JP2015193856A - Asphaltene dispersant-containing lubricating compositions - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide lubricating compositions, and specifically, marine diesel engine lubricating compositions.SOLUTION: The present invention relates to lubricating compositions, and specifically to marine diesel engine lubricating compositions, comprising: (a) an oil of lubricating viscosity; (b) an asphaltene dispersant comprising a cyclic head group that contains a nitrogen atom and at least one other heteroatom; and (c) a detergent derived from an alkyl phenol. The invention further provides methods of using such compositions in the operation of engine, particularly marine diesel engines.

Description

  The present invention relates to a lubricating oil composition, and more particularly to a lubricating oil composition suitable for a medium speed diesel engine or a low speed diesel engine, for example, a marine diesel engine including a four-stroke trunk piston engine.

  Lubricating oils for such engines are known and typically include various additives that perform various functions. However, the industry recognizes the problem that these lubricating oil compositions are contaminated with unburned residual fuel oil. This creates a significant problem with the cleanliness of the engine during operation, and this problem is sometimes referred to as “black paint” of asphaltene deposits. This problem is particularly noticeable in marine diesel engines, for example, 4-stroke trunk piston engines where dirty cam chambers and crank chambers face this problem, and usually one type for the crankcase and one type for the cylinder. Often occurs in two-stroke crosshead engines using a separate lubricant. These heavy deposits can occur in the crankcase of these two-stroke engines.

  Lubricating compositions that address the problems of asphaltenes and / or “black paint” deposits such as found in marine diesel engines without reducing the performance of the lubricating composition in other areas, including overall cleanliness Things are needed.

  The present invention relates to a lubricating composition, for example: (a) an oil of lubricating viscosity; (b) an asphaltene dispersant comprising a cyclic head group containing a nitrogen atom and at least one other heteroatom; A marine diesel engine lubricating composition comprising a detergent derived from an alkylphenol is provided.

  In certain embodiments, the compositions of the present invention contain a minimum amount, for example, at least 1% by weight of an alkylphenol detergent, and further include (d) a salicylate detergent, and the total base of the entire composition. Of the number (TBN), some maximum amount, for example, 50% or less, comes from the salicylate detergent, or contains combinations thereof.

  Furthermore, the present invention provides a method of using such compositions during operation of engines, particularly marine diesel engines.

  Various features and embodiments of the invention are described below using non-limiting examples.

(Asphaltene dispersant)
The composition of the present invention contains an asphaltene dispersant comprising a cyclic head group containing a nitrogen atom and at least one other heteroatom.

  In certain embodiments, the asphaltene dispersant contains at least one amidine head group, urea head group, guanidine head group, or combinations thereof. In other embodiments, the head group of the asphaltene dispersant comprises a 5-membered ring, a 6-membered ring, or a combination thereof.

  More specifically, asphaltene dispersants suitable for use in the compositions and methods of the present invention include compounds represented by the following formula:

Wherein for each of formulas (I) and (II), each R ⁰ is independently hydrogen or a hydrocarbyl group containing ¹ to 250 carbon atoms, and each R ¹ is independently A hydrocarbyl group containing 1 to 10 carbon atoms, each R ² is independently hydrogen, a hydroxyalkyl group, or a hydrocarbyl group containing 1 to 50 carbon atoms, and Y is carbon An atom or a nitrogen atom, n is 1 or 2, and m is 0 or 1.

In certain embodiments, each R ⁰ is a hydrocarbyl group containing a sufficient number of carbon atoms to render the compound oil soluble. In other embodiments, R ⁰ is a hydrocarbyl containing 8 or more carbon atoms, or 8 to 250 carbon atoms. In certain embodiments, each R ¹ is a hydrocarbyl group containing 1 to 6 carbon atoms, 1 to 2 carbon atoms, or 1 carbon atom. In certain embodiments, each R ² is hydrogen or a hydrocarbyl group containing 1 to 4 carbon atoms. The hydrocarbyl group present in this formula may include heteroatoms, and in certain embodiments, the hydrocarbyl group (eg, R ⁰ ) is —CH ₂ (CH ₂ ) _m OH or —CH ₂ (CH ₂₎ it may be a group such as _m NH _2, in this case, m is 0-249, or 7-249, or at least 7.

In certain embodiments, the asphaltene dispersant of the present invention is a compound represented by any of the following formulas:
Formula (III):

Formula (IV):

Formula (V):

Formula (VI):

In which each R ¹ is independently a hydrocarbylene group containing 1 to 10 carbon atoms, for each of the above formulas (III), (IV), (V), (VI), R ² is independently hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms, and each R ³ is independently a hydrocarbyl group containing 1 to 50 carbon atoms. , R ⁴ is a hydrocarbyl group containing 1 to 200 carbon atoms, and X is a hydrocarbyl derived from an amine or polyamine containing 1 to 20 carbon atoms and 1 to 5 nitrogen atoms. It is a len group.

In certain embodiments, each R ¹ is 1-6 carbon atoms, 1-2 carbon atoms, or 1
A hydrocarbylene group containing carbon atoms. In other embodiments, at least one R ¹ group contains 1 carbon atom. In certain embodiments, each R ² is hydrogen or a hydrocarbyl group containing 1 to 4 carbon atoms. In certain embodiments, each R ³ is a hydrocarbyl group containing 8 or more carbon atoms, 8-30 carbon atoms, 12-24 carbon atoms, or 12-22 carbon atoms. In other embodiments, at least one R ³ group contains a sufficient number of carbon atoms to render the compound oil soluble. In certain embodiments, R ⁴ is a hydrocarbyl group containing 20 to 200 carbon atoms or 50 to 150 carbon atoms. In certain embodiments, X is 1-5 nitrogen atoms, 1-3 nitrogen atoms, or 2 nitrogen atoms in addition to 2-10 carbon atoms, 4-8 carbon atoms. Or a hydrocarbylene group derived from an amine or polyamine containing 6 carbon atoms.

In certain embodiments, at least one R ² group present in any of the compounds described above is a monounsaturated hydrocarbyl group. In certain embodiments, the R ⁴ group of formula (VI) is derived from polyisobutylene. In certain embodiments, X is derived from a polyalkylene polyamine.

  As shown below, the various hydrocarbyl groups described for the above formula may contain heteroatoms and cyclic groups, which bind two or more hydrocarbyl groups present in the compound. A cyclic group formed by forming a ring. In certain embodiments, the hydrocarbyl group of the above formula contains an alkylamine group and / or a hydroxy group.

  In addition to the compounds described above, the asphaltene dispersants of the present invention may include five-membered urea, imidazoline, imidazole, tetrazole, tetrazoline, tetrazolone, lactam, sultam, thiourea, triazole, triazoline, pyridone, pyrimidone, or combinations thereof The compound containing this may be included.

  Still other examples of compounds that may be present in the asphaltene dispersants of the present invention include dihydropyrimidine, tetrahydropyrimidine, pyrazole, imidazoline, dihydropyrimidinone, triazine, dihydrotriazine, tetrahydrotriazine, oxadiazole, thiadiazole , Dihydrooxadiazole, dihydrothiadiazole, or combinations thereof.

  The above asphaltene dispersant compounds may be used alone or in combination with each other.

(Alkylphenol detergent)
The composition of the present invention includes a detergent derived from an alkylphenol.

  Suitable alkylphenol detergents include phenate detergents such as phenate sulfide (including calcium phenate sulfide). In certain embodiments, the calcium phenate sulfide is a neutral detergent, and in other embodiments, the calcium phenate sulfide is an overbased detergent. The phenate may be a sulfur containing phenate, a methylene bridged phenate, or a mixture thereof. In one embodiment, the phenate is a sulfur-containing phenate.

  In certain embodiments, the alkylphenol detergent is present in the composition of the present invention in an amount of 1% or more by weight of the total composition. In other embodiments, the alkylphenol detergent is present at least 2, 3, 4, 6, 8 or 10% by weight of the total composition.

