CN107001960A - Control the method and purposes of the greasy filth in engine - Google Patents

Abstract

The combination of following ingredients controls the purposes of additive as the greasy filth in the fuel composition of spark-ignition internal combustion engine or compression ignition gasoline engine：A. the aromatic compounds that alkyl replaces；With b. polyene amine.The fuel composition can also be used for safeguarding oil circuit and/or lubrication in engine.

Description

Control the method and purposes of the greasy filth in engine

The present invention relates to method and purposes, control spark-ignition internal combustion engine or compression ignition gasoline are related in particular aspects The method of sludge formation in internal combustion engine, in terms of other in be related to the combination of additive and be used as the combustion of spark-ignition internal combustion engine Greasy filth in feed composition controls the purposes of additive.The invention further relates to safeguard the method for the oil circuit in engine and lubrication.

In the running of spark-ignition internal combustion engine, crankcase lubricating oil can be dilute by fuel, water and/or cooling agent Release.The lubricating oil can also can be accelerated the chemical substance of oil ageing to dilute.The example of these chemical substances includes can be with Enter the wear metal and oxidisability nonmetallic substance of crankcase by gas blowby.The lubricating oil is also subject to high temperature.Due to these changes Learn and physical condition, it may occur however that the oil ageing, polymerization and agglomeration, what this was produced referred to as greasy filth from degraded oil The tarry matters of high viscosity.Greasy filth can also be incorporated to the material derived from fuel, water, cooling agent, cigarette ash and wear metal. Greasy filth can be accumulated on many parts of engine, including one or more rocker covers, camshaft baffle plate, timing chain cover, oil Disk and its baffle plate, oil screen and bonnet area.

Greasy filth can reduce the performance of engine.For example, during engine sludge can be impaired oil circuit and engine lubrication A factor.This can cause engine failure.

Generally, using the formation of the additive control greasy filth in lubricating oil.According to US3784474 summary, contain hydrocarbon The lubricating oil of amine ashless detergent, polyoxyalkylene derivative and alkaline-earth metal that base replaces mitigates or prevented in the inside of internal combustion engine Paint film, greasy filth and deposit are formed on metal surface.

But, it is still desirable to it is included as spark-ignition internal combustion engine and suitable detergency is provided but the component of sludge formation is controlled Fuel composition.

According to its paragraph [0145], US2013/000584 discloses a kind of fuel composition, and it is used comprising one or more In poly- (hydroxycarboxylic acid) derivative with terminal amido for suppressing sludge formation.It is somebody's turn to do in US2013/000584 without open The detergency of fuel composition.

According to its paragraph [0002], US2006/0277820 is related to a kind of sediment monitoring additive for fuel and combined Thing, it includes the PIBA of the mean molecule quantity with about 700 to about 1000（PIBA）This is used as with Mannich base The collaboration component of sediment monitoring additive formulations.

US 2006/0277820 paragraph [0015] statement：

“Mannich base has been combined alone or with diamines for reducing the deposit in evaporator surface.It is such as disclosed herein, lead to Cross using Mannich base and PIBA as the collaboration component of sediment monitoring additive formulations and realized surprising result, Substantially reduce the deposit on vaporizer and make the port fuel injector in gasoline-fueled spark-ignition internal combustion engine Keep clean with intake valve ".

US2006/0277820 paragraph [0069] is related to the use Mercedes Benz according to CEC F-20-A-98 M111 Engine inlet valve deposits are tested and paragraph [0070] is related to port fuel injector fouling bench test. Disclosure in US2006/0277820 does not solve the formation of greasy filth.

Therefore, there is still a need in terms of reducing or at least mitigating the method and purposes of the problem of being such as identified above.

There is provided in one kind control spark-ignition internal combustion engine or compression ignition gasoline engine according to the first aspect of the invention Sludge formation method, methods described includes supplying a kind of fuel composition to the engine, and it is comprising following ingredients Combination：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.

According to another aspect of the present invention spark-ignition internal combustion engine or compression ignition gasoline internal combustion are used as there is provided following ingredients Greasy filth in the fuel composition of machine controls the purposes of additive：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.

Reduced according to another aspect of the present invention there is provided one kind for spark-ignition internal combustion engine or compression ignition gasoline internal combustion The method of the sludge formation trend of the fuel composition of machine, methods described is included in one or more steps to the fuel stack It is incorporated in compound：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine

To be produced when producing comprising the additive combined and being used in the engine than being used in the engine The fuel composition of the few greasy filth of the greasy filth that the is formed during fuel composition combined without the additive.

It is used to improve fuel there is provided the compositions of additives of the combination comprising following ingredients according to another aspect of the present invention The purposes of greasy filth control performance of the composition in spark-ignition internal combustion engine or compression ignition gasoline engine：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.

Safeguarded according to another aspect of the present invention there is provided one kind in spark-ignition internal combustion engine or compression ignition gasoline engine Oil circuit and/or lubrication method, methods described includes supplying a kind of fuel composition to the engine, its comprising it is following into The combination divided：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.

According to another aspect of the present invention spark-ignition internal combustion engine or compression ignition gasoline internal combustion are used as there is provided following ingredients The purposes of oil circuit and/or lubricated maintenance additive in the fuel composition of machine：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.

In embodiments, the aromatic compounds of alkyl substitution is Mannich base additive.In embodiments, this gathers Enamine is PIBA.

The many-sided of the present invention solves specific technology by the way that the aromatic compounds and polyene amine of alkyl substitution is applied in combination Problem etc..

Especially it has been found that comprising alkyl replace aromatic compounds and polyene amine combination fuel composition for Beneficial sludge formation control is shown during spark-ignition internal combustion engine.

Polyene amine

The polyene amine can be poly- C_1-10- enamine.For example, the polyene amine can be polyvinylamine, polypropylene amine, polybutene amine, Polypenthylene amine or polyhexene amine.In instances, the polyene amine is polybutene amine, particularly PIBA.

PIBA is sometimes referred to as polyisobutyl group amine or PIBA.The example of suitable PIBA includes poly- different Butylene（The polyisobutene and isobutene and minor amount of homopolymer form including such as isobutene（Such as most 20 weight %）'s One or more other monomers, including such as polyisobutene of the polymer form of n-butene, propylene and its mixture）List Amine, diamines and polyamines.

The example of suitable PIBA includes US4832702, US6140541, US6909018 and/or US7753970 Disclosed in and/or method as described in it obtain or obtained by PIBA.

The example of suitable PIBA includes disclosed in US4832702 and/or obtained by the method described in it Obtain or obtainable PIBA.Therefore, suitable PIBA includes the compound shown in structural formula I：

Wherein R₁Be can be derived from or poly- butyl or polyisobutyl group derived from isobutene and most 20 weight % n-butenes and

R₂And R₃It is identical or different and be each independently：

Hydrogen；

Aliphatic series or aromatic hydrocarbyl；

Primary or secondary, aromatics or aliphatic amino alkylidene or poly- amino alkylidenyl；

Polyoxyalkylenes；

Heteroaryl or heterocyclic radical；Or

Formed together with the nitrogen-atoms that they are bonded and other heteroatomic rings may be present.

In at least some examples, R₂And R₃It is identical or different and be each independently：

Hydrogen；

Alkyl；

Aryl；

Hydroxyalkyl；Or

Amino alkylidenyl shown in logical formula (II)：

Wherein R₄It is alkylidene and R₅And R₆It is identical or different and be each independently：Hydrogen；Alkyl；Aryl；Hydroxyalkyl；Poly- butyl； Or polyisobutyl group；Or

Poly- amino alkylidenyl shown in logical formula (III)：

[– R₄ – NR₅]_m R₆ (III)

Wherein R₄Group is identical or different and R₅Group is identical or different, and R₄、R₅And R₆With above-mentioned implication and m is 2 to 8 Integer；Or

Polyoxyalkylenes shown in logical formula (IV)：

[– R₄ – O–]_n X (IV)

Wherein R₄Group is identical or different and with above-mentioned implication, X be alkyl or H and n be 1 to 30 integer.

