CN101126039B - Fuel additive compounds and method of making the compounds - Google Patents

Fuel additive compounds and method of making the compounds Download PDF

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CN101126039B
CN101126039B CN2007101464681A CN200710146468A CN101126039B CN 101126039 B CN101126039 B CN 101126039B CN 2007101464681 A CN2007101464681 A CN 2007101464681A CN 200710146468 A CN200710146468 A CN 200710146468A CN 101126039 B CN101126039 B CN 101126039B
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alkyl
compound
amine
aldehyde
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CN101126039A (en
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D·J·马尔菲尔
A·卡德克霍达彦
M·托马斯
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Afton Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/16—Reaction products obtained by Mannich reactions
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • 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

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present application is directed to detergent base products and processes for forming the detergent base products. One embodiment of the process comprises forming a bis-Mannich intermediate compound by reacting (i) at least one hydroxyl substituted aromatic ring compound having on the ring an aliphatic hydrocarbyl substituent derived from a polyolefin having a number average molecular weight of about 500 to about 3000; (ii) at least one primary amine; and (iii) at least one aldehyde. The resulting bis-Mannich intermediate compound is then reacted with at least one second amine compound chosen from primary and secondary amines to form the detergent base product.

Description

Fuel dope compound and preparation method thereof
Technical field
The application relates to the preparation sanitising agent and comprises the novel method of the fuel composition of this sanitising agent.
Background technology
For many years, for the additive of the formation of deposits in the fuel drawing-in system of control (prevent or reduce) spark-ignition type internal combustion engine, made a large amount of work.Particularly, can effectively control the additive of fuel injector deposition, suction valve deposition and combustion chamber deposit, represent the focus of a large amount of research work in this area, although and made these achievements, but still need further to improve.
(port-fuel injection, PFI) engine is by spraying into gasoline the even premixture of inlet mouth formation gasoline and air for traditional port fuel injection.Direct injection gasoline (DIG) engine is as diesel motor gasoline directly to be sprayed into the combustion chamber, to such an extent as to may form stratified fuel mixture, this mixture contains the fuel more than stoichiometric near sparking plug, but in whole combustion chamber is the height lean burn.
For PFI and DIG engine, the major sedimentary problem area relevant with fuel is injector, suction valve and combustion chamber.As everyone knows, the Mannich base fuel dope is used to control this type of deposition problems in petroleum industry.Yet, though traditionally the Mannich base additive to be used to control suction valve deposition be very outstanding, they can not be with the deposition of injector in required extent control PFI and/or the DIG engine.Therefore, wish that in petroleum industry production is suitable for the fuel dope that uses in PFI and/or DIG engine, and develop the method for producing this type of fuel dope that wherein this additive can provide improved engine deposit control.
Summary of the invention
According to disclosed content, the application's a embodiment relates to a kind of method for preparing detergent base product.This method comprises: form (i) aromatic compound that replaces of at least a hydroxyl of two Mannich intermediate compounds (bis-Mannich intermediate compound) by making the reaction of following compound, having on the ring of this compound derived from number-average molecular weight is about 500～about 3000 polyolefinic aliphatic alkyl substituting group; (ii) at least a primary amine; (iii) at least a aldehyde.Consequent pair of Mannich intermediate compound reacts to form this detergent base product with at least a second amine compound that is selected from primary amine and secondary amine then.
Another embodiment of the application relates to and is used for a kind of method for preparing Mannich reaction products.This method comprises: at least a amine compound and a kind of two mannich compounds with general formula I I that will be selected from primary amine and secondary amine react,
Figure S071E6468120070910D000021
Wherein, R 1Be selected from hydrogen base and C 1-6Alkyl; R 3Be hydroxy aromatic compound, having by number-average molecular weight on the ring of this compound is the aliphatic alkyl substituting group that about polyolefin derivative of 500～about 3000 obtains; And R 4Be straight chain, side chain or cyclic, replacement or unsubstituted, saturated or unsaturated alkyl amine group.
Another embodiment of the application relates to a kind of fuel composition, and said composition comprises: basic fuel; With the detergent base product that comprises the mixture of compound shown in general formula (VI) and the general formula (VII),
Figure S071E6468120070910D000022
Wherein, R 1And R 3For being independently selected from hydrogen base, C 1-6Alkyl and number-average molecular weight are the substituting group of about hydrocarbyl substituent of 500～about 3000, and condition is R 1And R 3In at least one is a hydrocarbyl substituent; R 4It is a kind of substituting group that is selected from alkyl, aryl, alkenyl, alkylamino, dialkyl amido, alkylamino alkyl and dialkyl aminoalkyl; R 5And R 6Be independently from each other hydrogen base, alkyl, cycloalkyl, aryl, alkaryl and aromatic alkyl group, condition is R 5And R 6In at least one is not the hydrogen base.
