WO2012167530A1 - 一种润滑油清净剂及其生产工艺 - Google Patents

一种润滑油清净剂及其生产工艺 Download PDF

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Publication number
WO2012167530A1
WO2012167530A1 PCT/CN2011/081332 CN2011081332W WO2012167530A1 WO 2012167530 A1 WO2012167530 A1 WO 2012167530A1 CN 2011081332 W CN2011081332 W CN 2011081332W WO 2012167530 A1 WO2012167530 A1 WO 2012167530A1
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Prior art keywords
component
acid
oil
lubricating oil
alkaline earth
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PCT/CN2011/081332
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English (en)
French (fr)
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缪金清
史争鸣
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无锡南方石油添加剂有限公司
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Priority to EP11827764.9A priority Critical patent/EP2565177B1/en
Priority to US13/519,064 priority patent/US9102895B2/en
Priority to CA2785979A priority patent/CA2785979C/en
Publication of WO2012167530A1 publication Critical patent/WO2012167530A1/zh

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • 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
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • 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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • 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
    • C10N2030/52—Base number [TBN]
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to an additive for producing lubricating oil and a method for producing the same, and particularly to a lubricating oil alkaline earth high alkaline detergent and a production method thereof, and more specifically It relates to a lubricating oil detergent and a method for producing the same.
  • a lubricating oil detergent and a method for producing the same BACKGROUND OF THE INVENTION
  • various additives such as an extreme pressure agent and a detergent are often added to the lubricating base oil. , dispersants, antioxidants, tackifiers, etc.
  • a detergent is a surface active substance that adsorbs solid particulate contaminants in lubricating oil and suspends contaminants on the surface of the lubricating oil to ensure that the oil that participates in the lubrication cycle is clean to reduce high temperatures and paint.
  • the existing lubricating oil detergents mainly include low alkalinity synthetic calcium alkylbenzenesulfonate, high alkalinity linear alkylbenzene synthetic calcium sulfonate, long chain linear alkylbenzene high alkalinity synthetic calcium sulfonate, high alkali.
  • the alkaline earth metal salt of the organic carboxylic acid has dispersibility, which helps to ensure that the inside of the engine cylinder is kept clean, and the carbon deposit in the groove of the piston and the piston is offset, thereby preventing the piston ring from sticking, so that it can be cleaned as lubricating oil.
  • the agent cleaning dispersant
  • the preparation process of alkaline (or overbased) alkaline earth metal salts of organic acids is also a known process. Overbasing provides an alkaline reserve, so when an alkaline (or overbased) alkaline earth metal salt of an organic acid is used as a lubricating oil component, it neutralizes the acidic compound formed during engine operation.
  • any sludge which may be present is dispersed due to the dispersibility of the organic acid alkaline earth metal salt, and the acidic substance which accelerates the formation of the sludge is neutralized.
  • Overbased salicylic acid is prepared by overbasing the corresponding alkyl salicylic acid or methyl salicylate.
  • the alkyl group typically has a long chain alkyl group of greater than about 14 carbon atoms to achieve sufficient oil solubility.
  • the conventional preparation method of alkyl salicylic acid is to first alkylate phenol to form alkylphenol, and then carbonate by the Corbe-Schmidt reaction to form alkyl salicylic acid; or use ⁇ -olefin under catalyst catalysis, For example, sulfuric acid, methane acid, acid clay, etc., are directly alkylated with salicylic acid or methyl salicylate.
  • US Patent No. 1998 750 A discloses the condensation of salicylic acid with any non-aromatic monohydric alcohol having 5 to 7 carbon atoms, or the formation of a pentyl, hexyl, cyclohexyl, heptyl compound with salicylic acid and any in the presence of sulfuric acid.
  • U.S. Patent No. 3,372,116 A discloses the preparation of alkaline salicylic acid, which is substituted with (A) a hydrocarbon substituted phenol or a neutral or alkaline earth metal salicylic acid between 25 ° C and reflux temperature. Salt, (B) about 1-10 equivalents per equivalent of (A) basic calcium, and (C) carbon dioxide, in an amount equivalent to about 0.002-0. 2 equivalents of a carboxylic acid or alkali metal containing about 100 carbon atoms, The alkaline earth metal salt is reacted in the presence of the equivalent amount of the basic calcium to obtain an alkaline salicylic acid.
  • 4,810,398 A discloses the preparation of a basic alkaline earth metal organic salt of a mixed carboxylic acid.
  • the preparation method comprises: (a) preparing in a hydrocarbon solvent: one equivalent of an organic mixture mixed with a carboxylic acid, and one equivalent or more of an alkaline earth metal hydroxide and/or an oxide; (b) introducing an equivalent of each in the mixture Equivalent excess of alkaline earth metal of at least 0.5 equivalents of carbon dioxide; and (c) removal of residual solids and aqueous layers, if any.
  • the mixed organic carboxylic acid comprises a C8-C30-containing alkylsalicylic acid and one or more carboxylic acids, wherein the alkyl group in the carboxylic acid may be branched and contains 4 to 40 carbon atoms.
  • This mixed carboxylic acid organic salt has dispersing properties and is suitable for use in lubricating oils and fuels.
  • U.S. Patent 4,869,837 A discloses the preparation of a basic alkaline earth metal organic salt of a mixed carboxylic acid.
  • the preparation method comprises: (a) preparing one equivalent of an organic mixture mixed carboxylic acid in a hydrocarbon solvent, and one or more equivalents of an alkaline earth metal hydroxide and/or an oxide; (b) introducing a equivalent equivalent of each equivalent in the mixture The excess alkaline earth metal is at least 0.5 equivalents of carbon dioxide; and (c) the residual solids and water layers are removed, if any.
  • the mixed organic carboxylic acid comprises an oil-soluble alkylsalicylic acid and one or more substituted succinic or succinic anhydrides having an alkyl number average molecular weight of from 120 to 5,000.
  • 4,876,020 A discloses a lubricating oil formulation comprising a lubricating base oil, one or more highly alkaline alkaline earth metal aromatic carboxylates, and a polyalkane having a molecular weight of from 150 to 1500. A stabilizer for oxy alcohols.
  • U.S. Patent No. 5,049, 685 A discloses a substituted salicylic acid and its salts which are said to have good solubility in water, organic solvents or organic polymeric materials. The substituted salicylic acid and its salt are excellent in sterilization, can kill microbial compounds, and have a stabilizing effect on a polymer or a recording material developer.
  • 5,415,792 A discloses an overbased alkylsalicylic acid component for use in lubricating oil additives.
  • the highly basic alkylsalicylic acid component imparts detergency and dispersibility to the lubricating oil and provides a base value reserve.
  • U.S. Patent No. 5,434,293 A discloses a process for the alkylation of alkylsalicylic acid using a solid acid alkylation catalyst. In the process, the molar amount of alkylation feedstock and alkylsalicylic acid is about equal.
  • U.S. Patent 5,451,331 A discloses a process for producing a lubricant additive having a total base number greater than 300.
  • the process comprises a reaction process for reacting an alkylsalicylic acid, an alkaline earth metal base, a lubricating oil, carbon dioxide and an alcohol at a high temperature, in which an inorganic halide or an alkanoic acid ammonium salt must be used.
  • U.S. Patent No. 5,458,790 A discloses a lubricating oil additive having a total base number greater than 300.
  • the additive comprises a reaction-modified lubricating oil soluble overbased alkaline earth metal hydrocarbyl salicylic acid, which mainly comprises: (a) an aldehyde, (b) 2 to 40% by weight of the additive, at least (i) a carboxylic acid Or (ii) a bis- or poly-carboxylic acid or anhydride, acid chloride or ester having from 36 to 100 carbon atoms, and a lubricating oil.
  • U.S. Patent No. 5,652,203 A discloses the preparation of a lubricating oil additive.
  • an aromatic carboxylic acid ester is first subjected to a cycloalkylation reaction with an olefin, and then reacted with an oxide or hydroxide or alkoxide of a divalent metal and with carbon dioxide, and then removed from the reaction mixture. Water and/or alcohol formed.
  • the lubricating oil additive provides excellent oxidative stability, low carbonization and cleanliness compared to conventional commercially available additives.
  • U.S. Patent No. 5,734,078 A discloses an alkyl salicylic acid production process.
