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

• This invention relates to a Mannich base, and more particularly to a Mannich base suitable for use in the manufacture of detergents.
• the invention also relates to a process for the manufacture of the Mannich base and to the use thereof in the manufacture of detergents. Background technique
• the generation which seriously affects the working performance of the engine, causes problems such as difficulty in starting the engine, unstable idle speed, poor driving performance, poor acceleration, and serious power loss.
• the prior art has developed a large number of detergents.
• the Mannich base is produced by reacting a hydrocarbyl-substituted alkyl o-cresol 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 desired compound with an aldehyde or an amine, and as a detergent, it is possible to suppress the formation of engine deposits.
• a Mannich base comprising the structural unit (I) and the structural unit (II) as follows:
• each R' is the same or Different, each independently selected from hydrogen and a linear or branched alkyl group, preferably selected from hydrogen and methyl, more preferably hydrogen;
• R 2 is selected from Cw 2 straight or branched alkyl, more preferably from C 5 _ 12 linear or branched alkyl;
• R 3 is selected from linear or branched alkyl, preferably selected from d- 4 straight or branched alkyl, more preferably methyl;
• R4 is selected from number average molecular weight Mn of 300-3000 Hydrocarbyl groups (preferably 500-2000, more preferably 500-1500); each y being the same or different, each independently selected from an integer of 2-5, preferably 2 or 3.
• each A is the same or different and is independently selected from each other
• argon 3 is preferred
• 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 a fluorenyl group, more preferably hydrogen; each being the same or different, each independently selected from hydrogen, CM straight chain Branched alkyl and More From the hydrogen sum, provided that at least one Ra is; each R b is the same or different, each independently selected from hydrogen,
• a linear or branched pit base preferably selected from the group consisting of hydrogen,
• a mercapto group more preferably selected from the group consisting of hydrogen and The premise is at least one R,
• R 2 is selected from D- C12 straight-chain or branched alkyl, more preferably from ⁇ : 512 straight-chain or branched-chain alkyl group
• R 3 is selected from a straight-chain or branched alkyl, preferably straight CM.
• 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 y is the same or different and each independently selected from 2 An integer of -5, preferably 2 or 3; each c is the same or different and is each independently selected from an integer from 0 to 10, preferably from an integer from 2 to 5, more preferably 2 or 3.
• a method for producing a Mannich base comprising a compound of the formula (V), a phenol compound of the formula (VI), a polyalkylene polyamine of the formula (VII), and a d-Oz linear or branched chain.
• a step of a Mannich reaction in which a saturated fatty aldehyde (preferably acetaldehyde or formaldehyde, more preferably furfural, especially in the form of aqueous formaldehyde, paraformaldehyde or paraformaldehyde),
• a saturated fatty aldehyde preferably acetaldehyde or formaldehyde, more preferably furfural, especially in the form of aqueous formaldehyde, paraformaldehyde or paraformaldehyde
• R 2 is selected from Cw 2 straight or branched alkyl, more preferably C 5 . 12 straight or branched alkyl;
• R 3 is selected from linear or branched alkyl, preferably selected from C M straight a chain or 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); each R b 'is the same or different, each independently selected From hydrogen and a linear or branched pit group, preferably selected from the group consisting of hydrogen and methyl, more preferably hydrogen, provided that at least two R b 'is hydrogen, more preferably the molecular chain of the polyalkylene polyamine of formula (VII) At least one R b ' is hydrogen at each of the opposite ends; y is selected from an integer from 2 to 5, preferably 2 or 3; c' is selected from an integer from 1 to 11, preferably
• First step the desired compound of the formula (VI), the polyalkylene polyamine of the formula (VII) and the d-linear or branched saturated fatty aldehyde at a reaction temperature of 50 e C-200°
• a Mannich reaction occurs at C (preferably 60 ° C - 150 ° C, most preferably 80 ° C - 130 ° C) to form an intermediate product; and
• the intermediate product is associated with the structural formula (V)
• the phenolic compound and the (C 7 linear or branched saturated fatty aldehyde occur at a reaction temperature of 40 ° C to 200 ° C (preferably 60 ° C to 150 ° C, most preferably 80 ° C to 130 ° C). Reaction, generating the Mannich base,
• Mode (2) Includes the following steps:
• First step The desired compound of the formula (V), the polyalkylene polyamine of the formula (VII) and the Ci-C 7 linear or branched saturated fatty aldehyde are allowed to react at a reaction temperature of 40. C-200.