Other purpose and advantage of the disclosure will partly proposed in the specification sheets subsequently, and can obtain by the enforcement of disclosure.Purpose that the disclosure is other and advantage can be by the technical characterictic that particularly in additional claims, proposes and technical characterictic the realization and the acquisition of combination.
According to a first aspect of the invention, the invention provides a kind of preparation method of detergent base product, this method comprises:
By following compound being reacted form two Mannich intermediate compounds,
(i) aromatic compound that replaces of at least a hydroxyl, having on the ring of this compound derived from number-average molecular weight is about 500～about 3000 polyolefinic aliphatic alkyl substituting group;
(ii) at least a primary amine; With
(iii) at least a aldehyde and
With this pair Mannich intermediate compound and at least a second amine compound reaction that is selected from primary amine and secondary amine, form this detergent base product.
A second aspect of the present invention is the method according to above-mentioned first aspect, and the aromatic compound that wherein at least a hydroxyl replaces has general formula I,
Figure S071E6468120070910D000031
R wherein 1, R 2And R 3For being independently selected from hydrogen base, C 1-6Alkyl and number-average molecular weight are the substituting group of about hydrocarbyl substituent of 500～about 3000, and condition is R 1, R 2And R 3In at least one is a hydrocarbyl substituent.
According to a second aspect of the invention, R wherein 1, R 2And R 3In one be C 1-6Alkyl is selected from methyl, ethyl, propyl group, sec.-propyl, butyl and isobutyl-.
According to a second aspect of the invention, wherein said hydrocarbyl substituent is to be selected from following group: polypropylene group, polybutene group, poly-α-olefin group and ethylene/alpha-olefin copolymer group.
According to a second aspect of the invention, wherein said hydrocarbyl substituent is the multipolymer group, and this multipolymer group has at least a monomer that is selected from butylene, iso-butylene and propylene and at least aly is selected from the monomer that monoene belongs to comonomer.
According to a second aspect of the invention, wherein said hydrocarbyl substituent is a polyisobutylene group.
According to a second aspect of the invention, R wherein 1Be methyl, R 2Be hydrogen group, R 3It is polyisobutylene group.
A third aspect of the present invention is the method according to above-mentioned first aspect, and wherein said at least a primary amine is the compound shown in the general formula (II),
Figure S071E6468120070910D000041
R wherein 4For being selected from the substituting group of alkyl, aryl, alkenyl, alkylamino, dialkyl amido, alkyl amino alkyl and dialkylaminoalkyl.
According to a third aspect of the invention we, R wherein 4Be-C 1-6NR ' R ", the C of this group wherein 1-6Part is the straight or branched alkyl, and R ' and R " be independently selected from hydrogen base, methyl, ethyl, propyl group and butyl group.
According to a first aspect of the invention, wherein at least a primary amine is selected from dimethylaminopropyl amine, diethylamino propyl group amine and dimethylamino butylamine.
According to a first aspect of the invention, wherein said at least a aldehyde is selected from formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde, stearyl aldehyde, phenyl aldehyde, salicylic aldehyde, furfural, thiophene aldehyde and paraformaldehyde.
According to a first aspect of the invention, aromatic compound, described at least a primary amine and described at least a aldehyde that wherein at least a hydroxyl replaces are pressed following mixed: aromatic compound, about 0.3～about 0.7 mole of primary amine and about 0.8～about 1.5 moles of aldehyde that about 1 mole of hydroxyl replaces.
According to a first aspect of the invention, wherein at least a second amine is the compound shown in the general formula (IV),
Figure S071E6468120070910D000051
Wherein, R 5And R 6Be independently from each other hydrogen base, alkyl, cycloalkyl, aryl, alkaryl and aromatic alkyl group, condition is R 5And R 6In at least one is not the hydrogen base.
Fourth aspect present invention is the method according to first aspect present invention, and wherein at least a second amine is the compound shown in the logical formula V:
Figure S071E6468120070910D000052
R wherein 7Be straight chain, side chain or cyclic has the alkyl of 1-10 carbon atoms.
According to a forth aspect of the invention, R wherein 7It is saturated straight chain hydrocarbon with 1-6 carbon atoms.
According to a forth aspect of the invention, R wherein 7Be optional by 4-8 yuan of replacement or the unsubstituted naphthenic hydrocarbon of isocyclic that have of one or more methyl, ethyl or propyl group replacement.
According to a first aspect of the invention, wherein said at least a second amine is selected from dimethylamine, diethylamine, dipropyl amine, dibutylamine and diamylamine.
