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

Definitions

• This invention relates to over-based, oil-soluble magnesium salts of sulphonic acids having metal ratios ranging from approximately 10 up to approximately 40 and processes for preparing such over-based magnesium salts of sulphonic acids.
• Over-based, oil-soluble magnesium salts of sulphonic acids are used as additives in oil-based compositions, such as lubricants, greases, fuels, and the like. They function as detergents and acid neutralizers, thereby reducing wear and corrosion and extending the engine life.
• over-based magnesium sulphonates may be prepared in a one-step operation by using a reaction promoter system comprising (1) a carboxylic compound selected from the group of compounds consisting of lower carboxylic acids, lower carboxylic anhydrides, substituted lower carboxylic acids, metal salts and esters of lower carboxylic acids and mixtures thereof, all having from 1 to 5 carbon atoms; (2) water and optionally (3) an alcohol selected from the group of compounds consisting of lower alkanols, lower alkoxy alkanols and mixtures thereof, all having from 1 to 5 carbon atoms.
• a reaction promoter system comprising (1) a carboxylic compound selected from the group of compounds consisting of lower carboxylic acids, lower carboxylic anhydrides, substituted lower carboxylic acids, metal salts and esters of lower carboxylic acids and mixtures thereof, all having from 1 to 5 carbon atoms; (2) water and optionally (3) an alcohol selected from the group of compounds consisting of lower alkanols, lower alkoxy alkanols and
• Additional water and/or alcohol may be added continuously or portion-wise to the reaction mixture during the time that the acidic gas is contacted with the mixture.
• the amount of water used in total should not exceed 30 equivalents per equivalent of sulphonic acid and the total amount of alcohol used should not exceed 35 equivalents per aquiva- lent of sulphonic acid.
• Preferred oil-insoluble carboxylic compounds of his invention are acetic acid, propionic acid, butanoicacid, glycine, chloroacetic acid, bromoacetic acid, glyolic acid, ethyl acetoacetate, sodium acetate, calcium acetate, and magnesium acetate. These compounds may be ued individually or in combination with one another where the amount of this promoter ranges from .5 up to 5 equivalent per equivalent of oil-soluble sulphonic acid. Preferable the amount ranges from 0.7 to 1.3 equivalents.
• the initial reaction mixture should have at least 2 equiva- lente of water per equivalent of sulphonic acid.
• the mixture may have up to 15 equivalents of water where the preferred range in the initial mixture is from 2 to 8 equivalents of water per equivalent of sulphonic acid.
• the total amount of water added to the mixture over the entire reaction time should not exceed 30 equivalents per equivalent of oil-soluble sulphonic acid used.
• the optimum amount of water to be used is determined by the amount of magnesium oxide used and the metal ratio desired because-a larger amount of water results in a product having a higher metal ratio.
• the alcohols used in this process include lower aliphatic alkanols, alkoxy alkanols, and mixtures thereof, where the number of carbon atoms does not exceed 5.
• the alcohols include methanol, ethanol, isopropanol, n-propanol, butanol, and pentanol.
• The'preferred alcohol is methanol because of the low cost and ease of removal from the reaction mixture.
• the alkoxy alkanols include methoxy ethanol and ethoxy ethanol.
• the sulphonic acids to be used in this process are those which are widely known by thoee skilled in the art as oil-soluble sulphonic acids. Such compounds may be derived from natural petroleum fractions or various synthetically prepared sulphonated compounds. Typical oil-soluble sulphonic acids which may be used include:
• the process according to this invention is operative with low sulphonate concentrations which thereby allows the use of oil-based feed stock compositions containing as little as 10% by weight of magnesium sulphonate without further concentration of the oil-based stock.
• the temperatures at which the contacting of the gas with the reaction mixture according to a preferred embodiment may vary from 10 to 93.3°C (50 to 200°F), although preferably within the 48.9 to 76.7°C (120 to 170°F) range.
• magnesium oxide used in a preferred embodiment of the process is the light or active form.
• Such magnesium oxides are sold under the Trade Marks: MAGNESITE, available from Martin Marietta Chemicals, Hunt Valley, Maryland; MICHIGAN No. 3, MICHIGAN No. 15, MICHIGAN No.