  In certain embodiments, the alkylphenol detergent provides at least 50% of the total composition TBN. In other embodiments, the alkylphenol detergent provides at least 60%, 70%, 75%, 90% or 95% of the total TBN of the composition. In still other embodiments, the compositions of the present invention are substantially free of other detergents, so that the alkylphenol detergent is greater than 99% and greater than 99.5% of the total TBN of the composition. Or even 100%. In still further embodiments, the alkylphenol detergent may provide at least 50, 60, 75, 90, 99%, or even 100% of the total detergent TBN present in the overall composition.

  The phenate detergent may be a neutral material or an overbased material. Overbased materials, otherwise referred to as overbased or superbasic salts, are generally neutralized according to the stoichiometry of the metal and the particular acidic organic compound that reacts with the metal. It is a single-phase, homogeneous Newtonian system characterized by an excess of metal beyond what would be required for The amount of excess metal is generally expressed in terms of the ratio of substrate to metal. The term “ratio of substrate to metal” is the ratio of the total equivalent of metal to the equivalent of substrate. A more detailed description of this metal ratio terminology can be found in “Chemistry and Technology of Lubricants”, 2nd edition, R.A. M.M. Mortier and S.M. T. T. et al. Orszulik, pages 85 and 86, 1997.

  The overbased alkali metal phenate detergent or alkaline earth metal phenate detergent has a metal ratio of 0.8 or 1.0 to 10, or 3 to 9, or 4 to 8, or 5 to 7. May be. The phenate detergent may be overbased using calcium hydroxide.

  In different embodiments, the alkali metal phenate detergent or alkaline earth metal phenate detergent may have a total base number (TBN) of 30 or 50 to 400, or 200 to 350, or 220 to 300. In this embodiment, it may be 255. In other embodiments, the phenate detergent may have a TBN of 30, 40 or 50-220, 205, or 190, and in another embodiment 150. In still other embodiments, the phenate detergent has a TBN of 300 or more, 350 or more, or 400 or more, or 300 or 350-400, in another embodiment, 395.

  More detailed descriptions of suitable alkali metal phenate detergents or alkaline earth metal phenate detergents can be found in US Pat. No. 6,551,965 and European Patent Publication Nos. 1903093A, 0601721A, 0271262B2, and 0273588B2. To be found.

Suitable phenate detergents may be formed by reacting alkylphenols, alkaline earth metal bases and sulfur, typically the reaction is conducted in the presence of a promoter solvent and is sulfurized. A metal phenate is formed. The alkylphenols useful in the present invention have the formula R (C ₆ H ₄ ) OH, where R contains 8 to 40 carbon atoms, preferably 10 to 30 carbons. It is a linear or branched alkyl group, and the (C ₆ H ₄ ) moiety is a benzene ring. Examples of suitable alkyl groups include octyl, decyl, dodecyl, tetradecyl, and hexadecyl groups.

The alkaline earth metal base may be a calcium, barium, magnesium, and strontium base. Preferred are calcium and magnesium. The most frequently used bases are the above-mentioned metal oxides and hydroxides, such as calcium oxide, calcium hydroxide, barium oxide, barium hydroxide, magnesium oxide and the like. Calcium hydroxide is generally called slaked lime and is most often used.

  The accelerator solvent, sometimes referred to as a mutual solvent, can be any stable organic liquid with appropriate solubility in alkaline earth metal bases, alkylphenols, and sulfurized metal phenate intermediates. Good. Suitable solvents include glycols and glycol monoethers (eg, ethylene glycol, 1,4-butanediol) and derivatives of ethylene glycol (eg, monomethyl ether, monoethyl ether, etc.). In one embodiment, the solvent is one or more vicinal glycols, and in another embodiment, the solvent includes ethylene glycol.

  Sulfur used in this reaction may be elemental sulfur or may be sulfur in a molten form.

  In certain embodiments, the phenate detergent is prepared in the presence of a cosurfactant. Suitable co-surfactants include low basic alkyl benzene sulfonates, hydrocarbyl substituted acylating agents such as polyisobutenyl succinic anhydride (PIBSA), and succinimide dispersants such as polyisobutenyl succinimide. Can be mentioned. Suitable sulfonates include alkylbenzenes derived from olefins having a chain length of C15-C80 or C2-C4 olefins having a chain length of C15-C80 and alkaline earth metals (eg, calcium, barium, magnesium, etc.). Examples thereof include sulfonates derived from sulfonic acids having a molecular weight of preferably more than 400, which are obtained by sulfonating the sulfonic acid. Suitable co-surfactants include PIBSA and / or may be derived from PIBSA, which is itself from polyisobutylene having a number average molecular weight of 300-5000, or 500-3000, or 800-1600. Be guided.

  As noted above, these phenate detergents can be overbased by reacting with carbon dioxide gas in the presence of additional alkaline earth metal bases, typically in the presence of a promoter solvent. Good.

  In one embodiment, the phenate sulfide detergent of the composition may be represented by the following formula:

Where the number y of sulfur atoms may range from 1 to 8, preferably from 1 to 6, even more preferably from 1 to 4, and R ⁵ may be hydrogen or a hydrocarbyl group. , T is hydrogen or a hydrogen-terminated (S) _y bond, ionic or non-phenolic hydrocarbyl group, w may be an integer from 0 to 4, M is hydrogen, a metal of some valence Ions, ammonium ions, and mixtures thereof.

  When M is an equivalent metal ion, the metal may be a monovalent, divalent, trivalent metal, or a mixture of such metals. When monovalent, the metal M may be an alkali metal such as lithium, sodium, potassium, or a combination thereof. When divalent, the metal M may be an alkaline earth metal such as magnesium, calcium, barium, or a mixture of such metals. When trivalent, the metal M may be aluminum. In one embodiment, the metal is an alkaline earth metal and in another embodiment, the metal is calcium.

  The monomer units of structure (VII) are combined in such a manner that they themselves fold together to form an oligomer of hydrocarbylphenol. Oligomers are described as dimers, trimers, tetramers, pentamers, and hexamers when x is 0, 1, 2, 3, 4. Typically, the number of oligomers represented by x is 0-10, preferably 1-9, more preferably 1-8, even more preferably 2-6, even more preferably 2-5. It may be a range. Typically, oligomers are present in significant amounts when the concentration is greater than 0.1 wt%, preferably greater than 1 wt%, and even more preferably greater than 2 wt%. Typically, when the concentration is less than 0.1% by weight, the oligomer is present in trace amounts, for example, oligomers having 11 or more repeating units may be present. Generally, x is 2 or more in at least 50% of the molecules. In certain embodiments, the sulfur-containing phenate detergent comprises a total of less than 20 wt% dimer structure.

In structure (VII), each R ⁵ is hydrogen or a hydrocarbyl group containing 4-80, 6-45, 8-30, or even 9-20, or 14 carbon atoms It may be. In each aromatic ring, the number (w) of R ⁵ substituents other than hydrogen may be in the range of 0-4, 1-3, and may be 1-2, or 1. When more than one hydrocarbyl group is present, the hydrocarbyl groups may be the same or different and are present in hydrocarbyl substituents on all rings to ensure oil solubility. The minimum total number of carbon atoms to do will be 8 or 9. Preferred components include 4-alkylated phenols containing 9 to 14, for example, 9, 10, 11, 12, 13, 14 and 14 alkyl groups, and mixtures thereof. It is done. 4-alkylated phenols typically contain sulfur at the 2-position. The phenate detergent represented by structure (VII) above may be overbased using an alkaline earth metal base (eg, calcium hydroxide).

