Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
  • C10M133/54—Amines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
  • C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
  • C07C215/48—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
  • C07C215/50—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/08—Butenes
  • C08F110/10—Isobutene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • 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
  • C10M159/16—Reaction products obtained by Mannich reactions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/30—Amines; Substituted amines ; Quaternized amines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3723—Polyamines or polyalkyleneimines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/0415—Light distillates, e.g. LPG, naphtha
  • C10L2200/0423—Gasoline
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
  • C10L2200/0446—Diesel
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
  • C10L2250/04—Additive or component is a polymer
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
  • C10M2215/26—Amines
• • 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
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/043—Mannich bases
• • 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
  • C10N2030/04—Detergent property or dispersant property

Definitions

• the present invention relates to a lubricating oil composition, and more particularly to a lubricating oil composition excellent in clean dispersing performance and rust preventing performance.
• the invention also relates to a method of making the lubricating oil composition. Background technique
• the Mannich base is produced by reacting a hydrocarbyl-substituted fluorenyl orthoquinone with an aldehyde or an amine, and is effective as a detergent for suppressing engine deposit formation.
• the Mannich base is produced by reacting a phenolic compound with an aldehyde or an amine, and as a detergent, it is possible to suppress the formation of engine deposits.
• diesel engine lubricating oil continues to develop with the requirements of diesel engine structure, operating conditions and energy saving and emission reduction, and diesel engine lubricating oil is frequently upgraded.
• Diesel engine lubricant product specifications are gradually upgraded from CF-4 to CH-4, CI-4 and the latest CJ-4, diesel engine EGR exhaust gas cycle system application, NOx emissions are reduced, resulting in increased amount of soot in the lubricant
• the problem is that the proportion of carbon black in the diesel engine oil used is gradually increased from 2% of the CF-4 grade to 6.7% of the CJ-4 grade. The cleanliness of the piston of the oil and the dispersibility of the soot. keep improving.
• the inventors have diligently studied on the basis of the prior art and discovered a novel Mannich base, and through further research, found that the novel Mannich base is used as a detergent dispersant to manufacture a lubricating oil combination.
• the foregoing problems can be solved, and the present invention has been completed.
• the present invention relates to the following aspects.
• a lubricating oil composition comprising a Mannich base and a lubricating base oil, wherein the Mannich base comprises the following structural unit (I) and structural unit (II): (-CH 2 -) - N one
• each is the same or different, each independently selected from hydrogen, CM straight or branched alkyl and a single bond, preferably selected from the group consisting of hydrogen, methyl and a single bond, more preferably selected from hydrogen and a single bond; each R' is the same Or different, each independently selected from hydrogen and d. 6 straight or branched alkyl, preferably selected from hydrogen and methyl, more preferably hydrogen; R 2 is selected from d. 12 straight or branched pit base, more preferably a linear or branched alkyl group selected from C 5 .
• R 3 is selected from a linear or branched chain group, preferably selected from a linear or branched alkyl group, more preferably a fluorenyl group; and R 4 is selected from a number average molecular weight Mn of a hydrocarbon group of 300 to 3000 (preferably 500 to 2000, more preferably 500 to 1500); each y is the same or different and each independently selected from an integer of 2 to 5, preferably 2 or 3.
• a lubricating oil composition comprising Mannich base and a lubricating base oil, wherein said structural formula (III):
• Each R' is the same or different and is each independently selected from hydrogen and a linear or branched alkyl group, preferably selected from the group consisting of hydrogen and methyl, more preferably hydrogen; each Ra is the same or different, each independently selected from hydrogen, preferably selected From hydrogen, sulfhydryl and More preferably selected from hydrogen and
• Ra is the same or different
• R b are independently selected from hydrogen
• a linear or branched alkyl group preferably selected from hydrogen
• R b ⁇ R 2 is selected from d 12 12 straight or branched alkyl groups, more preferably selected from C 5 . 12 straight or branched alkyl groups;
• R 3 is selected from C straight or branched chain groups, preferably selected from d 4 straight chains Or a branched alkyl group, more preferably a methyl group;
• R4 is selected from a hydrocarbon group having a number average molecular weight Mn of from 300 to 3,000 (preferably from 500 to 2,000, more preferably from 500 to 1,500);
• y are the same or different and are each independently selected from an integer of 2 to 5, preferably 2 or 3;
• each c is the same or different, each independently selected from an integer of 0 to 10, preferably an integer selected from 2 to 5, more preferably 2 Or 3.
• a lubricating oil composition comprising a Mannich base and a lubricating base oil, wherein the Mannich base is produced by a manufacturing method, wherein the manufacturing method comprises a compound of the formula (V) a compound of the formula (VI), a polyarylene polyamine of the formula (VII) and a C r C 7 linear or branched saturated fatty aldehyde (preferably acetaldehyde or formaldehyde, more preferably formaldehyde, especially an aqueous furfural solution, Paraformaldehyde or paraformaldehyde form)
• a manufacturing method comprises a compound of the formula (V) a compound of the formula (VI), a polyarylene polyamine of the formula (VII) and a C r C 7 linear or branched saturated fatty aldehyde (preferably acetaldehyde or formaldehyde, more preferably formaldehyde, especially an aqueous furfural solution, Paraformaldehyde or
• R 2 is selected from d- 12 straight or branched alkyl groups, more preferably selected from C 5 . 12 straight or branched alkyl groups;
• R 3 is selected from linear or branched alkyl groups, preferably selected from linear chains Or a branched alkyl group, more preferably a fluorenyl group;
• R4 is selected from a hydrocarbon group having a number average molecular weight Mn of from 300 to 3,000 (preferably from 500 to 2,000, more preferably from 500 to 1,500); each of R b 'is the same or different and each independently selected from Hydrogen and ( ⁇ -4 linear or branched pit groups, preferably selected from the group consisting of hydrogen and methyl, more preferably hydrogen, provided that at least two R b are hydrogen, more preferably polyalkylene polyamines of formula (VII)
• the molecular chain has at least one R b ' at each of its two ends is hydrogen; y is selected from an integer from 2 to 5, preferably 2 or 3; c' is
• Mode (1) Includes the following steps:
• First step the desired compound of the formula (VI), the polyalkylene polyamine of the formula (VII) and the C r C 7 linear or branched saturated fatty aldehyde at a reaction temperature of 50 ° C -
• the Mannich reaction occurs at 200 ° C (preferably 60 ° C - 150 ° C, most preferably 80 ° C - 130 ° C) to form an intermediate product;
• Second step the intermediate product is reacted with the desired compound of the formula (V) and the C r C 7 linear or branched saturated fatty aldehyde at a reaction temperature of 40 ° C to 200 ° C (preferably 6 (rC- A Mannich reaction occurs at 150 ° C, most preferably 8 trC - 130 ° C) to form the Mannich machine,
• Mode (2) Includes the following steps:
• First step the compound of the formula (V), the polyalkylene polyamine of the formula (VII) and the C r C 7 linear or branched saturated fatty aldehyde are reacted at a reaction temperature of 40 ° C - 200. Mannich reaction occurs at C (preferably 60 ° C - 150 ° C, most preferably 80 ° C - 130 ° C) to form an intermediate product;
• Second step reacting the intermediate product with the phenol compound of the formula (VI) and the C7 linear or branched saturated fatty aldehyde at a reaction temperature of 50 ° C to 200 ° C (preferably 60 ° C to 150 ° C) , most preferably, a Mannich reaction occurs at 80 ° C - 130 ° C) to form the Mannich machine,
• Mode (3) comprising a compound of the formula (V), a phenol compound of the formula (VI), a polyalkylene polyamine of the formula (VII), and the Ci-C 7 straight chain or
• the branched saturated fatty aldehyde is subjected to a Mannich reaction at a reaction temperature of from 40 ° C to 200 ° C (preferably from 60 ° C to 150 ° C, most preferably from 80 ° C to 130 ° C) to form the Mannich base. step.
