CN102482601A - Ashless controlled release gels for fuels - Google Patents

Ashless controlled release gels for fuels Download PDF

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Publication number
CN102482601A
CN102482601A CN2010800319303A CN201080031930A CN102482601A CN 102482601 A CN102482601 A CN 102482601A CN 2010800319303 A CN2010800319303 A CN 2010800319303A CN 201080031930 A CN201080031930 A CN 201080031930A CN 102482601 A CN102482601 A CN 102482601A
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Prior art keywords
fuel
acid
compsn
group
dope
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Chinese (zh)
Inventor
D·B·斯库沙
F·M·范莱尔
J·D·伯灵汤姆
G·A·伽尔文
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Lubrizol Corp
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Lubrizol Corp
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    • 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • 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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • 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
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1888—Carboxylic acids; metal salts thereof tall oil
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • 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
    • 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
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Abstract

The present invention relates to a control release gel for delivery of additives to fuels where the gel compositions are free of ash producing components, or are substantially free of ash producing components, such that the gel compositions of the present invention do not supply any ash to the fuel compositions with which they are used. Further, the invention provides for the use of such compositions in the operation of an internal combustion engine.

Description

The ashless controlled release gel that is used for fuel
Technical field
The present invention relates to one or more fuel dopes are released into the fuel dope controlled release gelatinous compsn in the fuel composition; Wherein gelatinous compsn is ashless basically to ashless; This is because in the engine operation process that uses this fuel; Promptly when consume fuel, the gelatinous compsn and/or the component that get into fuel do not produce any ash content.In addition; The present invention relates to gelatinous compsn, use the method for this gelatinous compsn operation mover and use the fuel-control assembly of this gelatinous compsn; Wherein this gelatinous compsn release additives is to fuel, need not add the component of containing metal (promptly producing ash content).
Background technology
Hope that it is ash free keeping fuel composition as far as possible, does not promptly comprise the component that contains the material (like metal) that might cause forming sulfate ash.Because this demand, fuel dope generally must low ashes or ashless.The ash-free fuel additive is favourable, because their protection finishing apparatuss also can reduce sedimental formation in the oil engine.
Owing to oxidation, temperature effect, in mover or similar devices operational process abominable sometimes chemical environment and many other reasons of fuel system, fuel dope can diminish along with time degraded and/or validity.In other cases; Can be benefited from adding fuel dope at mover run duration fuel composition, but before the fuel system that it is supplied to mover and/or mover these additives to be joined in the fuel before bringing into operation can be inconvenient and/or unpractiaca and/or infeasible.
The gelatinous compsn of use controlled release is considered to additive is supplied to the means of functional fluid such as machine oil.The ashless gelatinous compsn of use controlled release is considered to additive is supplied to the means of functional fluid such as machine oil.Referring to the open 2008-0015126 of US patented claim.
The present invention relates to thereby one or more ash-free fuel additives have been improved the motor performance of using said fuel from ash-free fuel additive gel compsn controlled release to fuel, and use therein gelatinous compsn.
The invention summary
The present invention provides a kind of fuel dope gelatinous compsn, comprising: a) the soluble dispersion agent of fuel; B) the soluble acid of fuel, it is selected from the group that and the following is formed: contain in the skeleton in the tensio-active agent that contains acidic-group in the acid, polyprotonic acid compound, skeleton of the polymer formation of acidic-group, the skeleton and contain emulsifying agent of acidic-group and composition thereof; And c) randomly at least a other fuel dope; Wherein gelatinous compsn does not contain the component that produces ash content basically, and wherein gelatinous compsn can discharge its fuel composition a kind of or the various ingredients entering contacts with it in time.
The present invention further provides the fuel dope gelatinous compsn, and wherein fuel dope gel at least 50% dissolves in the fuel that uses it, is benchmark with weight.In other words, at least 50% gel originally is soluble and originally soluble in fuel less than 50% gel in fuel.Also comprise ashless basically and complete ashless gelatinous compsn, just gelatinous compsn only comprises ashless or ashless basically component and gelatinous compsn only comprises ashless component.
The present invention also provides a kind of method of operation of combustion engine, comprising:
1) fuel system of one or more fuel dope gelatinous compsn to oil engines is provided, wherein the fuel dope gelatinous compsn can be any embodiment described here; With 2) during internal combustion engine operation, fuel is contacted with the fuel dope gelatinous compsn, make at least a additive controlled release in the fuel dope gelatinous compsn to fuel; With 3) supply said fuel to mover at the mover run duration.
The present invention also provides a kind of fuel-control assembly, comprises fuel dope gelatinous compsn and the equipment that comprises said gelatinous compsn; Wherein the fuel dope gelatinous compsn can be any embodiment described here; Wherein this fuel-control assembly can be placed on oil engine fuel system the inside and/or be connected with it.Fuel-control assembly allows the fuel of fuel system to contact with the fuel dope gelatinous compsn, makes the mover run duration at supply of fuel to mover.
Detailed Description Of The Invention
The present invention provides a kind of fuel dope gelatinous compsn, and a kind of or various ingredients sustained release is to fuel with it.The component of gelatinous compsn is ashless basically and/or ashless, makes gelatinous compsn of the present invention in the mover that uses the associated fuel compsn, not supply and/or cause and forms any ash content.
The gel of controlled release comprises: a) the soluble dispersion agent of fuel; B) the soluble acid of fuel, it is selected from the group that and the following is formed: contain in the skeleton in the tensio-active agent that contains acidic-group in the acid, polyprotonic acid compound, skeleton of the polymer formation of acidic-group, the skeleton and contain emulsifying agent of acidic-group and composition thereof; And c) randomly at least a other fuel dope.