In certain embodiments, the phenate detergent used in the present invention is an overbased sulfurized alkaline earth metal hydrocarbyl phenate, optionally with the formula R—CH (R ¹ ) —COOH ( Wherein R is a C ₁₀ -C ₂₄ straight chain alkyl group and R ¹ is hydrogen) which may be modified by incorporating at least one carboxylic acid, or carboxylic anhydride or ester. Good. Such overbased phenates may be added (a) a sulfurized alkaline earth metal hydrocarbyl phenate that is not overbased, as described above, (b) may be added all at once or in stages. polyhydric alcohols including good alkaline earth metal base, the (c) 2 to 4 carbon atoms, di - or tri - _(C 2 ~C ₄₎ glycol, or alkylene glycol alkyl ether or polyalkylene glycol alkyl ether (D) lubricating oil present as a diluent, (e) carbon dioxide added after each addition of component (b), and optionally (f) at least one carboxylic acid as defined above. It may be prepared by reacting.

  Component (b) may be from any of the above mentioned earth metals, and in certain embodiments is calcium hydroxide.

Component (c) may be either a dihydric alcohol (eg, ethylene glycol or propylene glycol) or a trihydric alcohol (eg, glycerol). Di - or tri - _(C 2 ~C ₄₎ glycol, either diethylene glycol or triethylene glycol may be appropriate. The alkylene glycol alkyl ether or polyalkylene glycol alkyl ether has the formula R (OR ¹ ) _x OR ² (wherein R is a C ₁ -C ₆ alkyl group, R ¹ is an alkylene group, and R ² is , Hydrogen or C ₁ -C ₆ alkyl and x is an integer from 1 to 6) may be suitable. Suitable examples include monomethyl ether or dimethyl ether of ethylene glycol, diethylene glycol, triethylene glycol or tetraethylene glycol. A particularly suitable solvent is methyldigol. Moreover, you may use the mixture of glycol and glycol ether. In certain embodiments, glycols or glycol ethers are used in combination with inorganic halides. In one embodiment, component (c) is either ethylene glycol or methyldigol, and methyldigol is combined with ammonium chloride and acetic acid.

  In certain embodiments, component (f) is a carboxylic acid used to modify the phenate and has an R group that is an unbranched alkyl group, which has 10 to 24, Or it may contain 18 to 24 carbon atoms. Examples of suitable saturated carboxylic acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. Also, a mixture of acids may be used. Instead of or in addition to the carboxylic acid, an acid anhydride or ester derivative of this carboxylic acid may be used, and preferably an acid anhydride may be used. In one embodiment, the acid used is stearic acid.

  In certain embodiments, sulfur may be added to the reaction mixture in addition to the sulfur already present by component (a). The above reaction may be performed in the presence of a catalyst. Suitable catalysts include hydrogen chloride, calcium chloride, ammonium chloride, aluminum chloride, and zinc chloride.

(Salicylate detergent)
The composition of the present invention may further contain a salicylate detergent. A typical salicylate detergent is a metal overbased salicylate containing a hydrocarbon substituent long enough to promote solubility in oil. Hydrocarbyl substituted salicylic acid can be prepared by reacting the corresponding phenol with its alkali metal salt and carbon dioxide. The hydrocarbon substituents may be those described for carboxylate detergents or phenate detergents.

  More specifically, the hydrocarbon-substituted salicylic acid may be represented by the following formula:

Wherein each R is an aliphatic hydrocarbyl group and y is independently 1, 2, 3, or 4, provided that R and y are at least a total number of carbon atoms provided by the R group. It ’s like seven. In one embodiment, y is 1 or 2, and in one embodiment, y is 1. The total number of carbon atoms provided by the R group is 7-50, in one embodiment 12-50, in one embodiment 12-40, in one embodiment 12-30, in one embodiment 16- 24, in one embodiment 16-18, in one embodiment 20-24. In one embodiment, y is 1 and R is an alkyl group containing 16 to 18 carbon atoms. Overbased salicylic acid detergents and their preparation are described in more detail in US Pat. No. 3,372,116.

  In one embodiment, the metal salt is a product supplied by Infineum USA LP, identified as calcium salicylate dispersed in oil, having a TBN of 168, a calcium content of 6.0% by weight, and a diluent oil Infineum M7101, the concentration of which is 40% by weight.

  In certain embodiments, the salicylate detergent provides 50% or less of the total TBN of the composition. In other embodiments, the salicylate detergent provides 40% or less, 30% or less, 25% or less, 10% or less, or 5% or less of the total TBN of the composition. In yet other embodiments, the composition of the present invention provides that the salicylate detergent is substantially free of salicylate detergent, resulting in no more than 0.5% of the total composition TBN, or composition This leads to 0% of the total TBN. In certain embodiments, the salicylate is present in the compositions of the present invention in an amount such that no more than 30%, or no more than 25% of the total TBN of the composition is provided by the salicylate detergent.

(Oil of lubricating viscosity)
The present invention further includes an oil of lubricating viscosity. Suitable oils include natural and synthetic oils, hydrocracked oils, hydrogenated oils, hydrofinishing oils, unrefined oils, refined oils, oils derived from rerefined oils, and mixtures thereof. Can be mentioned.

  Unrefined oils are generally oils obtained directly from natural or synthetic sources without (or with little) further refining processing.

  Refined oils are similar to unrefined oils, except that they are further processed in one or more refining steps to enhance one or more properties. Purification techniques are known in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, permeation and the like.

  Rerefined oil, also known as reclaimed or reprocessed oil, is obtained by a process similar to that used to obtain refined oil, to remove used additives and oil breakdown products Often further processed by this technique.

  Natural oils useful in making the lubricants of the present invention include animal oils, vegetable oils (eg, castor oil, lard oil), mineral lubricating oils such as liquid petroleum, and paraffinic, naphthenic or paraffin-naphthenic mixtures. These include types of solvent-treated or acid-treated mineral lubricants and oils derived from coal or shale, or mixtures thereof.

Synthetic lubricants are useful and hydrocarbon oils such as polymerized olefins and interpolymerized olefins (eg, polybutylene, polypropylene, propylene isobutylene copolymers); poly (1-hexene), poly (1-octene), Poly (1-decene), and mixtures thereof; alkyl-benzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di- (2-ethylhexyl) -benzene); polyphenyls (eg, biphenyl, terphenyl, Alkylated polyphenyl); alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogs and homologs, or mixtures thereof.

  Other synthetic lubricating oils include, but are not limited to, liquid esters of phosphorus containing acids (eg, tricresyl phosphate, trioctyl phosphate, and diethyl ester of decanephosphonic acid), and polymeric tetrahydrofuran. Synthetic oils may be produced by the Fischer-Tropsch reaction and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes.

The oil of lubricating viscosity is American Petroleum Institute.
It can also be defined as specified in (API) Base Oil Interchangeability Guidelines. The five types of base oil groups are as follows. Group I (sulfur content> 0.03% by weight and / or saturates <90% by weight, viscosity index 80-120); Group II (sulfur content ≦ 0.03% by weight and saturates ≧ 90% by weight) , Viscosity index 80-120); group III (sulfur content ≦ 0.03% by weight, and saturate ≧ 90% by weight, viscosity index ≧ 120); group IV (all polyalphaolefins (PAO)); group V (All others not included in Group I, II, III or IV). Oils of lubricating viscosity include API Group I, Group II, Group III, Group IV, Group V oils, and mixtures thereof. Preferably, the oil of lubricating viscosity is an API Group I, Group II, Group III, Group IV oil, and mixtures thereof. More preferably, the oil of lubricating viscosity is an API Group I, Group II, Group III oil, and mixtures thereof.

(Lubricating composition)
As mentioned above, the composition of the present invention comprises (a) an oil of lubricating viscosity and (b) an asphaltene dispersant comprising a cyclic head group containing a nitrogen atom and at least one other heteroatom; c) cleaning agents derived from alkylphenols.

  In certain embodiments, the composition of the present invention has a TBN of at least 25. In such embodiments, the amount of TBN resulting from the alkylphenol detergent may be any of the minimum percentages described above. In such embodiments, the amount of TBN resulting from the salicylate detergent may be any of the maximum percentages described above.

  In certain embodiments, the lubricating composition of the present invention is a marine diesel engine lubricant.