  • the alkylsalicylic acid has a substituted alkyl group having at least 6 carbon atoms which is prepared by using salicylic acid and an olefin having at least 6 carbon atoms at a high temperature using sulfuric acid as a catalyst.
  • the alkylsalicylic acid is overbasrated at 50-100 ° C in the presence of a solvent.
  • U.S. Patent No. 5,792,735 discloses a lubricating oil composition suitable for use in low or medium speed diesel engines.
  • the composition comprises a fuel oil and some hydrocarbyl-substituted phenolates having a total base number greater than 30 G, and at least one hydrocarbyl-substituted salicylate, and a hydrocarbyl-substituted sulfonate, and a lubricating oil component.
  • the hydrocarbyl-substituted phenate is modified by a formula of RCH ⁇ CO ⁇ , wherein R is a C10-C24 alkane
  • the base is hydrogen or an alkyl group of C, C4, such as stearic acid.
  • U.S. Patent No. 6,034,039 A discloses a composite detergent which provides better deposition control and corrosion protection of crankcase lubricating oil.
  • the lubricating oil composition contains a mixture of at least two metal detergents, the detergent (a) is a metal phenate, a sulfonate, a salicylate, a naphthenate or a carboxylate, and the detergent (b) is A calcium overbased detergent comprising a surfactant system derived from at least two surfactants, at least one of which is a gramified or unvulcanized phenol or a derivative thereof, another or at least The other is a non-phenolic surfactant which, as described herein, has a ratio of said phenol in the surfactant system of at least 45 wt%, ⁇ : »/ of the overbased detergent.
  • the ratio of surfactants is at least 14, preferably at least 15, especially at least 19.
  • U.S. Patent No. 6,2009,36 A discloses the process of aromatic hydrocarbons containing salicylic acid and their overbased products and their use as lubricating oil additives.
  • U.S. Patent No. 6,348,438 A discloses the preparation of a highly basic monoaromatic cyclic hydrocarbon-based salicylic acid alkaline earth metal salt which is a single aromatic which is overbased.
  • a mixture of cycloalkyl salicylic acid, at least one solvent, a metal hydroxide, and an alkyl polyol alkaline earth metal hydroxide are reacted with carbon dioxide, the alkyl group of which contains one to five carbon atoms.
  • the overbased metal monoaromatic cyclic hydrocarbyl salicylic acid is treated with a long chain carboxylic acid before, during or after overbasing to form a monoaromatic cyclic hydrocarbyl salicylic acid-carboxylate.
  • U.S. Patent Nos. 6,596, 038 A and 6,682, 874 A disclose a linear compound oligomer or polymer comprising an unsubstituted or substituted phenol, and an unsubstituted or substituted salicylic acid, and a synthetic process thereof.
  • the compounds are useful lubricants and fuel additives, and the metal salts of these compounds are useful lubricating oils.
  • Patent 6,599,867 A discloses an overbased detergent containing organic aromatic carboxylic acids, such as hydrocarbons.
  • Salicylic acid salt used as a lubricant additive.
  • the overbased detergent has a total base number of 200 or more, an active ingredient of 70% by weight or more, a kinematic viscosity at 100 Torr of less than 1000 crypt 7s and a basicity index (BI) of less than 13.
  • BI basicity index
  • U.S. Patent No. 7,009,072 A discloses the production of oil-soluble alkylsalicylic acid with a linear alpha-olefin alkylated salicylic acid of C14 or higher, which is subsequently neutralized with lime and then with methanol.
  • a hydrocarbon is used as a solvent, and under a condition of less than 60 ° C or a boiling point close to methanol, carbon dioxide is overbased, and a hydrocarbon solvent is filtered and removed to obtain an overbased oil-soluble alkylsalicylic acid product.
  • U.S. Patent No. 7,045,654 A discloses an alkyl salicylic acid production process. The process comprises reacting salicylic acid with an olefin having at least four carbon atoms at elevated temperature under conditions of a perfluorodecylsulfonic acid, alkylsulfonic acid or acidic clay as a catalyst.
  • 7,087,575 A discloses the use of styrenated salicylates having antioxidant properties as additives.
  • the neutralization reaction and the overbasing reaction are carried out under the conditions of using methanol as a promoter to obtain an overbased styrenated calcium salicylate or a magnesium salt thereof.
  • No. 7,456,136 A discloses a linear compound and a metal or boron-containing metal salt thereof comprising one or more carboxy-containing phenols or derivatives thereof, one or more hydroxyaromatic hydrocarbons having an average of at least C18 hydrocarbyl groups substituted Or a unit thereof, the unit being bridged by one or more divalent groups.
  • a concentrate comprising a linear compound or a metal salt and an organic diluent, and a composition of a lubricating oil comprising a small amount of a linear compound or a metal salt thereof and a large amount of a lubricating base oil.
  • lubricating oil detergents of the above kind in the preparation of the above detergents, it is necessary to use an inorganic halide or an alkanoic acid ammonium salt, and a hydrocarbon solvent is used in the preparation process, so that the carbon residue is used. The value is higher.
  • the present invention is directed to the deficiencies of the prior art, and provides an alkyl salicylic acid alkaline earth metal salt detergent used in lubricating oil and a production process thereof.
  • the alkyl salicylic acid alkaline earth metal salt of the present invention is prepared by mixing an oil-soluble alkylsalicylic acid or an alkyl salicylate into a mineral oil diluent (SN 150 ), adding an approximately equivalent amount of Ca0, and then The mixture is heated to 120 ° C, ethylene glycol is slowly added dropwise at this temperature, and the alkyl salicylic acid is stirred and neutralized, followed by drying nitrogen to drive off all the water formed in the reaction, and then adding more in portions. CaO and ethylene glycol, and at the same time pass carbon dioxide.
  • an alkylsalicylic acid or alkyl salicylate having the following specific molecular structural formula prior to neutralization or overbasing is used in the present invention:
  • The is hydrogen or an alkyl group containing 1 to 3 broken atoms
  • the R 2 is an alkyl group containing 10 to 50 carbon atoms
  • n is an integer from 1 to 2.
  • the invention relates to an alkaline earth metal salicylate production process, the process comprising the steps of:
  • step (B) neutralized oil-soluble alkylsalicylic acid or alkane obtained in step (A) under the conditions of adding ethylene glycol and optionally carboxylic acid or carboxylic anhydride at a temperature of from 120 ° C to 180 ° C Basal salicylate Carbon is overbased alkalinized oil-soluble alkylsalicylic acid or alkyl salicylate;
  • the alkaline earth metal salicylate production process of the present invention does not require the use of an inorganic halide or an alkanoic acid ammonium salt, and the production process does not require the use of a hydrocarbon solvent.
  • an oil-soluble alkylsalicylic acid or methyl salicylate may be used as the raw material, but an oil-soluble alkylsalicylic acid is preferred.
  • Alkyl salicylic acid can be prepared from the Kolbe-Schmi t t reaction route and can also be obtained by direct alkylation of salicylic acid with an olefin.
  • the oil-soluble alkylsalicylic acid may contain more than one, for example two or three substituted alkyl groups.
  • the substituted pit base has a carbon number of at least 12, preferably between 14 and 30.
  • the alkyl group preferably contains from 14 to 26 carbon atoms.
  • the alkyl group may be linear or branched, but is preferably linear.
  • Suitable olefins include, but are not limited to, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icosylene, 1-eicoadiene, 1-tetracosene, and the above olefins. Mixture, etc.
  • the oil-soluble alkylsalicylic acid is mixed with a mineral oil diluent (SN150), and then an equivalent equivalent of CaO is added, and the mixture is heated and stirred at 120 ° C to neutralize the alkylsalicylic acid.
  • Ethylene glycol was added dropwise at 120-180 ° C while the generated water was removed by dry nitrogen, then more CaO and ethylene glycol were added, and alkalized by carbon dioxide.
  • the invention relates to a process for preparing or producing an alkaline earth metal salicylic acid comprising the steps of:
  • the process for preparing or producing an alkaline earth metal salicylic acid of the present invention also does not require the use of an inorganic facet or an alkanoic acid ammonium salt as compared to the prior art, and the production process does not require the use of a hydrocarbon solvent.