The compositions of additives form is a gel.Said composition is the mixture of ashless dispersant and acid, when combining, forms gel.The gel of controlled release does not contain the component that produces ash content basically, and is not containing the component that produces ash content in the embodiment in addition.
Gel is the material that comprises the mixture of two kinds or more kinds of materials, more to exist as the semi-solid state of solid rather than liquid.A kind of gel to be more to exist as the semi-solid state of solid rather than liquid, referring to Parker, and Dictionary of Scientific and Technical Terms, Fifth Edition, McGraw Hill, (c) 1994.Also can be referring to Larson; " The Structure and rheology of Complex Fluids ", Chapter 5, Oxford University Press; New York; New York,
Figure BPA00001515637100031
1999, each is incorporated among the present invention as quoting.The rheological property of gel can be measured through the small amplitude oscillation shearing test.This commercial measurement gel constitutional features and produce the term that is called storage modulus represent the storage elasticity energy and the out-of-phase modulus of representing the energy viscous loss.The ratio of out-of-phase modulus/storage modulus is called loss tangent, or " tan Δ ", should be worth>=1 for the material as liquid, should be worth≤1 for picture solid material.In one embodiment, additive gel has approximately≤1 or≤0.95 tan Δ value, about in another embodiment≤0.75, its in another embodiment about≤0.5 or≤0.3.
Gelatinous compsn also can use the taper penetrometer to estimate according to ASTM D 217.The taper penetrometer that obtains (awl pen) value is that gel rigidity and/or firmness one measures.In one embodiment, the awl pen value of fuel dope gelatinous compsn of the present invention is 300 or still less, 200 or still less, or from 30 to 200, or from 40 to 165.
Fuel dope gelatinous compsn of the present invention comprises at least two kinds when it is combined to form the additive of gel.In some embodiments, the fuel dope gel prepares through combining ashless basically dispersion agent and ashless basically acid to form gel.In one embodiment, additive gel does not comprise any purification agent that contains ash content, includes but not limited to the overbased metal sulphonath purification agent.In one embodiment, gel forms through combined acid and ashless succinimide dispersants.In one embodiment, ashless dispersant is from about 1: 100 to about 100: 1 with the ratio of acid, in another embodiment from about 1: 50 to about 50: 1, or from 10: 1 to about 1: 10 or from 5: 1 to about 1: 5. The soluble dispersion agent of fuelThe soluble dispersion agent of suitable fuel comprises the additive that generally can be described as dispersion agent or purification agent.Dispersant additives is commonly referred to purification agent when in fuel applications, using.In the present invention, the soluble dispersion agent of fuel had both comprised the additive that is commonly referred to as dispersion agent, had also comprised the fuel dope that is commonly referred to as purification agent equally.Dispersion agent component of the present invention can comprise mannich dispersant, polymeric dispersant, carboxyl dispersion agent, amine dispersion agent and combination and mixture.Suitable dispersion agent is ashless basically to ashless fully, and wherein ashless finger does not contain the component or the group of any generation ash content.In one embodiment, dispersion agent is the polyisobutenyl succinimide dispersion agent.
Suitable dispersion agent also dissolves in the fuel composition that uses gelatinous compsn.In some embodiments, dispersion agent dissolves in one or more fuel described herein.Dispersion agent dissolves in gasoline, diesel oil fuel, biofuel or its combination in some embodiments.To more describe term used herein " fuel is solvable " in detail below.
The characteristics of ashless type dispersants are that polar group is connected on the hydrocarbon chain with higher molecular weight.Typical ashless dispersant comprises the substituted long chain alkenyl succinimides of the N-with chemical structures, generally comprises:
Figure BPA00001515637100041
Each R wherein 1Be alkyl independently, be generally the polyisobutenyl that molecular weight is 500-5000, and R 2Be alkylene group (alkenylene group), be generally inferior second (C 2H 4) base.Succinimide dispersants is described in USP 4234435 more fully, incorporates the present invention into as quoting.The dispersion agent of in this patent, describing is effective especially for gel produced according to the present invention.
In some embodiments, the ashless dispersant component is a kind of ashless dispersant such as polyisobutenyl succinimide and analogue thereof.Polyisobutenyl succinimide ashless dispersants is commodity; Normally reacted by polyisobutene with about 300 to 10000 number-average molecular weights (" Mn ") and maleic anhydride one and form polyisobutylene succinic anhydride (" PIBSA "), products obtained therefrom and the per molecule polyamines that contains 1 to 10 ethyleneimino usually reacts and prepares then.The gained dispersion agent is formed by the mixture of different compounds usually, can characterize through various variable, and the amine that comprises it replaces the degree (equivalence ratio of promptly amino and carboxyl; Or N: CO ratio); Its maleic anhydride level of conversion (be the mol ratio of the PIB in its acid anhydrides and the PIBSA structure, like institute's definition in the USP 4234435, document conduct is quoted at this and incorporated the present invention into); The Mn of its PIB group, and preparation method (hot auxiliary succinic acid esterification (succination) vs.Cl 2-auxiliary succinic acid esterification).Also can use similar compound with other polyamines (like polypropylene-base) preparation.For example USP 4234435 has been described such ashless dispersant, and the document is incorporated the present invention into as quoting at this.
The N of general these polyisobutenyl succinimide ashless dispersants: CO is more typically about 0.7 to 1.4 or even 0.7 to 1.2 than for about 0.6 to 1.6.In addition or selectively, it is about 1.3 that the maleic anhydride level of conversion of these polyisobutenyl succinimide ashless dispersants is at least usually, be more typically at least 1.5 or even 1.6 or more than.In addition or selectively, the Mn of the polyisobutene of these polyisobutenyl succinimide ashless dispersants part is general >=about 350, more generally at least 1200, at least about 1500 or even 1800 or more than.In addition or selectively, these polyisobutenyl succinimide ashless dispersants also adopt Cl 2-auxiliary succinic acid esterification rather than hot auxiliary succinic acid esterification preparation, because compare with thermogenetic PIBSAs, this produces higher PIBSAs and transforms (thermogenetic PIBSAs is called as DA or direct addition PIBSAs).