According to a first aspect of the invention, wherein said at least a second amine is selected from hexahydroaniline, 1,3-propylene diamine, 1,2-quadrol, 1,4-butanediamine, 1,6-hexanediamine, 1,2-cyclohexanediamine, 1,2-diamino-3-methylcyclohexane, 1,2-diamino-4-methylcyclohexane, N-methylamine methane diamines and 3,3-dimethylaminopropyl amine.
The invention still further relates to detergent base product by the method preparation of first aspect present invention.
Another aspect of the present invention is a kind of method for preparing Mannich reaction products, and this method comprises:
Make at least a amine compound and two mannich compound reactions that is selected from primary amine and secondary amine with general formula III,
Figure S071E6468120070910D000061
Wherein, R 1Be selected from hydrogen base and C 1-6Alkyl;
R 3Be hydroxy aromatic compound, having on the ring of this compound derived from number-average molecular weight is about 500～about 3000 polyolefinic aliphatic alkyl substituting group; With
R 4Be straight chain, side chain or cyclic, replacement or unsubstituted, saturated or unsaturated alkyl amine group.
Another aspect of the present invention is a kind of fuel composition, comprising:
Basic fuel; With
Detergent base product, this detergent base product comprise the mixture of compound shown in general formula (VI) and the general formula (VII),
Figure S071E6468120070910D000062
Wherein, R 1And R 3For being independently selected from hydrogen base, C 1-6Alkyl and number-average molecular weight are the substituting group of about hydrocarbyl substituent of 500～about 3000, and condition is R 1And R 3In at least one is a hydrocarbyl substituent; R 4It is the substituting group that is selected from alkyl, aryl, alkenyl, alkylamino, dialkyl amido, alkylamino alkyl and dialkyl aminoalkyl; R 5And R 6Be independently from each other hydrogen base, alkyl, cycloalkyl, aryl, alkaryl and aromatic alkyl group, condition is R 5And R 6In at least one is not the hydrogen base.
Should be appreciated that the two only is demonstration and illustrative for the general introduction of front and following detailed description, is not the restriction content of the present disclosure that claim limited.
Embodiment
The application's method relates to uses two Mannich intermediates to prepare detergent base product.In embodiment, reaction mechanism can comprise dual stage process, and wherein, two Mannich intermediates are to form in the fs, then, generates this detergent base product in subordinate phase and amine reaction.The reaction of fs and subordinate phase will be described now.
The two Mannich intermediates of preparation
In the application's embodiment, the described pair of Mannich intermediate compound can be by making following compound prepared in reaction: (i) aromatic compound that replaces of at least a hydroxyl, and having by number-average molecular weight on the ring of this compound is the aliphatic alkyl substituting group that about polyolefin derivative of 500～about 3000 obtains; (ii) at least a primary amine; (iii) at least a aldehyde.Can use the aromatic compound of any hydroxyl replacement of in Mannich contracts and reacts, reacting easily.Be used to prepare the aromatic compound that the representational hydroxyl of the two Mannich intermediates of the application replaces and represent by general formula I,
Figure S071E6468120070910D000071
Wherein, R 1, R 2And R 3Can be selected from hydrogen base, C independently of one another 1-6Alkyl or number-average molecular weight are about hydrocarbyl substituent of 500～about 3000, and condition is R 1, R 2And R 3In at least one is a hydrocarbyl substituent.Representational C 1-6Alkyl group comprises methyl, ethyl, propyl group, sec.-propyl, butyl and isobutyl-.
Representational hydrocarbyl substituent can comprise the polypropylene group; The polybutene group; Polyisobutylene group; The poly-alpha olefins group, for example: poly-1-octene group; With the ethylene/alpha-olefin copolymer group.Also can use other similar long chain hydrocarbon groups substituting group.Example comprises the multipolymer group, wherein this multipolymer group has at least a monomer that is selected from butylene, iso-butylene and propylene, and can belong to comonomer with the monoene that is selected from of its copolymerization, as at least a monomer of ethene, 1-amylene, 1-hexene, i-octene, i-decene etc., wherein this copolymer molecule contains butylene and/or the iso-butylene and/or the propylene units of at least 50% weight.Can be aliphatic and also can contain non-aliphatic group, for example: vinylbenzene, o-vinyl toluene, p-vinyl toluene, divinylbenzene or the like with the comonomer of propylene or this type of butene polymerization.Consequent polymkeric substance that is used to prepare compound shown in the general formula (I) and multipolymer are the aliphatic hydrocarbon polymkeric substance on substantially.In some embodiments, described hydrocarbyl substituent can be saturated basically, only contains remaining degree of unsaturation.