  The lubricating oil component (a) is present in the lubricating composition of the present invention in an amount of 55-99.9 wt%, 60-98 wt%, 65-96 wt%, or 67-94 wt%. May be. The asphaltene dispersant as component (b) is 0.1 to 6.0 wt%, 0.2 to 5.0 wt%, or 0.5 to 4.0 wt% in the lubricating composition of the present invention. , Or even in an amount of 1.0-4.0% by weight, or 3.0% by weight. The detergent derived from the alkylphenol component (c) is 0.5-30 wt%, 1-25 wt%, 2-22 wt%, or 5-20 wt% in the lubricating composition of the present invention. May be present in an amount of. When present, component (d), the salicylate detergent, is present in the lubricating composition of the present invention in an amount greater than 0 wt% to 10 wt%, 0.1 to 8 wt%, or 0.5 to 5 wt%. May be present in an amount.

The compositions of the present invention may contain additional performance additives that are different from components (a) to (d). If present, these additional additives are present in the lubricating composition of the present invention (separately or in combination) 0-10%, 0.1-7%, 0.0. It may be present in an amount of 2-5% by weight, or even 1-5% by weight.

  Additional performance additives, particularly those that have been used in marine diesel cylinder lubricants, may be present in the lubricating compositions described herein. Among known lubricating additives, there are metal phosphates containing metal compounds represented by the following formula:

In the formula, the R ⁶ group and the R ⁷ group independently are typically hydrocarbyl groups that do not contain an acetylenically unsaturated part and usually do not contain an ethylenically unsaturated part. These groups are typically alkyl groups, cycloalkyl groups, aralkyl groups, or alkaryl groups and contain 3-20, 3-16, or 3-13 carbon atoms. Alcohols that react to give R ⁶ and R ⁷ groups are mixtures of secondary and primary alcohols, such as mixtures of 2-ethylhexanol and 2-propanol, or secondary alcohols (such as 2-propanol and 4 -Methyl-2-pentanol). Such materials are often referred to as zinc dialkyldithiophosphates or simply zinc dithiophosphates. These materials are well known and readily available to those skilled in the field of lubricating formulations. The amount of metal phosphate in the fully formulated lubricant, if present, is 0.1 to 4 wt%, 0.5 to 2 wt%, or 0.75 to 1.25 wt% Also good.

  Additional performance additives that may be present in the compositions of the present invention include metal deactivators, dispersants, antioxidants, antiwear agents, corrosion inhibitors, antiscuffing agents, poles. Examples include pressure agents, foam inhibitors, demulsifiers, friction modifiers, viscosity modifiers, pour point depressants, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

  Metal deactivators may be present, such as benzotriazole, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, 2-alkyldithiobenzothiazole, 2- (N, N-dialkyldithio Carbamoyl) benzothiazole, 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole, 2,5-bis (N, N-dialkyldithiocarbamoyl) -1,3,4-thiadiazole, and 2- Examples thereof include derivatives of alkyldithio-5-mercaptothiadiazole. In one embodiment, the metal deactivator is 5-methylbenzotriazole (tolyltriazole).

Additional dispersants may be present that differ from the asphaltene dispersants described above and are derived from N-substituted long chain alkenyl succinimides such as polyisobutylene having a number average molecular weight of 350 to 5000, or 500 to 3000. An isobutylene succinimide is mentioned. In one embodiment, the present invention further comprises at least one dispersant derived from polyisobutylene succinimide derived from polyisobutylene having a number average molecular weight of 350-5000, or 500-3000. Another type of dispersant that does not contain ash is Mannich base. Mannich dispersants are the reaction products of alkylphenols with aldehydes and amines, where the alkyl group typically contains at least 30 carbon atoms.

  Antioxidants may be present and include diphenylamine, hindered phenols, molybdenum dithiocarbamates, sulfurized olefins and mixtures thereof. Phenol antioxidants include butyl substituted phenols containing 2 or 3 t-alkyl groups, especially t-butyl groups. Also, the para position of the phenol may be occupied by a hydrocarbyl group, including an ester-containing group or a group that bridges two aromatic rings. Antioxidants also include aromatic amines such as alkylated diphenylamines (including, for example, mixtures of nonylated diphenylamine, di-nonylated amine and mono-nonylated amine); sulfurized olefins such as monosulfide or disulfide Or mixtures thereof; and molybdenum compounds. These materials may also perform other functions such as anti-friction agents.

  Corrosion inhibitors may be present, such as amine salts of carboxylic acids such as octylamine octanoate (octylamine salt of octanoic acid), dodecenyl succinic acid or anhydride and fatty acids (eg oleic acid) and polyamines. Condensation products as well as half esters of alkenyl succinic acid with alkenyl containing 8 to 24 carbon atoms reacted with polyglycols.

  Anti-scuffing agents may be present, organic sulfides and polysulfides such as benzyl disulfide, bis- (chlorobenzyl) disulfide, dibutyl tetrasulfide, di-tertiary butyl polysulfide, sulfurized whale oil, sulfurized methyl ester of oleic acid , Sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, sulfurized Diels-Alder adduct, alkylsulfenyl N, N-dialkyldithiocarbamate, reaction product of polyamine and polybasic acid ester, chloro of 2,3-dibromopropoxyisobutyric acid Butyl esters, acetoxymethyl esters of dialkyldithiocarbamic acids, and acyloxyalkyl ethers of xanthogenic acids, and mixtures thereof.

  Extreme pressure (EP) agents may be present, including oil-soluble sulfur-containing EP agents and sulfur chloride-containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents.

  Foam suppressors may be present and include organic silicones such as polyacetates, dimethyl silicones, polysiloxanes, polyacrylates or mixtures thereof. Examples of foam suppressors include polyethyl acrylate, poly 2-ethylhexyl acrylate, polyvinyl acetate, and mixtures thereof.

  Demulsifiers may be present and include propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkylamines, aminoalcohols, diamines or derivatives of polyamines, or mixtures thereof, reacted sequentially with ethylene oxide or substituted ethylene oxide. It is done. Examples of demulsifiers include trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, (ethylene oxide-propylene oxide) polymers, and mixtures thereof.

Pour point depressants may be present, maleic anhydride-styrene copolymer esters; polymethacrylates; polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and aromatics; vinyl carboxylate polymers; and fumaric acid Dialkyl, fatty acid vinyl esters, ethylene-vinyl acetate copolymers, alkylphenol formaldehyde condensation resins, alkyl vinyl ether terpolymers, and mixtures thereof.

  Friction modifiers may be present, such as glycerol esters (eg glycerol monooleate), borated glycerol esters, fatty phosphites, fatty acid amides, fatty epoxides, borated fatty epoxides, alkoxylated fatty amines, borated alkoxyls And fatty amines and esters, including alkylated fatty amines, metal salts of fatty acids, sulfurized olefins, fatty imidazolines, condensation products of carboxylic acids and polyalkylene-polyamines, and amine salts of alkyl phosphoric acids.

  Viscosity modifiers may be present, hydrogenated styrene-butadiene rubber, ethylene-propylene copolymer, polyisobutene, hydrogenated styrene-isoprene polymer, hydrogenated radical isoprene polymer, polymethacrylic acid ester, polyacrylic acid ester, polyalkyl. Styrene, alkenyl aryl conjugated diene copolymers, polyolefins, polyalkyl methacrylates, maleic anhydride-styrene copolymers, and mixtures thereof.

(Industrial use)
The lubricating composition of the present invention is useful in, for example, stationary combustion engines (eg, power plant combustion engines; diesel fuel engines, gasoline fuel engines, natural gas fuel engines or gasoline / alcohol mixed fuel engines). In one embodiment, the internal combustion engine is a four-stroke engine, and in another embodiment is a two-stroke engine, hi one embodiment, the diesel engine is a marine diesel engine.

  The present invention also includes a method of operating an engine (eg, a marine diesel engine and a power plant combustion engine) by lubricating the engine with the composition of the present invention. These methods include operating the engine and supplying the composition described above to the engine.