In at least some examples, R₂And R₃With they be bonded nitrogen-atoms together with formed morpholinyl, pyridine radicals, piperidyl, Pyrrole radicals, pyrimidine radicals, pyrrolinyl, pyrrolidinyl, pyrazinyl or pyridazinyl.

In at least some examples, R₁It is to be derived from or can containing derived from isobutene and most 20 weight % n-butenes The poly- butyl or polyisobutyl group of 20 to 400 carbon atoms.

In at least some examples, R₁It is to be derived from or can containing derived from isobutene and most 20 weight % n-butenes The poly- butyl or polyisobutyl group of 32 to 200 carbon atoms, and R₂And R₃It is identical or different and be each independently：Hydrogen, methyl, second Base, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, phenyl ,-CH₂ – CH₂ – NH₂、– CH₂ – CH₂ – CH₂ –N(CH₃)₂Or-[- CH₂ – CH₂ –NH]_p – CH₂ – CH₂ –NH₂（Wherein p is 1 to 7, Such as 1 to 3 integer）、– CH₂ – CH₂ – OH、–[– CH₂ – CH₂ –O]_q – CH₂–OH（Wherein q be 1 to 30 it is whole Number）Or form morpholinyl together with the nitrogen-atoms that they are bonded.

The example of suitable PIBA additive also includes disclosed in US6140541 and US6909018 and/or logical The method described in it is crossed to obtain or obtainable PIBA.Therefore, the example of suitable PIBA includes formula (V) Shown compound：

Wherein R₇、R₈、R₉And R₁₀Be respectively independently of one another hydrogen or show most 40000 number-average molecular weight unsubstituted or Replace, saturation or list-or how unsaturated aliphatic group, at least one group R₇To R₁₀The number for showing 150 to 40000 is divided equally Son amount, and

R₁₁And R₁₂H is respectively independently of one another；Alkyl, such as C₁To C₁₈Alkyl；Cycloalkyl；Hydroxyalkyl；Aminoalkyl；Alkenyl； Alkynyl, aryl；Aryl alkyl；Alkylaryl；Heteroaryl；Alkylidene-imido grpup shown in formula (VI)：

Wherein：

Alk is straight or branched alkylidene

M is 0 to 10 integer；And

R₁₃And R₁₄H is respectively independently of one another；Alkyl, such as C₁To C₁₈Alkyl；Cycloalkyl；Hydroxyalkyl；Aminoalkyl；Alkenyl； Alkynyl, aryl；Aryl alkyl；Alkylaryl；Heteroaryl, or heterocycle structure is formed together with the nitrogen-atoms that they are bonded, or

R₁₁And R₁₂Heterocycle structure is formed together with the nitrogen-atoms that they are bonded.

In at least some examples, R₁₁、R₁₂、R₁₃And R₁₄The alkyl with hydroxyl or amino being attached independently of one another Substitution.

The example of suitable PIBA additive also includes disclosed in US7753970 and/or by described in it Method obtain or obtainable PIBA.Therefore, the example of suitable PIBA includes being derived from or can deriving From the PIBA of polyisobutene, the polyisobutene is derived from or can be derived from isobutene or isobutylene monomer mixture, Such as mixture of isobutene and most 20 weight % n-butenes.Suitable PIBA includes being derived from or can be derived from logical Cross identical or different straight or branched C₄Olefinic monomer（They are suitably randomly distributed in polymerization production at least some examples In thing）Polymerization it is derivative or can derivative polyisobutene PIBA.Suitable PIBA includes being derived from or can PIBA derived from highly reactive polyisobutenes.Highly reactive polyisobutenes contain the terminal double bond of high content（Sometimes Also referred to as alpha-alefinically double bond and/or ethenylidene double bond）, such as total olefinic double bond in polyisobutene at least 20% or extremely Few 50% or at least 70%.These are represented by following universal architecture sometimes：

。

Highly reactive polyisobutenes can be manufactured for example, by the method described in US4152499.

In at least some examples, the PIBA, which contains, shows about 200 to about 10000, and such as about 500 To about 5000 or about 700 to about 1500 or about 800 to about 1200 or about 850 to about 1100, for example greatly The polyisobutylene group of about 1000 number-average molecular weight.

In at least some examples, the PIBA, which is derived from or can be derived from, shows at least one following property Polyisobutene：

(i) it can be derived from or derived from isobutene and most 20 weight % n-butenes；

(ii) it can be derived from or the ethenylidene derived from least 70 moles % containing the total olefinic bonds accounted in polyisobutene is double The isobutene mixture of key；

(iii) at least 85 weight % isobutene units are contained；

(iv) 1.05 to 7 polydispersity.

Manufacture is for example described in US4832702, US6140541, US6909018 and/or US7753970 suitable poly- The method of isobutyl enamine.

In at least some examples, there is/use more than one polyene amine.If there is/more than one polyene amine is used, Each polyene amine can be PIBA.

In at least some examples, the polyene amine is with least about 50 ppm activity concentration, such as with least about 70 ppm activity concentration is present in/is used in fuel composition.In at least some examples, the polyene amine is with most about 500 ppm activity concentration, for example, be present in/be used in fuel composition with most about 300 ppm concentration.At least In some examples, the polyene amine is with about 50 ppm to about 500 ppm, such as about 70 ppm to about 300 ppm activity Thing concentration is present in/is used in fuel composition.Activity concentration refers to the concentration of activity poly enamine, does not consider for example any molten Agent etc..Technical staff is it is clear that be herein weight ppm with the ppm activity concentrations represented.

Generally, the polyene amine be present in about 50 ppm to about 160 ppm activity concentration/be used for fuel fabrication In thing.But, in some instances, higher height reason rate can be used.In this case, the polyene amine can be with about 160 Ppm to about 500 ppm concentration are present in/are used in fuel composition.

If use more than a kind of polyene amine, the total concentration of polyene amine is as described herein.

The aromatic compounds of alkyl substitution

The aromatic compounds of alkyl substitution can be the hydroxy aromatic compound of alkyl substitution, and the phenolate of such as alkyl substitution is closed Thing.Hydrocarbyl substituent can be connected to the ortho position of phenol ring, meta or para position.

The hydrocarbyl substituent of the aromatic compounds of alkyl substitution can show about 700 to about 1500, such as about The number-average molecular weight of 900 to about 1300.

In embodiments, Mannich base additive can be used in the fuel composition.

Hydroxy aromatic compound, amine and the aldehyde that the example of Mannich base additive includes replacing by alkyl contract in Mannich Close reaction condition under reaction obtain or it is obtainable those.Suitable reaction condition includes at least one（For example own）It is following Condition：

At a temperature of 40 DEG C to 200 DEG C；

In the case where being not present or there is solvent；

The reaction time of 2 to 4 hours；With

In the case where azeotropic distillation removes water accessory substance.

The example of aldehyde suitable for preparing Mannich base additive includes：

Aliphatic aldehydes, including such as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde and stearaldehyde；

Aromatic aldehyde, including such as benzaldehyde and salicylide；With

Heterocyclic aldehydes, including such as furfural and thiophene aldehyde.

Formaldehyde precursor, including such as paraformaldehyde and formalin can also be used at least some examples, including Such as formalin.

The example of the representative hydrocarbyl substituent of the hydroxy aromatic compound of alkyl substitution includes such as polyolefin polymer, Such as polypropylene, polybutene, polyisobutene, ethyleneα-olefincopolymer.Other examples include butylene and/or isobutene and/ Or propylene and one or more mono-olef iotan co-monomers that can be with its copolymerization（Such as ethene, 1- amylenes, 1- hexenes, 1- octenes, 1- Decene etc.）Copolymer, the wherein comonomer molecule contains at least 50 weight % butylene and/or isobutene and/or propylene list Member.In some instances, the copolymer is aliphatic series and contains non-aliphatic group in some instances（Such as styrene, adjacent first Base styrene, p-methylstyrene, divinylbenzene etc.）, resulting polymers are substantially aliphatic polymerized hydrocarbon under any circumstance Thing.