• the lubricating oil composition according to any of the preceding aspects, wherein in the manufacturing method, in the first step of the mode (1), the phenol compound of the formula (VI), the structural formula (VII)
• the molar ratio between the polyalkylene polyamine and the C C7 linear or branched saturated aliphatic aldehyde is from 1:0.3 to 3:0.3 to 3.5, preferably from 1:0.4 to 2:0.4 to 2.5, more preferably 1: 0.5-1.5:0.5-2; in the second step of the mode (1), the intermediate product and the phenol compound of the formula (V) and the c r c 7 linear or branched saturated fatty aldehyde
• the phenol compound of the formula (VI) is a compound of the formula (IV) and a number thereof in the presence of an alkylation catalyst
• the polyolefin having a molecular weight Mn of from 300 to 3,000 (preferably from 500 to 2,000, more preferably from 500 to 1,500) is produced by alkylation of the polyolefin, preferably by homopolymerization of ethylene, propylene or Crdoa-olefin or by these a polyolefin obtained by copolymerization of two or more kinds of olefins, more preferably polyisobutylene,
• R 3 is defined in the same way as aspect 3.
• lubricating oil composition of any of the preceding aspects, further comprising one or more lubricating oil additives selected from the group consisting of antioxidants, dispersants, detergents, antiwear agents, and friction modifiers, wherein by mass, The antioxidant accounts for 0-10% (preferably 0.1% to 5%, more preferably 0.2% to 3%) of the total mass of the lubricating oil composition, and the dispersing agent accounts for 0.5% of the total mass of the lubricating oil composition.
• the detergent accounts for 0.2%-20% of the total mass of the lubricating oil composition (preferably 0.8%-15%, more preferably 1.2%-10%)
• the anti-wear agent accounts for 0.1%-10% (preferably 0.2-8%, more preferably 0.5-5%) of the total mass of the lubricating oil composition
• the friction modifier accounts for 0.01% to 5% (preferably 0.02% to 4%, more preferably 0.05% to 3%) of the total mass of the lubricating oil composition.
• the antioxidant is selected from the group consisting of an amine type antioxidant, a phenol ester type antioxidant, a thiopanate type antioxidant, and a phenol type antioxidant
• the dispersing agent is selected from the group consisting of polyisobutylene succinimide dispersing agents
• a boronated polyisobutylene succinimide dispersant and a succinate dispersant preferably selected from the group consisting of polyisobutylene succinimide dispersant and boronated polyisobutylene succinimide dispersion
• the detergent is selected from the group consisting of a sulfonate detergent, an alkylphenolate detergent, a sulfurized alkylphenolate detergent, a salicylate detergent, and a naphthenate
• the anti-wear agent is selected from a dialkyl group Dithioate antiwear agent, phosphate type extreme pressure antiwear agent, sulfurized olefin antiwear agent, dialkyldithiocarbamate antiwear agent and thiadiazole
• the biological antiwear agents preferably selected from the group consisting of dialkyl diphosphosphate antiwear agents, phosphate ester extreme pressure antiwear agents, hydrophobic hydrocarbon antiwear agents, and dialkyl dithio amino groups
• One or more of a formate antiwear agent, and the friction modifier is selected from one or more of an oil-soluble organic molybdenum friction modifier, an ashless friction modifier, and an organic borate friction modifierkind (preferably one or more selected from the group consisting of an oil-soluble organic molybdenum friction modifier and an ashless friction modifier).
• a method of producing a lubricating oil composition according to any of the preceding aspects comprising the step of mixing said Mannich base with said lubricating base oil.
• the lubricating oil composition according to the present invention exhibits excellent detergency and rust-preventing properties, and fully satisfies the gasoline of SL/GF-3, SM/GF-4 and SN/GF-5 and above.
• Figure 1 is a nuclear magnetic hydrogen spectrogram of the polyisobutenyl o-cresol of Example 1.
• Fig. 2 is a chart showing the nuclear magnetic resonance spectrum of the benzene ring region of the polyisobutenyl group.
• Figure 3 is a comparison of the nuclear magnetic resonance spectra of the Mannich base of Example 2 and the polyisobutenyl phthalate of Example 1.
• Figure 4 is a graph showing the comparison of the nuclear magnetic resonance spectrum of the Mannich base of Example 2 and the benzene ring region of the polyisobutenyl o-cresol of Example 1.
• Figure 5 is a GPC spectrum of the polyisobutenyl phthalate of Example 1.
• Figure 6 is a GPC diagram of the Mannich base of Example 2.
• Figure 7 is a GPC chart of the Mannich base of Example 5. detailed description
• the number average molecular weight Mn is determined by gel permeation chromatography (GPC) unless otherwise specified.
• any measurement conditions relating to gel permeation chromatography (GPC) or GPC spectra are: unless otherwise specified: Instruments: Waters Model 2695 Gel Permeation Chromatography Analyzer, Waters, USA; The mobile phase was tetrahydrofuran, the flow rate was 1 mL/min, the color column temperature was 35 ° C, the efflux time was 40 min, and the sample mass fraction was 0.16%-0.20%.
• each R' is the same or different, each independently selected from Hydrogen and a linear or branched alkyl group
• R 2 is selected from 12 straight or branched alkyl groups
• R 3 is selected from a C 1-6 straight or branched alkyl group
• R 4 is selected from a number average molecular weight Mn of 300-3000.
• Hydrocarbyl; each y is the same or different and is each independently selected from an integer from 2 to 5.
• each is independently selected from the group consisting of hydrogen, a methyl group and a single bond, and more preferably each independently selected from hydrogen and a single bond.
• one of the two sides of the left side is a single bond, and the other is a methyl group or a hydrogen.
• one of the two on the right side is a single bond, and the other is a methyl group or a hydrogen.
• one of the two groups is a single bond and the other is a methyl group or a hydrogen.
• said R' are each the same or different, preferably the same, and are preferably each independently selected from the group consisting of hydrogen and methyl, more preferably hydrogen.
• said R 2 is preferably selected from C 5 . 12 straight or branched alkyl groups, more preferably C 8-12 straight or branched alkyl groups, such as octyl, decyl, fluorenyl, eleven pits Or a dodecyl group, especially a linear octyl, decyl, decyl, undecyl or decyl group.
• said R 3 is preferably selected from a C M straight or branched alkyl group, more preferably a methyl or ethyl group.
• the hydrocarbon group having a number average molecular weight Mn of from 300 to 3,000 for example, a polyolefin having a number average molecular weight Mn of from 300 to 3,000 (particularly the terminal of the polyolefin molecular chain) may be used, and one hydrogen atom is removed.
• the hydrocarbon group obtained (referred to as a polyolefin residue).