Mannich dispersant is that wherein alkyl group comprises at least about the alkylphenol of 30 carbon atoms and the product of aldehyde (particularly formaldehyde) and amine (especially polyalkylenepolyamines) reaction.Mannich base (comprising various isomer and analogue) with following general structure attracts people's attention especially.
Figure BPA00001515637100051
Another kind of ashless dispersant is nitrogenous carboxyl dispersion agent.The example of these " carboxyl dispersion agents " is described in USP 3219666.
The amine dispersion agent is the reaction product of relative high-molecular weight aliphatic halide and amine (preferred polyalkylenepolyamines).The example has description in USP 3565804.
Polymeric dispersant be oily lyotropy monomer such as decyl-octyl methacrylate, vinyl ether in the last of the ten Heavenly stems and high molecular weight olefin and the monomer that contains polar substituent (as acrylic-amino alkyl ester or acrylic amide with gather-(oxygen ethene)-substituted propenoate) interpolymer.The example of corresponding polymer dispersion agent is open in following USP: 3329658 and 3702300.
Dispersion agent also can carry out aftertreatment through reacting with any all ingredients.Urea, thiocarbamide, dimercapto thiazole, dithiocarbonic anhydride, aldehyde, ketone, carboxylic acid, the substituted succinyl oxide of hydrocarbon, nitrile, epoxide, boron cpd and phosphorus compound are wherein arranged.
Ashless dispersant described herein can be used alone or in combination.The dispersion agent component can be from about 0.001wt% to about 99.5wt%, and 0.01% to 50%, or the existence of 0.05% to 25% scope.The dispersion agent scope that possibly exist in other embodiments, from about 1wt% to about 70wt% gel, or from about 5wt% about 50wt% extremely, in the gross weight of gel.
Acid constituentsAcid constituents can comprise the polymkeric substance that contains acidic-group in the skeleton; For example; Polymkeric substance derived from vinylbenzene and maleic anhydride; The polymkeric substance of derived from propylene esters of gallic acid (comprising vinylformic acid, propenoate, methylacrylic acid and ester thereof) is derived from the polymkeric substance of HMW (Cn is n≤12 wherein) ester with acid, derived from the polymkeric substance of the maleic anhydride-styrene copolymers of esterification; But derived from the also maleic anhydride of partial esterification and the polymkeric substance of terminal olefin, derived from the polymkeric substance of the ethylene propylene diene monomer multipolymer of MAA-grafting esterification; The tensio-active agent that contains acidic-group in the skeleton; The emulsifying agent that contains acidic-group in the skeleton; Polyprotonic acid compound, for example polyprotonic acid tensio-active agent and/or polyprotic dispersing agents; Functional derivative of listed every kind of component and composition thereof here.
In one embodiment, acid is formed by vinylbenzene and maleic anhydride polymerization.In one embodiment, this multipolymer is used one or more C 6To C 32Use C in alcohol or alcohol mixture partial esterification and another embodiment 8To C 18The alcohol moiety esterification.Alcohol and the equivalence ratio of acid groups be about 0.45wt% about 0.95wt% extremely from about 0.1wt% to about 0.99wt% with in another embodiment.In one embodiment, this polyprotonic acid tensio-active agent comprises maleation OCP (olefin copolymer of ethene and propylene).This acid is the maleation multipolymer of terminal olefin and/or the multipolymer of maleation terminal olefin in another embodiment.In another embodiment, this polyprotonic acid tensio-active agent comprises polyisobutene Di Sukan (disuccan), derives from the reaction of polyisobutene and maleic anhydride.In one embodiment, polyprotic dispersing agents comprises the succinimide that is generated by＜1 normal quadrol polyamines and maleation OCP reaction.In another embodiment, this polyprotic dispersing agents comprises the succinimide that is generated by＜1 normal quadrol polyamines and polyisobutene Di Sukan (disuccan) reaction.This TAN >=1, (like KOH/g, and oil is 75cSt when accounting for 100 ℃ of about 10% o'clock oil blend viscosity, and is 10cSt 100 ℃ the time in another embodiment in TAN >=3 in another embodiment.In one embodiment, acid must have the residual acid group of total acid value >=1 and in another embodiment >=3.
Suitable acid also dissolves in the fuel composition that will use gelatinous compsn.In some embodiments, acid dissolves in one or more fuel described herein.In some embodiments, acid dissolves in gasoline, diesel oil fuel, biofuel or its combination.To more describe term used herein " fuel is solvable " in detail below.
Acid can be used alone or in combination.Acid constituents can be from about 0.01wt% to about 99.5wt%, and 0.1% to 75%, or the existence of 1% to 50% scope.In other embodiments, acid constituents is from about 0.1wt% to about 90wt%, or about 1wt% is to the scope existence of about 80wt%.
Other optional fuel dopeGenerally, the fuel dope gelatinous compsn further comprise at least a other additive with controlled release in fuel.These other additives can comprise viscosity modifier, friction modifiers, ashless detergent, cloud point depressant, pour point reducer; Emulsion splitter, FLOW IMPROVERS, static inhibitor, the ashless dispersant beyond described in the component (a); Ashless inhibitor, skimmer, corrosion/rust inhibitor, anti-extreme pressure agent/anti-wear agent; Sealed expander, lubricating auxiliary agent, antifogging agent, and their mixture; Thereby other additive controlled release that gel will be chosen wantonly along with the time when the fuel dope gelatinous compsn contacts with fuel is to fuel.Other optional binder component can be from about 0wt% to about 95wt%, and 30% to 95%, or the existence of 40% to 95% scope, in the gel gross weight.