The hydrocarbyl substituent that the example of suitable Mannich base additive includes wherein aromatic group is or comprising poly- isobutyl The Mannich base additive of alkene.Such compound is sometimes referred to as PIB- Mannich base additives.

In at least some examples, alkyl substitution hydroxy aromatic compound hydrocarbyl substituent include be obtained from or available from The polymer of pure or substantially pure 1- butylene；It is obtained from or available from the polymer of pure or substantially pure isobutene；Be obtained from or can Polymer obtained from the mixture of 1- butylene, 2- butylene and isobutene.In at least some examples, the hydroxyl virtue of alkyl substitution Race's reactant is obtained from or available from highly reactive polyisobutenes.Highly reactive polyisobutenes contain the terminal double bond of high content（Have When be also referred to as alpha-alefinically double bond and/or ethenylidene double bond）, such as total olefinic double bond in polyisobutene at least 20% or extremely Few 50% or at least 70%.The reality of high response polybutene containing the relatively a high proportion of polymer molecule containing terminal vinylidene Example include as US4152499 and DE2904314 described in method acquisition or obtained by those.

In at least some examples, the hydrocarbyl substituent contains some residual degrees of unsaturation, but they are generally substantially saturated.

In at least some examples, the hydrocarbyl substituent is to show 1 to 4, such as 1 to 2 for example to pass through gel infiltration Chromatography（Sometimes referred to as GPC）The polymer of the polydispersity measured.

In some instances, for the hydrocarbyl substituent for the hydroxy aromatic compound for preparing Mannich base additive（Its It is or comprising polyisobutene under certain situation）About 700 to about 1500 may be shown, such as about 900 to about 1300 Number-average molecular weight.

The example of suitable Mannich base additive includes US5634951, US5697988, US6800103, US7597726 And/or disclosed in US20090071065 and/or method as described in it obtain or obtained by those.

The example of suitable Mannich base additive includes disclosed in US5634951 and/or by the side described in it Method obtain or it is obtainable those.Therefore, the example of suitable Mannich base additive is included by (i) 1 molar part at least A kind of hydroxyl for the aliphatic hydrocarbyl substituent that the polyolefin derived from the number-average molecular weight for showing 500 to 3000 is included on ring At least one of aromatic compounds, at least one aldehyde of (ii) 0.8 to 1.3 molar part and (iii) 0.8 to 1.5 molar part exists The aliphatic polyamines of the primary or secondary amino of mannich condensation reaction can occur with (i) and (ii) comprising one in molecule（In the molecule Other amino（If any）It is substantially inert to participating in such mannich condensation reaction）Reaction can obtain or obtain Those, condition is that the mol ratio of aldehyde and amine is 1.2 or lower.

The example of suitable hydroxy aromatic compound (i) includes the hydroxy aromatic compound that high molecular weight alkyl replaces, bag Include poly- propyl phenoxy（Including phenol is alkylated into those to be formed by using polypropylene）, poly- butylphenol（Including by using polybutene and/ Or phenol is alkylated those to be formed by polyisobutene）With the poly- poly- propyl phenoxy of butyl -co-（Including by using butylene and/or isobutene Phenol is alkylated those to be formed with the copolymer of propylene）.Other hydroxy aromatic compounds include such as long chain alkylphenol, for example By using butylene and/or isobutene and/or propylene and one or more mono-olef iotan co-monomers that can be with its copolymerization（Including for example Ethene, 1- amylenes, 1- hexenes, 1- octenes, 1- decene etc.）Copolymer by phenol be alkylated be made those, for example wherein this be total to Polymers contains those of at least 50 weight % butylene and/or isobutene and/or propylene units.The comonomer can be aliphatic series , it can also contain non-aliphatic group（Such as styrene, o-methyl styrene, p-methylstyrene, divinylbenzene）.Properly Example include poly- butylphenol（For example phenol is alkylated to be formed by using polybutene）, the polybutene is including for example by pure or basic The polymerization that two kinds in pure 1- butylene or isobutene and 1- butylene, 2- butylene and isobutene or the mixture of all three are made Thing.High response polybutene is also the suitable example for manufacturing the hydroxy aromatic compound of suitable alkyl substitution.Alkyl takes The example of the hydroxy aromatic compound in generation includes the hydroxy aromatic compound of contraposition substitution.The hydroxy aromatic compound of alkyl substitution Example include containing one, two or more hydrocarbyl substituents those.

The alkylidene that the example of suitable polyamine reactant (iii) is included for example containing single reactive primary or secondary amino is more Amine.Example includes including other groups（Including such as hydroxyl, cyano group, acylamino-）Those.The example bag of suitable polyamines Include aliphatic diamine, for example those containing a primary or secondary amino and tertiary amino.Example includes N, N, N ", N "-tetraalkyl Two alkylene triamines；N, N, N ', the alkylidene tetramine of N "-tetraalkyl three；N, N, N ', the alkylidene tetramine of N ", N " '-five alkyl three；N, N- dihydroxyalkyl-α, ω-Alkylenediamine；N, N, N '-three hydroxyalkyl-α, ω-Alkylenediamine；Three (dialkyl aminoalkyls) Aminoalkyl methane etc., including such as wherein identical or different those of alkyl, including usually contain not more than 12 carbon atoms, Such as 1 to 4 carbon atom, each such as those of methyl and/or ethyl.The anti-of mannich condensation reaction is may participate in containing one Answering property primary or secondary amino and at least one can not directly participate in Mannich reaction steric hindrance amino polyamines example include for example N- (tert-butyl group) -1,3- propane diamine；N- neopentyl -1,3- propane diamine；N- (tert-butyl group) -1- methyl isophthalic acids, 2- ethylenediamines；N- (uncles Butyl) -1- methyl isophthalic acids, 3- propane diamine and 3,5- bis- (tert-butyl group) aminoethylpiperazine.

The example of suitable Mannich base additive also includes disclosed in US5697988 and/or by described in it Method obtain or it is obtainable those.Therefore, the example of suitable Mannich base additive takes including (i) high molecular weight alkyl The Mannich reaction products of the phenol in generation, (ii) amine and (iii) aldehyde, wherein (i), (ii) and (iii) is with 1.0:0.1-10.0: 0.1-10 ratio reaction.In at least some examples, the Mannich reaction products are by making alkyl-substituted hydroxyaromatic Compound（Its alkyl substituent has 600 to 14000 number-average molecular weight (Mn)）, such as poly- alkyl phenol（Its poly- alkyl substituent It is derived from or can be derived from and shows 600 to 3000, the 1- mono-olefins polymer of such as 750 to 1200 number-average molecular weight）； Contain at least one>The amine of NH groups, such as formula H₂N-(A-NH-)_xAlkylene polyamine shown in H（Wherein A is containing 1 to 10 The divalent alkyl and x of carbon atom are 1 to 10 integers）；And aldehyde, such as formaldehyde is condensed in the presence of solvent to be obtained or can obtain .Suitable reaction condition includes one or more of following：

Zero in room temperature to operating at a temperature of 95 DEG C；

Zero makes compound alone or in the presence of the solvent easily removed, such as benzene, dimethylbenzene, toluene or solvent refining neutral oil Reaction；

Zero uses formaldehyde（Such as formalin）It is used as aldehyde；

Zero in elevated temperature（Such as 120 DEG C to 175 DEG C）Lower heating reactant mixture, while for example blasting inertia stripping Gas（Such as nitrogen, carbon dioxide）Until dehydration is complete；With

Zero filtering reaction product is simultaneously diluted with solvent.