• the amount of magnesium oxide used is dependent upon the metal ratio desired in the final product.
• the metal ratio is the ratio of the number of equivalents of magnesium in the over-based compound to the equivalents of sulphonic acid in the over-based compound.
• the non-volatile diluents are generally mineral or synthetic lubricating oils, such as lubricating oils having a viscosity around 100 SUS at 37.8°C (100°F) or higher.
• the volatile diluents which are inert to the reaction are preferably hydrocarbons with boiling points ranging from 65.6 to 148.9°C (150 to 300°F). These can be aliphatic, aromatic, or a mixture of both types of solvents. For example, naptha is a particularly useful diluent.
• Suitable diluents include Stoddard solvent, cycloaliphatic and aromatic hydrocarbons, and corresponding halogenated hydrocarbons, such as chlorobenzene, and other conventional organic diluents generally employed in the over-basing procedures in this particular art of manufacture.
• the amount of diluents used is sufficient to lower the viscosity of the reaction mixture to facilitate mixing thereof during the introduction and contacting of the acidic gases with the mixture.
• the length of time that the acidic gas is contacted with the reaction mixture depends upon the desired level of magnesium in the over-based magnesium sulphonate.
• the contacting of the gas with the mixture may be continued until no further gas is absorbed to indicate that substantially all of the magnesium oxide originally introduced into the system has been reacted to form an over-based magnesium sulphonate.
• the flow rate of the acidic gas being introduced is compared to the flow rate of the gas leaving the system.
• the flow rate of leaving gas almost equals the flow rate of the introduced gas, then the absorbtion is substantially complete.
• An oil-soluble magnesium sulphonate was prepared by charging into a 1 litre reactor, equipped with stirrer, dropping funnel, thermometer, cooling and vent, 310 gm. of a solvent refined lubricating oil having a viscosity of 330 SUS at 37.8°C (100°F) and while stirring vigorously, 103 gm. of 25 percent by weight oleum was added dropwise over a half hour period. The temperature was maintained at 32.2 to 43.3°C (90 to 110°F). The mixture was stirred for an additional 10 minutes and then quenched with 25 gm. water, 310 gm. VM&P naphtha was added and the mixture allowed to settle in a separatory funnel for 3 hours; 80 gm.
• the mixture was heated near its reflux temperature 65.6°C (150°F) and carbon dioxide was introduced while mixing via the dispersion tube into the mixture at a flow rate of 100 ml/min. Carbonation was continued for 2-1/2 hours, during which 8 gm. water and 8 gm. methanol were added after 40 minutes of carbonation and further 4 gm. of water and 8 gm. methanol were added after 80 minutes of carbonation.
• Table 1 illustrates the effect on the metal ratio in varying the amounts of methanol and water used during the carbonation step.
• the procedure is as for Example 2 with water/ methanol additions made at 0, 40 and 80 minutes during the carbonation step.
• Table 2 summarises results of a series of experiments which illustrate the effect of adding the water/methanol at different time intervals. The procedure used in each experiment is similar to that used in Example 2.
• Table 4 summarises the results of a series of experiments which illustrate the use of different promoters. All conditions of the procedure in each experiment are similar to that used in Example 2 except for using an equivalent molar amount of the different promoters as listed.
• over-based magnesium salts of sulphonic acids may be manufactured and used as additives in lubricating oils, greases and other types of oil-based products, such as fuel oils, bunker oils, etc., where the metal ratio of the additives are in the range of 5 to 40.
• the products are permanently soluble in many organic environments and therefore find application as additives in the field of lubricants and fuels.

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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)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Lubricants (AREA)

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Citations (6)

• 1978
  • 1978-11-14 EP EP19780300625 patent/EP0011069B1/fr not_active Expired
  • 1978-11-14 DE DE7878300625T patent/DE2862080D1/de not_active Expired

Patent Citations (6)

Non-Patent Citations (1)

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