Other performance additive can be added in the fuel composition through gelatinous compsn of the present invention; And the selection of these additives can be depending on Several Factors, comprising the operational condition of fuel used type, fuel mass and mover operation of the type of oil engine and mover.
This other performance additive can comprise: inhibitor such as hindered phenol or derivatives thereof and/or diarylamine or derivatives thereof; Corrosion inhibitor; And/or purification agent/dispersant additives, except fuel dope of the present invention,, include but not limited to PIB amine dispersion agent, quaternary ammonium salt dispersants and succinimide dispersants like polyetheramine or nitrogenous purification agent.
This other performance additive also can comprise: the multipolymer of cold flow improver such as maleic anhydride and cinnamic esterified copolymer and/or ethene and vinyl-acetic ester; Froth suppressor and/or skimmer such as silicone fluid; Emulsion splitter is as gathering alkoxyl alcohol; Lubricant such as aliphatic carboxylic acid; Metal passivator such as aromatic triazole or derivatives thereof include but not limited to benzotriazole; And/or valve seat rollback additive (recession additive) is like basic metal sulphur SUMATRIPTAN SUCCINATE.
Suitable skimmer also comprises organosilicon such as YSR 3286, gathers ethylsiloxane, gathers di-ethyl siloxane, polyacrylic ester and Rohm tech inc, trimethylammonium-three fluoro-propyl group methylsiloxane and analogue thereof.
Other additive also can comprise microbiocide; Static inhibitor, deicing agent, liquid agent such as MO and/or gather (terminal olefin) and/or polyethers and ignition dope such as octane or n-Hexadecane improving agent.
Other performance additive that can in fuel additive composition of the present invention and fuel composition, exist also comprises by diprotic acid (like tartrate) and/or triprotic acid (like Hydrocerol A) and amine and/or pure diester, diamide, esteramides and the ester imide friction modifiers of choosing prepared in reaction in the presence of known esterifying catalyst wantonly.These friction modifiers generally derived from tartrate, Hydrocerol A, or derivatives thereof, also can make friction modifiers originally in its structure, have a large amount of branched hydrocarbyl radical derived from the amine and/or the alcohol of branching.The example that is used to prepare the suitable branching alcohol of these friction modifiers comprises 2-Ethylhexyl Alcohol, different tridecyl alcohol, Guerbet alcohol or its mixture.
Other performance additive can comprise aforesaid one or more dispersion agents, and this dispersion agent that understanding exists as other fuel dope can be different with one or more dispersion agents that constitute said components.
Other performance additive can comprise the quaternary salt that contains following reaction product: (i) at least a compound; Be selected from: (a) acylating agent of hydrocarbyl substituted with have can with the condensation product of the compound of the oxygen of said acylating agent condensation or nitrogen-atoms, and said condensation product also has tertiary amino group; (b) has the substituted amine of polyalkylene of at least one tertiary amino group; (c) have the mannich reaction products of tertiary amino group, said mannich reaction products is by phenol, aldehyde and the amine prepared in reaction of hydrocarbyl substituted; (ii) be suitable for converting the tertiary amino group of compound (i) into the quaternizing agent of quaternary nitrogen, wherein this quaternizing agent is the for example carbonate of dialkyl sulfate, benzyl halogenide, hydrocarbyl substituted of alkylphenol agent; With sour bonded alkyl epoxide or its mixture.
Be described in instance of quaternary ammonium salt and preparation method thereof patent below, incorporate the present invention into, US4253980, US3778371, US4171959, US4326973, US4338206 and US5254138 as quoting at this.
Suitable skimmer comprises silicone resin, like YSR 3286, gather ethylsiloxane, gather di-ethyl siloxane, polyacrylic ester and Rohm tech inc, trimethylammonium-three fluoro-propyl group methylsiloxane etc.
That suitable anti-propellant comprises is very high (＞100,000Mn) polyolefine, (for example trade(brand)name is Vistanex like the polyisobutene of 1.5Mn RMaterial), or contain 2-(N acrylamide base), the 2-methyl propane sulfonic acid (is also referred to as AMPS R) polymkeric substance, or derivatives thereof etc.
Suitable corrosion inhibitor comprises alkylating succsinic acid and acid anhydride verivate thereof, organophosphate etc.
Ashless metal passivator comprises OR 10154 such as tolyl-triazole, N; N-two (heptyl)-ar-methyl isophthalic acid H-benzotriazole-1-methylamine, N; N-two (nonyl)-ar-methyl isophthalic acid H-benzotriazole-1-methylamine, N; N-two (decyl) ar-methyl isophthalic acid H-benzotriazole-1-methylamine, N; N-(undecyl) ar-methyl isophthalic acid H-benzotriazole-1-methylamine, N, N-two (dodecyl) ar-methyl isophthalic acid H-benzotriazole-1-methylamine, N, N-two (2-ethylhexyl)-ar-methyl isophthalic acid H-benzotriazole-1-methylamine and composition thereof.Metal passivator is N in one embodiment, N-two (1-ethylhexyl) ar-methyl isophthalic acid H-benzotriazole-1-methylamine; 1,2,4-triazole, benzoglyoxaline, 2-alkyl dithio benzoglyoxaline; 2-alkyl dithio benzothiazole; 2-N, N-dialkyl dithio-formamyl) benzothiazole; 2,5-two (alkyl-dithio)-1,3,4-thiadiazoles be as 2,5-two (uncle-octyl group dithio)-1,3; 4-thiadiazoles, 2,5-two (uncle-nonyl dithio)-1,3,4-thiadiazoles, 2,5-two (uncle-decyl dithio)-1,3; 4-thiadiazoles, 2,5-two (uncle-undecyl dithio)-1,3,4-thiadiazoles, 2,5-two (uncle-dodecyl dithio)-1,3; 4-thiadiazoles, 2,5-two (uncle-tridecyl dithio)-1,3,4-thiadiazoles, 2,5-two (uncle-tetradecyl dithio)-1,3; 4-thiadiazoles, 2,5-two (uncle-octadecyl dithio)-1,3,4-thiadiazoles, 2,5-two (uncle-nonadecyl dithio)-1; 3,4-thiadiazoles, 2,5-two (uncle-eicosyl dithio)-1,3,4-thiadiazoles and composition thereof; 2,5-two (N, N-dialkyl dithio formamyl)-1,3,4-thiadiazoles; 2-alkyl dithio-5-dimercaptothiodiazole etc.
