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
  • C10M173/00—Lubricating compositions containing more than 10% water
• • 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
  • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
  • C10M135/10—Sulfonic acids or derivatives 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
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/02—Water
• • 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
  • 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
• • 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
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/01—Emulsions, colloids, or micelles

Definitions

• the invention relates to the use of salts of esters of long-chain fatty alcohols with ⁇ -sulfofatty acids.
• DE-AS 11 49 843 discloses half-amides of saturated or unsaturated dicarboxylic acids and their salts with aliphatic primary amines as additives for fuel oils and ⁇ lubricating oils ⁇ . Although these additives significantly improve corrosion protection, they have an extremely strong tendency to foam, which cannot be accepted in such additives.
• DE-AS 12 98 672 discloses alkali metal or amine salts of sulfonamidocarboxylic acids as corrosion inhibitors with good lubricating properties and little tendency to foam.
• Agents containing these compounds have the disadvantage that they can only be prepared in processes which are complex in terms of manufacturing technology, and because of the relatively high content of sulfonamide groups they can sometimes have a toxic effect or at least have toxic effects expected, which necessitates corresponding toxicological tests.
• the object of the present invention was to provide corrosion-inhibiting compounds for use in oil-containing systems which do not have the disadvantages of the prior art mentioned.
• the compounds should not only be accessible inexpensively in large quantities from regenerable sources, but should also have a corrosion-inhibiting effect which is at least equivalent to the known corrosion inhibitors.
• they should be ecologically and toxicologically harmless, and in particular should be more biodegradable than compounds previously used.
• the salts (III) of esters of long-chain fatty alcohols with ⁇ -sulfofatty acids used according to the invention are derived from long-chain fatty alcohols of the general formula (I) in which R 1 can represent an unbranched or branched alkyl radical or alkenyl radical having 8 to 36 carbon atoms. Although in particular all unbranched or branched alkyl radicals or alkenyl radicals with 8, 9, 10, 11 etc. carbon atoms can be considered for R 1 , those alcohols with alkyl radicals R 1 which are available in large numbers from native sources are particularly preferred Amounts are accessible inexpensively. These are, for example, alcohols (I) in which R 1 represents an unbranched alkyl radical, preferably having 8 to 22 carbon atoms.
• n-alkanols from the group octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, uneicosanol and docosanol are suitable as such.
• Such alcohols, especially the representatives of this group an even number of carbon atoms in the alkyl radical are inexpensive from natural fats and oils via the corresponding fatty acids by reactions known per se for the hydrogenation of the carboxyl group and are available in large quantities on an industrial scale.
• ester salts used according to the invention can not only be derived from the pure long-chain fatty alcohols of the general formula (I), but can also be ester salt mixtures which result from mixtures of such long-chain fatty alcohols (I) obtained in the industrial production process.
• Mixtures of this type in which ester salts of long-chain fatty alcohols of the general formula (I) occur, in which R 1 represents a mixture of unbranched alkyl radicals in the range from 12 to 18, can be regarded as the alcohol mixtures sold under the trademark "Lorol"
• Ester salt mixtures from mixtures of long-chain fatty alcohols (I) can preferably be used, which consist of mixtures of cetyl alcohol, i.e.
• ester salts used according to the invention can also be derived from long-chain fatty alcohols (I) in which R 1 represents a branched alkyl radical.
• R 1 represents a branched alkyl radical.
• Alcohols with such branched alkyl radicals can arise, for example, by subjecting alcohols of synthetic or native origin to the so-called "Guerbet reaction", from which essentially 2-alkylalkan-1-ols are obtained.
• branched alcohols examples include 2-ethylhexanol, 2-hexyldecanol and 2-hexadecyleicosanol. Dimerized unsaturated fatty alcohols can also be used for the esterification. Such alcohol can be considered, for example, dimerized oleyl alcohol ("Sovermal R ").
• the ester salts used according to the invention can also be derived from long-chain fatty alcohols of the general formula (I), the radical R 1 of which is a mono- or polysethylated alkyl radical.
• Such radicals R1 have 8 to 18 carbon atoms in the alkyl radical and also contain 1 to 10 oxethyl groups, it being emphasized that the number of oxethyl groups per alcohol molecule (I) is to be regarded as the average degree of oxethylation of the respective alcohol and, as a result of the production process, in a more or less narrow range can fluctuate.