The example of Mannich reaction products is included by making alkyl phenol, ethylene and formaldehyde with 1.0:0.5-2.0: 1.0-3.0 respective molar ratio reaction generation or those that can be generated, the alkyl of the wherein alkyl phenol shows 600 to 3000, Such as 740 to 1200 or 800 to 950 or such as 900 number-average molecular weight（Mn）.The reality of alkyl-substituted hydroxy aromatic compound Example includes the monoalkyl phenol and adjacent monoalkyl phenol and dialkyl phenol of contraposition substitution.The example of amine reactant includes polyamines, for example, gather Vinylamine.The example of amine reactant also includes single and two-amino alkane and their substitution analog, such as ethylamine, diformazan Base amine, dimethylaminopropyl amine and diethanol amine；Aromatic diamine（Such as phenylenediamine and diamines naphthalene）；Heterocyclic amine（Such as morpholine, Pyrroles, pyrrolidines, imidazoles, imidazolidine and piperidines）；Melamine；With their substitution analog.The example of amine reactant includes Alkylene polyamine, such as straight chain, side chain or cyclic polyamine；The mixture of straight chain and/or side chain and/or cyclic polyamine, wherein respectively Alkylidene contains 1 to 10 carbon atom, such as 2 to 20 carbon atoms.The example of polyamines includes that containing 3 to 7 nitrogen-atoms A bit.

The example of suitable Mannich base additive also includes disclosed in US6800103 and/or by described in it Method obtain or it is obtainable those.Therefore, the example of suitable Mannich base additive is included by making (i) at least one The aliphatic hydrocarbyl substituent and (b) of the polyolefin for the number-average molecular weight for showing 500 to 3000 are derived from containing (a) on ring C_1-4The substituted hydroxy aromatic compound of alkyl；(ii) at least one secondary amine；The mixture of (iii) at least one aldehyde is anti- Should obtain or it is obtainable those.In at least some examples, make component (ii) and (iii) pre- anti-before addO-on therapy (i) Should be to form intermediate.In at least some examples, heated at a temperature of higher than 40 DEG C by component (i), (ii) and (iii) shape Into mixture, mannich condensation reaction occurs at this temperature.

In at least some examples, the Mannich reaction products are by making dibasic hydroxy aromatic compound（Wherein hydrocarbon Base substituent (a) includes polypropylene, polybutene or the second for showing 500 to 3000 number-average molecular weight and 1 to 4 polydispersity Alkene alpha olefin copolymer）, one or more secondary amine and at least one aldehyde reaction obtain or can obtain.In at least some examples, Using dibutylamine as amine, formaldehyde or formalin as aldehyde, and the hydroxy aromatic compound of substitution:Dibutylamine:Formaldehyde Mol ratio be respectively 1: 0.8-1.5 :0.8-1.5, such as respectively 1: 0.9-1.2 : 0.9-1.2.

The example of representational dibasic hydroxy aromatic compound includes those shown in logical formula (VII)：

(VII)

Wherein each R is H, C_1-4Alkyl or show 500 to 3000 number-average molecular weight hydrocarbyl substituent, condition is that a R is H, a R is C_1-4An alkyl and R is hydrocarbyl substituent.

The example of the representative hydrocarbyl substituent of the hydroxy aromatic compound (ii) of alkyl substitution includes polyolefin polymer, Such as polypropylene, polybutene, polyisobutene, ethyleneα-olefincopolymer.Other examples include butylene and/or isobutene and/ Or propylene and one or more mono-olef iotan co-monomers that can be with its copolymerization（Such as ethene, 1- amylenes, 1- hexenes, 1- octenes, 1- Decene etc.）Copolymer, the wherein comonomer molecule contains at least 50 weight % butylene and/or isobutene and/or propylene list Member.In some instances, the copolymer is aliphatic series and contains non-aliphatic group in some instances（Such as styrene, adjacent first Base styrene, p-methylstyrene, divinylbenzene etc.）, resulting polymers are substantially aliphatic polymerized hydrocarbon under any circumstance Thing.High response polybutene is also applied for manufacturing the hydroxy aromatic compound of suitable alkyl substitution.

The example of suitable dibasic hydroxy aromatic compound is included adjacent first by using above-mentioned heavy polymer Phenol alkylation obtain or it is obtainable those.

In at least some examples suitably, the hydrocarbyl substituent is in the contraposition of dibasic hydroxy aromatic compound, And C_1-4Alkyl substituent is on ortho position.

The example of representative secondary amine (ii) includes those shown in logical formula (VIII)：

(VIII)

Wherein R ' and R ' ' are each independently containing 1 to 30 carbon atom, such as 1 to 18 carbon atom or 1 to 6 carbon atom Alkyl, cycloalkyl, aryl, alkaryl or aralkyl.Example includes dimethyl amine, diethylamide, dipropylamine, dibutyl Amine, diamyl amine and dicyclohexylamine.

The example of suitable Mannich base additive also includes disclosed in US7597726 and/or by described in it Method obtain or it is obtainable those.Therefore, the example of suitable Mannich base additive includes (i) and contains steric hindrance primary amino radical Polyamines, (ii) alkyl substitution hydroxy aromatic compound and (iii) aldehyde mannich condensation reaction product.Contain steric hindrance primary The example of the polyamines (i) of amino includes (A) the aliphatic cyclic polyamine containing steric hindrance primary amino radical, and (B) contains steric hindrance primary amino radical Acyclic aliphatic polyamines and combinations thereof.In at least some examples, the Mannich reaction products are by making (1) 1,2- diamino basic rings Hexane, the cresols of (2) polyisobutene substitution and/or phenol and (3) formaldehyde react and obtain or can obtain, for example wherein reactant (1), (2) and (3) are reacted in Mannich reaction with equimolar ratio.In at least some examples, the Mannich reaction is produced Thing is dispersed in liquid carrier fluid.In at least some examples, the polyamine reactant removes at least one in identical polyamine molecule Mannich outside the individual reactive amino for participating in Mannich reaction also containing the hydroxyaromatic reactant for being not involved in replacing with alkyl The amino of condensation reaction.The example of reactive amino includes primary and secondary amino, such as reactive primary amino radical of non-steric hindrance.Containing anti- The example of the polyamines of answering property amino and steric hindrance amino includes those shown in formula (IX)：

(IX)

Wherein X and Z are individually methylene, and Y is alkylidene or alkylidene amino, and n is 0 or 1, Q are that suitable and X and Z-shaped cyclization are tied The optional alkylidene of structure, E is alkyl, and t is 0 or 1, R¹It is alkyl or hydrogen, if it is 1, R that condition, which is n,¹It is alkyl, R²Be hydrogen or Alkyl, m is 0 or 1, and condition is that then m is 0 if there is Q.If R¹And/or R²It is alkyl, then the example of such alkyl includes C₁To C₈Alkyl（Such as methyl, ethyl, propyl group, isopropyl, the tert-butyl group）.When n is 1, Y example includes C₁To C₈Alkylene Base；Alkylidene amino（Such as methene amido (- CH₂N (H) -), dimethylene amino (- CH₂N(H)-CH₂-), methylene ammonia Base-ethyl methene amido (- CH₂N(H)-C₂H₄N(H)-CH₂-) etc.）.When t is 1, E example includes methylene, sub- second Base, isopropylidene etc..Q example includes alkylidene chain, such as C₂-C₄Alkylidene chain.The example of polyamines containing steric hindrance primary amino radical Including aliphatic cyclic polyamine, including such as polyamino cycloalkane, such as polyamino hexamethylene, including 1,2- diaminocyclohexane （1,2-diaminodicyclohexane）, 1,3- diaminocyclohexanes（1,3-diaminodicyclohexane）With 1,4- bis- Aminocyclohexane（1,4-diaminodicyclohexane）, such as shown in following Formula X a, Xb and Xc：