  • the present invention is directed to an alkaline earth metal alkyl salicylate detergent prepared by the process of the present invention, comprising an alkyl salicylate, an alkyl salicylate detergent, or a mixture thereof.
  • the alkali is added in an amount sufficient to provide an overbased salt, that is, the equivalent ratio of the equivalent of the metal component to the alkyl salicylic acid is usually greater than 1.2, sometimes as high as 1 or more. Big.
  • the overbased alkaline earth metal alkyl salicylate of the present invention may be obtained by overbasing a neutral alkaline earth metal alkyl salicylate to produce an alkaline earth metal carbonate such as calcium carbonate and magnesium carbonate. Or alkaline earth metal borate, such as magnesium borate.
  • the base number of the ketone salicylate detergent is not limited, but usually its total base number ranges from about 100 to 400 mg of potassium hydroxide per gram, preferably from about 150 to 350 mg of potassium hydroxide per gram. .
  • ethylene glycol may be added once in the course of the reaction, or may be added in multiple portions during the reaction.
  • the metal base may be added once in the course of the reaction, or may be added in multiple portions during the reaction.
  • the preparation process of the present invention is preferably a hydrocarbon-free solvent, however, an inert hydrocarbon solvent may be used, which may be aliphatic or aromatic.
  • Suitable examples include diterpene, naphtha, aliphatic alkanes and cycloalkanes.
  • a base oil as a diluent.
  • the base oil can be animal oil, vegetable oil or mineral oil.
  • the base oil is preferably a petroleum derived base oil such as a cycloalkyl, paraffinic or mixed base oil.
  • the lubricating oil may be a synthetic oil such as a synthetic ester or a polyolefin lubricating oil, or a semi-synthetic oil.
  • the carbon dioxide used in the preparation of the overbased alkyl salicylate may be in the form of a gas or a solid, preferably a gas, which may be directly blown into the reaction mixture. Carbon dioxide is usually introduced after the addition of a metal base.
  • calcium oxide is the sole reserve base which is used in the reaction mixture in an amount that achieves a minimum excess of the desired total base number.
  • a particular limitation on the amount of calcium oxide used is based on the fact that the reaction efficiency is high and that almost no solid residue is present after the reaction, and the product is more easily filtered. The limitation of the amount of calcium oxide used in the present invention is more favorable than other processes.
  • the overbasing process does not require a metal halide catalyst.
  • the catalyst can also be used in the process of overbasing the production of overbased metal salts.
  • the catalyst may be an inorganic compound or an organic compound, but is preferably an inorganic compound.
  • Suitable inorganic compounds include [3 ⁇ 4 hydrogen, metal halides, ammonium halides, metal alkanoates, ammonium alkanoates or mono-, di-, tri- or tetra-alkyl ammonium or alkanoates.
  • suitable catalysts include calcium chloride, ammonium chloride, calcium acetate, ammonium acetate, zinc acetate, and tetramethyl (ammonium acetate). The catalyst is usually used in an amount of up to about 2% by weight.
  • Suitable reaction temperatures for the process of the present invention range from about 50 to 200 ° C, preferably from about From 100 ° C to 180 ° C, more preferably from about 120 ° C to 160 ° C, the time of passing carbon dioxide is such that sufficient carbon dioxide is delivered to the reaction mixture to complete the reaction.
  • the process of the present invention does not contain a solvent after the ethylene glycol is removed by vacuum distillation, and the highly basic alkyl salicylic acid obtained after filtration. If necessary, it may be further steamed to remove a portion of the diluent oil to increase the base number of the overbased alkyl salicylate to above 400.
  • the process for preparing a high base alkyl salicylate comprises: alkylsalicylic acid, optionally with other carboxylic acids or carboxylic anhydrides or calcium or potassium cross-acids (for convenience)
  • alkylsalicylic acid optionally with other carboxylic acids or carboxylic anhydrides or calcium or potassium cross-acids (for convenience)
  • this process can be applied to magnesium compounds in a mixture of cerium and magnesium), in a diluent oil with calcium oxide or hydrogen. Calcium oxide reacts and introduces carbon dioxide bubbles, thereby adding excess calcium carbonate to the alkyl salicylate. If calcium sulfonate or calcium carboxylate is present, it is also incorporated into the sulfonic acid 4 or calcium carboxylate to impart a product.
  • the desired reserve base value is also incorporated into the sulfonic acid 4 or calcium carboxylate to impart a product.
  • Dispersants are optional components in the process of producing highly basic alkyl salicylates.
  • a useful dispersant is a product of the reaction of a hydrocarbyl-substituted succinic acid or anhydride with an amine containing at least one primary or secondary amine, for example: polyenepolyamines meet this requirement, and in this regard, ammonia also satisfies this Claim.
  • the bis-succinamide dispersant is a useful dispersant prepared by reacting a hydrocarbyl-substituted succinic acid or succinic anhydride with an amine containing at least two primary and/or secondary nitrogens.
  • Such bis-succinamides such as diene diamine, diethylene triamine, triethylenetetramine or tetraethylene pentamine and N-decyldipropylene triamine bis-polyisobutylene succinamide (for example, Beno it, U.S. Patent No. 3,438,899 A).
  • the above dispersing agents may be used singly or in combination.
  • the preparation process is different from the prior art, but the amount of the raw materials used may be the same as that of the prior art, or may be specifically set according to the reaction formula by those skilled in the art, and the invention of the present invention is not limited thereto. Therefore, the present invention does not specifically limit the amount of the raw material to be added.
  • the highly basic calcium alkylsalicylate detergent of the present invention may be added to the engine or lubricating oil at a weight of from about 0.1 to 25% by weight.
  • the invention is applicable to a variety of lubricating oils.
  • the lubricating oil can be one or more natural oils, one or more synthetic oils, or a mixture thereof.
  • Natural oils include animal and vegetable oils (such as castor oil, lard), liquid petroleum and hydrorefined oils, solvent treated or acid treated paraffinic mineral oils, cyclodecyl based lubricating oils and mixed paraffinic oils.
  • Lubricating oil viscosity base oils derived from coal or shale oil are also suitable for use in the highly basic calcium alkylsalicylate detergents of the present invention.
  • Synthetic lubricating oils include hydrocarbon oils and halogen-substituted hydrocarbon oils such as olefin polymers such as polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutenes, poly(1-hexene), poly( 1-octene) or poly(1-decene); alkylbenzene, such as dodecylbenzene, tetradecylbenzene, dinonylbenzene or di(2-ethylhexyl)benzene; polyphenyl, for example Biphenyl, terphenyl or alkylated polyphenols; alkylated diphenyl ethers; alkylated diphenyl sulfides and derivatives; analogs and/or homologs of the above.
  • olefin polymers such as polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated poly
  • the olefinic oxide polymer and the terminal hydroxyl group are modified derivatives such as esterification and/or etherification to constitute another known synthetic lubricating oil.
  • An example of these polymers is a polyether polymer prepared by the polymerization of ethylene oxide or propylene oxide. Typical but non-limiting examples of these polyether polymers are: methyl polyisopropenol ether having an average molecular weight of 1,000, polyethylene glycol diphenyl ether having a molecular weight of 500 to 1 000, or a molecular weight of 1000 to 1500.
  • Polypropylene glycol ether mono-polycarboxylates such as acetate, mixed C3 to C8 fatty acid esters, and C3 3 oxyacid tetraethylene glycol diester.
  • Another suitable synthetic lubricating oil includes dibasic acid esters such as phthalic acid, succinic acid, and alkane.
  • Succinic acid and alkenyl succinic acid maleic acid, azelaic acid, suberic acid, azelaic acid, fumaric acid, adipate, linoleic acid dimer, malonic acid, alkylmalonic acid And/or alkenylmalonic acid; and esters of various alcohols, typical but non-limiting examples of such alcohols such as butanol, n-hexanol, decadiol, diethylhexanol, ethylene glycol, diethyl Typical but non-limiting examples of glycol monoethers and/or propylene glycols, specific esters include dibutyl adipate, bis(2-ethylhexyl) sebacate, di-n-hexyl fumarate, sebacic acid Dioctyl ester, diisooctyl sebacate, dioctyl sebacate, dioctyl phthalate, dinonyl phthalate,
  • Useful ester synthetic oils also include monocarboxylic acids from C5 to C12, and esters formed from polyols, polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.