Emulsion splitter comprises Vilaterm and polypropylene oxide multipolymer etc.Emulsion splitter can be used alone or in combination.
Lubricating auxiliary agent comprises XU 61518.10, sorbitan monooleate etc.Slip additive also comprise additive with acid functionality with and ester and amide derivatives, wherein suitable reagent comprises 8 to 50 carbon atoms usually.Slip additive can be used alone or in combination.FLOW IMPROVERS comprises vinyl-vinyl acetate copolymer etc.
Cloud point depressant and pour point reducer comprise alkylphenol and verivate thereof, vinyl-vinyl acetate copolymer, fumarate-vinyl acetate copolymer etc.
Sealed expander includes organic sulfur compound such as thiophene, 3-(oxygen base in the last of the ten Heavenly stems) tetrahydrochysene-1,1 dioxide, phthalic ester etc.
Randomly, can other component be added into the fuel dope gelatinous compsn, comprise fuel, base stock, inert support, dyestuff, fungistat, solid particulate additive etc., as long as these components do not stop the formation of gel and/or gel is had detrimentally affect.
FuelThe fuel that can use fuel dope gelatinous compsn of the present invention is not by excessive restriction, as long as the component of gelatinous compsn is that fuel is enough soluble.Fuel is soluble at least a little for all components of gelatinous compsn in some embodiments.All in other embodiments gel components fuel basically are soluble.Gelatinous compsn itself must be at least a little in other embodiments, or fuel is soluble basically.In another other embodiment, gained gelatinous compsn and its component both must be at least a little, or fuel is soluble basically.In some embodiments, fuel dope gel at least 50% of the present invention dissolves in the fuel that uses it, is benchmark with weight.
Here with claim in the term " fuel is solvable " that uses might not mean that all compsns in question and/or component can the miscible or dissolvings of any ratio in all fuel.More precisely, its purpose is meant that compsn is solvable in fuel (hydrocarbon, nonhydrocarbon, mixture etc.), and wherein it is meant to work to a certain extent and allows solution to show one or more required performances.Equally, this " solution " to there is no need be real solution on strict physics or the chemical sense.They can replace microemulsion or aqueous colloidal dispersion, for the purposes of the present invention, show enough those character near true solutions, and from practical purpose, they can exchange within the scope of the present invention.
Suitable fuel is those fuel that can be used for IC engine supply.In some embodiments, the fuel of suitable the present invention's use comprises that any commerce can get fuel and any in some embodiments commerce can get diesel oil fuel and/or biofuel.
The fuel that is fit to the present invention's use is not by excessive restriction.In general, suitable fuel is liquid down in envrionment conditions such as room temperature (20 ℃～30 ℃) usually.Liquid fuel can be a hydrocarbon fuel, nonhydrocarbon fuel (non-petroleum-based fuel), or its mixture.
Hydrocarbon fuel can be a petroleum distillate, comprises by defined gasoline of the standard specifications D4814 of american society for testing and materials (ASTM) or the defined diesel oil fuel of the standard specifications D975 of american society for testing and materials (ASTM).Liquid fuel is a gasoline in one embodiment, and liquid fuel is a white gasoline in another embodiment.Liquid fuel is a diesel oil fuel in another embodiment.Hydrocarbon fuel can be to be comprised for example through the hydrocarbon like the Fischer-tropsch process preparation by the hydrocarbon that gas to liquid process prepares.In some embodiments, the present invention is fuel used is diesel oil fuel, biodiesel fuel or its combination.
Nonhydrocarbon fuel can be to contain the oxygen compsn, is commonly referred to oxygenate, and it comprises alcohol, ether, ketone, carboxylicesters, nitroparaffins or its mixture.Nonhydrocarbon fuel can comprise like the transesterify of methyl alcohol, ethanol, MTBE, methyl ethyl ketone, plant and animal and/or non-esterified oil and/or fatty, like vegetable seeds methyl ester and soybean methyl ester and/or vegetables oil, and Nitromethane 99Min..
Hydrocarbon and nonhydrocarbon fuel mixture can comprise like gasoline and methyl alcohol and/or ethanol, diesel oil fuel and ethanol, and the vegetables oil of diesel oil fuel and transesterify such as vegetable seeds methyl ester and other biologically-derived fuel.Also can use biodiesel fuel, comprise the various blends of biofuel, include but not limited to the blend of scope from B100 and B99.9 to B20 and B2.Liquid fuel is the emulsion of water in hydrocarbon fuel, nonhydrocarbon fuel or its mixture in one embodiment.Liquid fuel can have in some embodiments of the present invention, is benchmark with weight, 5000ppm or still less, 1000ppm or still less, 300ppm or still less, 200ppm or still less, 30ppm or still less or 10ppm or sulphur content still less.
