CN104513686B

CN104513686B - Quaternary ammonium cleaning agent fuel additive

Info

Publication number: CN104513686B
Application number: CN201410524352.7A
Authority: CN
Inventors: S.D.施瓦布; X.方
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 2013-10-08
Filing date: 2014-10-08
Publication date: 2017-01-04
Anticipated expiration: 2034-10-08

Abstract

The invention discloses quaternary ammonium cleaning agent fuel additive.For the fuel soluble additives of Diesel engine, improve the method for fuel injector performance and the method for the fuel injector of cleaning Diesel engine.Described fuel soluble additives includes quaternary ammonium salt, this quaternary ammonium salt comprises the alkylamine of at least one tertiary amino derived from (a), b () is selected from the epoxide of (+)-2,3-Epoxy-1-propanol, glycidyl ether, glycidyl esters, poly epihydric alcohol base ether, poly epihydric alcohol base ester and combinations thereof, wherein the substituent group of glycidyl has averaged less than five each hetero atoms of carbon atom, and the reaction of (c) optionally proton donor.

Description

Quaternary ammonium cleaning agent fuel additive

Technical field

Present disclosure relates to diesel-dope and can be used for improving the diesel fuel including this additive of direct fuel jet engine performance.Specifically, present disclosure relates to the quaternary ammonium salt fuel additive effectively strengthening the direct fuel injector performance of Diesel engine.

Background technology

It is well known that liquid fuel comprises to degrade at electromotor run duration and form the component of deposit.This deposit can cause non-complete combustion of fuel, produces more emission and worse fuel economy.Cleaning agent is the additive in known liquid fuel, helps to form deposit to minimize.But, along with power and mechanism's development of electromotor, the requirement to fuel and additive must evolve to catch up with these development of engines.Such as, current electromotor has the ejector system possessing less tolerance and running under high pressures, to strengthen to compression or the injected fuel spray of combustor.Deposit prevents from and reduces having become crucial for optimum operation, and it is thus desirable to acceptable performance can be provided to promote the new cleaning agent of optimal engine operation in liquid fuel within.

It addition, indirectly there is significant difference between fuel injection Diesel engine, and more modern high-pressure common rail (HPCR) direct fuel injection Diesel engine.Additionally, low-sulfur diesel fuels and ultra low sulfur diesel fuel are conventional in this type of market engine present." low-sulfur " diesel fuel represents that based on fuel gross weight sulfur content by weight be 500 The fuel of ppm or less." super-low sulfur " diesel fuel (ULSD) represents based on the fuel that fuel gross weight sulfur content by weight is 15 ppm or less.Compared with older electromotor and fuel injection system, the fuel injector in HPCR electromotor works under much higher pressure and temperature.The combination of low-sulfur or ULSD and HPCR electromotor already leads to injector deposits type and the change of injector deposits forming frequency having now found that in market.

Therefore, the fuel composition for direct fuel jet engine often produces undesirable deposit on interior engine surface and fuel filter.Accordingly, it would be desirable to be able to prevent accumulation of deposits, for vehicle ages, keep the improvement compositions of the cleannes of " as new ".It is desirable that can clean dirty fuel injector, by performance recovery to before the same combination of " as new " state will be to need and valuable equally in reducing the discharge of airborne waste gas and improving the trial of engine power performance.

It is known that the quaternary ammonium salt detergents that use polyisobutenyl succinimide (PIBSI) is derivative in fuel composition is as additive, formed by reducing, minimize and control deposit, promote that optimal engine runs, such as fuel economy improves, vehicle drive performance is more preferable, and emission reduces and engine maintenance is less.Such quaternized cleaning agent is typically derived from PIBSI compound, and it has can pass through hydrocarbyl epoxides, such as expoxy propane alkylation, the most quaternized pendant tertiary amine site.The example of such reaction and product is included in United States Patent (USP) 8,147,569 and U.S. Publication 2012/0138004.

Have also been disclosed new improvement kind derived from polyisobutcnyl succinic amide and/or the quaternary ammonium salt detergents of ester.Such additive it is said the quaternary ammonium cleaning agent more thermal-stable more derivative than PIBSI, and can be by the most energy-intensive method manufacture.