• the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500 to 2,000, more preferably 500 to 1,500.
• polystyrene resin for example, homopolymerization by ethylene, propylene or a C 4 -C 1C) a-olefin such as n-butene, isobutylene, n-pentene, n-hexene, n-octene or n-decene can be mentioned. Or a polyolefin obtained by copolymerization of two or more of these olefins, more preferably polyisobutylene (PIB).
• PIB polyisobutylene
• the y are the same or different, preferably the same.
• the y is preferably 2 or 3, more preferably 2.
• the so-called "Mannich base comprises structural unit (I) and structural unit (11), which means that the structural unit (I) can be detected in the Mannich base Coexisting with the structural unit (II).
• the Mannich base may be a single compound in which the simultaneous presence of the two structural units, ie, the structure of the compound simultaneously, can be detected or resolved.
• the Mannich base may be a mixture of a plurality of compounds as long as the simultaneous presence of the two structural units can be detected or distinguished from the mixture.
• the two structural units may exist in the structure of the same compound at the same time, or may exist in the structures of different compounds, respectively, of which the former is preferred.
• the mixture comprises at least one compound in which the two structural units are present simultaneously in the structure of the compound.
• the detection or resolution means referred to herein is conventionally used in the art, and examples thereof include iH-NMR or gel permeation chromatography (GPC).
• Units can be shared by each other
• Bonding also through the connection base a group (the definition of y is the same as before, and preferably the same as y in the structural unit (I) and the structural unit ( ⁇ ); the definition is the same as the former; the X is an integer of 0-8, preferably 0-3 An integer, more preferably 1) indirect bonding at the respective single bond or (only when 1 ⁇ is a single bond).
• the molar ratio of the structural unit (I) to the structural unit ( ⁇ ) is generally from 1:1 to 1:15, preferably from 1:1 to 1:8. More preferably, it is 1:2 to 1:6, or 1:2 to 1:4.
• the Mannich base consists essentially of the structural unit (1), the structural unit (II) and optionally the linking group.
• the term "substantially” as used herein means that other structural units or groups other than the structural unit (1), the structural unit (II) and the linking group, if present, only occupy the entire Mannich base. It is 5 mol% or less, preferably 2 mol% or less, more preferably 0.5 mol% or less, or exists as an (inevitable) impurity.
• the Mannich base is represented by the following structural formula (III).
• each A is the same or different and is independently selected from each other
• R 'and hydrogen provided that at least one A is R ';
• R' is the same or different and is each independently selected from hydrogen and d. 6 straight or branched alkyl; each Ra is the same or different, each independently selected from hydrogen, C14 straight or branched alkyl and each R b is the same or different and is independently selected from hydrogen,
• R 2 is selected from d- 12 straight or branched chain groups
• R 3 is selected from linear or branched alkyl groups
• R4 is selected from hydrocarbon groups having a number average molecular weight Mn of 300 to 3000
• each y is the same or different and is independently The ground is selected from an integer from 2 to 5
• each c is the same or different and is each independently selected from an integer from 0 to 10.
• said A is preferably the same, more preferably both R '.
• said R' are each the same or different (preferably the same), and are preferably each independently selected from the group consisting of hydrogen and methyl, more preferably hydrogen.
• said Ra are preferably each independently selected from the group consisting of hydrogen, fluorenyl and
• said R b are preferably each independently selected from the group consisting of hydrogen,
• Thiol groups more preferably each independently selected from hydrogen and
• R b is hydrogen or sulfhydryl.
• said R 2 is preferably selected from C 5 . 12 straight or branched fluorenyl groups, more preferably C 12 straight or branched fluorenyl groups, such as octyl, decyl, decyl, undecyl or Dodecyl, especially linear octyl, decyl, decyl, undecyl or dodecyl.
• said R 3 is preferably selected from the group consisting of d-4 linear or branched alkyl groups, more preferably methyl or ethyl.
• the hydrocarbon group having a number average molecular weight Mn of from 300 to 3,000 for example, a polyolefin having a number average molecular weight Mn of from 300 to 3,000 (particularly the terminal of the polyolefin molecular chain) may be used, and one hydrogen atom is removed.
• the hydrocarbon group obtained (referred to as a polyolefin residue).
• the number average molecular weight Mn as the polyolefin or the polyolefin residue is preferably 500 to 2,000, more preferably 500 to 1,500.
• polystyrene resin for example, Homopolymerization by ethylene, propylene or CrCio Ct-olefins such as n-butene, isobutylene, n-pentene, n-hexene, n-octene or n-decene or by copolymerization of two or more of these olefins
• PIB polyisobutylene
• the y are the same or different, preferably the same.
• the y is preferably 2 or 3, more preferably 2.
• the cs are the same or different, and are preferably each independently selected from an integer of from 2 to 5, more preferably 2 or 3.
• the aforementioned Mannich base may be present, produced or used in the form of a mono-(pure) compound, or may be present in a mixture of two or more thereof (in any proportion), manufactured or This does not affect the implementation of the effects of the present invention.
• the aforementioned Mannich base can be produced, for example, by the following production method.
• the production method comprises the steps of: a phenol compound of the formula (V), a compound of the formula (VI), a polyalkylene polyamine of the formula (VII), and a QC 7 linear or branched saturated fatty aldehyde.
• the steps of the Nixi reaction are the steps of: a phenol compound of the formula (V), a compound of the formula (VI), a polyalkylene polyamine of the formula (VII), and a QC 7 linear or branched saturated fatty aldehyde.
• R 2 is selected from a C 1-12 straight or branched alkyl group
• R 3 is selected from a linear or branched alkyl group
• R 4 is selected from a number average molecular weight Mn of 300-3000 a hydrocarbon group
• each R b ' is the same or different, each independently selected from hydrogen and C M straight or branched alkyl, provided that at least two R b 'is hydrogen
• y is selected from an integer from 2 to 5; An integer selected from 1-11.
• said R 2 is preferably selected from C 5 -12 straight or branched alkyl groups, more preferably C 8 - 12 linear or branched fluorenyl groups, such as octyl, decyl, fluorenyl, eleven pits Or a dodecyl group, especially a linear octyl, decyl, decyl, undecyl or dodecyl group.
• said R 3 is preferably selected from a C M straight or branched alkyl group, more preferably a methyl or ethyl group.
• a hydrocarbon group having a number average molecular weight Mn of from 300 to 3,000 for example, a polyolefin having a number average molecular weight Mn of from 300 to 3,000 (particularly the terminal of the polyolefin molecular chain) may be used, and one hydrogen atom is removed. Hydrocarbon group obtained (also known as polyolefin residue).
• the number average molecular weight Mn of the polyolefin or the polyolefin residue is preferably 500 to 2,000, more preferably 500 to 1,500.
• the polyolefin residue may be saturated (presented as a long chain alkyl group) or may contain a certain amount in the polymer chain.
• the genus double bonds (such as those remaining in the polyolefin manufacturing process), but this does not affect the realization of the effects of the present invention, and the present invention is not intended to be clear about the amount.
• polystyrene resin for example, homopolymerization by ethylene, propylene or a C 4 -C 10 a-olefin such as n-butene, isobutylene, n-pentene, n-hexene, n-octene or n-decene may be mentioned or A polyolefin obtained by copolymerization of two or more of these olefins, of which polyisobutylene (PIB) is more preferable.