Liquid fuel of the present invention exists with main amount in fuel composition, generally greater than 95wt% with in other embodiments with greater than 97wt%, exist greater than 99.5wt% or greater than 99.9wt%.
Industrial applicationThe invention provides a kind of method of operation of combustion engine in one embodiment.The fuel dope gelatinous compsn can be in fuel filter or fuel circuit jar or any other means that make gel contact with fuel be passed to fuel; Comprise the embodiment that wherein fuel and fuel dope gel contact in hold-up vessel; Be supplied to the fuel fuel system of incendiary oil engine therein then, fuel contacts in the fuel system of oil engine with the fuel dope gel in other embodiments.Can use any container/transfer equipment in the fuel system.
The fuel dope gelatinous compsn can be placed in the fuel system, and anywhere gel will contact with fuel, includes but not limited to be placed on the fuel container in the fuel system; Fuel filter, fuel circuit, case lid; The fuel bypass circulation, jar and/or cover and/or bag and/or bag.The fuel dope gelatinous compsn can be included in and be arranged in engine fuel system the inside and/or connected fuel-control assembly (as comprise the fuel filter of gelatinous compsn and/or contain the fuel tank cap of a certain amount of fuel composition).This gelatinous compsn can exist in one or more positions in fuel system, can use the different preparatons of gelatinous compsn in each position.
In one embodiment, gel is arranged in any position of fuel filter.This strainer is an ideal position of placing gel because can remove gel and/or exhausted gel at an easy rate, and in the refuelling strainer gel that more renew and/or recycling.
Gel need contact fuel, the gel that contacts with fuel in one embodiment account for fuel system about 100% to about 1%, about 75% to about 25%, be benchmark with the volume and/or be benchmark with the fuel flow rate.Gel contacts with fuel with the scope that accounts for fuel system about 50% in another embodiment, is benchmark with the volume and/or is benchmark with the fuel flow rate.
Fuel additive component depends primarily on gel formulation from the rate of release of gel to fuel.Rate of release also depends on the form and/or the addition manner of gel.This gel can be positioned at and make special additive obtain specified and required dissolution rate and the desired position.The preparaton of gel can be made up of one or more components, the optionally dissolving fully in fuel of this component, or be partly dissolved and make the part component remain to finish in its in work-ing life, or its combination.
Gel adds fuel system through any known method, depends on the desired form of gel, required interpolation speed, required rate of release, required operational mode and/or above-mentioned any combination.In one embodiment compositions of additives be gel and through the container in syringe pump or the fuel filter or be installed in fuel container and mover between burning line on online tube add fuel system to.Gel adds fuel system to through interpolation equipment such as screw feeding system (auger system) in one embodiment.
The performance of giving through the fuel dope that is sent to fuel in one embodiment comprises dispersiveness, oxidation-resistance, corrosion-inhibiting, anti-wear, anti-scratch, anti-spot corrosion (comprising microcosmic and macroscopical spot corrosion), improves pour point control, foam control or its mixing of frictional behaviour (comprise and increase and/or reduce frictional coefficient), detergency, use viscosity modifier.
Term used herein " hydrocarbyl substituent " or " hydrocarbyl group " use with the well-known general meaning of those skilled in the art.Specifically, it is meant that carbon atom is connected directly to the molecule remainder and mainly contains the group of hydrocarbon characteristic.The example of hydrocarbyl group comprises: hydrocarbon substituent; I.e. aliphatic (for example alkyl or alkenyl); Alicyclic (for example naphthenic base or cycloalkenyl group) substituting group; With aromatics, aliphatic series and alicyclic substituted aromatic substituent, and wherein encircle the cyclic substituents of accomplishing through other part of molecule (for example two substituting groups form ring together); Substituted hydrocarbon substituent; The substituting group that in context of the present invention, promptly contains non-hydrocarbyl group does not change substituent dominant hydrocarbon characteristic (like halogen (especially chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group and sulphur oxygen base (sulfoxy)); Hetero atom substituents, though dominant hydrocarbon characteristic is promptly arranged in context of the present invention, otherwise contain the substituting group of the atom beyond the carbon in the ring formed by carbon atom or the chain.Heteroatoms comprises sulphur, oxygen, and nitrogen, and comprise substituting group such as pyridyl, furyl, thienyl and imidazolyl.Generally per ten carbon atoms existence are no more than two in alkyl, preferably are no more than a non-hydrocarbon substituent; Usually in alkyl, there is not non-hydrocarbon substituent.
As everyone knows, more above-described materials possibly interact in last preparaton, make that the component of final preparaton maybe be different with those of initial adding.For example metals ion (for example in the purification agent) can be moved to other acidity or the anion site of other molecule.The product that forms thus comprises the product that uses compsn of the present invention in its set purposes, to form, and possibly be not easy simple description.Yet all these modifications and reaction product all comprise within the scope of the present invention; The present invention includes through mixing the compsn of component preparation mentioned above.
Specific embodiments
The present invention will further specify through following Example, wherein propose useful especially embodiment.But example is to be used for explaining the present invention, rather than limits it.
Prepare various ash-free fuel additive gel compsns through the component of in the following table each embodiment being listed is mixed, the value in table is PBW.Every kind of mixture is 100 ℃ of maintenances at least 1 hour, but is no more than 8 hours, so that mixture solidified forms gel.
Table 1-is in the gelatinous compsn preparaton of PBW embodiment
The 1-oleic acid glyceride also is called as XU 61518.10.
2-TOFA is a ready denier oil acid.
3-Ethomeen T/12 is the tensio-active agent available from Akzo Nobel.