In one embodiment, described hydrocarbyl substituent is the polybutene group.Unless point out in addition herein, otherwise term " polybutene " being used in general sense to comprise by " pure " or " pure basically " 1-butylene or iso-butylene preparation polymkeric substance and the polymkeric substance that makes by the mixture of two or three in 1-butylene, 2-butylene and the iso-butylene.This base polymer of commercial grade also can contain a spot of other alkene.
In some embodiments, contain a high proportion of relatively highly reactive polyisobutenes that has the polymer molecule of terminal vinylidene and can be used for forming hydrocarbyl substituent.In embodiment, at least 20% of whole terminal alkene double bonds can contain alkyl vinylidene isomer in this class highly reactive polyisobutenes.For example at least 50% of whole terminal alkene double bonds and in other embodiments, at least 70%, can contain alkyl vinylidene isomer.Suitable highly reactive polyisobutenes for example is disclosed in the U.S. Patent No. 4,152,499 and W.German Offenlegungsschrift29 04 314, and its disclosure is intactly introduced with for referencial use at this.In other embodiments, number-average molecular weight is 500～3000 ethylene, wherein contains terminal ethylidene degree of unsaturation at least about this polymer chain of 30%, can be used to form described hydrocarbyl substituent.
In one embodiment, the compound of general formula (I) can be by obtaining with above-mentioned high-molecular-weight hydrocarbons based polyalcohol alkylation o-cresols.For example, o-cresols is ortho-methyl phenol for example, can react with polyisobutene (PIS), thereby form the ortho-methyl phenol of PIS group at para-orientation.The appropriate method of the hydroxy aromatic compound of alkylation in the application is open is known in the art.GS1,159,368 and U.S. Patent No. 4,238,628,5,300,701,5,876,468 and 6,800,103 instructed some suitable being used to prepare the known method that hydroxyl replaces aromatic compound, its disclosure is intactly introduced with for referencial use at this.
In one embodiment, the R in the aromatic compound of the replacement of the hydroxyl shown in the general formula I 1Can be C 1 -4Alkyl; R 2It can be the hydrogen base; And R 3It can be the hydrocarbyl substituent that is selected from above-mentioned hydrocarbyl substituent.For example, R 1It can be methyl; R 2It can be the hydrogen base; And R 3It can be polyisobutenyl.In other embodiments, R 1And R 2All be the hydrogen base, and R 3It is the hydrocarbyl substituent that is selected from above-mentioned hydrocarbyl substituent.
The amine that can use in the fs reaction is included in any primary amine that is suitable in the Mannich reaction of described pair of Mannich intermediate of preparation.In embodiment, this primary amine has general formula (II):
Figure S071E6468120070910D000091
Wherein, R 4It can be any substituting group that is selected from alkyl, aryl, alkenyl, alkyl ammonia, dialkyl amino, alkylamino alkyl and dialkyl aminoalkyl.
The representational example of suitable secondary amine comprises: dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine.The representational example of suitable primary amine comprises: hexahydroaniline, 1,3-propylene diamine, 1,2-quadrol, 1,4-butanediamine, 1,6-hexanediamine, 1,2-cyclohexanediamine, 1,2-diamino-3-methylcyclohexane, 1,2-diamino-4-methylcyclohexane, N-aminomethyl-1,1-methane diamines and 3,3-dimethylaminopropyl amine.
In some embodiments, the amine shown in the general formula (II) can be hydrocarbon chain, and an end of this hydrocarbon chain is replaced by primary amino, the other end by primary, second month in a season or uncle is amino replaces.For example, the R4 in the compound is-C shown in the general formula (II) 1-6NR ' R ", this substituent C wherein 1-6Part is the straight or branched alkyl, and R ' and R " can be independently selected from hydrogen, methyl, ethyl, propyl group and butyl substituting group.The example of this compounds comprises dialkyl aminoalkyl amine, for example: dimethylaminopropyl amine, diethylamino propyl group amine and dimethylamino butylamine.
Any aldehyde that is applicable to Mannich reaction may be used to prepare described pair of Mannich intermediate.The nonrestrictive example of suitable aldehyde comprises aliphatic aldehyde, for example: formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde and stearyl aldehyde.Operable aromatic aldehyde comprises: phenyl aldehyde and salicylic aldehyde.Illustrative heterocyclic aldehydes used herein comprises: furfural and thiophene aldehyde (thiophene aldehyde) etc.The reagent that produces formaldehyde also is useful, for example: paraformaldehyde.In one embodiment, the aldehyde of selection is formaldehyde.