Quaternary detergents it is frequently necessary to use inflammable and dangerous epoxide, such as expoxy propane, and needs further exist for using special and expensive pressure vessel to produce for it.Alkoxylation step needs carboxylic acid as proton donor.Gained carboxylate deposit may be caused to be formed and with additive and fuel present in the other problem relevant with carboxylate.

It addition, polyisobutcnyl succinic amide and/or ester intermediate tend to very thickness, and it is difficult to process during manufacture process.Product often comprises different amounts of polyisobutenyl succinimide, making it difficult to add epoxide and or the acid of correct amount in reactant mixture.

It addition, clean-up performance may need nonetheless remain for improving, particularly in the fuel comprising biodiesel fuel component.

Summary of the invention

Present disclosure relates to a class more effective quaternary ammonium cleaning agent, and it can be prepared by the reaction of tertiary amine with (+)-2,3-Epoxy-1-propanol, glycidyl ether and glycidyl esters.Generally, the substituent group of glycidyl epoxide has less than five each hetero atoms of carbon atom.Such epoxide is the most ready-made, it is not necessary to the special pressure reactor for process.

According to present disclosure, exemplary provide fuel soluble additives and for Diesel engine prepare product, comprise the fuel of this additive, fuel additive concentrate, improve the method for fuel injector performance and the method for the fuel injector of cleaning Diesel engine.Described fuel additive includes quaternary ammonium salt, this quaternary ammonium salt comprises the alkylamine of at least one tertiary amino derived from (a), b () is selected from the epoxide of (+)-2,3-Epoxy-1-propanol, glycidyl ether, glycidyl esters, poly epihydric alcohol base ether, poly epihydric alcohol base ester and combinations thereof, wherein the substituent group of glycidyl has averaged less than five each hetero atoms of carbon atom, and the reaction of (c) optionally proton donor.Described fuel additive concentrate comprises described fuel additive and one or more components and/or solvent.

Another embodiment of present disclosure provides the method for the injector performance improving direct fuel injection Diesel engine.The method includes making electromotor run based on diesel fuel composition, described diesel fuel composition comprises major amount of diesel fuel and quaternary ammonium salt based on fuel composition gross weight by weight about 5 to about 200 ppm, this quaternary ammonium salt comprises the alkylamine of at least one tertiary amino derived from (a), b () is selected from (+)-2,3-Epoxy-1-propanol, glycidyl ether, glycidyl esters, poly epihydric alcohol base ether, the epoxide of poly epihydric alcohol base ester and combinations thereof, wherein the substituent group of glycidyl has averaged less than five each hetero atoms of carbon atom, (c) optional proton donor.

Fuel soluble additives for fuel injection Diesel engine is provided in another embodiment, comprise quaternary ammonium salt, this quaternary ammonium salt comprises the alkylamine of at least one tertiary amino derived from mixing (a), b () is selected from the epoxide of (+)-2,3-Epoxy-1-propanol, glycidyl ether, glycidyl esters, poly epihydric alcohol base ether, poly epihydric alcohol base ester and combinations thereof, wherein the substituent group of glycidyl has averaged less than five each hetero atoms of carbon atom, and (c) optionally proton donor.

Present disclosure another embodiment provide make direct fuel injection Diesel engine run method.The method includes making fuel composition burn within the engine, this fuel composition comprises major amount of fuel and quaternary ammonium salt based on fuel composition gross weight by weight about 5 to about 200 ppm, this quaternary ammonium salt comprises the alkylamine of at least one tertiary amino derived from (a), b () is selected from the epoxide of (+)-2,3-Epoxy-1-propanol, glycidyl ether, glycidyl esters, poly epihydric alcohol base ether, poly epihydric alcohol base ester and combinations thereof, wherein the substituent group of glycidyl has averaged less than five each hetero atoms of carbon atom, and (c) optionally proton donor.

The advantage of fuel additive described herein is the amount that this additive is possible not only to reduce the deposit formed on fuel injector, and this additive can also clean dirty fuel injector effectively, it is sufficient to provide the power improved to recover for electromotor.

Part in detailed description subsequently is illustrated by other embodiment and the advantage of present disclosure, and/or can be learned by the enforcement of present disclosure.Should be understood that above-mentioned general explanation and described further below be only exemplary and explanat, as claim, not limit present disclosure.

