be carried out according to any known method. However, best results are obtained by using the following preferred method:
• the reaction mixture under vigorous stirring and under an inert atmosphere with respect to the reactants, is brought to a temperature of from 145 to 175C, during a period of, for example, from to hours.
• the temperature is increased to l 80-200C, during a period of, for example, from 2 to 4 hours.
• a minor portion of the reacted sulfur close to 10 by weight of the total sulfur, is removed in the form of hydrogen sulfide.
• the product obtained, after filtration, is the sulfurized composition according to the invention.
• a composition of unsaturated esters diluted in an amount of, for example, from 10 to 40 by weight of a substrate such as a light mineral oil corresponding for example to grade SAE 10 W or 5 W or a synthetic oil such for example as, isodecyl adipate.
• a substrate such as a light mineral oil corresponding for example to grade SAE 10 W or 5 W or a synthetic oil such for example as, isodecyl adipate.
• the esters obtained by total esterification of an aliphatic alcohol having from 1 to 13 carbon atoms such for example as, n.hexanol, n,heptanol, 2-ethyl hexanol, isononanol or isodecanol
• one or more monocarboxylic acids having from 11 to 23 carbon atoms such as oleic acid (9-octadecenoic) or linoleic acid (9,12-octadecadienoic) or one or more dicarboxylic acids having from 4 to 12 carbon atoms such as maleic, fumaric, succinic, adipic and dodecanedioic acids.
• esters obtained by total esterification of one of the above-mentioned aliphatic alcohols by means of fatty acids of Tall Oil such as already described and particularly, the esters of 2-ethyl-hexanol and isononanol.
• the sulfurized products according to the invention are used as additives for lubricants, as well for mineral as for synthetic oils. Generally, they are added to the lubricant bases in amounts of from 0.5 to 10 by weight and preferably from 1 to 5 by weight of the lubricant bases. They confer to said bases anti-wear and extreme-pressure properties which are substantially improved, without noticeably modifying the pour point.
• the sulfurized products which are theoretically the most interesting for said uses are those which result from the sulfurization of unsaturated ester compositions as formed exclusively from complex esters of formula (1) (100 However in most cases, one has to make use of compositions which also contain a certain amount of unsaturated ester of general formula (2), in order to obtain additives which are miscible in the oils to a sufi'icient extent and which confer to the same satisfactory anti-wear and extreme-pressure properties as well as a good lubricity.
• the mixture of monocarboxylic acids with an aliphatic chain consists of a mix- I ture of fatty acids obtained by distillation of Tall Oil and have the following characteristics and composition:
• additive 111 having the following characteristics:
• EXAMPLE 5 According to the same procedure as in example 1, the reaction is conducted with 368.1 g (2 moles) of undecenoic acid, 135.5 g (1.3 mole) of neopentyl-glycol, 43.8 g (0.3 mole) of adipic acid and 5 g of paratoluene sulfonic acid in 300 ml of toluene.
• EXANIPLE 6 According to the same procedure as in example 1, the reaction is conducted with 565 g (2 moles) of oleic acid, 124.2 g (2 moles) of ethylene glycol, 146 g (1 mole) of adipic acid and 5 g of paratoluene sulfonic acid in 300 ml of benzene. After reflux for 8 hours, 72 g of water is recovered. The contents of the flask is then washed with water and the benzene evaporated. There is obtained 761 g of a composition of unsaturated ester. Thereafter, 200 g of this composition of unsaturated ester, are stirred with 15 g of sulfur and 2 g of zinc oxide under a nitrogen atmosphere for 7 hours at 160C and then for 3 hours at 185C.
• Viscosity at 989C Pour point Sulfur content
• each of them is dissolved, at a concentration of 3 by weight, in a base oil (A) and the properties of the resulting composition are estimated on testing machines.
• the base oil (A) consists of a mixture, by equal amounts, of a mineral oil Neutral and a mineral oil 400 Neutral.
• the testing machines used are, on the one hand, the so-called 4 ball machine (Extreme pressure tester) for determining the load-wear index (L.W.I.), according to the standard ASTM D 2783-71 and, on the other hand, the FZG machine for determining the damage level (i.e., the seizing level estimated in the range of l to 12), and the specific wear (i.e., the average slope of the wear curve before seizing, expressed in mg/hp.hour, according to the German standard DIN 51 354 of January 1970 with weighing of the gears).