Can use the reactant of any suitable proportion of formation that will cause described pair of Mannich intermediate.In one embodiment, described reactant can be with following mixed: the aromatic compound that about 1 mole of hydroxyl replaces; About 0.3～about 0.7 mole of primary amine; With about 0.8～about 1.5 moles of aldehyde.For example, described reactant can be with following mixed: the aromatic compound that about 1 mole of hydroxyl replaces; About 0.5 mole of primary amine; With about 1 mole of aldehyde.
Contracting and being reflected at about 40 ℃～about 200 ℃ of temperature between aromatic compound, described primary amine and the described aldehyde that described hydroxyl replaces carried out.This reaction can or not exist under thinner or the solvent in existence to be carried out.The example of suitable solvent comprises: aromatic solvent (aromatic solvents), for example dimethylbenzene, toluene, mesitylene, Aromatic100 and heptane, or the mixture of these solvents.Between this reaction period, discharge water outlet, and water can be removed by component distillation in reaction process.The typical reaction times is 2～4 hours, but can use the longer or shorter time as required.
Resulting pair of Mannich intermediate compound is the compound shown in the general formula (III):
Figure S071E6468120070910D000101
Wherein, R 1, R 3And R 4Definition as above.From general formula (III) as can be seen: this pair Mannich intermediate comprises the aromatic ring group of two hydroxyls replacements that formed by compound of reaction shown in the above-mentioned general formula (I), and the aromatic ring group that above-mentioned two hydroxyls replace by the tertiary amino group bridging together.In the subordinate phase reaction, this pair Mannich intermediate can be used for being equipped with required detergent base product, and this will be described below.
Prepare sanitising agent alkali by described pair of Mannich intermediate
In the subordinate phase of reaction process, two Mannich intermediates shown in the general formula (III) can react to form required detergent base product with primary amine or secondary amine.Described primary amine or secondary amine can be the amine shown in the general formula (IV):
Wherein, R 5And R 6Be selected from hydrogen base, alkyl, cycloalkyl, aryl, alkaryl and aromatic alkyl group independently of one another, condition is R 5And R 6In at least one is not the hydrogen base.Described alkyl, cycloalkyl, aryl, alkaryl and aromatic alkyl group can be not substituted, are perhaps replaced by suitable functional group, for example carbonyl, hydroxyl and amino.Described alkyl, cycloalkyl, aryl, alkaryl and aromatic alkyl group can contain, for example, 1～30 carbon atom, 1～18 carbon atom for example, or in other embodiments, 1～6 carbon atom.
In some embodiments, R 6Elect the hydrogen base as, and R 5The alkyl that is replaced by primary amine.The amine that obtains is the diamines shown in the logical formula V:
Figure S071E6468120070910D000111
Wherein, R 7Be straight chain, side chain or cyclic contains the alkyl group of 1～10 carbon atom.For example, R 7It can be the saturated straight chain hydrocarbon that contains 1～6 carbon atom.In another embodiment, R 7Can be to have 4～8 yuan of isocyclic to replace or unsubstituted naphthenic hydrocarbon, can choose wantonly by one or more methyl, ethyl or propyl group replacement.
The representational example of suitable secondary amine comprises: dimethylamine, diethylamine, dipropyl, dibutylamine and diamylamine.The representational example of suitable primary amine comprises: hexahydroaniline, 1,3-propylene diamine, 1,2-quadrol, 1,4-butanediamine, 1,6-hexanediamine, 1,2-hexamethylene diamino (DACH), 1,2-diamino-3-methylcyclohexane, 1,2-diamino-4-methylcyclohexane, N-aminomethyl-1,2,1-methane diamines and 3,3-dimethylaminopropyl amine.
Two Mannich intermediates shown in the general formula (III) mix with primary amine shown in the general formula (IV) or secondary amine and react.Can use the reactant of any suitable proportion that will cause forming required the finished product.In one embodiment, described reactant can use the mixed of about 1 mole of primary amine or secondary amine with every mole of two Mannich intermediates.
This reaction can be at about 125 ℃～about 200 ℃, and for example about 150 ℃ are carried out.Reaction times can be 2～4 hours, yet also can use the longer or shorter time as required.The solvent that comes from first step of reaction may reside in second step of reaction, and/or can add other suitable solvent in second step of reaction if desired.
This second step of reaction produce following general formula (VI) and (VII) shown in product:
Figure S071E6468120070910D000121
Wherein, R 1, R 3, R 4, R 5And R 6Definition as above.From general formula (VI) and (VII) as can be seen: this reaction is decomposed the two Mannich intermediates shown in the general formula (III), forms the aromatic compound of two kinds of hydroxyls replacements, and they are except by R 1, R 3Beyond the hydroxyl substituent replacement, also all replaced separately by amine groups.The compound of general formula (VI) is replaced by the amine groups that the primary amine reaction thing by first step of reaction forms, and the compound of general formula (VII) is replaced by the amine groups that primary amine or secondary amine reactant by second step of reaction form.