  In certain embodiments, the compositions of the present invention are used as marine diesel engine system oils and / or crankcase oils. In certain embodiments, the composition of the present invention is not a cylinder oil for marine diesel engines and is not used as a cylinder oil in marine diesel engines.

  Marine diesel engines suitable for use with the compositions and methods of the present invention are not so limited. Suitable engines include 4-stroke trunk piston engines and 2-stroke crosshead engines that utilize system oil. The use of a lubricating oil composition can provide one or more of increased cleanliness, reduced cylinder wear, and reduced deposits, reduced “black paint” build-up.

  The present invention is also derived from (a) an oil of lubricating viscosity, (b) an asphaltene dispersant comprising a cyclic head group containing a nitrogen atom and at least one other heteroatom, and (c) an alkylphenol. A process for preparing a lubricating composition of the present invention comprising mixing with a cleaning agent. Mixing conditions are typically 15 ° C to 130 ° C, 20 ° C to 120 ° C, or even 25 ° C to 110 ° C for 30 seconds to 48 hours, 2 minutes to 24 hours, or even 5 minutes to 16 hours. In the period, the pressure is 86.4 kPa to 266 kPa (650 mmHg to 2000 mmHg), 91.8 kPa to 200 kPa (690 mmHg to 1500 mmHg), or even 95.1 kPa to 133 kPa (715 mmHg to 1000 mmHg).

  This process includes mixing other performance additives as described above into the composition, if desired. Performance additives as required may be added sequentially, separately or as a concentrate.

  When the present invention is in the form of a concentrate (this concentrate may be combined with additional oil to form a finished lubricant, in whole or in part), each of the above-mentioned dispersants, other The ratio of ingredients to diluent oil is typically 80:20 to 10:90 on a weight basis.

(Preparation of asphaltene dispersant)
The following examples provide specific embodiments of the asphaltene dispersants of the present invention and methods for preparing the dispersants. The method for preparing such additives may be generalized and is envisaged to be part of the present invention.

  For example, the additive of the present invention comprises at least one oxygen atom and at least two nitrogen atoms, wherein the nitrogen atoms are separated by two or three carbon atoms and are substantially linear. Which reacts with itself to form a ring structure containing two nitrogen atoms. The substantially linear compound itself comprises a compound containing at least one —COOR group and at least two nitrogen atoms, the nitrogen atoms being separated by two or three carbon atoms. (R may be hydrogen or a hydrocarbyl group, and may contain one or more heteroatoms).

In certain embodiments, the substantially linear compound contains at least 2 nitrogen atoms, and the fatty acid reacts with a compound in which the nitrogen atom is separated by 2 or 3 carbon atoms (eg, Carboxylic acid). In certain embodiments, the carboxylic acid used to prepare the substantially linear compounds, ^'' have, each R -O-C (O) -R ' and R ^"structure R is Independently, it is a hydrogen or hydrocarbyl group, and in certain embodiments, R ^" contains 1-250, 5-200, 10-50, or 16-20 carbon atoms. R ^" May be derived from oleic acid or tallowic acid. In certain embodiments, the nitrogen-containing compound has the structure (R ′) (R ′) N
A fatty acid having —R ″ —N (R ′) — R ″ —Y, wherein Y is —N (R ′) (R ′) or —OR ′, wherein each R ′ is independently hydrogen Or each R ″ is independently a hydrocarbyl group.) Examples of suitable compounds include diethylenetriamine, aminoethylethanolamine, N, N-dimethylaminopropylaminopropylamine, poly Examples include isobutylene succinimide dispersants, and combinations thereof.

In certain embodiments, the substantially linear compound comprises a compound containing at least 2 nitrogen atoms, the nitrogen atom being separated by 2 or 3 carbon atoms, and an oxygen-containing compound. Derived from reacting with. The nitrogen-containing compound is a polyamine such as N1-coco-propane-1,3-diamine, 1- (3-aminopropyl) -imidazole, N-tallowpropyldiamine, N-dodecylpropylamine, or combinations thereof. It may be. Oxygen-containing compounds generally may have the structure R′—O—C (O) — (CH ₂ ) _n [C (O)] _m —O—R ″, where R ′ is hydrogen or a hydrocarbyl group, n is 0, 1 or 2, m is 0 or 1, and R ″ is hydrogen or a hydrocarbyl group. Suitable examples include glycolic acid, diethyl carbonate, and polyisobutylene succinic anhydride, guanidine carbonate, and combinations thereof.

The above reaction is carried out at an elevated temperature, optionally in the presence of a solvent such as toluene. The product is often vacuum stripped and / or filtered to remove unused reactants. The resulting substantially linear compound is then further reacted with the compound itself, also at elevated temperatures, to obtain a compound containing a ring structure.

  While not wishing to be bound by theory, it is contemplated that the asphaltene dispersants of the present invention may go through one or more intermediate structures before reaching the desired structure. These intermediate structures may include any structure represented by the following formula:

Wherein for each of the above formulas (X) and (XI), each R ² is independently hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms, and each R ³ is Independently, a hydrocarbyl group containing 1 to 50 carbon atoms, each R ⁴ is a hydrocarbyl group containing 1 to 200 carbon atoms, and X is 1 to 20 carbon atoms and 1 Hydrocarbylene groups derived from amines or polyamines containing ˜5 nitrogen atoms.

  In certain embodiments, the compositions of the present invention comprise the above-described asphaltene dispersant in combination with one or more intermediates described above. All these materials, including intermediates, can give superior performance over the starting succinimide, which is often used for preparation.

  As used herein, the terms “hydrocarbyl” and “hydrocarbylene”, when used with groups and / or substituents, have their ordinary meanings well known to those skilled in the art. Specifically, these terms both refer to a group containing a carbon atom directly attached to the rest of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl and hydrocarbylene groups include hydrocarbon substituents and / or linking groups, ie, aliphatic substituents (eg, alkyl or alkenyl), alicyclic substituents (eg, cycloalkyl, cycloalkenyl) , And aromatic substituted aromatic substituents, aliphatic substituted aromatic substituents, aromatic substituents substituted with alicyclic groups, and cyclic substitutions in which the ring is completed through another part of the molecule A group (eg, two substituents together form a ring), a substituted hydrocarbon substituent, ie, a group that is not a hydrocarbon (in terms of the present invention, Substituents that do not change (eg, halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfoxy)); Hetero substituents, that is, while maintaining the properties of the predominantly hydrocarbon, in terms of the present invention, substituents include those other than carbon ring or chain, which is composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. In general, no more than 2, preferably no more than 1 non-hydrocarbon substituent may be present for every 10 carbon atoms of a hydrocarbyl group, typically a hydrocarbyl group containing a hydrocarbon There may be no non-substituent.

It is known that some of the materials mentioned above interact in the final formulation and that the components of the final formulation may differ from the components added initially. For example, metal ions (eg, detergent metal ions) may migrate to other acidic or anionic sites of other molecules. The product formed thereby may not simply be described, including the product formed when the composition of the invention is used in the intended application. Nevertheless, all such modifications and reaction products are included within the scope of the present invention, which includes compositions prepared by admixing the components described above.

  The invention is further illustrated by the following examples describing particularly useful embodiments. While examples are given to illustrate the present invention, these examples are not intended to limit the invention.