• PIB polyisobutylene
• the phenol compound of the formula (VI) can be obtained by reacting a compound of the formula (IV) with the polyolefin (the number average molecular weight Mn is from 300 to 3,000, preferably 500-) in the presence of an alkylation catalyst. 2000, more preferably 500-1500) is produced by an alkylation reaction.
• the compound of the formula (VI) can also be used directly as a commercially available product.
• R 3 is as defined in the formula (VI), more preferably a methyl group.
• the polyolefin is preferably a polyolefin obtained by homopolymerization of ethylene, propylene or a C 4 -C 1 ⁇ ) a-olefin or by copolymerization of two or more of these olefins.
• the Crdoa-olefin include n-butene, isobutylene, n-pentene, n-hexene, n-octene and n-decene.
• At least 20% by weight (preferably at least 50% by weight, of these polyolefins, More preferably, at least 70% by weight of the polymer chain contains an olefinic double bond at its end.
• the olefinic double bond is generally present in the form of a highly reactive vinylidene or vinyl group.
• polybutene is more preferred as the polyolefin.
• polybutene as used herein, unless otherwise indicated, broadly includes polymers obtained by homopolymerization of 1-butene or isobutylene, and two of 1-butene, 2-butene and isobutylene. Or three polymers obtained by copolymerization. Commercially available products of such polymers may also contain negligible amounts of other olefin components, but this does not affect the practice of the invention.
• polyisobutylene PIB
• HR-PIB highly reactive polyisobutylene
• a Lewis acid catalyst such as aluminum trichloride, boron trifluoride, tin tetrachloride, titanium tetrabromide, boron trifluoride, phenol, trifluoride may be mentioned.
• a boron' alcohol complex and a boron trifluoride ether complex of which boron trifluoride. diethyl ether complex and/or boron trifluoride 'sterol complex are preferred.
• These alkylation catalysts can be directly used as commercially available products.
• the molar ratio between the polyolefin, the phenol compound of the formula (IV), and the alkylation catalyst may be, for example, 1: 1-3: 0.1. -0.5, preferably 1: 1.5-3: 0.1-0.4, most preferably 1: 1.5-3: 0.2-0.4, but sometimes it is not limited thereto.
• the reaction time of the alkylation reaction is, for example, 0.5 h to 10 h, preferably 1 h to 8 h, and most preferably 3 to 5 h, but is sometimes not limited thereto.
• the reaction temperature of the alkylation reaction is, for example, 0 ° C to 200 ° C, preferably 10 ° C to 150 ° C, and most preferably 20 ° C to 100 ° C, but sometimes it is not limited thereto. .
• the alkylation reaction can be carried out in the presence of a solvent.
• a solvent for example, a C 6-10 alkane (such as hexane, heptane, octane, decane or decane) can be mentioned.
• hexane and heptane are preferably used, and hexane is more preferably used.
• the alkylation catalyst, the unreacted reactant, and the unreacted reactant are removed from the finally obtained reaction mixture by a conventional manner.
• the solvent which can be used the compound of the formula (VI) is obtained.
• said R b ' is the same or different, preferably each independently selected from the group consisting of hydrogen and mercapto. More preferably, the molecular chain of the polyalkylene polyamine of the formula (VII) has at least one R b ' at each of the two ends, that is, hydrogen, that is, the following formula (VII-1).
• R b ', y and c' are as defined in the formula (VII).
• examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and heptaethylamine.
• diethylenetriamine triethylenetetramine
• tetraethylenepentamine pentaethylenehexamine
• hexaethyleneheptamine hexaethyleneheptamine
• heptaethylamine One or more of octaylamine, ninethamine, and decanthinamine, of which diethylenetriamine is preferred.
• the polyalkylene polyamine can be produced, for example, by reacting ammonia with a dihaloalkane such as dichloroalkane, or a commercially available product can be used as it is.
• y is preferably 2 or 3.
• c' is preferably selected from an integer from 3 to 6, more preferably 3 or 4.
• the dC 7 linear or branched saturated fat cheese is preferably acetaldehyde or formaldehyde, more preferably formaldehyde.
• the formaldehyde may be, for example, an aqueous solution, a paraformaldehyde or a paraformaldehyde form, and is not particularly limited.
• the method for producing the Mannich base can be carried out, for example, in one of the following manners.
• Mode (1) Includes the following steps:
• First step bringing the compound of the formula (VI), the polyalkylene polyamine of the formula (VII) and the c r c 7 linear or branched saturated fatty aldehyde at a reaction temperature
• the Mannich reaction occurs at 50 ° C - 200 ° C (preferably 60 ° C - 150 ° C, most preferably 80 ° C - 130 ° C) to form an intermediate product;
• Second step subjecting said intermediate product to said face compound of formula (V) and said dC 7 linear or branched saturated fatty aldehyde at a reaction temperature of from 40 ° C to 200 e C (preferably from 60 ° C to 150 °) A Mannich reaction occurs at C, most preferably 80 ° C - 130 ° C) to form the Mannich machine.
• Mode (2) Includes the following steps:
• First step the phenol compound of the formula (V), the polyalkylene polyamine of the formula (VII) and the dC 7 linear or branched saturated fatty aldehyde at a reaction temperature of 40 ° C to 200 ° Mannich reaction occurs at C (preferably 60 ° C - 150 ° C, most preferably 80 ° C - 130 ° C) to form an intermediate product;
• a second step the intermediate product is reacted with the desired compound of the formula (VI) and the CrC 7 linear or branched saturated fatty aldehyde at a reaction temperature of 50 e C-20 CTC (preferably 60 ° C to 150 ° C, Most preferably, a Mannich reaction occurs at 80 C-130 ° C to form the Mannich machine.
• Mode (3) comprising a phenol compound of the formula (V), a desired compound of the formula (VI), a polyalkylene polyamine of the formula (VII), and the Ci-C 7 straight chain or
• the branched saturated fatty aldehyde is subjected to a Mannich reaction at a reaction temperature of 40 ° C to 200 ° C (preferably 6 (TC - 150 ° C, most preferably 80 ° C - 130 ° C) to form the Mannich base. step.
• the formula (1) is preferred.
• the desired compound of the formula (VI), the polyalkylene polyamine of the formula (VII) and the c r c 7 linear chain is 1:0.3-3:0.3-3.5, preferably 1:0.4-2:0.4-2.5, more preferably 1:0.5-1.5:0.5-2.
• the reaction time of the step of the present invention is not particularly limited, and examples thereof include lh to 10 h, preferably 2 to 8 h, and most preferably 3 to 6 h.
• the molar ratio of the intermediate product to the compound of the formula (V) and the CrC 7 linear or branched saturated aliphatic aldehyde is 1 : 0.2-1.5: 0.2-2, preferably 1:0.3-1: 0.2-1.5, more preferably 1:0.3-0.8:0.3-1.5.
• the reaction time of the step of the present invention is not particularly limited, and examples thereof include lh to 10 h, preferably 2 to 8 h, and most preferably 3 to 6 h.
• the oxime compound of the formula (V), the polyalkylene polyamine of the formula (VII) and the dC 7 linear chain The molar ratio between the branched saturated aliphatic aldehydes is 1: 1.5-2.5: 1.5-3, preferably 1: 1.7-2.5: 1.7-2.8, more preferably 1: 1.7-2.2: 1.7-2.5.
