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
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
  • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
  • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
  • F02B1/00—Engines characterised by fuel-air mixture compression
  • F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
  • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder

Definitions

• the present invention relates to detergent-dispersant additives for lubricating oils based on alkylarylsulfonates of alkaline earth metals which do not exhibit a foaming tendency and this regardless of the nature of the starting alkylarylsulfonic acid.
• the Applicant has found additives based on alkylarylsulfonates which do not exhibit a foaming tendency, whether during their preparation or during their use and this whatever the nature of the alkyl radical (s), namely linear, branched or partially branched.
• alkylarylsulfonic acids will be understood below as the acids obtained by sulfonation of at least one alkylbenzene, alkylorthoxylene or alkyltoluene in which the alkyl radical (s) (that or those attached to the benzene, orthoxylene or toluene group) contain from 15 to 40 carbon atoms and are derived from linear olefins, branched olefins and / or olefin oligomers, as well as those obtained by sulfonation of petroleum fractions or mixtures of said acids.
• alkyl radical that or those attached to the benzene, orthoxylene or toluene group
• the molecular mass of said acids expressed as the sodium salt generally corresponds to a value of 400 to 600; they are generally used in solution at least around 40% in dilution or non-diluted Itnile.
• basic alkaline earth base is understood to mean the theoretical part of an alkaline earth base to be dispersed in the medium, that is to say that which is not attached to the alkylaryl sulfonic acid.
• a variant of the said process consists in introducing in the 1st stage all or part of the reagents present in the 2nd stage.
• Another variant of the process consists in carrying out a carbonation stage using carbon dioxide from the medium obtained in the second stage, prior to stage 3) of elimination of water and alcohol, and this when the alkaline earth base / alkylarylsulfonic acid molar ratio is at least 1.2, preferably at least 1.3.
• alkaline-earth bases which can be used, mention may be made of calcium oxides, hydroxides or carbonates, barium, magnesium, and more particularly lime and "active" magnesium oxide.
• those with a boiling point higher than 100 ° C. are preferably chosen such as linear or branched aliphatic monoalcohols containing from 4 to 10 carbon atoms such as isobutanol, alfol 6, 2-ethylhexanol, C 8 -C 10 OXO alcohols. It is advantageous industrially to use those immiscible with water (that is to say those whose solubility in water is less than 10% by weight at ordinary temperature) because they can be recycled at will by simple decantation of the aqueous phase.
• the amount of alcohol to be used depends on the linearity rate of the "alkyl” radical (s); the higher this rate, the greater the quantity of alcohol.
• the chloride ions can be used via ammonium chloride, calcium chloride, zinc chloride, etc.
• paraffinic oils such as 100 Neutral oil, as well as naphthenic or mixed oils.
• the amount of oil favorably used is such that the amount of oil contained in the final product (including that optionally coming from the starting alkylaryl sulfonic acid) represents from 20 to 60% by weight of said product, preferably 25 to 55% and very particularly from 30 to 40% by weight of the said product.
• the detergent-dispersant additives for lubricating oil obtained by the process described above have a TBN (Total Basic Number - Standard ASTM D 2896) which can range up to around 40, an alkaline-earth / alkylarylsulfonic acid molar ratio of between 0.51 and 1.3 (preferably between 0.55 and 1.2) being then sufficient.
• TBN Total Basic Number - Standard ASTM D 2896
• alkaline-earth / alkylarylsulfonic acid molar ratio between 0.51 and 1.3 (preferably between 0.55 and 1.2) being then sufficient.
• Higher TBN products of up to about 100 can be obtained by using in the 1st step an alkaline earth / alkaryl sulfonic acid molar ratio of up to 1.8 (preferably up to 1.6 ) and by carrying out an additional carbonation step prior to step 3) of elimination of water and alcohol.
• This carbonation step is favorably carried out at a temperature between 90 and 180 ° C, preferably between 110 and 170 ° C, using an amount of C0 2 between that which can be completely absorbed by the reaction medium and 30% excess of this amount. If necessary, a mixture of water and alcohol can be introduced at the end of carbonation to reduce the viscosity of the medium to a value of the order of 100 to 600 cst at the temperature of the reaction.
• Said detergent-dispersant additives can be added to the lubricating oils in an amount which can range up to 1.7% by weight (which corresponds to approximately 0.04% of calcium) for a petrol engine oil; up to 3.5% (which corresponds to approximately 0.08% of calcium) for a diesel or marine engine oil; up to 11.5% (which corresponds to approximately 0.25% calcium) for a protective oil.
• the lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as naphthenic, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products.
• hard coal and synthetic oils for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide in the presence water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkyl biphenyl ethers, polymers of silicon.