• the Mannich reaction occurs at C (preferably 60 ° C - 150 ° C, most preferably 80 ° C - 130 ° C) to form an intermediate product; and the second step: the intermediate product is associated with the structural formula (VI)
• the desired compound and the dC 7 linear or branched saturated fatty aldehyde are generated at a reaction temperature of from 50 ° C to 200 ° C (preferably from 60 ° C to 150 ° C, most preferably from 80 ° C to 130 ° C). Reacting to form the Mannich base,
• Mode (3) comprising a phenolic compound of the formula (V), the structural formula (VI)
• the compound, the polyalkylene polyamine of the formula (VII) and the C r C 7 straight or branched chain and fatty aldehyde are at a reaction temperature of 40.
• linear or branched saturated aliphatic aldehyde 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; in the second step of the mode (1), the molar between the intermediate product and the compound of the formula (V) and the CrC 7 linear or branched saturated aliphatic aldehyde The ratio 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; in the first step of the mode (2), the The molar ratio of the desired compound of the formula (V), the polyalkylene polyamine of the formula (VII) to the linear or branched saturated aliphatic aldehyde of the CrC 7 is 1: 1.5-2.5: 1.5-3, Preferred 1: 1.7-2.5: 1.7-2.8, more preferably 1: 1.7-2.2: 1.7-2.5; in the second step of the mode (2), the intermediate product and the phenolic compound of the formula (VI
• phenol compound of the formula (VI) is obtained by reacting a phenol compound of the formula (IV) with a number average molecular weight Mn in the presence of an alkylation catalyst.
• a polyolefin of 300-3000 preferably 500-2000, more preferably 500-1500 is produced by alkylation reaction, preferably by homopolymerization of ethylene, propylene or C 4 -C 1 ( )a-olefin Or a polyolefin obtained by copolymerization of two or more of these women hydrocarbons, more preferably polyisobutylene,
• R 3 is defined in the same way as aspect 3.
• a detergent comprising Mannich base or any one of the foregoing according to any of the preceding aspects
• a Mannich base produced by the method of producing a Mannich base, and optionally comprising a diluent selected from one or more of the group consisting of polyolefins, mineral base oils, and polyethers.
• a detergent according to any of the preceding aspects wherein the Mannich base accounts for 10 to 70%, preferably 10 to 60%, most preferably 10 to 50% by mass of the total mass of the detergent.
• a fuel oil composition comprising a Mannich base according to any of the preceding aspects, a Mannich base produced according to the method for producing a Mannich base according to any of the preceding aspects, or a detergent according to any of the foregoing aspects.
• a base fuel wherein the Mannich base or the detergent is added in an amount of 30 to 2000 mg/kg, preferably 50 to 2000 mg, based on the total mass of the fuel oil composition, based on the mass of the fuel oil composition. /kg, more preferably 50 ⁇ 1000mg/kg.
• Figure 1 is a nuclear magnetic hydrogen spectrogram of the polyisobutenyl o-cresol of Example 1.
• Figure 2 is a nuclear magnetic hydrogen spectrogram of the benzene ring region of the polyisobutenyl o-cresol of Example 1.
• Figure 3 is a comparison of the nuclear magnetic resonance spectrum of the Mannich base of Example 2 and the polyisobutyl ketone o-cresol of Example 1.
• Figure 4 is a graph showing the comparison of the NMR spectra of the Mannich base of Example 2 and the benzene ring region of the polyisobutenyl ortho-phenol of Example 1.
• 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 1.
• Figure ⁇ is a GPC spectrum of the Mannich base of Example 5.
• the number average molecular weight Mn is determined by gel permeation chromatography (GPC) unless otherwise specified.
• any gel permeation chromatography (GPC) or GPC spectra involved 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 column temperature was 35 ° C, the outflow time was 40 min, and the sample mass fraction was 0.16%-0.20%.