• the reaction time of the step of the present invention is not particularly limited, and may, for example, be 1 to 10 h, preferably 2 to 8 h, and most preferably 3 to 6 h.
• the molar ratio between the intermediate and the fans of formula (VI) with the compound of hope C r C 7 straight-chain or branched-chain saturated aliphatic aldehyde The ratio is 1:1.5-3:1.5-3, preferably 1:1.7-2.5:1.7-3, more preferably 1:1.7-2.3:1.7-2.5.
• the reaction time of the step of the present invention is not particularly limited, and examples thereof include lh to 10 h, preferably 2 to 8 h, and most preferably 3 to 6 h.
• the molar ratio between r C 7 linear or branched saturated aliphatic aldehyde is 1:1-5:1-3:2-8, preferably 1:1.5-4,5:1.5-2.5:3-7, more preferably 1:1.8-4.3: 1.8-2.3: 3.5-6.5.
• the reaction time of the mode (3) of the present invention is not particularly limited, and examples thereof include lh to 10 h, preferably 2 to 8 h, and most preferably 3 to 6 h.
• the aforementioned Mannich reaction can be carried out in the presence of a diluent and/or a solvent.
• a diluent for example, one or more selected from the group consisting of polyolefins, mineral base oils, and polyethers can be mentioned.
• the solvent for example, a C 6 .20 aromatic hydrocarbon (such as toluene and diphenyl) can be given. Among them, toluene or dinonylbenzene is preferably used.
• the diluent and/or solvent may be added at any stage of the Mannich reaction according to conventional amounts in the art.
• the start or the progress of the second step the start or the course of the first step of the mode (2) and/or The method (2) is added during the start or the progress of the second step, or the start or the progress of the method (3), and is not particularly limited.
• one or more of API I, II, III mineral lubricating base oils may be selected, preferably selected from 4CTC viscosity of 20-120 cSt (cSt). , mineral oil base with a viscosity index of at least 50 or more ⁇ !
• One or more of the oils are more preferably one or more selected from the group consisting of mineral lubricating base oils having a viscosity of 28 to 110 centistokes (cSt) at 40 ° C and a viscosity index of at least 80 or more.
• the polyolefin for example, it may be exemplified by homopolymerization of ethylene, propylene or a C 4 -C 10 ⁇ -olefin or by copolymerization of two or more of these olefins.
• a polyalphaolefin (PAO) having a viscosity of from 2 to 25 centistokes (cSt) at 100 ° C (preferably a viscosity of 6 to 10 centistokes (cSt ) at 100 ° C) kind.
• examples of the C 4 -C 10 a-olefin include n-butene, isobutylene, n-pentene, n-hexene, n-octene and n-decene.
• the number average molecular weight Mn of the polyolefin is generally from 500 to 3,000, preferably from 500 to 2,500, and most preferably from 500 to 1,500.
• the polyether for example, a polymer produced by reacting an alcohol with an epoxide can be mentioned.
• the alcohol for example, ethylene glycol and/or 1,3-propanediol can be mentioned.
• ethylene oxide and/or propylene oxide can be mentioned.
• the number average molecular weight Mn of the polyether is generally from 500 to 3,000, preferably from 700 to 3,000, and most preferably from 1,000 to 2,500.
• the Mannich reaction is generally carried out under the protection of an inert gas atmosphere.
• the inert gas may, for example, be nitrogen gas or argon gas, and is not particularly limited.
• the Mannich base is obtained by removing moisture and a solvent which may be present from the finally obtained reaction mixture by any conventionally known means.
• the present invention also relates to a Mannich base produced by the aforementioned method for producing a Mannich base according to the present invention.
• a single Mannich base having a very high purity can be produced as a reaction product by a method for producing a Mannich base as described above, and a plurality of Manni can also be produced.
• the Mannich base of the present invention is particularly suitable for the production of a detergent dispersant, particularly a lubricating oil-purifying dispersant, which exhibits excellent deposit formation inhibiting properties and rust-preventing properties.
• the detergent dispersant comprises any of the aforementioned Mannich bases of the present invention (or a mixture thereof in any ratio) or a Mannich base produced according to the aforementioned Mannich base production method of the present invention.
• the aforementioned diluent may be further added to the Mannich base.
• the diluent may be used singly or in combination of two or more kinds.
• the Mannich base of the present invention already contains a certain amount of the diluent after the production as described above, then the amount of the diluent added can be correspondingly reduced, even without further adding the said
• the diluent can be used directly as a detergent dispersant, as will be apparent to those skilled in the art.
• the Mannich base accounts for 10 - 70%, preferably 10 - 60%, most preferably 10 - 50% by mass based on the total mass of the detergent dispersant.
• the Mannich base is mixed with the diluent (if used) at 20 ° C to 60 ° C for 1 h to 6 h.
• the Mannich base or the detergent dispersant of the present invention is also particularly suitable for the production of a lubricating oil composition which exhibits excellent detergency (sediment formation inhibition property) and rust prevention performance. Therefore, according to the present invention, further relates to a lubricating oil composition comprising any Mannich base (or a mixture thereof in any ratio) of the present invention, which is produced according to the method for producing a Mannich base according to the present invention. Mannich base or the aforementioned detergent dispersant of the present invention, and a lubricating base oil.
• the aforementioned Mannich base (or a mixture thereof in any ratio) of the present invention Mannich base produced by the above-described method for producing Mannich base according to the present invention
• the above-mentioned detergent dispersant of the present invention may be uniformly mixed as a lubricating oil additive, a lubricating base oil, and other lubricating oil additives used as needed in a predetermined ratio or an added amount.
• each of the above lubricating oil additives may be separately added to the lubricating base oil, or the above lubricating oil additives may be mixed to form a concentrate and then added to the lubricating base oil. Medium, heat and mix well.
• the mixing temperature at this time is generally from 40 ° C to 90 ° C, and the mixing time is generally from 1 hour to 6 hours.
• the amount of the Mannich base or the detergent dispersant added the amount of the Mannich base or the detergent dispersant (the shield basis) based on the Mannich base is occupied.
• the total mass of the lubricating oil composition is from 0.01% to 20%, preferably from 0.02% to 16%, more preferably from 0.1% to 15%.
• the lubricating oil composition comprises any of the aforementioned Mannich bases of the present invention (or a mixture thereof in any ratio) or a Mannich base produced according to the method for producing a Mannich base according to the present invention. , as well as lubricating base oils.
• the Mannich base accounts for 0.01% to 20% by mass, preferably 0.02% to 16%, more preferably 0.1% to 15% by mass based on the total mass of the lubricating oil composition.
• the lubricating oil composition may further include an antioxidant, a dispersing agent (other than the Mannich base of the present invention), a detergent, an antiwear agent, and a friction modifier.
• an antioxidant other than the Mannich base of the present invention
• a dispersing agent other than the Mannich base of the present invention
• a detergent other than the Mannich base of the present invention
• a friction modifier one or more other lubricating oil additives.
• the antioxidant for example, one selected from the group consisting of an amine type antioxidant, a phenol ester type antioxidant, a deuterated phenol ester type antioxidant, and a desired antioxidant may be mentioned. kind or more.
• an alkylated diphenylamine antioxidant for example, an alkylated diphenylamine antioxidant can be mentioned.