In one embodiment, wherein, the primary amine of logical formula V is as the amine of subordinate phase, and the product of this reaction comprises the compound that is replaced by the amine of aforesaid general formula (VI).Yet in this embodiment, described product also is included in the primary amine substituting group on one of aromatic compound of hydroxyl replacement, shown in following general formula (VIII):
Figure S071E6468120070910D000122
Wherein, R 1, R 3, R 4And R 7Definition as above.In product mixtures, general formula VI changes with the parameter of ratio regular meeting basis such as the reactant of reaction conditions and/or use of compound shown in the general formula VIII.For example, the ratio of compound shown in general formula VI and the general formula VIII can be about 1:4～about 4:1.In some embodiments, this ratio can be about 1:1.
The product that the application's amine replaces can be as the sanitising agent alkali in the fuel composition.In some embodiments, this sanitising agent alkali can be used for fuel additive concentrate, and this enriched material can separate with basic fuel packs and be sold to the human consumer.Multifunctional additive for lubricating oils of the present invention can contain, and for example, the sanitising agent of about 12～about 69wt% and for example about 22～about 50wt% is based on activeconstituents.Described multifunctional additive for lubricating oils also can contain carrier fluid, and its level is determined by the ratio of required carrier and sanitising agent alkali.
Described carrier fluid can be broad variety, for example liquid poly-alpha-olefin oligopolymer, liquid polyalkylene hydrocarbon are (for example, polypropylene, polybutene, polyisobutene, or the like), the polyalkylene hydrocarbon handled of hydrogenated liquid (for example, hydrogenant polypropylene, hydrogenant polybutene, the hydrogenant polyisobutene, or the like), mineral oil, hydrogenant mineral oil, liquid polyoxyalkylene compounds, liquid alcohol or polyvalent alcohol, liquid ester and similar liquid carrier or solvent.Also can use the mixture of these two or more carriers or solvent.
When allotment the time, use the described sanitising agent alkali and the carrier fluid (containing or do not contain other additive) that are enough to reduce or suppress formation of deposits quantity in the oil engine according to the application's fuel composition.Therefore, fuel can contain the as above a small amount of described sanitising agent alkali and the described liquid carrier fluid of ratio, with the formation of control or minimizing engine deposit, for example formation of suction valve and injector deposition.
In some embodiments, the application's fuel, based on activeconstituents, the quantity of the described Mannich base sanitising agent that can contain is about 5～about 300ptb (the weight pound of the fuel dope that per thousand stavings are long-pending), for example, is about 10～about 200ptb.The weight of following material is got rid of on described activeconstituents basis: (i) unreacted component, for example relevant with a product of producing and using and remaining polyalkylene compound wherein; (ii) during sanitising agent forms or be used to prepare the thinner or the solvent (if present) of sanitising agent after forming, if use carrier, should be before the interpolation carrier.
Fuel and multifunctional additive for lubricating oils also can contain other optional additive, and for example, one or more dissolve in antioxidant, the emulsion splitter of fuel; Antioxidant is hindered phenol and amine for example; Rust-preventive agent or corrosion inhibitor, metal passivator, combustion modifiers, co-solvent, octane enhancer, discharging depressant, friction improver, lubricant, auxiliary sanitising agent/dispersing additive agent, markers, tinting material and multifunction additive (for example: methyl cyclopentadienyl tricarbonyl manganese and/or other cyclopentadienyl tricarbonyl manganese compound).These components can be present in the composition with any required concentration.For example, the amount that every kind of component can exist in final fuel composition is to be enough to bring into play its predetermined function at least.
The basic fuel that is used for allocating fuel disclosed herein can be any He all basic fuels that are applicable to the spark-ignition type internal combustion engine operation, for example, non-lead gasoline for car and aviation spirit, with so-called reformulated gasoline (reformulated gasoline), this reformulated gasoline contains the hydrocarbon in the gasoline boiling range scope usually and dissolves in the blend components through oxidation (oxygenatedchemicals (oxygenates)) of fuel.The example of available suitable oxygenate comprises alcohol, for example methyl alcohol and ethanol; Dissolve in the ether of fuel, for example methyl number butyl ether, Ethyl Tertisry Butyl Ether and tert amyl methyl ether(TAME); Mixture with these materials.When using oxygenatedchemicals, it can be present in the basic fuel with any required amount.The oxygenatedchemicals of selection significant quantity belongs to the common practise of this area.