(Example 1)
Asphaltene dispersant for reaction, oleic acid (50 grams), toluene (50 grams), N1- (3-dimethylamino-propyl) -propane-1,3-diamine (29.63 grams), overhead Prepare by placing in a 250 mL round bottom flask (Flask A) fitted with a stirrer, heating mantle, thermocouple, Dean-Stark trap water cooled condenser, and nitrogen inlet. In a flask, the material is mixed at 250 rpm and heated to 100 ° C. The mixture is continued to mix for 1 hour, then heated to 110 ° C. and the mixing is maintained overnight. The mixture is then heated to 120 ° C., the mixture is maintained for 1 hour, heated to 130 ° C., the mixture is maintained for 1 hour, heated to 135 ° C., the mixture is maintained overnight, heated to 140 ° C., Mixing is maintained for 1 hour, heated to 150 ° C. and mixing is maintained overnight. The reaction mixture is then cooled and left over the weekend. The reaction mixture is then heated to 160 ° C., mixing is maintained for 1 hour, heated to 170 ° C., mixing is maintained for 1 hour, heated to 185 ° C. and mixing is maintained for 30 hours. The reaction is monitored by IR investigating a large amide peak at 1646 cm ⁻¹ that contains an amidine peak as a shoulder peak. The collected product (71.81 grams) is a pale yellow liquid.

The collected product (61.4 grams) was then added to a 250 mL 3-neck round bottom flask equipped with a Dean-Stark trap and water-cooled condenser, magnetic stirrer, heating mantle, and thermocouple, and nitrogen inlet ( Place in flask B). While mixing this material at 100 rpm, it is heated to 200 ° C. and maintained for 0.5 hour to bring the system to equilibrium. The material is then heated to 210 ° C. and mixing is maintained for 1.5 hours. The material is cooled to room temperature overnight and then heated to 220 ° C. and mixing is maintained for 4 hours. The material is then cooled to 100 ° C. and collected. The process is monitored by investigating the increase in peak intensity at 1615 cm ⁻¹ (amidine) and the decrease in peak intensity at 1646 cm ⁻¹ (amide) by IR. The resulting material (61.4 grams) is a viscous clear orange oil with a total base number (TBN) of 216 mg KOH / g. The resulting material comprises 2-alkyl-tetrahydro-pyrimidine, specifically 2-oleyl-1- (3-dimethylaminopropyl) -1,4,5,6-tetrahydro-pyrimidine.

(Example 2)
Asphaltene dispersant is prepared by placing oleic acid [2- (2-hydroxy-ethylamino) -ethyl] -amide (83.29 grams) in a 250 mL flask fitted with Flask B above. This material is heated to 200 ° C. over 0.5 hours with stirring at 100 rpm. The material is then heated to 220 ° C. and mixing is maintained for 2 hours. The material is cooled to room temperature overnight. The material is then heated to 220 ° C. and mixing is maintained for 4 hours. The material is then cooled to 100 ° C. and collected. The process is monitored by investigating IR for an increase in peak intensity of 1605 cm ⁻¹ (amidine) and a decrease in peak intensity of 1650 cm ⁻¹ (amide). The resulting material (73.6 grams) is a viscous clear orange oil with a TBN of 149 mg KOH / g. The resulting material comprises 2-alkyl-imidazoline, specifically 2-oleyl-1- (2-hydroxyethyl) -imidazoline.

(Example 3)
The procedure of Example 1 except that the asphaltene dispersant is placed in a reaction flask with N1-tallow-propane-1,3-diamine (50 grams), toluene (50 grams) and glycolic acid (11.75 grams). Prepare according to Within flask A, the first part of the process yields 50.22 grams of a waxy solid. Within the system of Flask B, depending on the second part of the process, 34.32 grams of 1-alkyl-tetrahydro-pyrimidine, specifically (1-tallow-1,4,5,6-tetrahydropyrimidine-2- I) Methanol is obtained.

Example 4
A 1 L reaction flask equipped with asphaltene dispersant, polyisobutylene succinic anhydride (PIBSA) (502.5 grams) derived from polyisobutylene having a number average molecular weight (Mn) of 2300, similar to Flask A above. To prepare. The material is heated to 150 ° C. with mixing at 350 rpm under nitrogen. Then 1- (3-aminopropyl) -imidazole (22.8 grams) is added dropwise to the flask over 0.5 hours. After the feed is complete, the reaction mixture is maintained at 150 ° C. for 3.5 hours. The reaction is monitored by examining the large imide peak at 1702 cm ⁻¹ by IR. The resulting material (515.5 grams) is a dark brown material and contains 1-alkylimidazole, specifically (1-polyisobutenesuccinimidylpropyl) imidazole.

(Example 5)
By placing the asphaltene dispersant in a 250 mL reaction flask equipped with N1-coco-propane-1,3-diamine (55.36 grams) and diethyl carbonate (29.45 grams) as in Flask A above. Prepare. The mixture is heated to 100 ° C. while mixing at 300 rpm under nitrogen. The mixture is maintained at this temperature for 16 hours while mixing, then heated to 135 ° C., mixing is maintained for 5 hours, then heated to 150 ° C. and mixing is maintained for 3 hours. The mixture is then cooled to room temperature and then heated to 120 ° C. and maintained for 16 hours, then heated to 180 ° C., maintained for 2 hours, then heated to 190 ° C. and mixed to 1 Keep time. The reaction is monitored by IR. The resulting material (51.09 grams) is a white soft waxy solid that contains 1-alkyl-tetrahydro-pyrimidin-2-one, specifically 1-coco-tetrahydro-pyrimidin-2-one. Including.

(Example 6)
Asphaltene dispersant, Duomeen ^™ O (1126 grams), iminodiacetic acid (228.9 grams), and xylene (1500 ml), mechanical overhead stirrer, thermocouple, and heating mantle, subsurface nitrogen sparge line, and condenser Prepare by placing in a 5 L round bottom flask fitted with a Dean-Stark trap fitted with Polydimethylsiloxane (6 drops) is added and the mixture is heated to 145 ° C. over 4.5 hours with stirring. The mixture is then maintained at 150 ° C. for 2 hours, then maintained at 155 ° C. for 2.5 hours, then maintained at 160 ° C. for 1.5 hours, then maintained at 170 ° C. for 1.5 hours, then Maintain at 180 ° C. for 1.5 hours, then maintain at 200 ° C. for 6.5 hours, then maintain at 220 ° C. for 16 hours, then maintain at 230 ° C. for 8 hours, evaporating xylene while raising the temperature To do. The flask is cooled and maintained at various temperatures overnight and resumed at the same temperature the next day. The resulting material (1175 grams) is cooled and collected.

(Example 7)
Asphaltene dispersant is prepared by placing Duomeen ^™ T (2504.6 grams) and ethylene glycol (437.6 grams) in a 5 L round bottom flask attached as described in Example 5 above. This material is heated to 105 ° C. with stirring. When ethylene carbonate (620.67) is added over 1 hour, the mixture exotherms to 108 ° C. The mixture is then maintained with mixing at 105 ° C. for 1 hour, then at 130 ° C. for 5 hours and then at 180 ° C. for 6.5 hours. The mixture is then vacuum distilled at 180 ° C. and about −0.9 bar for 3 hours to remove the ethylene glycol solvent. The flask is cooled and maintained at various temperatures overnight and resumed at the same temperature the next day. The resulting material (2654.5 grams) is cooled and collected.

(Example 8)
An asphaltene dispersant is prepared by placing diethylenetriamine (164.65 grams) and toluene (350 ml) in a 1 liter reaction flask fitted as in Flask A above. Heat the mixture to 100 ° C. while mixing. The mixture is then heated to 135 ° C. and oleic acid (151.11 grams) is added dropwise over 5 hours. The mixture is then heated to 135 ° C. and maintained for 17 hours while mixing. Excess toluene and diethylenetriamine are vacuum stripped from the flask at 135 ° C. and about −0.9 bar over 3 hours. The flask is cooled and maintained at various temperatures overnight and resumed at the same temperature the next day. The resulting material (169.9 grams) is cooled and collected.

Example 9
Asphaltene dispersant is prepared by placing oleic acid (300 grams) and toluene (100 grams) into a 1 liter reaction flask fitted as in flask A above. The mixture is heated to 125 ° C. with stirring and then aminoethylethanolamine (110.6 grams) is added over 1 hour. The reaction mixture is then heated to 135 ° C. and maintained with mixing for 2 hours, then heated to 170 ° C. over 1 hour, collected, distillate removed from the system, then heated to 210 ° C. Maintain for 2 hours with stirring, then heat to 215 ° C. and maintain for 3 hours with stirring. The reaction mixture is then distilled under reduced pressure at 215 ° C. and 100 mbar for 0.5 hour. The resulting material (363.45 grams) is cooled and collected.