• an alkylated diphenylamine antioxidant IRGANOX L-OK IRGANOX L-57 from BASF, Germany, T534 from Beijing Xingpu Co., Ltd., LZ5150A from Lubrizol Lanner Additive Co., Ltd., Vanderbilt, USA Production of VANLUBE NA, VANLUBE 961, dioctyldiphenylamine VANLUBE 81, dimercaptodiphenylamine VANLUBE DND, a pair produced by TÜV Rheinland, a pair of diisooctyldiphenylamine RC7001, etc., preferred alkylated diphenylamine
• the antioxidant is tert-butyl/isooctyldiphenylamine (for example, T534 manufactured by Beijing Xingpu Co., Ltd.).
• ester type antioxidant for example, 2,2'- ⁇ bis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ethyl ester] (for example, Sichuan) Antioxidant 1035 produced by Yongye Chemical Co., Ltd., IRGANOX L115 produced by BASF, Germany.
• the antioxidant a combination of the alkylated diphenylamine antioxidant and the thiophenolate-type antioxidant is preferred, wherein the alkylated diphenylamine accounts for the total mass of the combination.
• the antioxidant accounts for 0 to 10% by mass, preferably 0.1% to 5%, more preferably 0.2% to 3% by mass based on the total mass of the lubricating oil composition.
• the other dispersing agent for example, one selected from the group consisting of a polyisobutylene succinimide dispersing agent, a borated polyisobutylene succinimide dispersing agent, and a succinate dispersing agent may be mentioned.
• a plurality of, preferably one or more selected from the group consisting of a polyisobutylene succinimide dispersant and a borated polyisobutylene succinimide dispersant for example, one selected from the group consisting of a polyisobutylene succinimide dispersing agent, a borated polyisobutylene succinimide dispersing agent, and a succinate dispersing agent.
• polyisobutylene succinimide dispersant a polyisobutylene succinimide ashless dispersant is preferred, wherein the polyisobutylene (PIB) moiety has a number average molecular weight of from 800 to 4,000, preferably from 900 to 3,000, more preferably from 1,000. -2400, for example, T161 produced by Suzhou Special Oil Products Factory, T161A, T161B produced by Jinzhou Petrochemical Company's Additives Factory, LZL157 produced by Lubrizol Lansing Additives Co., Ltd., LZ6418, LZ6420 produced by Lubrizol Corporation Hitec 646 produced by Fulton Company.
• PIB polyisobutylene
• the polyisobutylene portion preferably has a number average molecular weight of 500 to 4,000, preferably 700 to 2,500, preferably 1,000 to 2,300.
• MX3316 manufactured by Agip Petroli Co., Ltd. may be used.
• a combination of the polyisobutylene succinimide ashless dispersant and the boronated polyisobutylene succinimide dispersant is preferred, and the mass ratio of the two in the combination is generally from 1:1 to 3: 1.
• the dispersant accounts for 0.5% to 15%, preferably 1% to 10%, more preferably 1.5% to 8% by mass based on the total mass of the lubricating oil composition.
• a salt selected from a sulfonate can be mentioned.
• a solvent an alkylphenolate detergent, a sulfide pit phenate detergent, a salicylate detergent, and a naphthenate detergent, preferably selected from the group consisting of a sulfonate detergent, an alkyl sulfide One or more of a phenate detergent and a salicylate detergent.
• sulfonate detergent for example, calcium sulfonate can be mentioned.
• sulfurized alkylphenolate detergent for example, a calcium alkyl phosphate can be mentioned. Preferred is a base number
• a mixture of (100-450) mgKOH/g calcium sulfonate and sulfurized alkylphenol calcium preferably a high base calcium sulfonate having a base number of (200-450) mgKOH/g and a base number (100 - ⁇ 200) mgKOH/g of a medium-base sulfurized mixture of calcium alkylphenolates, the mass ratio between the two being between 0.2:1 and 4:1, preferably between 0.5:1 and 2:1.
• the calcium sulfonate and the sulfurized alkylphenol calcium for example, T101, T102, T103 produced by Shanghai Shanglian Additive Factory, T106 produced by Jinzhou Petrochemical Company's additive factory, LZ6478, LZ6446, LZ75 produced by Lubrizol Corporation can be selected.
• the detergent accounts for 0.2% to 20%, preferably 0.8% to 15%, more preferably 1.2% to 10% by mass based on the total mass of the lubricating oil composition.
• a dialkyldithiocarbamate anti-wear agent for example, a dialkyldithiocarbamate anti-wear agent, a phosphate-type extreme pressure anti-wear agent, a sulfurized olefin anti-wear agent, a dialkyl disulfide may be mentioned.
• a carbamate antiwear agent and a thiadiazole derivative antiwear agent preferably selected from the group consisting of a dialkyl dihalophosphate antiwear agent, a phosphate type extreme pressure antiwear agent, and a vulcanization agent
• an olefin antiwear agent and a dialkyldithiocarbamate antiwear agent preferably selected from the group consisting of a dialkyl dihalophosphate antiwear agent, a phosphate type extreme pressure antiwear agent, and a vulcanization agent.
• dialkyl dithiophosphate antiwear agent for example, one or more selected from the group consisting of zinc dialkyl dithiophosphates whose alkyl group is an alkyl group having 2 to 12 carbon atoms can be mentioned.
• alkyl groups having 2 to 8 carbon atoms such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, Isohexyl, n-octyl, 2-ethylhexyl, cyclohexyl, methylcyclopentyl.
• the zinc dialkyl dithiophosphate can be selected from T202, ⁇ 203 produced by Wuxi Southern Petroleum Additive Co., Ltd., and the primary alkyl hydrazine 202 and primary alkane produced by the Jinzhou Petrochemical Company Additives Factory.
• Examples of the phosphate type extreme pressure antiwear agent include triphenyl phosphite, trimethyl phosphite, tri-dodecyl phosphite, and tri-octadecyl phosphite.
• triphenyl phosphite trimethyl phosphite, tri-dodecyl phosphite, and tri-octadecyl phosphite.
• the antiwear agent accounts for 0.1% to 10%, preferably 0.2% to 8%, more preferably 0.5% to 5% by mass based on the total shield of the lubricating oil composition.
• the friction modifier for example, one or more selected from the group consisting of an oil-soluble organic molybdenum friction modifier, an ashless friction modifier, and an organic borate friction modifier may be mentioned, preferably selected.
• an oil-soluble organic molybdenum friction modifier and an ashless friction modifier may be mentioned, preferably selected.
• oil-soluble organic molybdenum friction modifier for example, molybdenum dialkyldithiophosphate, molybdenum dialkyldithiophosphate, molybdenum dialkyldithiocarbamate, molybdenum xanthate may be mentioned.
• molybdenum thioxanthate trinuclear molybdenum sulfur complex, molybdenum amine complex and molybdate oil-soluble organic molybdenum friction modifier.
• the organic molybdenum friction modifier has an organic group containing a sufficient number of carbon atoms to make the organic molybdenum friction modifier soluble or dispersible in a lubricating base oil, generally having a carbon number of 6-60. Preferably between 10 and 50.
• the oil-soluble organic molybdenum friction modifier may be selected, for example, from MolyVan L, 822, 855 manufactured by Vanderbilt, USA, 515, 525, 710, etc. manufactured by Asahi Chemical Co., Ltd., Japan.