Embodiment
The method of embodiment 1-described intermediate of preparation
Calculate and determine the initial substance of exact quantity based on the poly-isobutyl-phenol of 2-methyl-4-of 2:1:2, dimethyl amine propyl group amine (OMAPA) and formaldehyde mole ratio.The poly-isobutyl-phenol of 2-methyl-4-is joined in the round-bottomed flask, be added in then and prepare about 75% of the Aromatic100 solvent the amount of calculation used in this process.Under nitrogen protection, stir the mixture.In case mix, just add the DMAPA of calculated amount.The temperature of miscellany is about 40-45 ℃., add formaldehyde, make mixture be warming up to about 45～50 ℃.The heating miscellany, and use is set to 150 ℃ Dean Stark collector distillating mixture under nitrogen protection.In still-process, keep 150 ℃ about 2～2.5 hours of temperature.After the distillation, consider the loss of water, enough Aromatic100 solvents are added in this intermediate product so that the final packaging composition contains 25% solvent.
Said process forms the BIS product shown in the following reaction in theory:
Figure S071E6468120070910D000141
Embodiment 2-the prepare method of the finished product
The intermediate BIS product that uses embodiment 1 is as starting raw material, under room temperature and nitrogen protection, adds 1 while stirring, 2-hexamethylene diamino (DACH) in the ratio of 1:1 mol ratio.Temperature is made as 90 ℃ and kept 2 hours.Temperature is made as 145 ℃ and increase nitrogen flow then, keeps 2.5 hours.Said process causes following reaction in theory.
Figure S071E6468120070910D000151
Embodiment 3
Use the Fuel Petroleum composition of the finished product of embodiment 2 to carry out Engine Block Test, prove that according to this test these compositions are in the remarkable validity aspect the minimizing suction valve settling weight.Above-mentioned reaction product of the comparative example 2 and several other sanitising agent compound, comprise first control compounds, this compound is to prepare by Mannich reaction by the poly-isobutyl-phenol of the 2-methyl-4-of 1:1:1 mol ratio, dibutylamine and formaldehyde (" Mannich 1 additive "); Second control compounds, this compound prepares by Mannich reaction by the poly-isobutyl-phenol of the 2-methyl-4-of 1:1:1 mol ratio, DMAPA and formaldehyde (" Mannich 2 additives "); With the 3rd control compounds, it is a PIS amine.The compound of embodiment 2 and comparative compound mix with basic fuel respectively to form fuel composition, and these compositions are indicated with the additive compound of using (embodiment 2 compounds, Mannich 1, Mannich 2 and PIS amine) in table 1 and table 2.
Embodiment 1 compound, Mannich 1, Mannich 2 and not the first contrast IVD Engine Block Test utilization and operation of additivated basic fuel rises under the standard operation condition that engine is being used for determining settling formation on the suction valve in the Ford2.3-on the test board and carries out.The result is shown in following table 1.
Table 1-2.3LIVD Engine Block Test result
Example composition IVD (mg)
The fuel 478-527mg that does not have additive
Mannich 1 53-56mg
Mannich 2 67.9mg
Embodiment 2 compound 64.6mg
Embodiment 4
Embodiment 2 compounds, Mannich 1, Mannich 2, PIB amine and not additivated basic fuel second relatively the IVD Engine Block Test use IVO bench simulation device (Bench Simulator) (model L-2) to carry out, it can be used for testing gasolene cleaner IVO performance.This test simulation in engine IVD deposition.In test process, the fuel composition that is added with detergent additive passes through injector.Independent airflow enters injector by the air flowing pipe flow will.Airflow and gasoline stream mix on the top of injector, and this mixture is directed the metal sheet to heating.The temperature of plate is controlled at about 174 ℃.Gasoline stays settling and stain in the surface evaporation of this hot plate.
When this IVD bench simulation device end of test (EOT), the settling on the weighing metal sheet.The result is as shown in table 2 below.
Table 2-from the IVD engine bench test of China
Example composition fuel IVD (mg)
There is not additive 14-15mg
Comparative example 1 7.7mg
Comparative example 2 1.3mg
Embodiment 2 1.0mg
PIB amine 1.4mg
Clearly, experimental result according to above-mentioned table 1 and 2, reaction product among the embodiment 2 is compared with the basic fuel that does not have additive and is shown improved performance, and as indicated in the settling quantity that reduces in the Ford2.3L test, show the performance suitable with the additive of comparative example 1 and 2.In addition, as indicated in the settling quantity that reduces in the IVD engine bench test from China, the reaction product of embodiment 2 is compared with 2 additive with comparative example 1 with the basic fuel that does not have additive has improved performance.