• each R' is the same or different and each independently selected from hydrogen and a straight or branched alkyl group ;
• R 2 is selected from d. 12 linear or branched fluorenyl;
• R 3 is selected from a linear or branched alkyl group;
• R4 is selected from a hydrocarbon group 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.
• the preferences are each independently selected from the group consisting of hydrogen, fluorenyl and a single bond, 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 group.
• 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.
• the R 2 is preferably selected from a C 5-12 straight or branched alkyl group, more preferably a C 8 - 12 linear or branched alkyl group, such as octyl, decyl, fluorenyl, eleven Alkyl or dodecyl, especially straight-chain octyl, decyl, decyl, undecyl or dodecyl.
• said R 3 is preferably selected from C 14 straight or branched alkyl groups, more preferably fluorenyl 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, a terminal of the polyhydrazine hydrocarbon molecular chain) may be mentioned.
• Hydrocarbon group obtained afterwards (referred to 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.
• polystyrene resin for example, it is possible to pass ethylene, propylene or a C 4 -C 1 () ⁇ -olefin (such as n-butene, isobutylene, n-pentene, n-hexene, n-octene or n-decene).
• ⁇ -olefin such as n-butene, isobutylene, n-pentene, n-hexene, n-octene or n-decene.
• the y are the same or different, preferably the same.
• the y is preferably 2 or 3, more preferably choose 2.
• the "Mannich base comprises structural unit (I) and structural unit (II)", meaning that the structural unit (I) and the structure can be detected in the Mannich base Unit (II) coexists.
• the Mannich base may be a mono-type compound in which the simultaneous presence of the two structural units can be detected or distinguished, that is, the structure of the compound simultaneously exists.
• 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 read mixture.
• the two structural units may exist in the structure of the same compound at the same time, or may exist in the structure of different compounds, and 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 ⁇ -NMR or gel permeation chromatography (GPC).
• the two structural units can Direct bonding, also through
• X is an integer of 0-8, preferably an integer of 0-3, more preferably 1) at the respective single bond or (only when Indirect bonding at the time of a single key.
• the molar ratio of the structural unit (I) to the structural unit (II) 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. 5 mol% or less, preferably 2 mol% or less, more preferably 0.5 mol% or less, or as (inevitable) impurities.
• the Mannich base is represented by the following structural formula ( ⁇ ).
• each A is the same or different and is independently selected from each other Hydrogen, provided that at least one A is
• Each R' is the same or different and is each independently selected from hydrogen and a C 6 straight or branched alkyl group;
• each R a is the same or different and each independently selected from hydrogen, a straight or branched alkyl group and , provided that at least one is;
• each R b is the same or different, each independently selected from hydrogen,
• R 3 is selected from a straight-chain or branched alkyl
• R4 is selected from a hydrocarbon group having a number average molecular weight Mn of 300-3000
• same or different and each y are each independently selected from 2- An integer of 5
• each c is the same or different and is each independently selected from an integer of 0-10.
• the A is preferably the same, more preferably all .
• said R' are each identical or different (preferably identical), and preferably each independently It is selected from the group consisting of hydrogen and sulfhydryl, and more preferably hydrogen.
• Ra is each independently selected from the group consisting of hydrogen, methyl and More preferably, it is selected from the group consisting of hydrogen and 3 ⁇ 4.
• R a is hydrogen or methyl, or
• the R b is preferably methyl
• each is independently selected from hydrogen and
• R b is hydrogen or sulfhydryl.
• said R 2 is preferably selected from C 5 - 12 linear or branched alkyl groups, more preferably C 8 . 12 straight or branched alkyl groups, such as octyl, decyl, decyl, undecane Or a dodecyl group, especially a linear octyl, decyl, decyl, undecyl or dodecyl group.
• said R 3 is preferably selected from the group consisting of d- 4 straight 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 300 to 3,000 (particularly, a terminal of the polyolefin molecular chain) may be mentioned after removing a hydrogen atom.
• the hydrocarbon group obtained (referred to as a 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.
• polystyrene resin for example, homopolymerization by ethylene, propylene or a C 4 -C 10 ⁇ -olefin such as n-butene, isobutylene, n-pentene, n-hexene, n-octene or n-decene may be mentioned.