• ashless friction modifier for example, one or more selected from the group consisting of a fatty acid polyol ester, an aliphatic amine, and an aliphatic amide, wherein the aliphatic hydrocarbon group is between 6 and 60 carbon atoms, may be mentioned.
• a saturated or unsaturated hydrocarbon group preferably a saturated or unsaturated hydrocarbon group having from 10 to 50 carbon atoms.
• the fatty acid polyol ester includes a monoester, a diester or a compound of a compound such as a fatty acid glyceride, a fatty acid pentaerythritol ester, a fatty acid ethylene glycol ester, a fatty acid succinate, a fatty acid ethanolamine ester, a fatty acid diethanolamine ester, a fatty acid triethanolamine ester or the like.
• Esters such as oleic acid monoglyceride, oleic acid diglyceride, stearic acid monopenta a tetraol ester, a dodecyl glycol diester, an oleic acid monoglyceride, an oleic acid diethanolamine monoester, an oleic acid triethanolamine monoester, etc., the aliphatic amine including a hydrocarbyl-substituted monoamine or a polyamine, an alkoxylate
• the alkylated hydrocarbon group is substituted with a monoamine or a polyamine and an alkyl ether amine, etc., such as an ethoxylated tallow fatty amine and an ethoxylated tallow fatty ether amine
• examples of the aliphatic amide include oleic acid amide. , cocamide, oleic acid diethanolamide, etc.
• the ashless friction modifier may be, for example, F10 and
• a combination of the oil-soluble organic molybdenum friction modifier and the ashless friction modifier is preferred, wherein the oil-soluble organomolybdenum friction modifier comprises from 5 wt% to 50 wt%, preferably 10 wt% of the total mass of the combination. %-40wt%, the ashless friction modifier comprises from 50% by weight to 95% by weight of the total shield of the combination, preferably from 60% by weight to 90% by weight.
• the friction modifier accounts for 0.01% to 5%, preferably 0.02% to 4%, more preferably 0.05% to 3% by mass based on the total mass of the lubricating oil composition.
• lubricating base oil for example, one or more selected from the group consisting of mineral lubricating oils and synthetic lubricating oils can be mentioned.
• the mineral lubricating oil can vary in viscosity from light distillate mineral oil to heavy mineral oil, such as liquid paraffin oil and hydrorefined, solvent-treated alkane, naphthenic and mixed alkane-naphthenes.
• Type mineral lubricants usually classified into Group I, II, and III base oils. Common commercial brand numbers include Class I 150SN, 600SN, Class II 100N, 150N, etc.
• the synthetic lubricating oil may, for example, be a polymeric hydrocarbon oil, an alkylbenzene or a derivative thereof.
• polymeric hydrocarbon oil include, but are not limited to, polybutene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutene, poly(1-hex), poly(1-octene), poly( 1-decene), common commercial brands include PA04, PA06, PA08, PAO10, etc.
• alkylbenzene and derivatives thereof include, but are not limited to, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene, and derivatives of alkylbenzenes include Alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and homologs thereof.
• ester oil examples thereof include dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acid, and alkenyl succinic acid, maleic acid, sebacic acid, Suberic acid, azelaic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid) and various alcohols (such as butanol, Hexanol, lauryl alcohol, 2-ethylhexyl alcohol, An ester or a complex ester formed by a condensation reaction of ethylene glycol or propylene glycol.
• dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acid, and alkenyl succinic acid, maleic acid, sebacic acid, Suberic acid, azelaic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic
• esters include, but are not limited to, dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, sebacic acid Isooctyl ester, diisononyl sebacate, dioctyl phthalate, dinonyl phthalate, di(decyl) sebacate, 2-ethyl linoleic acid dimer Hexyl diester.
• Still another suitable type of synthetic lubricating oil is Fischer-Tropsch synthesis of hydrocarbon oils and lubricating base oils obtained by treating such synthetic hydrocarbon oils by hydroisomerization, hydrocracking, dewaxing, and the like.
• the lubricating base oil has a viscosity index generally greater than 80, a saturated hydrocarbon content mass fraction greater than 90%, and a ⁇ content mass fraction less than 0.03%.
• One or more other lubricating oil additives of a metal corrosion inhibitor, a rust preventive, a pour point depressant, and an antifoaming agent may also be added to the lubricating oil composition of the present invention. These additives may be used singly or in combination of two or more kinds, and the amount thereof is not particularly limited as it is conventionally used in the field.
• the metal corrosion inhibitor for example, one or more selected from the group consisting of a ternary derivative, a thiazole, a "bio and a thiadiazole", such as benzotriazole, benzothiazole, and toluene may be mentioned.
• the commodity grades are T551, ⁇ 561, ⁇ 706, etc. T551, T56U ⁇ 706, etc. produced by Jinzhou Kangtai Lubricant Additive Co., Ltd. can be used.
• rust inhibitor examples include imidazoles and/or alkenyl succinates such as 4,5-dihydroimidazole, alkenylimidazolium succinate, and alkenyl succinate. ⁇ 746, ⁇ 703, ⁇ 747 produced by Jinzhou Kangtai Lubricant Additive Co., Ltd. were selected.
• a poly- ⁇ -olefin, a vinyl acetate copolymer, and a dialkyl fumarate having a C8-C18 alkyl group, a polyalkyl methacrylate, and an alkyl group can be mentioned.
• a poly- ⁇ -olefin, a vinyl acetate copolymer, and a dialkyl fumarate having a C8-C18 alkyl group, a polyalkyl methacrylate, and an alkyl group can be mentioned.
• Common commercial brands include ⁇ 803 of Wuxi Southern Petroleum Additive Company and V385 of Runyinglian Company.
• the antifoaming agent for example, a silicone antifoaming agent such as silicone oil or polydithiosiloxane can be mentioned.
• the lubricating oil composition of the invention has excellent viscosity control and low temperature performance, shear stability, high temperature detergency and antiwear property, and satisfies SL/GF-3, SM/GF-4 and SN/GF- and above specifications.
• the reaction mixture is washed once with a potassium hydroxide solution having a mass fraction of 5%, and washed with hot water until neutral to remove
• the catalyst was then distilled off under reduced pressure to remove the solvent and unreacted o-cresol to obtain polyisobutylene o-cresol having a hydroxyl value of 53.49 mgKOH/g.
• the hydroxyl value is determined by reference to the acetic anhydride method in GB/T7383-2007.
• Fig. 1 is a nuclear magnetic hydrogen spectrogram of the polyisobutenyl o-cresol of Example 1
• Fig. 2 is a diagram of the nuclear magnetic hydrogen of the benzene ring region of the polyisobutenyl o-cresol of Example 1. It can be seen from Fig. 1 and Fig.
• the integral of the fluorenyl hydrogen is defined as 3, and the integral ratio of hydrogen, hydroxyhydrogen and methyl hydrogen on the benzene ring is 0.97:0.98:0.97:0.97:3.00, which is close to the theoretical 1:1:1:3, from Nuclear magnetic spectrum analysis revealed the expected para-substituted polyisobutenyl ortho-phenol alkylation product.
• Figure 3 is a comparison of the nuclear magnetic resonance diagram of the Mannich base of Example 2 and the polyisobutenyl o-cresol of Example 1
• Figure 4 is the Mannich base of Example 2 and the polyisobutenyl o-cresol benzene ring of Example 1.