Purpose for this specification and the appended claims book, unless otherwise specified, the numerical value of all expression amounts, per-cent or the ratio of using in specification sheets and claims and other numerical value all are understood that all to modify with term " about " in all cases.Therefore, unless indicate on the contrary, the numerical parameter that provides in specification sheets below and claims all is proximate, and its performance that depends on that the disclosure seeks out can change.At least, and be not to be intended to restriction application doctrine of equivalents arrive, each numerical parameter should be considered given number of significant figures at least and use the routine technology of rounding off to understand.
Be to be noted that singulative " ", " a kind of " and " being somebody's turn to do " comprise plural object as employed in specification sheets and additional claims, unless specially be expressed as an object clearly.Therefore, for example, mention " acid ", be meant the acid that comprises that two or more are different.Just as used herein, it is open that term " comprises " that the grammatical variants that has reached it means, and like this, in the tabulation enumerating of clauses and subclauses do not got rid of other similar clauses and subclauses, and these similar clauses and subclauses can replace or join cited a series of clauses and subclauses.
Though described specific embodiment, it will be appreciated by those skilled in the art that to be unpredictable replacement of arriving that predict or current, modification, variation, improvement and identical in fact mode.Therefore, the claims of submission and their later modifications mean and comprise that all this type of substitutes, revises, improves and identical in fact mode.

Claims (10)

1. the preparation method of a detergent base product, this method comprises:
By following compound being reacted form two Mannich intermediate compounds,
(i) aromatic compound that replaces of at least a hydroxyl, having on the ring of this compound derived from number-average molecular weight is 500～3000 polyolefinic aliphatic alkyl substituting group;
(ii) at least a primary amine; With
(iii) at least a aldehyde and
With this pair Mannich intermediate compound and at least a second amine compound reaction that is selected from primary amine and secondary amine, form this detergent base product.
2. the described method of claim 1, the aromatic compound that wherein at least a hydroxyl replaces has general formula I,
Figure FSB00000055991500011
R wherein 1, R 2And R 3For being independently selected from hydrogen base, C 1-6Alkyl and number-average molecular weight are the substituting group of 500～3000 hydrocarbyl substituent, and condition is R 1, R 2And R 3In at least one is a hydrocarbyl substituent.
3. the described method of claim 1, wherein said at least a primary amine is the compound shown in the general formula (II),
Figure FSB00000055991500012
R wherein 4For being selected from the substituting group of alkyl, aryl, alkenyl, alkylamino, dialkyl amido, alkyl amino alkyl and dialkylaminoalkyl.
4. the described method of claim 1, wherein said at least a aldehyde is selected from formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde, stearyl aldehyde, phenyl aldehyde, salicylic aldehyde, furfural, thiophene aldehyde and paraformaldehyde.
5. the described method of claim 1, aromatic compound, described at least a primary amine and described at least a aldehyde that wherein at least a hydroxyl replaces are pressed following mixed: 1 mole of aromatic compound, 0.3～0.7 mole of primary amine and 0.8～1.5 mole of aldehyde that hydroxyl replaces.
6. the described method of claim 1, wherein at least a second amine is the compound shown in the general formula (IV),
Figure FSB00000055991500021
Wherein, R 5And R 6Be independently from each other hydrogen base, alkyl, cycloalkyl, aryl, alkaryl and aromatic alkyl group, condition is R 5And R 6In at least one is not the hydrogen base.
7. the described method of claim 1, wherein said at least a second amine is selected from dimethylamine, diethylamine, dipropyl amine, dibutylamine and diamylamine.
8. by the detergent base product of the described method of claim 1 preparation.
9. method for preparing Mannich reaction products, this method comprises:
Make at least a amine compound and two mannich compound reactions that is selected from primary amine and secondary amine with general formula III,
Wherein, R 1Be selected from hydrogen base and C 1-6Alkyl;
R 3Be hydroxy aromatic compound, having on the ring of this compound derived from number-average molecular weight is 500～3000 polyolefinic aliphatic alkyl substituting group; With
R 4Be straight chain, side chain or cyclic, replacement or unsubstituted, saturated or unsaturated alkylamino group.
10. fuel composition comprises:
Basic fuel; With
Detergent base product, this detergent base product comprise the mixture of compound shown in general formula (VI) and the general formula (VII),
Figure FSB00000055991500031
Wherein, R 1And R 3For being independently selected from hydrogen base, C 1-6Alkyl and number-average molecular weight are the substituting group of 500～3000 hydrocarbyl substituent, and condition is R 1And R 3In at least one is a hydrocarbyl substituent; R 4It is the substituting group that is selected from alkyl, aryl, alkenyl, alkylamino, dialkyl amido, alkylamino alkyl and dialkyl aminoalkyl; R 5And R 6Be independently from each other hydrogen base, alkyl, cycloalkyl, aryl, alkaryl and aromatic alkyl group, condition is R 5And R 6In at least one is not the hydrogen base.
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