  • Silicon based oils such as polyalkyl-, polyaryl-, polyalkoxy- and polyaryloxysiloxane oils and silicate oils are another class of useful synthetic lubricating oils, including tetraethylsilicic acid.
  • Ester tetraisopropyl silicate, tetrakis-(2-ethylhexyl) silicate, tetrakis-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylbenzene) Base) silicate, hexa-4-methyl-2-pentyloxy)disiloxane, poly(methyl)siloxane, and poly(nonylphenyl)siloxane.
  • Other synthetic lubricating oils include esters of liquids formed from phosphorus-containing acids, such as triterpene phenyl phosphate, trioctyl phosphate and diethyl 1-mercaptophosphate, and polymeric tetrahydrofuran liquid esters.
  • Unrefined, refined, or regenerated lubricating oils can also be used in the present invention.
  • Unrefined oils are lubricants that are processed directly from natural or synthetic sources without further purification. For example, oil shale oil obtained directly from an oil shale retorting plant, oil obtained directly from a petroleum distillation plant, or an ester obtained directly from the esterification process without further treatment, are unrefined oils.
  • Refined oils are similar to unrefined oils, except that they have been treated through one or more further purification steps to improve one or more attributes.
  • Various purification techniques such as steaming, solvent extraction, acid or alkali extraction, filtration or seepage, are already in the field. Know the purification technology.
  • the process of obtaining reclaimed oil is similar to that of refined oil, but it is suitable for oils that have already been used.
  • This re-refined oil is referred to as reclaimed or reprocessed oil, which is typically treated by technical means to remove used and degraded additives.
  • the invention is particularly directed to motor oil formulations and additives, and therefore.
  • oil refers to oil that may be used as an engine lubricating oil, and by way of example, includes automotive oil or diesel engine oil.
  • the lubricating oil composition of the present invention is also suitable for use in marine oils, including four-stroke diesel piston engines and two-stroke crosshead engines.
  • the viscosity of the lubricating oil formulated by the present invention should be within the viscosity range of the lubricating oil, and is usually about 45 SUS to 6000 SUS at 100 °F (about 38 ° C).
  • the lubricating oil further comprises one or more overbased alkaline earth metal detergents, at least one of which is a metal containing a neutral and overbased alkyl salicylic acid salicylic acid as described herein. ⁇ 0.
  • the amount of the amount of the detergent composition which is usually from 0.01% to up to 25% by weight, more preferably from 0.1 to 10% by weight, preferably from 0.1 to 5.0%. All weight percentages are by weight of the entire lubricant unless otherwise stated.
  • the amount of additive in the finished lubricating oil will depend on the final properties of use. Marine lubricants typically provide a total base number of 9 to 100; automotive engine oils typically provide a total base number of 4 to 20.
  • the term "total base number" or “TBN” as used herein refers to the number of milligrams of potassium hydroxide per equivalent of one gram of additive. Therefore, a high total base number reflects the product's more alkaline, thus obtaining a larger alkalinity reserve.
  • the total base number component of the additive is readily measured by ASTM Test Method No. D2896 or other equivalent methods.
  • the finished lubricating oil may also contain sufficient one or more conventional lubricating oil additives, for example, viscosity index improvers, antiwear agents, antioxidants, dispersants, rust inhibitors or pour point depressants.