(Example 10)
Asphaltene dispersant is prepared by placing oleic acid (300 grams) and toluene (100 grams) into a 1 liter reaction flask fitted as in flask A above. The mixture is heated to 100 ° C. with stirring and then N, N-dimethylaminopropylaminopropylamine (100 grams) is added over 1 hour. The reaction mixture is then maintained for 0.5 hours, then heated to 130 ° C. and maintained for 0.5 hours with mixing, then heated to 150 ° C., maintained for 1 hour, and then heated to 175 ° C. Maintain with mixing overnight, then heat to 200 ° C. and maintain for 1 hour, then heat to 215 ° C., maintain for 1 hour, then heat to 220 ° C. and maintain for 3 hours. The reaction mixture is then distilled under vacuum at this temperature for 5 hours. The resulting material (386.11 grams) is cooled and collected.

(Example 11)
By placing the asphaltene dispersant in a 1 liter reaction flask equipped with 1000 Mn of PIBSA and polyisobutenyl succinimide dispersant (475.5 grams) derived from tetraethylenepentamine as in flask A above. Prepare. This material is heated to 175 ° C. with stirring and maintained for 1 hour. The material is cooled to 100 ° C. and tall oil fatty acid (43.9 grams) is added over 6 minutes. The mixture is then heated to 230 ° C. over 0.5 hours with stirring and then maintained for 22 hours. The resulting material (503.4 grams) is cooled and collected.

(Example 12)
Asphaltene dispersant is prepared by placing Duomeen ^™ T (300 grams) and glycolic acid (70.42 grams) in a 1 liter reaction flask fitted as in flask A above. This material is heated to 140 ° C. with stirring and maintained for 24 hours. The material is then heated to 220 ° C. and maintained for 8 hours, then cooled and maintained at room temperature overnight. This material (310.68 grams) is then collected. This material is a dark brown waxy solid at room temperature.

(Example 13)
Asphaltene dispersant is prepared by placing Duomeen ^™ T (300 grams) in a 1 liter reaction flask fitted as in Flask A above. This material is heated to 110 ° C. with stirring and guanidine carbonate (166.8 grams) is added over 1 hour. The reaction is then heated to 155 ° C. over 2 hours and then maintained for 1 hour, then heated to 185 ° C. and maintained overnight with stirring. The reaction mixture is then cooled to 120 ° C. and filtered using a FAX-5 filter aid. Collect the resulting material (165.4 grams) to obtain an ivory hard waxy solid.

(Results of asphaltene handling test)
To confirm the relative properties of these new asphaltene dispersants, the materials were screened using the blotter strip method. This method is performed using a dispersant as a single component. The base oil is prepared by blending 32.6 pbw fuel heavy oil and 67.4 pbw 150N diluent oil. The dispersant to be tested (2 g) is placed in a 28 cm ³ screw top vial with 10.15 grams of base oil. Each sample is mixed for 5 minutes using a Griffin flask shaker and then the sample is placed in a 66 ° C. oven for 90 minutes. The vial is then removed from the oven and shaken for an additional 5 minutes as described above. 15 μl of this mixture is placed on the blotter piece 19 mm from the bottom (spotting line). Using pentane, elute to a predetermined position of 153 mm from the spotting line. Each blotter piece is then visually ranked for the amount of material remaining in the original spot, i.e., ranked 1-6, where 1 is the worst and 6 is the best. A summary of the results is given below.

1—Reference to a particular example in the table above indicates that the dispersant is prepared in substantially the same process as described in the referenced example.
2—The salicylate used in this test is a commercially available calcium salicylate dispersant containing hydrocarbon side chains containing about 12 to 16 carbon atoms.

  This result shows that the asphaltene dispersant of the present invention has improved asphaltene handling properties compared to commercially available calcium salicylate.

(Further test results)
Several compositions were tested to evaluate the properties of the asphaltene dispersant described above. All tests were completed for the two formulations described below.

1—The amount of all additives in these formulations is based on the portion excluding the oil, and lists the amount of base oil and total diluent oil present in the additive as separate components.

  Formulation A is a formulation without salicylate, while Formulation B contains a mixture of salicylate detergent and phenate detergent. All formulations contain 4% by weight of the dispersant to be evaluated (in the same base oil) and the total base number (TBN) of each sample is 40.

  Based on Formulations A and B, compositions with different asphaltene dispersants were tested, and succinimide dispersants derived from polyisobutylene (PIB) having a number average molecular weight (Mn) of 1000 were used instead of asphaltene dispersants. Comparison with the composition used. The dispersants used in this test are listed below.

1—Reference to a particular example in the table above indicates that the dispersant is prepared in substantially the same process as described in the referenced example.

  The examples listed in the table above were tested in a Pressure Differential Scanning Calorimeter (PDSC) test that measures the oxidation induction time (OIT) of the composition. This test is a standard test procedure in the lube industry based on CEC L-85 T-99. In this test, the lubricating composition is heated to an elevated temperature, typically about 25 ° C. below the average decomposition temperature of the sample being tested (in this case 215 ° C. at 690 kPa), and decomposition of the composition begins. Measure time. The longer the test time reported in minutes, the better the oxidative stability of the composition and the additives present in the composition.

  The examples listed in the table above were tested in a modified IP48 test. This test measures the oxidative stability of a lubricant at high temperatures. During the test, air is passed through a test tube containing a certain amount of lubricant at 200 ° C. for 24 hours. The viscosity of the lubricant is measured before and after the test. The kinematic viscosity (KV100) of the lubricant at 100 ° C. was measured before and after the test, and the final KV100 / starting KV100 ratio gives an indication of the oxidative stability of the sample, , Indicating that the performance is good. Rams bottom residual carbon (RCR) was also measured before and after the test, and again, the ratio of final / starting RCR gives an indication of the oxidative stability of the sample, and again the ratio is close to 1 Is good.

  The examples listed in the table above are for the one pass MD Hot Tube Test (14% (w / w) fuel oil sample at 0.25 cc / hour and air at 10 cc / minute, glass In-house tests used to evaluate the antioxidant performance of lubricants based on the tendency of deposits to form by passing through the tube at 300 ° C. for 16 hours. This test also evaluates the handling performance of the test lubricant asphaltenes. The higher the rank, the better the performance of the lubricant.

  The test results are shown below.

  This result shows that the asphaltene dispersants of the present invention can impart improved properties to the lubricating compositions used compared to compositions containing commercially available salicylate dispersants or other alternative dispersants. These improvements may include improved oxidative stability.