Xa

Xb

Xc。

In at least some examples, in the aliphatic cyclic polyamine structure, when steric hindrance/shielded amino and reactive ammonia Base relative to each other with the arrangement beyond the configuration of ortho position in the presence of, steric hindrance alkyl is typically bonded to what is be bonded with steric hindrance primary amino radical On carbon atom identical carbon atom.In at least some examples（Such as compound Xc）, reactive amino is as being directly connected to Insertion substituent on ring structure（intervening substituent）A part presence.Make at least some examples With the mixture of isomers.The example of suitable acyclic aliphatic polyamine reactant include containing physically by space protection with The alkylene polyamine for preventing or at least significantly hindering it to participate in the primary amino radical of the ability of mannich condensation reaction.In at least some realities In example, the steric hindrance primary amino radical is typically connected on the secondary or tertiary carbon atom in the polyamine compounds.The acyclic aliphatic polyamines is in phase With the suitable reactivity amino in molecule with participation mannich condensation reaction（Such as primary or secondary）.In at least some examples, There are other substituents, such as hydroxyl, cyano group, acylamino-.The example of acyclic aliphatic polyamines containing steric hindrance primary amino radical includes Those shown in Formula X Ia, XIb, XIc and XId：

XIa

Wherein each R₁And R₂It is alkyl or hydrogen, condition is that wherein at least one is alkyl.The example of alkyl includes C₁To C₈Alkyl, Such as methyl, ethyl, propyl group, isopropyl；

XIb

XIc

Xid。

The example of the hydroxy aromatic compound (ii) of alkyl substitution includes those shown in Formula X II：

XII

Wherein each R is H, C_1-4Alkyl shows 300 to 2000, such as 500 to 1500 and for example passes through gel permeation chromatography The mean molecule quantity measured（Mw）Hydrocarbyl substituent, condition is that at least one R is that H and R is that alkyl as defined above takes Dai Ji.

The example of the representative hydrocarbyl substituent of the hydroxy aromatic compound (ii) of alkyl substitution includes polyolefin polymer, Such as polypropylene, polybutene, polyisobutene, ethyleneα-olefincopolymer.Other examples include butylene and/or isobutene and/ Or propylene and one or more mono-olef iotan co-monomers that can be with its copolymerization（Such as ethene, 1- amylenes, 1- hexenes, 1- octenes, 1- Decene etc.）Copolymer, the wherein comonomer molecule contains at least 50 weight % butylene and/or isobutene and/or propylene list Member.In some instances, the copolymer is aliphatic series and contains non-aliphatic group in some instances（Such as styrene, adjacent first Base styrene, p-methylstyrene, divinylbenzene etc.）, resulting polymers are substantially aliphatic polymerized hydrocarbon under any circumstance Thing.

In at least some examples, hydrocarbyl substituent includes being obtained from or available from the polymerization of pure or substantially pure 1- butylene Thing；It is obtained from or available from the polymer of pure or substantially pure isobutene；Be obtained from or available from 1- butylene, 2- butylene and isobutene Mixture polymer.In at least some examples, the hydroxyaromatic reactant of alkyl substitution is obtained from or available from high anti- Answering property polyisobutene.

In at least some examples, suitable dibasic hydroxy aromatic compound polymerize by using HMW alkyl Orthoresol is alkylated by thing, the hydrocarbyl polymers for for example showing 300 to 2000 mean molecule quantity, such as by using showing 300 to 2000, orthoresol or adjacent alkylation of phenol are obtained or can obtained by the polyisobutene of such as 500 to 1500 mean molecule quantity .

The example of suitable Mannich base additive also includes disclosed in US20090071065 and/or by wherein retouching The method stated obtain or it is obtainable those.Therefore, the example of suitable Mannich base additive includes：(i) there is primary amino radical Polyamines, the mannich condensation reaction product of the hydroxy aromatic compound of (ii) alkyl substitution and (iii) aldehyde, the wherein Manny Uncommon reaction is at (i):(ii):(iii) certain total moles are carried out than lower, and certain total moles ratio causes such as polyamines (i) hydroxy aromatic compound (ii) that can replace with alkyl is reacted to obtain substantially pure intermediate, and the intermediate can be with aldehyde (iii) reaction is to obtain Mannich reaction products, such as in one pot reaction method.The example of polyamines (i) includes 1,2- diaminourea Hexamethylene, 1,3- diaminopropanes and 1,2- diaminoethanes.Suitable mol ratio (i):(ii):(iii) example includes 1: 2:3 and 1:1:2.The example of the hydroxy aromatic compound of alkyl substitution includes those shown in formula (XIII)：

(XIII)

Wherein each R is H, C_1-4Alkyl shows 300 to 2000, such as 500 to 1500 and for example passes through gel permeation chromatography The mean molecule quantity measured（Mw）Hydrocarbyl substituent, condition is that at least one R is that H and R is that alkyl as defined above takes Dai Ji.The example of hydrocarbyl substituent includes polyolefin polymer, such as polypropylene, polybutene, polyisobutene and ethylene ' alpha '-olefin Copolymer and butylene and/or isobutene and/or propylene and one or more mono-olef iotan co-monomers that can be with its copolymerization（For example Ethene, 1- amylenes, 1- hexenes, 1- octenes, 1- decene etc.）Copolymer, the wherein copolymer contains at least 50 weight % butylene And/or isobutene and/or propylene units.In at least some examples, as high response ethenylidene isomers, polyolefin gathers Terminal position of the compound hydrocarbyl substituent in carbochain contains at least the 20% of its olefinic double bonds, such as 50% or 70%.Alkyl replaces The example of base include be obtained from or available from polyisobutene those, be for example obtained from or available from pure or substantially pure 1- butylene or different The polyisobutene of butylene and it is obtained from or available from the polymerization of two or three of mixture in 1- butylene, 2- butylene and isobutene Thing.The example of hydrocarbyl substituent includes being obtained from or available from the relatively high proportion of polymer containing terminal vinylidene At least 20%, 50% or 70% of total terminal ethylenic double bond in those of highly reactive polyisobutenes, such as polyisobutene is included Alkyl ethenylidene isomers.

In at least some examples, the aromatic compounds for existing/being replaced using more than one alkyl.When presence/use is more When the aromatic compounds that a kind of alkyl replaces, the aromatic compounds of each alkyl substitution can be Mannich base additive.

In at least some examples, the alkyl substitution aromatic compounds with least about 20 ppm activity concentration, For example it is present in/is used in fuel composition with least about 30 ppm activity concentration.In at least some examples, the hydrocarbon The aromatic compounds of base substitution is for example deposited with most about 300 ppm activity concentration with most about 120 ppm concentration It is/is used in fuel composition.In at least some examples, the aromatic compounds of alkyl substitution is with about 20 ppm to big About 300 ppm, such as about 30 ppm to about 120 ppm activity concentration is present in/is used in fuel composition.Active matter Concentration refers to the concentration of the aromatic compounds of active hydroxyl substitution, does not consider such as any solvent.

Generally, the aromatic compounds of alkyl substitution exists with about 20 ppm to about 70 ppm activity concentration In/be used in fuel composition.But, in some instances, higher height reason rate can be used.In this case, the hydrocarbon The aromatic compounds of base substitution can be present in/be used in fuel composition with about 70 ppm to about 300 ppm concentration.

If there is/the aromatic compounds that is replaced using more than one alkyl, the aromatic compounds of alkyl substitution it is total dense Degree is as described herein.

In some instances, polyene amine is present in/is used for about 50 ppm to about 500 ppm activity concentration and fired In feed composition and alkyl substitution aromatic compounds be present in about 20 ppm to about 300 ppm activity concentration/ For in fuel composition.Generally, polyene amine can be present in/be used with about 50 ppm to about 160 ppm activity concentration In fuel composition and alkyl substitution aromatic compounds can be deposited with about 20 ppm to about 70 ppm activity concentration It is/is used in fuel composition.But, in some instances, polyene amine can be with about 160 ppm to about 500 ppm's Activity concentration is present in/be used for the aromatic compounds that in fuel composition and alkyl replaces can be with about 70 ppm to about 300 ppm activity concentration is present in/is used in fuel composition.

In at least some examples, polyene amine:The active weight ratio of the aromatic compounds of alkyl substitution is about 10: 1 to about 1:10, such as about 5:1 to about 1:5.If there is/use more than one polyene amine and/or more than one alkyl Substituted aromatic compounds, all polyene amine:The active weight of the aromatic compounds of all alkyl substitutions is than as described herein.