• Additional additives may also be present in said lubricating oils alongside detergent-dispersants obtained according to the process of the invention: there may be mentioned, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives, etc.
• the medium is brought to 60 ° C. and a sulfonic acid solution sold by ESSO under the name AS 107 is introduced over 30 minutes; it is a solution of approximately 70% in an oil of an alkylaryl sulphonic acid having a branching rate of approximately 75%, consisting mainly of alkyl benzenesulphonic and whose molecular mass of the sodium salt is close to 490, which corresponds to an apparent molecular mass of the acid solution of approximately 650.
• the medium is brought to and maintained at 100 ° C.
• Example 8 prepared without formic acid is slightly viscous; the reaction is less complete but is however feasible industrially.
• the measurement methods are as follows:
• the viscosity is measured after diluting the product in 100 N oil until a solution with a total calcium level of 2.9% is obtained. When said product has a total calcium level of less than 2.9%, the viscosity is then measured on the product as it is.
• An additive is prepared based on monosuccinimide, zinc dithiophosphate and comprising approximately 75% of product to be tested, additive which is dissolved in 10% in a base oil 350 N CFR.
• the additive prepared for the compatibility test is subjected to the sequence 1 at 24 ° C. of the ASTM D 892 test carried out in a viscous oil SAE 50.
• Example 4 The operation described in Example 4 is carried out at a temperature of 110 ° C. instead of 100 ° C.
• Example 4 The operation described in Example 4 is carried out at a temperature of 85 ° C instead of 100 ° C.
• This example describes the preparation of an alkylbenzene sulfonate of low TBN (equal to 8).
• Example 4 The operation described in Example 4 is carried out by adding 2-ethylhexanol before water in the 2nd step. The results obtained are equivalent.
• a test is carried out according to the same general operating method, starting from a 40/60 mixture by weight of AS 107 and a solution of approximately 50% in an oil of a fully branched alkylbenzene sulfonic acid (consisting of 72% about acid monoalkylbenzene sulfonic and approximately 28% dialkylbenzene sulfonic acid), the molecular weight of the sodium salt of which is approximately 420, which corresponds to an apparent molecular weight of the acid solution of approximately 800 and obtained by sulfonation of heavy from the alkylation of benzene by the propylene tetramer.
• the ramification rate of the mixture is approximately 90%.
• Example 28 The operation described in Example 28 is carried out using a 70/30 mixture by weight of AS 107 and the 50% solution of fully branched alkylbenzene sulfonic acid used in the previous example.
• the branching rate is approximately 82.5%.
• Ethylhexanol is separated by decantation from the distillate obtained in Example 29, then it is recycled in a reaction medium identical to that of the 1st step of Example 29 and a new operation is carried out similar to that of Example 29 .
• Example 4 The operation described in Example 4 is carried out from an alkylorthoxylene sulfonic acid derived from a linear poly a olefin containing 18 carbon atoms (approximately 95% solution in an oil).
• the molecular weight of the acid is approximately 460.
• Example 4 The operation described in Example 4 is carried out by introducing the CaCl 2 solution and 2-ethylhexanol in the first step of the process instead of the second step.
• Example 21 The operation described in Example 21 is carried out by replacing acetic acid with the same weight of glycolic acid.
• a test is carried out according to the same general operating procedure, starting from a mixture of the 50% solution of fully branched alkylbenzene sulfonic acid used in Example 28 and an 85% solution of a totally branched alkylbenzene sulfonic acid.
• linear obtained from a mixture of 90% linear C 20 -C 24 olefin and 10 X linear C 24 -C 28 olefin
• the molecular weight of the sodium salt of which is approximately 490, which corresponds to an apparent molecular mass of the acid solution of approximately 550.
• Example 28 A test is carried out according to the same general operating procedure from the 50% solution of fully branched alkylbenzene sulfonic acid used in Example 28.
• An alkalinized alkylbenzene sulfonate is prepared from the 70/30 mixture by weight of sulfonic acids used in Example 29.
• the first two steps are carried out according to the general procedure using the quantities of products indicated in Table VII.
• the product obtained is then carbonated for 60 min at 100 ° C using 42 g of C0 2 , then a mixture of 52 g of water and 178 g of 2-ethylhexanol is added; the medium is left at 100 ° C for 45 min.

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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)
• Lubricants (AREA)

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• 1984
  • 1984-05-25 FR FR8408208A patent/FR2564830B1/fr not_active Expired
• 1985
  • 1985-05-15 DE DE8585400957T patent/DE3572007D1/de not_active Expired
  • 1985-05-15 EP EP85400957A patent/EP0164286B1/de not_active Expired
  • 1985-05-20 BR BR8502363A patent/BR8502363A/pt not_active IP Right Cessation
  • 1985-05-20 US US06/735,788 patent/US4764295A/en not_active Expired - Lifetime
  • 1985-05-21 JP JP60107090A patent/JPS6112793A/ja active Granted
  • 1985-05-23 MX MX027035A patent/MX172213B/es unknown
  • 1985-05-24 CA CA000482361A patent/CA1224804A/fr not_active Expired

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