• 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, 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 single (pure) compound, or may be present in a mixture of two or more thereof (in any proportion), manufactured or Use, 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 a compound of the formula (V), a phenol compound of the formula (VI), a polyalkylene polyamine of the formula (VII), and a C r C 7 linear or branched saturated fatty aldehyde.
• the step of the Mannich reaction occurs.
• R 2 is selected from a C M2 linear or branched alkyl group
• R 3 is selected from a linear or branched alkyl group
• R4 is selected from a hydrocarbon group having a number average molecular weight Mn of from 300 to 3,000
• each R b ' is the same or different,
• Each is independently selected from hydrogen and a straight or branched alkyl group, provided that at least two R b 'is hydrogen
• y is selected from an integer from 2 to 5
• c' is selected from an integer from 1 to 11.
• 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, decyl, undecane Or a dodecyl group, especially a linear octyl, decyl, decyl, undecyl or dodecyl group.
• said R 3 is preferably selected from a linear or branched alkyl group, more preferably a mercapto group or an 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 300 to 3,000 (particularly, a terminal of the polyolefin molecular chain) may be mentioned after removing a hydrogen atom.
• 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. Ethylene double bonds (such as those remaining in the polyolefin manufacturing process), but this does not affect the achievement of the effects of the present invention, and the present invention is not intended to be clear on the amount.
• polystyrene resin for example, homopolymerization by an ethylene-, propylene or C 4 -Cu) ⁇ -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 (yttrium).
• yttrium polyisobutylene
• the phenol compound of the formula (VI) can be obtained by reacting a compound of the formula (IV) with the polyolefin (number average molecular weight Mn of 300-3000, preferably 500-) in the presence of an alkylation catalyst. 2000, more preferably 500-1500) is produced by an alkylation reaction.
• the ruthenium compound of the structural formula (VI) can also be directly used 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 aco-olefin or by copolymerization of two or more of these olefins.
• Examples of the do a-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, more preferably at least 70% by weight) of the polymer chains of these polyolefins contain olefinic double bonds at their ends.
• the olefinic double bond is generally present in the form of a highly reactive vinylidene or vinyl group.
• polybutene is more preferable 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- ⁇ in such polyisobutylene at least 20% by weight (preferably at least 50% by weight, more preferably at least 70% by weight) is further preferred.
• the total terminal olefinic double bond is provided by a mercapto vinylidene group.
• 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. methanol complex are preferred.
• the molar ratio between the polyolefin, the desired 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, from 0 e C to 200 ° C, preferably from 10 ° C to 150.
• C is most preferably from 20 ° C to 100 ° C, but is sometimes 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. Among them, hexane and heptane are preferably used, and hexane is more preferably used.
• the structural formula is obtained by removing the alkylation catalyst, the unreacted reactant and the solvent which may be used from the finally obtained reaction mixture in a conventional manner.
• said R b ' is the same or different, preferably each independently selected from the group consisting of hydrogen and methyl. More preferably, the molecular chain of the polyalkylenepolyamine of the formula (VII) has at least one R b at each of the two ends, and 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 octaylamine, hexaethyleramine, and decanthinamine, of which diethylenetriamine is preferred.
• the polyalkylene polyamine can be produced, for example, by reacting ammonia with a dihalogenated alkane such as a 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 of from 3 to 6, more preferably 3 or 4.
• the C r C 7 linear or branched saturated fat cheese is preferably acetaldehyde or furfural, more preferably formaldehyde.
• the furfural may be, for example, an aqueous solution, a polyfurfural or a paraformaldehyde, 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 the desired compound of the formula (VI), the polyalkylene polyamine of the formula (VII) and the dC 7 linear or branched saturated fatty aldehyde at a reaction temperature of 50 C-200 ° C (preferably, from 60 ° C to 150 ° C, most preferably 8 (TC - 130 ° C), a Mannich reaction occurs to form an intermediate product; and a second step: the intermediate product is phenol with the structural formula (V)
• the compound and the dC 7 linear or branched saturated aliphatic aldehyde undergo a Mannich reaction at a reaction temperature of 40 ° C to 20 (TC (preferably 60 e C-150 e C, most preferably 80 ° C to 130 ° C) , generating the Mannich base.