• the results are given in table I hereunder.
• a sulfurized composition suitable for use as an additive for lubricants resulting from sulfurization of a composition comprising of from 10 to 100% by moles of at least one unsaturated complex ester of the general formula:
• radicals R contain to 23 carbon atoms and are monovalent aliphatic hydrocarbon remainders of monocarboxylic acids comprising at least one acid having an ethylenic aliphatic chain
• radicals R contain 2 to 6 carbon atoms and are selected from the divalent aliphatic hydrocarbon remainders of diols and the divalent groups of the formula R O m R wherein R is a divalent saturated aliphatic hydrocarbon radical and m is about 1 or 2 and the radical R contains l to 20 carbon atoms and is a divalent aliphatic hydrocarbon remainder of dicarboxylic acid, said sulfurization being conducted by heating the ester composition in the presence of sufficient elemental sulfur to obtain in said composition about 6-15% by weight of reacted sulfur.
• radicals R are derived from a mixture of monocarboxylic acids which contain at least one acid having a monoethylenic aliphatic chain and at least one acid selected from the acids with a saturated aliphatic chain and the acids whose aliphatic chain has more than one ethylenic unsaturation.
• composition according to claim 2 in which the radicals R contain from 15 to 17 carbon atoms.
• composition according to claim 2 in which the radicals R, are derived from a mixture of fatty acids issued from the distillation of Tall Oil.
• composition according to claim 1 in which the radicals R, are divalent groups of the formula ⁇ R 0),.
• composition according to claim 1 whereinthe degree of unsaturation of the esters prior to sulfurization is about 0.20 to about 0.60 ethylenic bonds per grams.
• composition according to claim 6 wherein the unsaturated ester complex ester comprises less than 100% of ester (1), and wherein the sulfurization is conducted in the presence of zinc oxide.
• composition as defined by claim 1 further reacted with phosphorous sesquisulfide.
• a composition according to claim 1, wherein the ester composition prior to sulfurization further contains about 10-40% by weight of an ester of a monohydric aliphatic alcohol having from 1 to 13 carbon atoms with a monocarboxylic acid having from 11 to 23 carbon atoms.
• a composition according to claim 12 wherein the unsaturated ester complex ester comprises less than 100% of ester (1), and wherein the sulfurization is conducted in the presence of zinc oxide.
• composition according to claim 5 in which the radicals R are derived from a mixture of fatty acids issued from the distillation of Tall Oil.
• a sulfurized composition suitable for use as an additive for lubricants resulting from sulfurization of a composition produced by the total esterification of at least one diol of the formula HO R Ol-l by a mixture of at least one monocarboxylic acid of the formula R CO OH and at least one dicarboxylic acid of the formula HO CO R CO OH, the proportion of dicarboxylic acid being 0.05 to 0.5 mole per mole of monocarboxylic acid in which the radicals R contain 15 to 17 carbon atoms and are monovalent aliphatic hydrocarbon remainders of monocarboxylic acids comprising at least one acid having an ethylenic aliphatic chain, radicals R contain 2 to 6 carbon atoms and are selected from the divalent aliphatic hydrocarbon remainders of diols and the divalent groups of the formula R O m R wherein R is a divalent saturated aliphatic ydrocarbon radical and m is about 1 or 2 and the radical R contains 4 to 6 carbon atoms and
• composition according to claim 1 wherein the sulfurization is conducted in the presence of zinc oxide.

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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)

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• 1972
  • 1972-03-30 FR FR7211419A patent/FR2177592B1/fr not_active Expired
  • 1972-09-15 FR FR7232928A patent/FR2199550B2/fr not_active Expired
• 1973
  • 1973-03-19 BE BE1004903A patent/BE796956A/xx not_active IP Right Cessation
  • 1973-03-27 DE DE2315119A patent/DE2315119A1/de not_active Ceased
  • 1973-03-27 US US345285A patent/US3915950A/en not_active Expired - Lifetime
  • 1973-03-27 GB GB1475873A patent/GB1417615A/en not_active Expired
  • 1973-03-30 NL NL7304514A patent/NL7304514A/xx not_active Application Discontinuation
  • 1973-03-30 IT IT22357/73A patent/IT981768B/it active

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