The 4-MSC multipolymer is the maleic anhydride/styrol copolymer with the mixture partial esterification of the C16-18 alcohol that contains 40% MO.
The 5-dispersion agent is the ashless dispersant by the DA PIBSA of number-average molecular weight 2000 and Triethylenetetramine (TETA) preparation.
6-actives per-cent is not to be the weight percent of the gelatinous compsn of gel matrix part, is not interact to form gel and be included in the per-cent that in the gel and when compsn uses, is discharged into the additive of the existence in the fuel.
7-taper penetrometer observed value uses a 1/4Pen is according to ASTMD 217 measurements and with ten of unjustified ratio/several millimeters records.Liquid can not obtain taper penetrometer observed value.
Prepare two comparative examples, use as above-mentioned identical component but these embodiment do not form gelatinous compsn, even reach a plurality of hours 100 ℃ of curing.Said composition is a viscous liquid.
Table 2-is in PBW comparative example's gelatinous compsn preparaton
Component Contrast Ex1 Contrast Ex2
Oleic acid glyceride 1
TOFA 2 80 90
Ethomeen?T/12 3
MSC?Copoly 4 16 8
Dispersion agent 5 4 2
The % actives 6 80 90
The awl pen 7 Liquid Liquid
See table 1 footnote.
Through 1.3 gram gelatinous compsns being added 50 gram normal benzene samples, measure embodiment 1 and 2 to estimate its whole solubleness in fuel.This sample remains on 23 ℃ and stirred overnight.After the test, observations is following: 72% has been dissolved into (consider preparaton, this gel matrix material that shows all activess of 25% and 63% has been delivered to fuel) in the fuel among the embodiment 1; 62% be dissolved in the fuel among the embodiment 2 (all activess of 40% and 36% gel matrix material).
Embodiment 2,3, and 4,9,10 and 11 have also carried out test to estimate its solubleness in fuel.The small amount of gel compsn of each listed embodiment is added in the standard diesel fuels of measuring vol and form fuel sample, wherein embodiment 2,3 and 4 is carried out the 1wt% Gel Treatment; Embodiment 9,10 and 11 is carried out the 0.33wt% Gel Treatment.Stir each sample and kept 3 days at 23 ℃.When EOT, all samples show to surpass 50% gel sample and has been dissolved in the fuel composition to be dissolved in 100% gel and uses in the sample that embodiment 4,9 and 10 handles.
Embodiment 9,10,11 and 12 is tested to estimate its influence to the HFRR test result.Sample is estimated according to ASTM D6079 in the HFRR test that is used for diesel oil fuel.In all tests, (comprise the baseline operation) and all use Startex chemistry diesel oil fuel A.Each fuel sample that is used to test is handled the diesel oil fuel preparation through the gelatinous compsn that uses 0.3% embodiment.All fuel sample through preparing at 23 ℃ of following propellant combinations and gel in 3 days.For the fuel sample of using embodiment 12, discharge test period fuel at vehicle and mix with gel.The HFRR test result is summarized in following table:
Table 3-HFRR test result
Figure BPA00001515637100151
The 1-average film thickness is the measuring of contact resistance (contact resistance) between ball and the disk, is measured by HFRR software.
2-COF is the frictional coefficient that the function calculation as the frictional force/load of executing goes out.
The grinding defect diameter of finding on the ball when 3-polishing scratch is EOT is with the micron record.
The result shows, has increased average film thickness through HFRR thermometrically gelatinous compsn of the present invention when being added into fuel, reduces frictional coefficient, and reduces polishing scratch.Gelatinous compsn of the present invention and material that to fuel composition in do not add any generation ash content solvable because of its fuel provides this advantage.
Though described embodiments more of the present invention for above, should be realized that and to carry out many modifications and do not break away from essence of the present invention and scope.All such modifications all are included in only by in the scope of the invention of following claim qualification.
Every part of file above-mentioned is incorporated this paper into as quoting.Remove in embodiment, or clearly expression is arranged in addition, all numerical quantities in describing material specified quantity, reaction conditions, molecular weight, carbonatoms etc. are interpreted as revising through " pact ".All percent value and ppm value are weight percent values and/or are that benchmark calculates with weight here except as otherwise noted.Except as otherwise noted, every kind of chemical or compsn that this paper mentions should be interpreted as the commercial grade material here, and it can comprise isomer, sub product, verivate and be generally understood as other this materials that exist with commercial grade.Yet the quantity of every kind of chemical composition is got rid of any solvent or the thinner that possibly in proprietary concentrate, exist usually, except as otherwise noted.Quantity, scope and the ratio that should understand the upper and lower bound that proposes here can be by independent combinations.Equally, the scope of each key element of the present invention and quantity can be used with the scope or the quantity of any other key element.As used herein, statement " basically by ... form " allow to comprise not the material that the basic and novel characteristics of the compsn in considering is produced materially affect.
In addition, above-mentioned all embodiments and all above-mentioned other embodiments can expect that all it is independent and unite use and these combinations are considered to a part of the present invention.Expect that the specific embodiments of above-mentioned amine and alcohol combines with the specific embodiments of useful in the present invention carboxylic acid.

Claims (15)

1. fuel dope gelatinous compsn comprises:
A) the soluble dispersion agent of fuel;
B) the soluble acid of fuel, it is selected from the group that is made up of and the following: contain in the skeleton in the tensio-active agent that contains acidic-group in the acid, polyprotonic acid compound, skeleton of the polymer formation of acidic-group, the skeleton and contain emulsifying agent of acidic-group and composition thereof; With
C) at least a other fuel dope of choosing wantonly;
Wherein gelatinous compsn does not contain the component that produces ash content basically, and wherein gelatinous compsn can discharge its fuel composition a kind of or the various ingredients entering contacts with it in time.