  • viscosity index improvers for example, viscosity index improvers, antiwear agents, antioxidants, dispersants, rust inhibitors or pour point depressants.
  • the alkylsalicylic acid of the present invention can be prepared according to Example 2 of U.S. Patent No. 7,045,654 A.
  • the alkyl salicylic acid preparation method is as follows: In a 6000 liter reactor equipped with a mechanical stirring and reflux condenser apparatus, salicylic acid powder (1100 kg) and C14-C18 ⁇ -olefin (1895 kg) are added.
  • ASTM D2273 is less than 0.05% precipitation.
  • At 100. C has a viscosity of 88 cS t and a total base number of 305, containing 1 1. 0% calcium.
  • the products of the above two examples are compared with the highly alkaline calcium salicylate prepared by other methods, such as the highly alkaline salicylic acid prepared by using decyl alcohol as a promoter.
  • ASTM D2273 has very little precipitation and very low Viscosity.
  • the product prepared by the invention passes the lacquering plate coking test to 'J test high temperature and clean'! ⁇ Raw and sediment control, there is no more than 20 mg of carbon deposit, under the above test conditions, the corresponding overbased sulfonate There is more than 80 mg of carbon.
  • the Applicant declares that the present invention illustrates the detailed composition and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed composition and process flow, that is, it does not mean that the present invention must rely on the above detailed process composition and process flow. Can be implemented. It is to be understood by those skilled in the art that the equivalent of any technical means or the specific mode of the invention is within the scope and the scope of the disclosure.

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Abstract

本发明涉及一种润滑油清净剂及其生产工艺，一种生产TBN从大约100到大约400的润滑油添加剂的工艺方法，所述工艺方法包括在较高的温度下使如下组分反应：组份（A）一种烷基水杨酸或烷基水杨酸酯；组份（B）一种碱土金属类碱，可以一次性添加完或在反应过程中分多次添加；组份（C）至少有一种化合物是（i）醇（ii）羧酸或酸酐；组份（D）基础油；组份（E）二氧化碳，在组份（B）加完后通入或每加一次组份（B）后通入；高碱化后反应混合物在真空下脱去低沸点溶剂，然后过滤得到明亮、清澈的液体产品。

Description

说 明 书
一种润滑油清净剂及其生产工艺 技术领域 本发明涉及一种用于生产润滑油使用中的添加剂及其生产方法， 具体涉及 一种润滑油碱土高碱性洗涤剂及其生产方法， 更具体而言涉及一种润滑油清净 剂及其生产方法。 背景技术 在润滑油的生产过程中， 为使润滑剂得到某种新的特性或改善润滑剂中已 有的一些特性， 往往在润滑油基础油中添加各种添加剂， 比如极压剂、 清净剂、 分散剂、 抗氧剂、 增粘剂等。 在种类繁多的润滑油用添加剂中， 清净剂用途十 分广泛， 在润滑油添加剂中占有很大的比重。 清净剂是一种具有表面活性的物质，它能吸附润滑油中的固体颗粒污染物， 并使污染物悬浮于润滑油的表面， 以确保参加润滑循环的油是清净的， 以减少 高温与漆膜的形成， 从而使得润滑油能将其氧化后生成的胶状物、 积炭等不溶 物或悬浮在油中， 形成稳定的胶体状态而不易沉积在部件上， 或者将已沉积在 发动机部件上的胶状物、 积炭等， 通过润滑油洗涂作用于洗涤下来。 由于上述 物质能同时起到分散剂的作用， 因此采用上述物质的清净剂又名清净分散剂。 现有的润滑油清净剂主要有低碱值合成烷基苯磺酸钙、 高碱值线型烷基苯 合成磺酸钙、 长链线型烷基苯高碱值合成磺酸钙、 高碱值合成二烷基苯磺酸钙、 长链线型烷基苯高碱值合成磺酸镁、 高碱值硫化烷基酚 、 聚异丁婦基丁二酰 亚胺、 硼化聚异丁烯基丁二酰亚胺、 高分子量聚异丁烯基丁二酰亚胺、 硼化高 分子量聚异丁烯基丁二酰亚胺等。 在现有技术中， 使用有机羧酸的碱土金属盐类化合物作为润滑油添加剂是 已知的。 所述有机羧酸的碱土金属盐有分散性， 有助于确保发动机汽缸内侧保 持清洁， 对活塞和活塞的凹槽沉积碳物有抵消作用， 从而防止活塞环粘， 因此 其可以作为润滑油清净剂 （清净分散剂）使用。 有机酸的碱性 （或高碱性）碱土金属盐类的制备工艺也是已知工艺。 过碱 化提供了一个碱性储备， 因此当有机酸的碱性（或高碱性）碱土金属盐作为润 滑油成分时， 其能与引擎工作过程中的形成的酸性化合物发生中和反应。 因此， 任何可能出现的污泥由于有机酸碱土金属盐的分散性被分散， 而能加速污泥形 成的酸性物质会被中和。 高碱性水杨酸是通过过碱化相应的烷基水杨酸或烷基水杨酸甲酯来制备 的。 所述烷基基团通常具有大于约 14个碳原子的长链烷基， 以达到足够的油溶 性。 烷基水杨酸的传统制备方法是先烷基化苯酚， 形成烷基苯酚，然后经科尔贝 -施密特反应碳酸化形成烷基水杨酸； 或用 α -烯烃在催化剂催化下， 比如硫酸、 甲烷橫酸、 酸性白土等， 直接烷基化水杨酸或水杨酸甲酯形成。 美国专利 US 1998750 A公开了水杨酸与任何有 5至 7个碳原子的非芳香族 一元醇縮合，或水杨酸与任何能够在硫酸存在下形成戊基、 己基、 环己基、 庚 基化合物的缩合， 以形成烷基水杨酸。 美国专利 US 3372116 A公开了碱性水杨酸的制备方法， 该方法在 25 °C和 回流温度之间， 用 （A )碳氢化合物取代的苯酚或中性碱金属或碱土金属的水杨 酸盐， （B )大约 1-10当量每当量（A)的碱性钙， 和（C )二氧化碳， 在相当于约 0. 002-0. 2 当量的含有约 100碳原子羧酸或碱金属， 碱土金属盐类每当量所述 的碱性钙存在下反应， 获得碱性水杨酸。 美国专利 US 4810398 A公开了一种混合羧酸的碱性碱土金属有机盐的制备 方法。所述制备方法包括： （a)在烃类溶剂中准备：一当量有机混合物混合羧酸， 和一个当量以上的碱土金属氢氧化物和 /或氧化物； （b)在混合物中引入相当于 每当量过剩的碱土金属至少 0. 5 当量的二氧化碳； 及（c)除去残余固体物和水 层， 如果有的话。 混合有机羧酸包括一个含 C8-C30的烷基水杨酸和一个或多个 羧酸， 所述羧酸中烷基可以是支链的， 其含 4到 40个碳原子。 这种混合羧酸有 机盐具有分散性能， 适合在润滑油和燃料中使用。 美国专利 US 4869837 A公开了一种混合羧酸的碱性碱土金属有机盐的制备 方法。 所述制备方法包括： （a)在烃类溶剂中准备一当量有机混合物混合羧酸， 和一个当量以上的碱土金属氢氧化物和 /或氧化物； （b)在混合物中引入相当于 每当量过剩的碱土金属至少 0. 