（ｉｉ）式（ＩＩ）によってあらわされる化合物；

を含み、
式中、上の式それぞれについて、各Ｒ^０は、独立して、水素であるか、または１〜２５０個の炭素原子を含むヒドロカルビル基であり、各Ｒ^１は、独立して、１〜１０個の炭素原子を含むヒドロカルビル基であり、各Ｒ^２は、独立して、水素、ヒドロキシ基、または１〜５０個の炭素原子を含むヒドロカルビル基であり、Ｙは、炭素原子または窒素原子であり、ｎは、１または２であり、そしてｍは、０または１である、上記項１または２のいずれか１項に記載の組成物。
（項５）
前記アスファルテン分散剤が、
（ｉ）式（ＩＩＩ）によってあらわされる化合物；

（ｉｉ）式（ＩＶ）によってあらわされる化合物；

（ｉｉｉ）式（Ｖ）によってあらわされる化合物；

（ｉｖ）式（ＶＩ）によってあらわされる化合物；または

（ｖ）これらの組み合わせを含み、
式中、上の式それぞれについて、各Ｒ^１は、独立して、１〜１０個の炭素原子を含むヒドロカルビル基であり、各Ｒ^２は、独立して、水素であるか、または１〜５０個の炭素原子を含むヒドロカルビル基であり、各Ｒ^３は、独立して、１〜５０個の炭素原子を含むヒドロカルビル基であり、Ｒ^４は、１〜２００個の炭素原子を含むヒドロカルビル基であり、そしてＸは、１〜２０個の炭素原子と、１〜５個の窒素原子とを含むアミンまたはポリアミンから誘導されるヒドロカルビレン基である、上記項１または２のいずれか１項に記載の組成物。
（項６）
Ｒ^２が、一不飽和であるか、または、Ｒ^４が、ポリイソブチレンから誘導されるか、または、Ｘが、ポリアルキレンポリアミンから誘導されるか、またはこれらの組み合わせである、上記項４に記載の組成物。
（項７）
前記アルキルフェノール洗浄剤が、前記組成物全体の１重量％以上の量で存在する、上記項１〜６のいずれか１項に記載の組成物。
（項８）
前記アルキルフェノール洗浄剤が、カルシウムフェネートスルフィドを含む、上記項１〜７のいずれか１項に記載の組成物。
（項９）
前記組成物の全塩基価が、少なくとも２５であり、前記組成物全体の塩基価の少なくとも５０％が、前記フェネート洗浄剤からもたらされる、上記項１〜８のいずれか１項に記載の組成物。
（項１０）
（ｄ）サリチレート洗浄剤をさらに含み、前記組成物全体のＴＢＮの５０％以下が、前記サリチレート洗浄剤からもたらされる、上記項１〜９のいずれか１項に記載の組成物。（項１１）
前記組成物が、船舶用ディーゼル機関潤滑剤または発電所の燃焼機関潤滑剤である、上記項１〜１０のいずれか１項に記載の組成物。
（項１２）
上記項１０に記載の潤滑組成物を機関に供給することを含む、内燃機関を潤滑化する方法。
（項１３）
前記内燃機関が、船舶用ディーゼル機関または発電所の燃焼機関である、上記項１２に記載の方法。
（項１４）
前記船舶用ディーゼル機関が、４ストロークトランクピストン機関であるか、または、前記船舶用ディーゼル機関が、２ストローククロスヘッド機関であって、そして前記潤滑組成物が、システム油である、上記項１３に記載の方法。
（項１５）
少なくとも１個の酸素原子と、少なくとも２個の窒素原子とを含有し、前記窒素原子が２個または３個の炭素原子によって隔てられている実質的に線状の化合物をそれ自身と反応させ、前記化合物が、前記２個の窒素原子を含む環構造を形成する工程を含む、アスファルテン分散剤を調製するプロセス。
（項１６）
前記実質的に線状の化合物が、少なくとも１個の−ＣＯＯＲ基を含む化合物と、少なくとも２個の窒素原子を含み、前記窒素原子が２個または３個の炭素原子によって隔てられている化合物との反応から誘導され、ここでＲが、水素またはヒドロカルビル基であってもよい、上記項１５に記載のプロセス。
Each of the documents referenced above is incorporated herein by reference. Except where explicitly stated in the examples or otherwise, all quantities described herein that specify the amount of a substance, reaction conditions, molecular weight, number of carbon atoms, etc. are modified by the term “about”. Should be understood. Unless otherwise indicated, all percentage values are weight percent and all ppm values are by weight. Unless otherwise indicated, all chemicals or compositions referred to herein are to be construed as commercial grade materials and are intended to be isomers, by-products, derivatives, commercial It may contain other such substances that are normally understood to be present in the grade. However, the amount of each chemical component is expressed except for any solvent or diluent oil that may customarily be present in commercial materials, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, ranges and amounts for each component of the invention may be used together with ranges or amounts for any other component. As used herein, the expression “consisting essentially of” is permitted to include substrates that do not materially affect the basic and new characteristics of the composition under consideration.
According to a preferred embodiment of the present invention, for example, the following is provided.
(Claim 1)
(A) an oil of lubricating viscosity;
(B) an asphaltene dispersant comprising a cyclic head group containing a nitrogen atom and at least one other heteroatom;
(C) A lubricating composition comprising a detergent derived from an alkylphenol.
(Section 2)
Item 2. The composition according to Item 1, wherein the cyclic head group of the asphaltene dispersant contains at least one amidine group, urea group, guanidine group, or a combination thereof.
(Section 3)
Item 3. The composition according to any one of Items 1 and 2, wherein the head group of the asphaltene dispersant includes a five-membered ring, a six-membered ring, or a combination thereof.
(Section 4)
The asphaltene dispersant is
(I) a compound represented by formula (I);

(Ii) a compound represented by formula (II);

Including
In which each R ⁰ is independently hydrogen or a hydrocarbyl group containing ¹ to 250 carbon atoms, and each R ¹ is independently 1 to 10 A hydrocarbyl group containing 1 carbon atom, each R ² is independently hydrogen, a hydroxy group, or a hydrocarbyl group containing 1-50 carbon atoms, and Y is a carbon atom or a nitrogen atom. 3. The composition according to any one of items 1 or 2, wherein n is 1 or 2, and m is 0 or 1.
(Section 5)
The asphaltene dispersant is
(I) a compound represented by formula (III);

(Ii) a compound represented by formula (IV);

(Iii) a compound represented by formula (V);

(Iv) a compound represented by formula (VI); or

(V) including these combinations,
In which each R ¹ is independently a hydrocarbyl group containing 1 to 10 carbon atoms and each R ² is independently hydrogen or 1 to 50 Each R ³ is independently a hydrocarbyl group containing 1 to 50 carbon atoms, and R ⁴ is a hydrocarbyl group containing 1 to 200 carbon atoms. And X is a hydrocarbylene group derived from an amine or polyamine containing 1 to 20 carbon atoms and 1 to 5 nitrogen atoms, according to any one of paragraphs 1 or 2 above The composition as described.
(Claim 6)
In paragraph 4, wherein R ² is monounsaturated, or R ⁴ is derived from polyisobutylene, or X is derived from a polyalkylene polyamine, or a combination thereof. The composition as described.
(Claim 7)
Item 7. The composition according to any one of Items 1 to 6, wherein the alkylphenol detergent is present in an amount of 1% by weight or more of the entire composition.
(Section 8)
Item 8. The composition according to any one of Items 1 to 7, wherein the alkylphenol detergent comprises calcium phenate sulfide.
(Claim 9)
Item 9. The composition according to any one of Items 1 to 8, wherein the total base number of the composition is at least 25 and at least 50% of the base number of the entire composition is derived from the phenate detergent. .
(Section 10)
(D) The composition according to any one of Items 1 to 9, further comprising a salicylate detergent, wherein 50% or less of the total TBN of the composition is derived from the salicylate detergent. (Item 11)
Item 11. The composition according to any one of Items 1 to 10, wherein the composition is a marine diesel engine lubricant or a power plant combustion engine lubricant.
(Clause 12)
A method of lubricating an internal combustion engine comprising supplying the lubricating composition according to item 10 to the engine.
(Section 13)
Item 13. The method according to Item 12, wherein the internal combustion engine is a marine diesel engine or a power plant combustion engine.
(Item 14)
In the above item 13, the marine diesel engine is a four-stroke trunk piston engine, or the marine diesel engine is a two-stroke crosshead engine, and the lubricating composition is a system oil. The method described.
(Section 15)
Reacting itself with a substantially linear compound containing at least one oxygen atom and at least two nitrogen atoms, the nitrogen atoms being separated by two or three carbon atoms; A process for preparing an asphaltene dispersant, wherein the compound comprises the step of forming a ring structure containing the two nitrogen atoms.
(Section 16)
The substantially linear compound comprising at least one -COOR group; and a compound comprising at least two nitrogen atoms, wherein the nitrogen atoms are separated by two or three carbon atoms; Item 16. The process according to Item 15, wherein R is a hydrogen or hydrocarbyl group.

Claims (1)

Invention described in the specification .