• Mode (2) Includes the following steps: ⁇ One step: the desired compound of the formula (V), the polybenzylene polyamine of the formula (VII) and the dC 7 linear or branched saturated fatty aldehyde at a reaction temperature of 40 ° C to 200 e C (preferably 60 ° C - 150 ° C, most preferably 80 ° C - 13 (TC) under the Mannich reaction to form an intermediate product; and second step: the intermediate product with the structural formula (VI)
• the hydrazine compound and the C r C 7 linear or branched saturated fatty aldehyde are produced at a reaction temperature of 50'C to 200 ° C (preferably 60 ° C to 150 ° C, most preferably 80 ° C to 130 ° C).
• the Nisch reaction produces the Mannich base.
• Mode (3) comprising a compound of the formula (V), an anthracene compound of the formula (VI), a polyalkylene polyamine of the formula (VII), and the C r C 7 straight chain or
• the branched saturated fatty aldehyde is at a reaction temperature of 40 ° C to 200 ° C.
• the step of generating a Mannich base by a Mannich reaction under C (preferably from 60 ° C to 150 ° C, most preferably from 80 ° C to 130 ° C).
• the mode (1) is preferred.
• the phenol compound of the formula (VI), the polyalkylene polyamine of the formula (VII), and the linear or branched The molar ratio between the chain saturated aliphatic aldehydes 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 - 10 h, preferably 2 h - 8 h, and most preferably 3 h - 6 h.
• the intermediate product in the second step of the mode (1), is between the phenol compound of the structural formula (V) and the C r C 7 linear or branched saturated fatty aldehyde.
• the molar ratio 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 for example, lh-10h, preferably 2h-8h, and most preferably according to the present invention
• the structural formula (V) in the first step of the mode (2), the structural formula (V)
• linear or branched saturated fat tunnel 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: 1.7-2.5technische
• the reaction time of the step of the present invention is not particularly limited, and examples thereof include, for example, 1 h to 10 h, preferably 2 h to 8 h, and most preferably 3 h. 6h.
• the molar between the intermediate product and the phenol compound of the formula (VI) and the C r C 7 linear or branched 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 may, for example, be 1 to 10 h, preferably 2 to 8 h, and most preferably 3 to 6 h.
• the molar ratio of the phenolic compound of the formula (VI), the polyalkylene polyamine of the formula (VII) and the C 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 diphenylbenzene can be mentioned. Among them, toluene or xylene 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 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 40 ° C viscosity of 20-120 cSt (cSt).
• the polyolefin for example, ethylene, propylene or C 4 -C 10 a- or more may be mentioned, and the viscosity at 100 ° C is preferably 2 to 25 cSt (the viscosity of cSt X is preferably 100 ° C is One or more of 6-10 centistokes (cSt) of polya-olefin (PAO).
• 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 500 to 3,000, preferably 700 to 3,000, and most preferably 1,000 to 2,500.
• Mannich reaction is generally carried out under the protection of an inert gas atmosphere.
• inert gas examples include nitrogen gas and argon gas, and are not particularly limited.
• the Mannich machine After the end of the manufacturing process of the Mannich base, any conventionally known By removing the moisture and the solvent that may be present from the finally obtained reaction mixture, the Mannich machine is obtained.
• the present invention also relates to Mannich reduction produced by the aforementioned method for producing Mannich base according to the present invention.
• a mono-type Mannich base having a very high purity (purity such as 95% or more) can be produced, and it can also be produced by various kinds of Mannich.
• These reaction products are all contemplated by the present invention, and the difference in their form of existence does not affect the achievement of the effects of the present invention. Therefore, in the context of the present specification, these reaction products are collectively referred to as Mannich bases without distinction.
• the Mannich base of the present invention is particularly suitable for the production of a detergent (detergent principal), particularly a fuel oil detergent, which exhibits excellent deposit formation inhibiting properties and rust preventing properties.
• the detergent comprises any of the aforementioned Mannich bases of the present invention (or a mixture of any ratio thereof) or a Mannich base produced according to the method for producing a Mannich base according to 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, as will be apparent to those skilled in the art.
• the Mannich base accounts for 10 to 70%, preferably 10 to 60%, and most preferably 10 to 50% by mass of the total shield of the detergent.
• the Mannich base and the diluent may be mixed at 20 ° C - 60 ° C for 1 h - 6 h.