Generally, the polyene amine, which contains, shows about 700 to about 1500（Such as about 800 to about 1200）Number it is equal The polyolefin group of molecular weight（polyalkylene group）And the hydrocarbyl substituent of the aromatic compounds of alkyl substitution（Its It is or comprising polyisobutene in some cases）Show about 700 to about 1500（Such as about 900 to about 1300）'s Number-average molecular weight.

Carrier fluid

In at least some examples, carrier fluid（Sometimes referred to as introduce auxiliary agent（induction aid）Or fluidizing reagent）In the presence of In/be used in the fuel composition, the purposes and/or methods described.In at least some examples, exist/use and be more than A kind of carrier fluid.

In at least some examples, the carrier fluid is provided together with polyene amine.In at least some examples, the carrier current Body is provided together with the aromatic compounds that alkyl replaces.In at least some examples, carrier fluid replaces with polyene amine and alkyl Each of aromatic compounds provide together, the carrier fluid can be with identical or different., should at least some examples Carrier fluid is provided independently of the aromatic compounds that polyene amine and alkyl replace.

The example of suitable carrier fluid is for example described into [0053] in US2009/0071065 paragraphs [0038].Cause This, the example of suitable carrier fluid includes liquid poly-alpha olefins oligomer, liquid polyolefin（Such as polypropylene, polybutene, poly- Isobutene etc.）, liquid hydrotreating polyolefin（The polypropylene of such as hydrotreating, the polybutene of hydrotreating, hydrotreating Polyisobutene etc.）, mineral oil, poly- (oxyalkylene) compound of liquid, liquid alcohol, liquid polyol, liquid ester etc..

The example of carrier fluid includes the blend of (1) mineral oil or mineral oil, for example, show the viscosity less than 120 Those of index；(2) a kind of blend of polyalphaolefin or polyalphaolefin, for example show 500 to 1500 mean molecule quantity Those；(3) polyethers, including poly- (oxyalkylene) compound, for example, show those of 500 to 1500 mean molecule quantity；(4) One or more liquid polyolefins；(5) it is selected from the mixture of two or more of (1), (2), (3) and (4).

The example of suitable mineral oil vehicle fluid includes paraffinic oils, naphthenic oil and coal tar, the oil of such as hydrotreating. The example of mineral oil shows to be less than 1600 SUS, such as 300 to 1500 SUS viscosity at 40 DEG C and/or shows small In 100, such as 30 to 60 viscosity index (VI).

The example of suitable polyalphaolefin carrier fluid includes the polyalphaolefin of hydrotreating and non-hydrotreating.Polyalphaolefin Example include trimer, tetramer and the pentamer of the alpha olefin monomers containing 6 to 12 carbon atoms.

Poly- (oxyalkylene) that the example of suitable polyethers carrier fluid includes showing 500 to 1500 mean molecule quantity is changed Compound, including such as poly- (oxyalkylene) single methanol of alkyl end-blocking.The example of poly- (oxyalkylene) compound includes one kind undiluted It is to show at least 70 cSt and the solvable liquid of the gasoline of at least 13 cSt viscosity at 100 DEG C at 40 DEG C under state Poly- (oxyalkylene) single methanol of alkyl or its mixture, including at least eight carbon atom, such as 10 to 18 carbon atoms are contained by one kind Alkanol or its mixture propoxylation formation such single methanol.

The example of suitable poly- (oxyalkylene) carrier fluid, which is included under undiluted state, to be shown at least 60 at 40 DEG C cSt（At least 70 cSt for example at 40 DEG C）With at least 11 cSt at 100 DEG C（At least 13 cSt for example at 100 DEG C）It is viscous Those of degree.The example of suitable poly- (oxyalkylene) carrier fluid, which is included under undiluted state, to be shown to be not more than at 40 DEG C 400 cSt（It is not more than 300 cSt for example at 40 DEG C）With no more than 50 cSt at 100 DEG C（It is not more than for example at 100 DEG C 40 cSt）Viscosity those.

The example of poly- (oxyalkylene) compound includes poly- (oxyalkylene) diol compound and its monoether derivative, for example, meet Those of above-mentioned viscosity requirement, including by making alcohol or polyalcohol used with alkylene oxide such as expoxy propane and/or epoxy butane Without using oxirane in the case of reaction obtain or it is obtainable those, such as the oxidation of at least 80 moles % in molecule Alkenyl group is derived from or can be derived from the product of 1,2- propylidene.

The example of poly- (oxyalkylene) compound includes public in US248664, US2425845, US2425755 and US2457139 Method open and/or as described in it obtain or obtained by those.

Poly- (oxyalkylene) carrier compound should contain enough branched oxyalkylene units（Such as methyl dimethylene epoxide Unit and/or the methylene epoxide unit of ethyl two）So that poly- (oxyalkylene) compound dissolves in gasoline.

The example of polyolefin carrier fluid includes being total to for polypropylene, polybutene, polyisobutene, polypenthylene, propylene and butylene Polymers, the copolymer of butylene and isobutene, the copolymer and propylene of propylene and isobutene, the copolymer of butylene and isobutene and Its mixture.

The example of polyolefin carrier the fluid also polypropylene including hydrotreating, the polybutene of hydrotreating, hydrotreating Polyisobutene etc..

The example of polybutene carrier fluid includes showing for example as ratio Mw / Mn, i.e., (weight-average molecular weight)/ Those for the Narrow Molecular Weight Distribution that (number-average molecular weight) is represented, the ratio is sometimes referred to as polydispersity index.Polybutene is carried The example of body fluid includes the ratio M shown as 1.4 or smaller for example as described in US6048373w(quality average mark Son amount)/MnThose for the Narrow Molecular Weight Distribution that (number-average molecular weight) is represented.The method of quality measurement mean molecule quantity includes static state Light scattering, low-angle neutron scattering, X-ray scattering and sinking speed.The equal molecular mass of number or molecular weight（Mn）Can be by solidifying Glue penetration chromatography determination.

In at least some examples, the carrier fluid is with least about 10 ppm concentration, such as with least about 35 Ppm concentration is present in/is used in fuel composition.In at least some examples, the carrier fluid is with most about 500 ppm Concentration, be for example present in/be used in fuel composition with most about 200 ppm concentration., should at least some examples Carrier fluid is present in/is used for about 10 ppm to about 500 ppm, such as about 35 ppm to about 200 ppm concentration In fuel composition.

If there is/more than one carrier fluid is used, the total concentration of carrier fluid is as described herein.

Fuel composition

The fuel composition is applied to such as spark-ignition internal combustion engine or compression ignition gasoline engine.

In at least some examples, the fuel composition has most 50.0 weight ppm, such as most 10.0 weight ppm Sulfur content.

The example of suitable fuel composition includes leading and lead-free fuel composition.

In at least some examples, the fuel composition meets for example such as BS EN 228:The EN's 228 illustrated in 2012 It is required that.In at least some examples, the fuel composition meets ASTM D 4814-14 requirement.

In at least some examples, the fuel composition for spark-ignition internal combustion engine is shown for example such as according to BS EN 228:As defined in 2012 it is following in one or more（For example it is whole）：- 95.0 minimum research octane number (RON), 85.0 are most Fractional motor method octane number, 5.0 mg/l maximum lead content, 720.0 to 775.0 kilograms per cubic meter of density, at least 360 minutes Oxidation stability, 5 mg/100 ml maximum actual gum content（Solvent is washed）, 1 class copper corrosion（3 is small at 50 DEG C When）, limpid bright outward appearance, 18.0 weight % maximum olefin(e) centent, 35.0 weight % maximum arene content and 1.00 volume % Maximum benzene content.

The example of suitable fuel composition includes such as hydrocarbon fuel, oxygenated fuel and combinations thereof.

Hydrocarbon fuel can be derived from mineral origin and/or derived from renewable source, such as biomass（Such as biomass liquefaction Source）And/or originate and/or originated derived from coal liquifaction derived from natural gas synthetic oil.