• esters of long-chain fatty alcohols (I) whose alkyl radical has 12 to 18 C atoms and a number of ethoxy groups in the molecule which is in the range from 3 to 6.
• the ⁇ -sulfofatty acid component of the ester salts used according to the invention has the general formula (II) in which R 2 represents unbranched or branched alkyl radicals having 10 to 20 carbon atoms and M represents half an equivalent of a metal from the group consisting of magnesium, calcium, barium and zinc.
• R 2 can thus be a straight chain Alkyl radicals from the group decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl or also represent the corresponding branched isomers of the alkyl radicals mentioned.
• the ⁇ -sulfofatty acid component of the esters according to the invention preferably originates from fatty acids of natural origin, which can be made available in large quantities from native fats and oils by fat cleavage.
• the naturally resulting fatty acids are converted into the ⁇ -sulfofatty acids of the general formula (II), which are one of the components for the ester salts of long-chain fatty alcohols with ⁇ , which are used according to the invention, by optionally necessary hydrogenating curing and subsequent, known per se, sulfonation in the ⁇ -position to the carboxyl group -Sulfo fatty acids are.
• the fatty acid mixtures resulting from the cleavage of natural fats and oils are preferably used for such esters.
• Preferred mixtures of such fatty acids are those whose C number is in the range from 12 to 18, so that R 2 is an even, unbranched alkyl radical in the range from 10 to 16 for the ⁇ -sulfofatty acid component of the ester salts used according to the invention.
• the educts which lead to the ⁇ -sulfofatty acid components (II) of the ester salts (III) in the manner shown are thus lauric acid, myristic acid, palmitic acid, stearic acid, lauroleic acid, myristoleic acid, palmitoleic acid and oleic acid.
• ester salts used according to the invention can originate from salts (II), in the formula M of which stands for half an equivalent of a divalent metal from the group consisting of magnesium, calcium, barium and zinc.
• Half an equivalent of one of the divalent metals mentioned means that a metal atom is capable of binding two monovalent ⁇ -sulfofatty acid residues.
• the process for producing the ester salts (III) of long-chain fatty alcohols with ⁇ -sulfofatty acid salts used according to the invention is known as such.
• the ester salts of the general formula (III) resulting from this process in which R 1 , R 2 and M can have the meanings given above arise, for example, by reacting the fatty alcohols (I) with ⁇ -sulfofatty acids or their salts of the general formula (II) in a suitable organic solvent - optionally in the presence of catalytic ones Amounts of acid - reacted, the solvent removed by methods known per se and, if desired, the products purified and isolated by methods which are also known.
• Inorganic mineral acids in particular sulfuric acid, in particular, have proven useful as catalysts for the process mentioned is preferred.
• acidic ion exchangers or other acidic catalysts known per se can also be used.
• the esterification reaction is usually carried out in an organic solvent. Examples of such solvents are toluene or xylene.
• the reaction temperatures of the esterification reaction vary depending on the alcohol (I) and oC-sulfofatty acids or their salts (II) used and are normally 0 to 140 ° C.
• the organic solvent is removed by methods known per se. This can be done for example by distillation at normal pressure or reduced pressure. If necessary, the product mixture obtained is then converted into the salts (III) used according to the invention by methods which are also known (neutralization).
• esters or their salts (III) or mixtures of different compounds are then obtained by the process route outlined, namely when as ⁇ -sulfo fatty acid starting material mixtures of compounds of general formula (II) or as fatty alcohol starting material (I) fatty alcohol mixtures were used.
• a preferred way of producing the ester salts of the general formula (III) used according to the invention is, however, to start from fatty acid alkyl esters, preferably fatty acid methyl esters, from partially synthetic or synthetic production, adding these esters according to known methods with SO 3 in the ⁇ -position sulfonate, adapt the sulfonation products by methods which are also known, for example by bleaching with hydrogen peroxide, to the customary quality standard and the fatty acid alkyl esters sulfonated in this way in the ⁇ -position with the addition of an excess of an alcohol R 1 - OH (I), in which R the has meanings given above, to transesterify.
• R 1 - OH (I) in which R the has meanings given above
• Both the salts of the esters of the general formula (III) and mixtures of various such compounds are particularly suitable as corrosion inhibitors in oils and oil-containing emulsions. They are particularly preferably used as corrosion protection agents in lubricating oils, greases, power transmission oils and metalworking emulsions based on mineral oils puts.