• the Mannich base or detergent of the present invention is also particularly suitable for the production of a fuel oil composition which exhibits excellent deposit formation inhibiting properties and rust preventing properties. Therefore, according to the present invention, further relates to a fuel oil composition comprising any of the aforementioned Mannich bases of the present invention (or a mixture thereof in any ratio), Mann manufactured according to the method for producing Mannich base according to the present invention Nixi base or The foregoing detergent of the present invention, and a base fuel.
• the Mannich base or the detergent is generally added in an amount of 30 to 2000 mg/kg, preferably 50 to 2000 mg/kg, based on the total mass of the fuel oil composition, based on the mass of the fuel oil composition. More preferably, it is 50-1000 mg/kg.
• a base fuel used in a spark ignition type or a compression ignition type internal combustion engine such as a fuel oil such as lead gasoline or lead-free motor gasoline, aviation gasoline or diesel oil, may be mentioned.
• additional additives may be included in the fuel oil composition.
• a scale agent for example, a scale agent, an antioxidant, a diluent, a metal passivator, a dye, a marker, a corrosion inhibitor, an insecticide, an antistatic agent, a damper, a demulsifier, and a broken agent can be mentioned. Aerosols, anti-watering additives, antiknock agents, lubricating additives and combustion improvers.
• These additional 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 art.
• the sediment formation inhibition performance was evaluated by the gasoline engine intake valve sediment simulation test method.
• the standard number is GB19592-2004.
• the method is to mix a quantitative test sample with air through a nozzle and spray it onto a sediment collector that has been weighed and heated to the test temperature under specified test conditions, and then weigh the resulting deposit.
• the anti-rust performance evaluation adopts the gasoline detergent anti-rust performance test method, and the method standard number is
• GB/T 19230.1-2003 GB/T 19230.1-2003.
• a cylindrical test bar is completely immersed in a mixture of 30 ml test sample and 30 ml of distilled water under stirring at a temperature of (38 ⁇ 1) ° C for 4 h rust test to observe the degree of corrosion of the test bar.
• the degree of corrosion is assessed as follows:
• Mild rust no more than 6 rust points, each rust point diameter is less than or equal to lmm;
• Moderate rust more than 6 rust points, but less than 5% of the surface area of the test bar;
• Severe rust The rust point exceeds 5% of the surface area of the test bar.
• a breakdown of the chemicals used in the examples and comparative examples is given in Table 1 below.
• Fig. 1 is a nuclear magnetic hydrogen diagram of the polyisobutenyl group of Example 1
• Fig. 2 is a nuclear magnetic resonance spectrum of the benzene ring region of the polyisobutenyl group of Example 1. It can be seen from Fig. 1 and Fig.
• the example reaction is as follows:
• Figure 3 is a comparison of the nuclear magnetic resonance spectrum of the Mannich base of Example 2 and the polyisobutenyl o-cresol of Example 1
• Figure 4 is a Mannich base of Example 2 and the polyisobutenyl o-cresol benzene ring of Example 1.
• Fig. 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 3
• Example 2 44.92 g (0.043 mol) of the polyisobutylene o-cresol obtained in Example 1 was added under a nitrogen atmosphere.
• 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 starting material involved in the Mannich reaction, thereby demonstrating that the desired Mannich base product was obtained.
• compositions and ratios of the Mannich bases and diluents of Examples 2 to 11 and Comparative Example 1, respectively, were 40. C mixed for 2 h, the detergent of Examples 12-21 and the cleanliness of Comparative Examples 3 and 4 were obtained. Table 2
• the detergents of Examples 12-21 and Comparative Examples 3 and 4 were mixed with the base gasoline, respectively, to obtain the fuel oil compositions of Examples 22-31 and the fuels of Comparative Examples 5 and 6.
• the base gasoline is selected from the standard 93 # unleaded gasoline without additives. In addition, the base gasoline without adding a detergent was used as a blank.
• the Mannich bases of Examples 2 to 11 and Comparative Example 1 were mixed with the base gasoline to obtain the fuel oil compositions of Examples 32 to 41 and Comparative Examples 7 and 8.
• the base gasoline is selected from the standard 93 # unleaded gasoline without additives.
• the base gasoline without adding a detergent was used as a blank.

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