2. the fuel dope gelatinous compsn of claim 1, wherein fuel dope gel at least 50% dissolves in the fuel that uses it, is benchmark with weight.
3. each fuel dope gelatinous compsn among the claim 1-2, wherein the fuel dope gelatinous compsn comprises ashless component fully, and wherein dispersion agent is about 0.01: 1 to about 100: 1 with the weight ratio of acid; Tan Δ value≤1 of gel wherein.
4. each compsn among the claim 1-2, wherein dispersion agent exists with the scope from about 0.001wt% to about 99.5wt%, and is preferred 0.01% to 50%, and more preferably 0.05% to 25%; Wherein acid with from about 0.01wt% extremely the scope of about 99.5wt% exist, preferred 0.1% to 75%, more preferably 1% to 50%; Other wherein optional additive with from about 0wt% extremely the scope of about 95wt% exist, preferred 30% to 95%, more preferably 40% to 95%, in the gross weight of gel.
5. each compsn among the claim 1-4; Wherein the dispersion agent component comprises one or more dispersion agents, is selected from by mannich dispersant, polymeric dispersant, carboxyl dispersion agent, amine dispersion agent, polyisobutenyl succinimide dispersion agent and the group that forms thereof; Wherein the dispersion agent component is that fuel is soluble and do not contain the component that forms ash content basically.
6. each compsn among the claim 1-5, wherein acid constituents comprises the acid derived from polymkeric substance, this polymkeric substance is selected from the group that and the following is formed: derived from vinylbenzene and maleic anhydride polymeric polymkeric substance; The polymkeric substance of derived from propylene acid; The polymkeric substance of derived from propylene acid esters; Polymkeric substance derived from methylacrylic acid; Polymkeric substance derived from methacrylic ester; Derived from the polymkeric substance of high-molecular weight ester with acid; The maleic anhydride-styrene copolymers of partial esterification; Polymkeric substance and partial esterification products thereof derived from maleic anhydride and terminal olefin; Polymkeric substance derived from the propylene diene hydrocarbon monomer multipolymer of the maleic anhydride graft of esterification; The polyprotonic acid compound; The tensio-active agent that in skeleton, contains acidic-group; The emulsifying agent that in skeleton, contains acidic-group; And combination.
7. each compsn among the claim 1-6, wherein acid constituents comprises the acid that is selected from the group that is made up of and the following: the acid that vinylbenzene and maleic anhydride polymerization form; Use one or more C 6-C 32The acid that the such multipolymer of alcohol or these pure mixture partial esterifications forms; And combination.
8. each compsn among the claim 1-7, wherein acid has the residual acid group of total acid value＞1, preferred 2-100, more preferably 5-50.
9. each compsn among the claim 1-8; Further comprise one or more other fuel dopes, be selected from the group that and the following is formed: viscosity modifier, friction modifiers, purification agent, cloud point depressant, pour point reducer, emulsion splitter, FLOW IMPROVERS, static inhibitor, other dispersion agent, inhibitor, skimmer, corrosion/rust inhibitor, anti-extreme pressure agent/anti-wear agent, sealed expander, lubricant, antifogging agent and their mixture;
And wherein when gel contacts with fuel at least a fuel dope in time controlled release in fuel.
10. the compsn of claim 9, wherein other fuel dope is friction modifiers and/or lubricant.
11. the method for an operation of combustion engine comprises:
I., the fuel system of one or more fuel dope gelatinous compsn to oil engines is provided, and wherein the fuel dope gelatinous compsn comprises:
A) the soluble dispersion agent of fuel;
B) the soluble acid of fuel, it is selected from the group that and the following is formed: contain in the skeleton in the tensio-active agent that contains acidic-group in the acid, polyprotonic acid compound, skeleton of the polymer formation of acidic-group, the skeleton and contain emulsifying agent of acidic-group and composition thereof; With
C) randomly at least a other fuel dope;
Wherein, gelatinous compsn does not contain the component that produces ash content basically;
II. during internal combustion engine operation, fuel is contacted with the fuel dope gelatinous compsn;
Make at least a additive controlled release in the fuel dope gelatinous compsn in fuel, wherein discharge and ash content is not added in the fuel basically; With
III. supply said fuel to mover at the mover run duration.
12. the method for claim 11, wherein fuel dope gelatinous compsn at least 50% dissolves in the fuel that uses it, is benchmark with weight.
13. each method among the claim 11-12, wherein the rate of release of binder component from the gelatinous compsn to fuel is by fuel and the decision of additive gel compsn preparaton; Wherein gel formulation comprises that one or more only are partly dissolved the additive in the fuel in time.
14. a fuel-control assembly comprises fuel dope gelatinous compsn and the equipment that comprises said gelatinous compsn; Wherein the fuel dope gelatinous compsn comprises:
A) the soluble dispersion agent of fuel;
B) the soluble acid of fuel, it is selected from the group that and the following is formed: contain in the skeleton in the tensio-active agent that contains acidic-group in the acid, polyprotonic acid compound, skeleton of the polymer formation of acidic-group, the skeleton and contain emulsifying agent of acidic-group and composition thereof; With
C) randomly at least a other fuel dope;
Wherein, gelatinous compsn does not contain the component that produces ash content basically;
Wherein fuel-control assembly can be placed on the fuel system the inside of oil engine and/or be connected with it; Wherein fuel-control assembly allows the fuel in the fuel system to contact with the fuel dope gelatinous compsn, makes the mover run duration at supply of fuel to mover.
15. the fuel-control assembly of claim 14, wherein fuel dope gelatinous compsn at least 50% dissolves in the fuel that uses it, is benchmark with weight.
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