The example of suitable oxygenated fuel component in the fuel composition include straight chain with 1 to 6 carbon atom and/ Or branched alkyl alcohol, such as methanol, ethanol, normal propyl alcohol, n-butanol, isobutanol, the tert-butyl alcohol.For spark-ignition internal combustion engine or pressure Suitable oxygen-containing component in the fuel composition of point reduction fire gasoline engine includes ether, such as former with 5 or more carbon Son, such as methyl tertiary butyl ether(MTBE) and ethyl tert-butyl ether (ETBE).In at least some examples, the fuel composition has 2.7 mass %'s Maximum oxygen content.In at least some examples, fuel composition has the oxygenatedchemicals as specified in EN 228 （oxygenate）Maximum, such as methanol:3.0 volume %, ethanol:5.0 volume %, isopropanol:10.0 volume %, isobutyl Alcohol:10.0 volume %, the tert-butyl alcohol:7.0 volume %, ether（For example with 5 or more carbon atoms）:10 volume % and other contain Oxygen compound（According to suitable final boiling point）:10.0 volume %.In at least some examples, fuel composition includes most 15 Volume %, such as ethanol for meeting EN 15376 of most volume % of 10 volume % or most 5.0 concentration.Contain oxygenatedchemicals The example of fuel composition include the fuel composition of E5, E10, E15 and the ethanol containing higher concentration, up to such as E85.

Reduced according to an aspect of the present invention there is provided one kind for spark-ignition internal combustion engine or compression ignition gasoline internal combustion The method of the sludge formation trend of the fuel composition of machine, methods described is included in one or more steps to the fuel stack It is incorporated in compound：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine

To be produced when producing comprising the additive combined and being used in the engine than being used in the engine The fuel composition of the few greasy filth of the greasy filth that the is formed during fuel composition combined without the additive.

In at least some examples, the aromatic compounds and the polyene amine of alkyl substitution are used as one or more additives Concentrate, one or more additive bags（package）And/or one or more additive packing bags（part pack）Group Divide and be incorporated to separately or together in fuel composition.

In at least some examples, the fuel composition and/or multifunctional additive for lubricating oils and/or additive bag and/or addition Agent packing bag includes at least one other fuel additive.In at least some examples, the greasy filth shape of the reduction fuel composition Method into trend includes being incorporated at least one other fuel additive in one or more steps.

In at least some examples, the additive is wrapped as one or more multifunctional additive for lubricating oils and/or additive packing It is mixed into and/or is incorporated to, optionally includes solvent or diluent.

In at least some examples, by one or more steps by one or more basic fuels（For example hydrocarbon fires Material, oxygenated fuel and combinations thereof）And its component is optionally mixed with one or more additives and/or portions additive bag concentrate To prepare the fuel composition.In at least some examples, in one or more steps by the additive, multifunctional additive for lubricating oils And/or portions additive bag concentrate is mixed with fuel or its component.

The example of such other fuel additives includes friction improver, antiwear additive, corrosion inhibiter, defogger/broken Emulsion, dyestuff, label, odorant, octane enhancing additive, combustion improver, antioxidant, antimicrobial, lubrication are improved Agent and valve seat shrinkage depression additive（valve seat recession additive）.

Additive in fuel composition（If there is）Representational suitable and more suitably independent quantities be listed in table 1 In.The concentration represented in table 1 is based on the weight of active additive compound, i.e., unrelated with any solvent or diluent.

In at least some examples, there is more than one all types of additives.In at least some examples, add all types of Plus in agent, there is the type additive of more than one classification.In at least some examples, there is being more than for additive of all categories A kind of additive.In at least some examples, additive is suitably supplied by manufacturer and/or supplier in solvent or diluent Should.

Table 1

Additive or ashless additive of the example of suitable friction improver and antiwear additive including generation ash content Those.The example of friction improver and antiwear additive includes ester（Such as glycerin mono-fatty acid ester）And aliphatic acid（For example oleic acid and Stearic acid）.

The example of suitable corrosion inhibiter includes ammonium salt, amine and the heterocyclic arene of organic carboxyl acid, such as alkylamine, imidazoline and Tolyl-triazole.

The example of suitable nonmetallic octane enhancing additive includes methylphenylamine.

The example of the suitable octane enhancing additive containing metal includes methyl cyclopentadienyl tricarbonyl manganese, ferrocene and four Lead ethyl.Suitably, the fuel composition is free of all additional metallic octane improvers, including methyl cyclopentadienyl three Manganese carbonyl, and other metallic octane improvers, including such as ferrocene and lead tetraethide.

The example of suitable antioxidant includes phenol antioxidant（Such as 2,4- di-t-butyls phenol and 3,5- bis--tertiary fourth Base -4- hydroxy-phenylpropionic acids）And amine antioxidants（Such as p-phenylenediamine, dicyclohexylamine and its derivative）.

The example of suitable valve seat shrinkage depression additive includes the inorganic salts of potassium or phosphorus.

In at least some examples, the compositions of additives includes solvent.The example of suitable solvent includes polyethers and virtue Race and/or aliphatic hydrocarbon, such as heavy naphtha such as Solvesso（Trade mark）, dimethylbenzene and kerosene.

In at least some examples, additive is present in fuel composition with 20 to 25000 weight ppm total amount.Cause This, the concentration of each additive in multifunctional additive for lubricating oils is correspondingly higher than in fuel composition, such as with 1: 0.00002 To 0.025 ratio.In at least some examples, additive is used as packing bag, such as a part of additive（It is sometimes referred to Make oil plant additive）Added in manufacturing process of the oil plant in alternative fuel, and a part of additive（Sometimes referred to as Terminal or sale additive）Added in terminal or distributing point.

In at least some examples, aromatic compounds and polyene amine is as oil plant additive or is used as pin that alkyl replaces Additive is sold to merge or mix with other components of fuel composition.

In at least some examples, the aromatic compounds and polyene amine of alkyl substitution are as sale additive, such as at end End or point of sale merge or mixed with other components of fuel composition.

In general, there is two kinds of spark-ignition internal combustion engine, its basis delivers fuel into engine chamber The type of system is classified.

Port fuel injecting type（PFI）Engine is that the mixture of fuel and air wherein is sprayed into air inlet, then Through one or more intake valves（Sometimes referred to as inlet valve or air intake valve（inlet port valve））Into engine combustion Burn the engine of room.The example of suitable port fuel injection spark-ignition internal combustion engine includes any suitable air intake duct combustion Expect injection spark-ignition internal combustion engine, including such as BMW 318i engines, Ford 2.3L Ranger engines and MB M111 Engine.

Toroidal swirl type（DI）Engine is through injector wherein by fuel（Sometimes referred to as direct injector directly sprays Injector nozzles）It is injected directly into engine chamber and by air through one or more intake valves（Sometimes referred to as air inlet valve Or air air intake valve）Introduce the engine of the combustion chamber.The example of suitable toroidal swirl type spark-ignition internal combustion engine includes Boosted direct injection formula spark-ignition internal combustion engine, such as direct spray of turbo charged direct injection engine and engine driven supercharging Penetrate formula engine.Suitable engine includes 2.0L boosted direct injection formula spark-ignition internal combustion engines.Suitable toroidal swirl type Engine includes those with the side-mounted direct direct injector of injector and/or middle.

Greasy filth in fuel composition control engine disclosed herein（Referred herein as engine sludge）Entirety Formed.

The fuel composition can also control the sludge formation in the particular elements of engine, including one or more rocking bars Lid, camshaft baffle plate, timing chain cover, food tray and its baffle plate, oil screen and bonnet area.In instances, fuel composition control is shaken The formation of bowl cover greasy filth.

Assessing the method for the greasy filth control performance of fuel composition includes being based on US Industry Standard Test methods：ASTM D- 6593（Version 10）Those, it is sometimes referred to as Ford 4.6L " Sequence VG " engine tests.This experiment is used In measure lubricant properties.It is however possible to use standard reference lubricant is used as lubricant and standard reference basic fuel（Xiang Qi Middle addition associated additives）The performance of fuel is tested as fuel.The experiment can be used for measuring engine sludge（In test Referred to as " mean engine greasy filth "）With rocker cover greasy filth.