• Nuclear magnetic resonance language map comparison chart It can be seen from Fig. 3 and Fig. 4 that the chemical shift 3.7 is the displacement peak of the hydrogen proton on the fluorene group formed by the conversion of formaldehyde carbonyl; the chemical shift 2.45 is the chemical shift peak of the protons on the two methylene groups on the ethylenediamine.
• Figure 5 is a GPC chart of the polyisobutenyl o-cresol of Example 1
• Figure 6 is a GPC chart of the Mannich base of Example 2.
• the molecular weight of the Mannich base product was increased due to the doubling of the starting material involved in the Mannich reaction, thereby demonstrating that the desired Mannich base product was obtained.
• Example 44.92 g (0.043 mol) of polyisobutylene o-cresol obtained in Example 1 was added under nitrogen to a 500 ml four-necked flask equipped with a stirrer, a thermometer and a dispenser, and then 4.64 g (0.043 mol) was added.
• the example reaction is as follows:
• Figure 7 is a GPC chart of the Mannich base of Example 5. As can be seen from Fig. 5, Fig. 6 and Fig. 7, the molecular weight of the Mannich base product was increased due to the doubling of the raw materials involved in the Mannich reaction, thereby demonstrating that the desired Mannich base product was obtained.
• Example 7 40.01 g (0.038 mol) of polyisobutylene o-cresol obtained in Example 1 was added under nitrogen to a 500 ml four-necked flask equipped with a stirrer, a thermometer and a dispenser, and then 3.61 g (0.019 mol) was added. Tetraethylpentamine, 3.25 g (0.040 mol) of formaldehyde, and 38 ml of xylene as a reaction solvent, reacted at 80 ° C for 1.5 h, and then cooled to room temperature. 2, 10 g (0,0095 mol) of 4-nonylphenol and 1.63 g (0.020 mol) of furfural were added and reacted at 70 ° C for 1 h. After the reaction was completed, the solvent and a small amount of water formed were distilled off under reduced pressure to give a final Mannich base.
• Example 7 40.01 g (0.038 mol) of polyisobutylene o-cresol obtained in Example
• the polyisobutylene was expected to be 45.11 g (0.043 mol). After the polyisobutylene o-cresol was completely dissolved, 3.40 g (0.043 mol) of a formaldehyde solution was added, and the temperature was raised to 120 ° C to continue the reaction for 2 h. After the reaction was completed, the solvent and a small amount of water formed were distilled off under reduced pressure to give a final Mannich base.
• the polyisobutylene orthoquinone prepared in Example 1 was expected to be added to a 500 ml package under the protection of nitrogen, 45.11 g (0.043 mol), tetraethylenepentamine 4.16 g (0.022 mol), 4-nonylphenol 2.42 g (0.011 mol).
• 50 ml of toluene was added as a reaction solvent, and the reaction system was stirred uniformly, and the temperature was raised to 45 to 50 ° C, and 5.92 g (0.073 mol) of oyster case was gradually added dropwise.
• the solution was controlled within 0.5 h.
• Example 1 The polyisobutylene o-phenol obtained in Example 1 was 48.27 g (0.046 mol) in nitrogen. Under protection, it was added to a 500 ml four-necked flask equipped with a stirrer, a thermometer and a dispenser, then 3.36 g (0.023 mol) of triethylenetetramine, 4.46 (0.055 mol) g of formaldehyde, and 45 ml of toluene were added. The reaction solvent was heated to the mixing temperature and stirred uniformly. 4.46 (0.055 mol) g of formaldehyde was added dropwise to the reactor, and the reaction was carried out at 80 ° C for 1.5 h. After completion of the reaction, the solvent and a small amount of water formed were distilled off under reduced pressure to give a final Mannich base. Examples 12 to 21 and Comparative Examples 3 to 6
• Examples 12-21 and Comparative Examples 3-6 The formulation composition of the gasoline engine lubricating oil composition is shown in Table 1. The components in the table were added to the blending container in a prescribed ratio, and heated and stirred at 50 ° C for 2 hours to prepare a SN 5W-30 grade gasoline engine lubricating oil composition.
• lubricating oil compositions were used as test samples to perform an engine crankcase focusing simulation test face simulating piston deposits.
• the method is to add 300ml test sample to the coke plate simulator, heat to 150 ° C, use a continuous method to splash oil to the aluminum plate with a temperature of 310 ° C, and weigh the amount of coke generated on the aluminum plate after 6 hours to simulate the piston. Sediment. The higher the amount of coke formation, the worse the cleanliness of the piston representing this test sample.
• the results of the coke plate test deposits of the respective lubricating oil compositions are shown in Table 1.
• the formulation compositions of the lubricating oil compositions of Examples 22 to 31 and Comparative Examples 7 - 10 are shown in Table 2.
• the components in the table were added to the blending container in a prescribed ratio, and heated and stirred at 50 ° C for 2 hours to prepare a CH-4 grade diesel engine lubricating oil composition having a viscosity grade of 10 W-40.
• lubricating oil compositions were used as test samples to perform an engine crankcase coke simulation test simulating piston deposits.
• the method is to add 300ml test sample to the coke plate simulator, heat to 100 ° C, use a continuous method to splash oil on the aluminum plate with a temperature of 330 ° C, and weigh the amount of coke generated on the aluminum plate after 5 hours, simulate Sediment on the piston. The higher the amount of coke formation, the worse the detergency of the piston representing this test sample.
• the results of the coke plate test deposits of the respective lubricating oil compositions are shown in Table 2.
• the formulation compositions of the gas engine lubricating oil compositions of Examples 32 to 41 and Comparative Examples 11 - 14 are shown in Table 3. Add the components in the table to the blending container in the specified proportion, under normal pressure 45. C was heated and stirred for 2 hours to prepare a gas engine lubricating oil composition having a viscosity grade of SN 5W-40.
• lubricating oil compositions were used as test samples to perform an engine crankcase coke simulation test simulating piston deposits.
• the method is to add 300ml test sample to the coke plate simulator, heat to 140 ° C, use a continuous method to splash oil on the aluminum plate with a temperature of 320 ° C, and weigh the amount of coke generated on the aluminum plate after 6 hours, simulate Sediment on the piston. The higher the amount of coke formation, the worse the cleanliness of the piston representing this test sample.
• the results of the coke plate test deposits of each lubricating oil composition are shown in Table 3.
• the BRT ball rust test is an alternative to the program II D engine bench test, which is mainly used to evaluate the corrosion resistance and corrosion resistance of engine oil. During the entire 18-hour bench test, the metal ball protected by the test oil is continuously exposed to the acidic liquid and air. After the test, the strength of the reflective surface of the metal ball is measured, and the gray scale test value is obtained to determine the corrosion area.
• the rust resistance of the test sample The injection rate of vinegar hydrobromide/hydrochloric acid/deionized water solution was 0.19 ml/hr, the air flow rate was 40 ml/min, and the oil temperature was 48 °C. The higher the score, the better the rust resistance of the test sample.
• the above-described ball rust test was carried out using the lubricating oil compositions of the inventive examples and comparative examples as test samples, and the test results are shown in Table 4.
• the test results show that the lubricating oil composition of the present invention has excellent rust preventive ability.

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