5 当量的二氧化碳； 及（c)除去残余固体物和水 层， 如果有的话。 混合有机羧酸包括一个含油溶性烷基水杨酸和一个或多个取 代琥珀酸或琥珀酐， 其中的烷基数均分子量为 120至 5000。 美国专利 US 4876020 A公开了一种润滑油配方， 所述润滑油包括一润滑油 基础油， 一个或多个高碱性的碱土金属的芳香羧酸盐， 和具有分子量从 150到 1500的聚烷氧基醇类的稳定剂。 美国专利 US 5049685 A公开了一种据说在水、 有机溶剂或有机高分子物质 中有很好溶解性的取代的水杨酸及其盐。 所述取代的水杨酸及其盐是很好的杀 菌， 能杀灭微生物化合物， 同时对聚合物或记录材料显色剂有稳定作用。 美国专利 US 5415792 A 公开了用于润滑油添加剂的高碱性烷基水杨酸成 分。 所述高碱性烷基水杨酸成分使润滑油具备去污力和分散性， 并能提供碱值 储备。 美国专利 US 5434293 A公开了一种使用固体酸烷基化催化剂来烷基化烷基 水杨酸的方法。 在所述方法中， 烷基化原料和烷基水杨酸的摩尔量大致相等。 美国专利 US 5451331 A公开了一种生产总碱值大于 300润滑油添加剂的工 艺。 所述工艺包含在高温下反应烷基水杨酸、 碱土金属碱、 润滑油、 二氧化碳 和醇的反应过程， 在所述工艺中， 必须使用无机卤化物或链烷酸铵盐。 美国专利 US 5458790 A公开了一种具有总碱值大于 300的润滑油添加剂。 所述添加剂含有反应修饰的润滑油可溶性高碱性碱土金属烃基水杨酸， 其主要 含有： （a)醛， （b)相当于添加剂 2至 40 %重量的， 至少（i)有一种羧酸， 或（i i) 一种含 36至 100个碳原子的双-或聚-羧酸或酸酐、 酰氯或酯， 和润滑油。 美国专利 US 5652203 A公开了一种润滑油添加剂的制备工艺。 在所述工艺 中， 一种芳香族羧酸酯先与烯烃进行环烷基化反应， 然后和二价金属的氧化物 或氢氧化物或醇化物以及和二氧化碳反应， 再从反应混合物清除反应中形成的 水和 /或醇。 与传统市售的添加剂相比， 该润滑油添加剂提供了极好的氧化稳定 性、 低炭化性和清洁度。 美国专利 US 5734078 A公开了一种烷基水杨酸生产工艺。 所述烷基水杨酸 具有取代烷基， 该取代烷基至少有 6个碳原子， 其是由水杨酸与至少含 6个碳 原子的烯烃在高温下用硫酸为催化剂制得。 所述烷基水杨酸在 50-100°C下和有 溶剂存在下过碱化。 美国专利 US 5792735公开了一种适用于低速或中速柴油发动机使用的润滑 油组成。 所述组成包含燃料油和一些含总碱值大于 30G的烃基取代酚盐， 和至 少一种烃基取代水杨酸盐， 和一种烃基替代磺酸盐， 以及润滑油成分。 所述烃 基取代酚盐最好是通过一个分子式为 RCH^CO^改性的，其中 R为 C10-C24的烷 基， 是氢或为 C卜 C4的烷基， 例如硬脂酸。 美国专利 US 6034039 A公开了一种能够提供更好的沉积控制和曲轴箱润滑 油腐蚀保护的复合清净剂。 润滑油组合物含有至少两种金属清净剂的混合物， 清净剂 （a )是一种金属酚盐、 磺酸盐、 水杨酸盐、 环烷酸盐或羧酸盐， 清净剂 ( b )是一种钙高碱性清净剂， 其含有由至少两种表面活性剂衍生的表面活性剂 体系， 其中的至少一种是石克化的或未硫化的酚或其衍生物， 另一种或至少另一 种是非酚表面活性剂， 按此处所述， 所测定的在表面活性剂体系中的所述酚的 比例是至少 45wt%， 该高碱性清净剂的 ΤΒΝ: »/。表面活性剂的比率至少为 14， 优 选是至少 15 , 特別是至少 19。 美国专利 US 6200936 A公开了含水杨酸的芳烃及其高碱化产品的工艺及其 作为润滑油添加剂的使用。 美国专利 US 6348438 A公开了高碱性单芳香环烃基水杨酸碱土金属盐的制 备方法， 所述高碱性单芳香环烃基水杨酸碱土金属盐是由过碱化的单一的芳香 环烃基水杨酸的混合物、 至少一个溶剂、 金属氢氧化物和烷基多元醇碱土金属 氢氧化物与二氧化碳反应制得， 所述烷基多元醇的烷基含一到五个碳原子。 在 过碱化之前、 期间或之后， 用长链羧酸对高碱性金属单芳香环烃基水杨酸进行 处理， 形成单芳香环烃基水杨酸-羧酸盐。 美国专利 US 6596038 A和 US 6802874 A公开了一种线性化合物低聚物或 高聚物， 其含有未取代或取代酚， 和未取代或取代的水杨酸， 及其合成工艺。 所述化合物是有用的润滑剂和燃料添加剂， 这些化合物的金属盐则是有用的润 滑油添力 p剂。 美国专利 US 6599867 A公开了含有机芳香羧酸类的高碱性清净剂， 比如烃 基水杨酸盐， 作为润滑油添加剂使用。 所述高碱性清净剂有 200或更大的总碱 值， 70wt %或更高的有效成分， 在 100Ό时的运动粘度小于 1000隱 7s和碱度指 数（BI ) 小于 13。 美国专利 US 7009072 A公开了用 C14或更高的线性 α -烯烃烷基化水杨酸 来生产油溶性烷基水杨酸， 该油溶性烷基水杨酸随后用石灰中和， 再用甲醇作 为促进剂， 用烃类做溶剂， 小于 60°C或接近甲醇的沸点的条件下， 通二氧化碳 过碱化， 经过滤和脱除烃类溶剂得到高碱性油溶性烷基水杨酸产品。 美国专利 US 7045654 A公开了一种烷基水杨酸生产工艺。 所述工艺包括在 高温下， 在一个全氟垸基磺酸、 烷基磺酸或酸性粘土做催化剂的条件下， 水杨 酸与至少有四个碳原子的烯烃反应。 美国专利 US 7087557 A公开了具有抗氧化性能的苯乙烯化水杨酸盐作为添 加剂使用。 在用甲醇做促进剂的条件下， 进行中和反应和过碱化反应， 得到高 碱性苯乙烯化水杨酸钙或其镁盐。 美国专利 US 7456136 A公开了一种线性化合物及其金属盐或含硼金属盐类 化合物，其包含一个或多个含羧基酚或其衍生物单位，一个或多个平均至少 C18 烃基取代的羟基芳烃或其衍生物单位，所述单位用一个或多个二价基团桥连接。 其还公开了包含线性化合物或金属盐和有机稀释剂的浓缩液， 以及一种包含少 量线性化合物或其金属盐类化合物和大量的润滑基础油的润滑油的组成。 尽管现有技术公开了上述种类的润滑油清净剂 , 但在上述清净剂的制备过 程中， 需要使用无机卤化物或链烷酸铵盐， 并且制备过程中须使用烃类溶剂， 因此其残炭值较高。 发明内容 本发明针对现有技术的不足， 提供了一种润滑油所使用的烷基水杨酸碱土 金属盐清净剂及其生产工艺。 本发明的烷基水杨酸碱土金属盐以油溶性烷基水杨酸或烷基水杨酸盐为原 料， 将其混入矿物油稀释剂 （SN 150 ), 加入接近等当量的 Ca0， 然后将混合物 加热到 120 °C， 在此温度下緩緩滴加入乙二醇， 搅拌中和烷基水杨酸， 随后通 入干燥氮气来驱除反应物中所有生成的水， 然后分批加入更多 CaO 和乙二醇， 并同时通入二氧化碳。 例如， 本发明中使用一种在中和或高碱化之前具有以下特定分子结构式的 烷基水杨酸或烷基水杨酸酯：
Figure imgf000008_0001
所述 ^是氢或包含 1到 3个破原子的烷基， 所述 R2是包含 1 0 到 50个碳原子的烷基， n是从 1 到 2的整数。 另一个方面， 本发明涉及一种碱土金属水杨酸盐生产工艺， 所述工艺包括 以下步骤：
A)中和油溶性烷基水杨酸或烷基水杨酸酯；
B)在 120 °C至 180 °C高温下，在加入乙二醇和可加可不加的羧酸或羧酸酐条 件下， 向步骤（ A )获得的中和的油溶性烷基水杨酸或烷基水杨酸酯通入二氧化 碳以过碱化油溶性烷基水杨酸或烷基水杨酸酯；
C) 过滤步骤（B)的产品；
D) 可视情况进一步真空蒸馏去除一些稀释剂进行浓缩。 相较于现有技术， 本发明的碱土金属水杨酸盐生产工艺无须使用无机卤化 物或链烷酸铵盐， 并且所述生产过程无须使用烃类溶剂。 在本发明的制备工艺中，原料可使用油溶性烷基水杨酸或烷基水杨酸甲酯， 但是， 首选油溶性烷基水杨酸。 烷基水杨酸可从 Kolbe-Schmi t t (科尔比 -施密 特反应）反应路线制得， 还可以从水杨酸与烯烃直接烷基化制得。 所述油溶性 烷基水杨酸可以包含不止一个， 例如两个或三个取代烷基。 取代坑基的碳原子 数至少为 12， 最好是介于 14至 30之间。 当烷基水杨酸主要包含只有一个烷基 取代基时， 则该烷基最好包含 14至 26个碳原子。 所述烷基可以是直链或支链 的， 但优选直链的。 适合的烯烃包括但不限于： 1-十四烯， 1-十六烯， 1 -十八 烯， 1-二十烯， 1-二十二烯， 1-二十四烯， 及上述烯烃的混合物等。 油溶性烷基水杨酸混入矿物油稀释剂 （SN150 ), 然后加入接近同等当量的 CaO, 混合物加热搅拌 120°C , 中和烷基水杨酸。 乙二醇在 120_180°C之间滴入， 同时通干燥氮气驱除生成的水， 然后加入更多的 CaO和乙二醇， 同时通入二氧 化碳进行过碱化。 另一个方面， 本发明涉及一种制备或生产碱土金属水杨酸的过程， 包括以 下步骤：
A) 碱中和油溶性烷基水杨酸或烷基水杨酸酯， 特别是烷基水杨酸甲酯；