• the salts (III) used according to the invention are excellently soluble in mineral oils or oil-containing emulsions and have the great advantage over the anticorrosive agents known from the prior art, such as petroleum sulfonates or comparable compounds, in that they are large in processes which have been known for a long time and have therefore been well studied Quantities can be made inexpensively accessible. In addition, they are completely harmless from a toxicological point of view and can generally be broken down better than the petroleum sulfonates conventionally used as corrosion protection agents.
• the amounts of the salts (III) used according to the invention are, depending on the field of use, in the range from 0.05 to 10% by weight, based on the respective oil base, preferably in the range between 0.5 and 5% by weight. Even at low concentrations, the corrosion-inhibiting effect is comparable to that of conventional agents known from the prior art, and in the case of application concentrations of the same order of magnitude, in some cases even better than the corrosion-inhibiting effect of synthetic sulfonates, such as petroleum sulfonates.
• Chain distribution 240 g (1 mol) of the ester (A) were sulfonated with 72 g (0.9 mol) of SO 3 by liberating the SO 3 contained from 100 g of 65% oleum and gaseous in a mixture with nitrogen in a ratio of 5 vol. -% SO initiated 3/95 vol .-% N 2 at a temperature of 80 ° C over a period of about 1 hour by the ester (a).
• the mixture was left to react at 80 ° C. for about 1/2 h.
• the black sulfonation product was lightened by adding 2% of 35% hydrogen peroxide.
• the ⁇ -sulfoester obtained by sulfonation and transesterification with oleyl alcohol according to Example 1 was neutralized with sodium hydroxide solution instead of calcium hydroxide. By extracting the aqueous isopropanol solution with petroleum ether, all unsulfonated portions were removed. Then the salt solution was evaporated in vacuo and dried. The dry evaporation residue was mixed with ethyl acetate (500 g of ethyl acetate to 20 g of residue) and treated in the heat for 10 minutes at the reflux temperature. The solution became fil trated and evaporated. 4.1% Na were analyzed in the evaporation residue (sodium salt) (calculated: 3.95% Na).
• steel rods material composition: C K 15, surface degreased and sanded
• stirred mixtures of mineral oil and artificial sea water in a ratio of 10: 1 (method B according to DIN 51585) stored at 60 ° C for 24 h.
• sandblasted steel sheets 088 St 1405 (degreased) (dimensions: 25 mm x 50 mm) were immersed in a naphthenic mineral oil that contained ester salts (III) as corrosion inhibitors.
• the test loaded with the corrosion-inhibiting mineral oil After a certain draining time or drying time, the bodies were hung in a moisture chamber and stored for 30 days in a water vapor-saturated atmosphere in accordance with DIN 51359, a continuous air supply of 875 l / h and a temperature of 50 ° C. and a relative humidity of 100% being set. After the prescribed test duration, the test specimens were assessed for signs of corrosion, the evaluation scale given in Example 10 being used as the basis for the degree of corrosion.
• gray cast iron chips were wetted on a round filter with a mineral oil-seawater emulsion in accordance with DIN 51360 / Part 2, this mineral oil emulsion also containing ester salts (III) as corrosion inhibitors in a concentration of 2% by weight contained. After an exposure time of 2 h at room temperature, the corrosion marks on the filter paper were assessed visually according to the method specified in the standard.
• the emulsions were prepared from a concentrate of the following composition by customary methods and using water which had a total hardness of 3.58 mmol CaCl 2 . 6H 2 0 and MgS0 4 . 7H 2 0.
• the gray cast iron chips were wetted with a mineral oil emulsion which did not contain an inhibitor.
• the recipe contained naphthenic mineral oil and emulsifier in a weight ratio of 4: 1.
• Example 13 steel sheets were exposed to a mineral oil emulsion which contained no inhibitor.
• the weight ratio of mineral oil: emulsifier in this emulsion was 4: 1.
• An adduct of 6.5 EO with nonylphenol was used as the emulsifier, and a naphthenic mineral oil was used as the oil.
• the specimens were then stored after a certain draining time and drying time in a humidity chamber with a water vapor-saturated atmosphere (100 % relative air humidity) for 30 days at room temperature. After the end of the test period, the steel sheets were assessed for signs of corrosion, based on the evaluation scale given in Example 10.
• the emulsions were prepared from the corresponding concentrates (see above) using customary methods and using water with a total hardness of 3.58 mmol CaCl 2 .6H 2 O and MgSO 4 . 7H20 manufactured.
• Example 14 Steel sheets of identical quality were treated in the manner given in Example 14, the emulsions not containing any inhibitor.

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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)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Lubricants (AREA)
• Colloid Chemistry (AREA)

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• 1986
  • 1986-05-24 DE DE19863617550 patent/DE3617550A1/de not_active Withdrawn
• 1987
  • 1987-05-16 EP EP87107130A patent/EP0247467A3/fr not_active Withdrawn
  • 1987-05-22 US US07/053,445 patent/US4735735A/en not_active Expired - Fee Related
  • 1987-05-22 BR BR8702639A patent/BR8702639A/pt unknown
  • 1987-05-25 JP JP62129584A patent/JPS62297391A/ja active Pending

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