Fuel composition used control sludge formation in the present invention, it may be desirable to they such as exist in other places of engine Also good detergency is shown on intake valve.This can by measure the fuel composition intake valve keep cleansing performance come Determine.The inlet valve deposits for measuring the fuel composition for spark-ignition internal combustion engine keep the method for cleansing performance to include base In US Industry Standard Test methods：ASTM D-6201（Version 04,2009）Those, it is sometimes also according to engine used Referred to as Ford 2.3L " Ranger " engine test.

Further aspect of the invention includes stated hereinabove but wherein uses Mannich base additive as component a side Face, embodiment, situation and example.In these aspects, the Mannich base additive can be, but do not have to be alkyl and take The aromatic compounds in generation.

The present invention, the wherein basis of embodiment 1 are only described by way of example referring now to drawings below, experiment and embodiment The present invention, A is not according to the present invention for experiment.

In the accompanying drawings, Fig. 1 graphically represents the fuel composition tested for basic fuel reference Greasy filth control performance.

Use US Industry Standard Test methods：ASTM D-6201（Version 04,2009）Fired using the L air intake ducts of Ford 2.3 Expect that injection spark-ignition internal combustion engine assesses inlet valve deposits（IVD）Keep cleansing performance.Ground using E10 gasoline base fuels Study carefully inlet valve deposits（IVD）Keep cleansing performance.

Use US Industry Standard Test methods：ASTM D-6593（Version 2 0100628）Fired using Ford 4.6L air intake ducts Expect that injection spark-ignition internal combustion engine assesses engine sludge and rocker cover sludge formation.Use the standard in ASTM D-6593 Comparative fuel（Associated additives are added thereto）It is used as fuel.

Test A- only polyisobutene

Assess the engine sludge and rocker cover greasy filth control performance of the fuel containing PIBA additives.Used in choice experiment PIBA amounts keep cleansing performance to provide typical port fuel injection valve.

Engine sludge and rocker cover greasy filth control performance are graphically used as relative % greasy filth control performances（Relative to Basic fuel reference）Display is in Fig. 1.

Embodiment 1The combination of-Mannich base additive and PIBA

Assess engine sludge and the rocker cover greasy filth control of the fuel of the combination containing Mannich base additive and PIBA additives Performance processed.Mannich base additive used and PIBA amount are protected with providing typical port fuel injection valve in choice experiment Cleansing performance is held, it is comparable to the fuel composition for testing A.

Engine sludge and rocker cover greasy filth control performance are graphically used as relative % greasy filth control performances（Relative to Basic fuel reference）Display is in Fig. 1.

The data display generated in A and embodiment 1 is tested in table 2.

Table 2

^*High value shows preferable control performance.

The as shown by data shown in table 2 and Fig. 1, includes the fuel stack of the Mannich base additive combined with PIBA Compound shows beneficial greasy filth control in spark-ignition internal combustion engine.Especially, as shown by data, comprising with PIBA knot The fuel composition of the Mannich base additive of conjunction is shown than additive-free fuel and only the fuel containing PIBA is more The good control of the greasy filth in spark-ignition internal combustion engine.When the use L port fuel injection spark-ignition internal combustions of Ford 2.3 Machine is according to Industry Standard Test method：It is when ASTM D-6201 are measured, such as dense to provide the additive for the detergency ability being comparable to Degree is compared with the fuel containing PIBA.

These data illustrate a kind of method for controlling the sludge formation in spark-ignition internal combustion engine, and methods described is included to institute State engine and supply a kind of fuel composition, it includes the combination of following ingredients：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.

Data also illustrate following ingredients as the greasy filth in the fuel composition of spark-ignition internal combustion engine and control additive Purposes：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.

Data also illustrate a kind of method for the sludge formation trend for reducing the fuel composition for spark-ignition internal combustion engine, Methods described includes being incorporated into the fuel composition in one or more steps：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine

To be produced when producing comprising the additive combined and being used in spark-ignition internal combustion engine than in the engine The fuel composition of the few greasy filth of the greasy filth that is formed during using the fuel composition combined without the additive.

Data are also shown that the greasy filth control of the fuel composition of the combination of the aromatic compounds replaced comprising alkyl and polyene amine Performance processed is improved compared with the fuel composition of the aromatic compounds replaced comprising polyene amine but without alkyl.Include alkyl The greasy filth control performance of the fuel composition of the combination of substituted aromatic compounds and polyene amine and the aromatics replaced comprising alkyl The compound but performance of fuel composition without polyene amine is compared to also being improved.Correspondingly, in some instances, using bag The compositions of additives of combination containing following ingredients improves greasy filth control performance of the fuel composition in spark-ignition internal combustion engine：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.

Claims (15)

1. a kind of method for controlling spark-ignition internal combustion engine or the sludge formation in compression ignition gasoline engine, methods described bag Include to the engine and supply a kind of fuel composition, the fuel composition includes the combination of following ingredients：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.

2. following ingredients are controlled as the greasy filth in the fuel composition of spark-ignition internal combustion engine or compression ignition gasoline engine The purposes of additive：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.

3. a kind of sludge formation for reducing the fuel composition for spark-ignition internal combustion engine or compression ignition gasoline engine becomes The method of gesture, methods described includes being incorporated into the fuel composition in one or more steps：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine

To be produced when producing comprising the additive combined and being used in the engine than being used in the engine The fuel composition of the few greasy filth of the greasy filth that the is formed during fuel composition combined without the additive.

4. the compositions of additives of the combination comprising following ingredients is used to improve fuel composition in spark-ignition internal combustion engine or pressure The purposes of greasy filth control performance in point reduction fire gasoline engine：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.

5. the method for claim 1 or claim 3, or claim 2 or claim 4 purposes, wherein the alkyl takes The aromatic compounds in generation is Mannich base additive.

6. the method for any one of claim 1,3 and 5, or any one of claim 2,4 and 5 purposes, wherein the polyene amine It is PIBA.

7. the method for any one of claim 1,3,5 and 6, or any one of claim 2 and 4 to 6 purposes, wherein the alkyl Substituted aromatic compounds is present in the fuel composition with about 20 ppm to about 300 ppm activity concentration.

8. the method for any one of claim 1,3 and 5 to 7, or any one of claim 2 and 4 to 7 purposes, wherein the virtue The hydrocarbyl substituent of compounds of group shows the number-average molecular weight of about 700 to about 1500.

9. the method for any one of claim 1,3 and 5 to 8, or any one of claim 2 and 4 to 8 purposes, wherein the virtue The hydrocarbyl substituent of compounds of group is or comprising vistanex.

10. the method for any one of claim 1,3 and 5 to 9, or any one of claim 2 and 4 to 9 purposes, wherein described poly- Enamine is present in the fuel composition with about 50 ppm to about 500 ppm activity concentration.

11. the method for any one of claim 1,3 and 5 to 10, or any one of claim 2 and 4 to 10 purposes, wherein described Polyene amine contains the polyolefin group for the number-average molecular weight for showing about 700 to about 1500.

12. the method for any one of claim 1,3 and 5 to 11, or any one of claim 2 and 4 to 11 purposes, wherein described Polyene amine in fuel composition:The active weight ratio of the aromatic compounds of alkyl substitution is about 5:1 to about 1:5.

13. the method for any one of claim 1,3 and 5 to 12, or any one of claim 2 and 4 to 12 purposes, wherein described Engine is spark-ignition internal combustion engine.

Spark-ignition internal combustion engine or oil circuit and/or the method for lubrication in compression ignition gasoline engine are safeguarded 14. a kind of, it is described Method includes supplying a kind of fuel composition to the engine, and the fuel composition includes the combination of following ingredients：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.

15. following ingredients as the oil circuit in the fuel composition of spark-ignition internal combustion engine or compression ignition gasoline engine and/ Or the purposes of lubricated maintenance additive：

A. the aromatic compounds that alkyl replaces；With

B. polyene amine.