B) 在 120 °C至 180 °C高温下， 在添加乙二醇或可加可不加的羧酸或羧酸酐 条件下， 通入二氧化碳以过碱化油溶性烷基水杨酸或烷基水杨酸酯；
C) 过滤步骤（Β)的产品；
D) 可视情况进一步真空蒸馏去除一些稀释剂进行浓缩。 相较于现有技术， 本发明的制备或生产碱土金属水杨酸的过程同样无须使 用无机面化物或链烷酸铵盐， 并且所述生产过程无须使用烃类溶剂。 另一方面， 本发明涉及由本发明的制备工艺制备的碱土金属烷基水杨酸盐 清净剂， 包括烷基水杨酸钙， 烷基水杨酸镁清净剂， 或其混合物。 在本发明的制备工艺中， 所述碱的加入量应足以提供高碱性盐， 即金属成 分碱的当量与烷基水杨酸的当量比值通常大于 1. 2， 有时可高达 1 0或更大。 本发明所述的高碱性碱土金属烷基水杨酸盐可以是通过过碱化一个中性的 碱土金属烷基水杨酸盐， 以产生碱土金属碳酸盐， 如碳酸钙和碳酸镁， 或碱土 金属硼酸盐， 如硼酸镁。 克基水杨酸盐清净剂的碱值是不受限制的， 但是， 通常其总碱值范围在约 100至 400毫克氢氧化钾 /克， 最好是从大约 150到 350毫克氢氧化钾 /克。 在本发明的制备工艺中， 乙二醇可以在反应过程中一次加完， 或在在反应 过程中分多次加。 在本发明的制备工艺中， 金属碱可以在在反应过程中一次加完， 或在在反 应过程中分多次加。 本发明的制备工艺过程最好是无烃类溶剂， 然而， 可以使用惰性烃类溶剂， 它可以是脂肪族或芳香族。 合适的例子包括二曱苯、 石脑油、 脂肪族烷烃和环 烷烃。 从高碱性烷基水杨酸盐作为润滑油添加剂的用途看来， 最好包括基础油作 为稀释剂。 基础油可以是动物油、 植物油或矿物油。 所述基础油最好是从石油 衍生的基础油， 如环烷基、 石蜡基或混合基础油。 另外， 所述润滑油可以是合 成油， 例如合成酯或聚烯烃润滑油， 或半合成油。 在所述高碱性烷基水杨酸盐制备工艺中用到的二氧化碳可以气体或固体形 式， 最好是气体形式， 其可以直接吹入反应混合物中。 二氧化碳通常在加入金 属碱后引入。 在本发明所述的制备工艺中， 氧化钙作为唯一的储备碱， 其在反应混合物 中使用的使用量达到所需总碱值的最小的过量。对于氧化钙使用量的特别限定， 是基于如此设置可使得反应效率高， 而且反应后几乎没有固体残留物存在， 产 品更容易过滤。 本发明对氧化钙使用量的限制， 相较于其他工艺过程更加有利， 如果用甲醇做促进剂、 氧化钙 /氢氧化钙做储备碱， 则往往需要较多过量的金属 碱， 来实现高总碱值和良好的过滤， 这样以来则使得反应后有大量固体残留物 存在， 不利于后续处理。 本发明所述制备工艺过程的另一个优点是， 过碱化过程无需金属卤化物催 化剂。 不过， 如果需要， 也可以在过碱化生产高碱性金属盐类过程中使用催化 剂。 所述催化剂可以是一种无机化合物或有机化合物， 但最好是无机化合物。 适用的无机化合物包括 [¾化氢、 金属卤化物、 卤化铵、 链烷酸金属盐、 链烷酸 铵盐或单-、 双-、 三-或四-烷基甲酸铵或链烷酸盐。 合适的催化剂的例子包括 氯化钙、 氯化铵、 醋酸钙、 醋酸铵、 醋酸锌和四甲基（醋酸銨）。 所述催化剂通 常用量约可达 2 %重量。 本发明所述工艺过程合适的反应温度范围从大约 50-200°C , 最好是从大约 100°C至 180 °C , 更优选从大约 120 °C至 160°C , 通二氧化碳的时间以使得足够 多的的二氧化碳被输送到反应混合物中完成反应为准。 本发明所述工艺在乙二醇被真空蒸馏脱除后， 和经过滤后获得的高碱性烷 基水杨酸益不含溶剂。 如果需要的话， 可以进一步蒸 以除去一部分稀释剂油， 把高碱性烷基水杨酸盐的碱值提高到 400以上。 在一般情况下， 制备高碱值烷基水杨酸盐的工艺过程包括： 把烷基水杨酸， 与可选可不选的其它羧酸或羧酸酐或蹟酸钙或横酸（为方便起见， 下面的讨论 将集中于钙化合物， 但所属领域的技术人员将随时了解， 通过类比， 这个过程 可以被应用到镁化合物， 以 Ά 和镁的混合物中）， 在稀释油中与氧化钙或氢氧 化钙反应， 并通入二氧化碳气泡， 从而把过量的碳酸钙纳入烷基水杨酸盐中， 如果存在磺酸钙或羧酸钙的话， 也纳入磺酸 4 或羧酸钙中， 从而赋予产品所期 望的储备碱值。 在这个过程中， 申请人发现， 添加低分子量醇， 特别是乙二醇， 在高温下能促进钙的碳酸盐形成很好的分散胶束。 分散剂是生产高碱性烷基水杨酸盐过程的可选组分。 一个有用的分散剂是 烃基取代丁二酸或酸酐与至少含一个伯胺或二级胺的胺反应的产物， 例如： 多 烯多胺满足这一要求， 并就此而言， 氨也满足这一要求。 双 -琥珀酰胺分散剂是 有用的分散剂，双 -琥珀酰胺由烃基取代丁二酸或琥珀酸酐同一个含有至少两个 一级和 /或二级氮的胺反应制备。 这种双 -琥珀酰胺， 例如二烯二胺、 二乙烯三 胺、 三乙烯四胺或四乙烯五胺和 N- 曱基二丙烯三胺的双-聚异丁烯琥珀酰胺等 (例如， Beno i t , 美国专利 US 3438899 A )。 上述分散剂可以单独^吏用， 也可 以混合使用。 本发明所述的生产 TBN从大约 100到大约 400的润滑油添加剂的工艺方法， 其制备工艺与现有技术不同， 但其采用的原料的添加量， 可以与现有技术相同， 也可以由所属技术领域的技术人员根据反应式具体设定， 本发明的发明点不在 于此， 因此本发明不对原料的添加量做具体限定。 本发明所述的高碱性烷基水杨酸钙清净剂可以按约 0. 1至 25 %或更多重量 添加到引擎或润滑油里。 本发明适用于各种润滑油。 润滑油可以是一种或多种天然油脂、 一种或多 种合成油， 或它们的混合物。 天然油脂包括动物油和植物油（如蓖麻油、猪油）， 液体石油和加氢精制油， 溶剂处理或酸处理的石蜡矿物油， 环炕基润滑油和混 合石蜡油。 从煤或页岩油产生的润滑油粘度基础油也适用于本发明的高碱性烷 基水杨酸钙清净剂。 合成润滑油包括碳氢油及卤素取代碳氢油类， 如烯烃聚合物， 例如聚丁烯、 聚丙烯、 丙烯-异丁烯共聚物、 氯化聚丁烯、 聚（1 -己烯）、 聚（1 -辛烯）或 聚（1 -癸烯）； 烷基苯， 例如十二烷基苯、 十四烷基苯、 二壬基苯或二（2- 乙基己基）苯； 聚苯， 例如联苯、 三联苯或烷基化聚多酚； 烷基化二苯醚； 烷 基化二苯基硫化物和衍生物； 上述物质的类似物和 /或同系物。 烯氧化聚合物及终端羟基被酯化和 /或醚化等改性衍生物，构成另一种已知 的合成润滑油类。 这些聚合物的典范是由环氧乙烷或环氧丙烷聚合制备的聚醚 聚合物。 这些聚醚聚合物的典型但非限制性的例子为： 平均分子量为 1 000的甲 基聚异丙烯醇醚、 分子量为 500-1 000的聚乙二醇二苯醚或分子量为 1000-1500 的聚丙烯乙二醇醚； 单 -聚羧酸酯， 例如醋酸酯， 混合 C3 至 C8脂肪酸酯， 和 C 1 3含氧酸的四甘醇双酯。 另一种合适的合成润滑油类包括二元酸酯， 例如邻苯二甲酸、 琥珀酸、 烷 基琥珀酸和烯基琥珀酸、 马来酸、 壬二酸、 辛二酸、 癸二酸、 富马酸、 己二酸 酯、 亚油酸二聚体、 丙二酸、 烷基丙二酸和 /或烯基丙二酸； 以及各种醇的酯， 所述醇的典型但非限制性的例子如丁醇、 正己醇、 十二醇、 二乙基己醇、 乙二 醇、二乙二醇单醚和 /或丙二醇， 具体酯的典型但非限制性例子包括己二酸二丁 酯、 癸二酸双（2 -乙基己基） 酯、 富马酸二正己基酯、 癸二酸二辛酯、 壬二酸 二异辛酯、 壬二酸二辛酯、 邻苯二甲酸二辛酯、 邻苯二甲酸二癸酯、 癸二酸双 二十烷醇酯、 对亚油酸二异辛酯酸二聚体以及一摩尔癸二酸与两个摩尔四甘醇 和两摩尔 2-乙基己酸反应所形成的复杂的酯。 有用的酯类合成油还包括从 C5到 C12的一元羧酸， 和多元醇， 多元醇醚， 如新戊二醇、 三羟甲基丙烷、 季戊四醇、 双季戊四醇、 三季戊四醇所形成的酯。 硅基油如聚烷基-、 聚芳基-、 聚烷氧基-和聚芳氧基硅氧烷油和硅酸酯油是 另一类有用的合成润滑油， 它们包括四乙基硅酸酯、 四异丙基硅酸酯、 四-（ 2- 乙基己基）硅酸酯、 四-（4-甲基- 2 -乙基己基）硅酸酯、 四-（对-叔丁基苯基） 硅酸酯、 六 -4-甲基- 2 -戊氧基 )二硅氧烷、 聚（甲基）硅氧烷和聚（曱基苯基 ) 硅氧烷。 其他合成润滑油包括含磷的酸形成的液体的酯， 例如三曱苯基磷酸酯、 磷酸三辛酯和 1 -癸基磷酸二乙酯， 以及高分子四氢呋喃液体酯。 未精炼、 精制、 或再生的润滑油也可以用在本发明中。 未精炼的油是直接 从天然或合成来源并没有进一步的纯化处理的润滑油。 例如， 从油页岩干馏厂 直接获得的油页岩油， 从石油蒸馏厂直接获得的石油， 或直接从酯化过程中获 得未经进一步处理的酯， 都是未精炼的油。 精炼的油与未精炼的油相似， 只不 过他们已在经过一个或多个进一步净化步骤处理， 来改善一个或多个属性。 各 种净化技术， 如蒸榴、 溶剂萃取、 酸或碱萃取、 过滤或渗漉， 在本领域均是已 知净化技术。 再生油的获得过程类似于精炼的油， 但适用于已经使用过的油。 这种重新精炼的油被称为再生或再加工油， 这种再生油通常通过技术处理来清 除使用过失效的添加剂和已分解的油。 本发明尤其针对机油配方和添加剂， 因此。 本文中所使用的术语 "机油" 是指可能用作发动机润滑油的油， 并通过举例的方式， 包括汽车油或柴油发动 机油。 本发明的润滑油成分还适用于船用油， 包括四冲程柴油机柱塞式发动机 和二冲程十字头发动机。 本发明所配制的润滑油的粘度应该在润滑油粘度范围内， 通常在 100°F (约 38°C) 时粘度约 45 SUS到 6000 SUS。 润滑油还包含一个或多个高碱性碱土金 属清净剂， 至少其中之一是含有金属根据本文所述的中性和高碱性烷基水杨酸 水杨酸。 清净剂成分的量， 这通常是 0. 01 %至高达 25重量％， 更好是 0. 1至 10重量％ , 最好是 0. 1至 5. 0 %。 除特别注明外， 所有的重量百分比是占整个 润滑油的重量。 在成品润滑油中的添加剂量将将取决于最终的使用性质。 船用润滑油通常 提供 9到 100的总碱值； 汽车发动机润滑油通常提供 4到 20的总碱值。 本文中所使用的术语 "总碱值" 或 "TBN" 指每 1克添加剂相当的氢氧化钾 的毫克数。 因此， 高总碱值数字反映了产品有更多的碱性， 因此获得一个更大 的碱度储备。 添加剂的总碱值成分很容易由 ASTM 试验方法编号 D2896或其他 等效方法测得。 成品润滑油还可以包含足够的一个或多个传统润滑油添加剂， 例如， 粘度 指数改进剂、 抗磨剂、 抗氧剂、 分散剂、 防锈剂或降凝剂等。 具体实施方式 本发明所述的烷基水杨酸可以根据美国专利 US 7045654 A的实例 2制得。 所述烷基水杨酸制备方法如下所示： 在一个装有机械搅拌和回流冷凝器装置的 6000 升反应器中加入水杨酸粉 ( 1100公斤）和 C14- C18的 α -烯烃（ 1895公斤）的混合物，然后开始以 250-300 转 /分钟搅拌。 一次性加入无水甲基橫酸（ 232公斤 )到所生成的白色悬浮液里。 在氮气保护下加热搅拌， 直到温度升至 120°C。 随着反应的进行， 悬浮物消失， 变成了暗红色的颜色。 在反应器较冷的部位存在升华的水杨酸晶体。 在 120°C 先经过 24个小时静置， 停止加热， 冷却反应混合物。 用轻石脑油 （ 2995公斤） 把产品从反应釜传输到有塑料内衬的沉淀池里， 经沉降得到上相和深色含使用 过的酸催化剂。 真空蒸榴上相来脱除溶剂 （90°C , <10 毫巴的真空）。 得到一 个清澈、 深棕色且不含溶剂的油。 该方法获得的坑基水杨酸的的酸值约为 136。 实施例 1
168克这种不含溶剂、暗棕色油溶性烷基水杨酸，加入到含有 78克基础油、 16克 CaO的反应容器里， 搅拌， 温度升高至 120°C, 慢慢滴加入 28克乙二醇， 通氮气赶除所有生成的水， 一旦没有更多的水出来， 再加入 8克 Ca0， 温度升 高到 160°C, 在 20分钟内通入 8-10克二氧化碳气体。 然后在真空下除去所有 的乙二醇， 蒸馏温度不超过 170°C， 将混合物冷却到大约 100°C, 加助滤剂进行 过滤， 最终得到明亮清晰的高碱性水杨酸钙， ASTMD2273小于 0.05%沉淀。 在 100°C的粘度 40 cSt, 总碱值为 170， 含 6.1 %的钙。 实施例 2
880克这种不含溶剂、 暗棕色油溶性烷基水杨酸， 加入到含有 310克基础 油、 90克 CaO的反应容器里， 搅拌， 温度升高至 120°C , 慢慢滴加入 125克乙 二醇， 通氮气赶除所有生成的水， 一旦没有更多的水出来， 再加入 90克 Ca0， 温度升高到 160 °C ,在 20分钟内通入 40-45克二氧化碳气体，再加入 78克 CaO , 在 20分钟内通入 35克二氧化碳气体。 然后在真空下除去所有的乙二醇， 蒸馏 温度不超过 170 °C , 将混合物冷却到大约 100 °C , 加助滤剂进行过滤， 得到明亮 清晰的高碱性水杨酸 。 ASTM D2273小于 0. 05 %沉淀。在 100。 C的粘度 88 cS t , 总碱值为 305， 含 1 1. 0% 的钙。 上述两个例子的产品在与其他方法制成的高碱性水杨酸钙相比较， 例如当 使用曱醇作为促进剂制备的高碱性水杨酸 ， ASTM D2273有很少的沉淀和非常 低的粘度。 本发明所制备的产品经过成漆板焦化试验来 'J试高温清净' !·生和沉积物控 制， 有不超过 20毫克的积碳， 在上述测试条件下， 相应的高碱性磺酸盐有大于 80毫克的积碳。 可以在不脱离本发明的要旨下对本发明进行很多改进，必须参考了解本发 明所附权利要求保护的范围。 申请人声明，本发明通过上述实施例来说明本发明的详细組成和工艺流程， 但本发明并不局限于上述详细組成和工艺流程， 即不意味着本发明必须依赖上 述详细工艺组成和工艺流程才能实施。 基于所属技术领域技术人员的理解， 任 何技术手段的等效替换或具体方式的选择， 均落在本发明公开范围和保护范围 之内。

Claims

权 利 要 求 书
1. 一种生产 TBN从大约 100到大约 400的润滑油添加剂的工艺方法，其特 征在于， 所述工艺方法包括在较高的温度下使如下組分反应：
组份（A)：一种在中和或高碱化之前具有以下特定分子结构式的烷基水杨酸 或烷基水杨酸酯：
Figure imgf000018_0001
所述 是氢或包含 1到 3个碳原子的烷基，
所述 R2是包含 1 0 到 50个碳原子的烷基，
n是从 1 到 2的整数；
组份（B)—种碱土金属类碱， 可以一次性添加完或在反应过程中分多次添 力 σ ;
组份（C) 至少有一种化合物是 （i ) 醇 （i i) 羧酸或酸酐；
组份（D) 基础油；
组份（E)二氧化碳，在组份（B)加完后通入或每加一次组份 (B)后通入； 高碱化后反应混合物在真空下脱去低沸点溶剂， 然后过滤得到明亮、 清澈 的液体产品。
2. 根据权利要求 1 所述的方法，其特征在于， 所述的碱土金属类碱是 CaO 或 Ca (0H) 2 , 或二者混合物。
3. 根据权利要求 1 所述的方法，其特征在于， 高碱化温度应该在 50°C到 200°C之间， 更好是在介于 1 00°C至 180 °C , 最好是介于 130 °C至 170°C之间。
4. 根据权利要求 1所述的方法，其特征在于， 所述醇是乙二醇。
5. 根据权利要求 4所述的方法，其特征在于， 乙二醇在 20°C到 200°C之间 加入， 更好是在介于 5G °C至 180 °C加入，最好是在介于 120Ό至 160Ό之间加入。
6. 根据权利要求 1所述的方法，其特征在于，所用羧酸或酸酐含 1 0到大约 200个碳原子。
7. 根据权利要求 1所述的方法，其特征在于， 二氧化碳的通入量对碱土金 属类碱 CaO来说过量。
8. 根据权利要求 1所述的方法，其特征在于， 在高碱化结束后， 过滤前脱 除乙二醇， 温度低于 170Ό。
9. 根据权利要求 1所述的方法，其特征在于， 加入一定量过滤助剂。
10.根据权利要求 1所述的方法，其特征在于， 产品可进一步真空蒸馏去除 一部分的稀释油浓缩。
PCT/CN2011/081332 2011-06-09 2011-10-26 一种润滑油清净剂及其生产工艺 WO2012167530A1 (zh)

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EP11827764.9A EP2565177B1 (en) 2011-06-09 2011-10-26 Cleaning agent for lubricating oil and production process thereof
US13/519,064 US9102895B2 (en) 2011-06-09 2011-10-26 Detergent for lubricant oil and production process thereof
CA2785979A CA2785979C (en) 2011-06-09 2011-10-26 Detergent for lubricant oil and production process thereof

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EP2565177A1 (en) 2013-03-06
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US9102895B2 (en) 2015-08-11
CA2785979A1 (en) 2012-12-09
CA2785979C (en) 2015-08-04
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US20140113846A1 (en) 2014-04-24
EP2565177B1 (en) 2016-09-14

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