Detailed description of the invention

The fuel additive component of the application to be used in major amount of fuel in a small amount, and can be added directly in fuel, or the component as multifunctional additive for lubricating oils joins in fuel.Can be by the tertiary amine of following formula for improving the specially suitable fuel additive component of the operation of explosive motor

Wherein R¹, R²And R³It each is selected from comprising the alkyl of 1 to 100 carbon atom, reacts preparation with proton donor and glycidyl quaternizing agent, it is provided that glycidyl ether quaternary ammonium salt.This reaction can be carried out in the presence of protonating agent, and this protonating agent has the acid ionization constant (pKa) of less than about 13, such as carboxylic acid or alkyl phenol.No matter how quaternary ammonium salt is prepared, and the key feature of present disclosure is that described amine comprises at least one tertiary amino.

As used herein, term " hydrocarbyl group " or " alkyl " are well known to a person skilled in the art that its conventional understanding uses.Especially, its expression has the carbon atom being directly connected to molecule remaining part the group with notable hydrocarbon characteristic.The example of alkyl includes:

(1) hydrocarbon substituent, i.e. aliphatic (such as alkyl or alkenyl), alicyclic (such as cycloalkyl, cycloalkenyl group) substituent group, and aromatic series-, aliphatic-and alicyclic-substituted aromatic substituents, and cyclic substituents, wherein this ring completes (such as, two substituent group cyclization together) by another part of molecule；

(2) substituted hydrocarbon substituent, i.e. contain the substituent group of non-hydrocarbon, in description of the invention context, described non-hydrocarbon will not change main hydrocarbon substituent (such as halogen (particularly chlorine and fluorine), hydroxyl, alkoxyl, sulfydryl, alkyl thiol, nitro, nitroso-group, amino, alkyl amino and sulfur epoxide)；

(3) hydridization substituent group, i.e. in this specification context, contains the substituent group of non-carbon while having main hydrocarbon characteristic in the ring being additionally made up of carbon atom or chain.Hetero atom includes sulfur, oxygen, nitrogen, and includes the substituent group of such as pyridine radicals, furyl, thienyl and imidazole radicals.Generally, in alkyl, every ten carbon atoms will exist at most two, or as other example, there is at most one substituents；In some embodiments, alkyl will there is no substituents.

As used herein, term " primary amount " is understood to mean that the gross weight relative to compositions, more than or equal to 50 wt%, the amount of e.g., from about 80 to about 98 wt%.It addition, as used herein, term " in a small amount " is understood to mean that relative to composition total weight, less than the amount of 50 wt%.

Amines

In one embodiment, acylating agent can form, with the reactive tertiary amine comprising nitrogen or oxygen atom can being condensed with acylating agent, the alkylamine comprising at least one tertiary amino.As used herein; term " acylating agent " represents that long chain hydrocarbon, the usually substituted polyolefin of coverlet unsaturated carboxylic acid reactant, described single unsaturated carboxylic acid reactant are such as (i) α; β-monounsaturated C4 to C10 dicarboxylic acids, such as fumaric acid, itaconic acid, maleic acid；(ii) anhydride of the derivant of (i), such as (i) or C₁To C₅The single or double ester that alcohol is derivative；(iii) α, β-monounsaturated C₃To C₁₀Monocarboxylic acid, such as acrylic acid and methacrylic acid；Or (iv) (iii) derivant, such as (iii) and the C of the expressed by the following formula any compound comprising ethylene linkage₁To C₅The ester that alcohol is derivative:

(R⁴)(R⁵)C═C(R⁶)(CH(R⁷)(R⁸))

Wherein R⁴And R⁵It is each independently hydrogen or group based on hydrocarbon.R⁶, R⁷And R⁸It is each independently hydrogen or group based on hydrocarbon；Wish that at least one is the group based on hydrocarbon comprising at least 20 carbon atoms.

In another embodiment, the tertiary amine including diamines and polyamines can be with C₁To C₅₄Carboxylic acid reaction, forms amido amine, and this amido amine can be reacted with quaternizing agent subsequently.The teritary amide ylamine compounds of suitable following formula can be used

Wherein R¹⁰And R¹¹It each is selected from comprising the alkyl of 1 to 50 carbon atom, R⁹, R¹², R¹³And R¹⁴Each can be independently selected from hydrogen or alkyl, x can be 1 to 6, and y can be 0 or 1, and z can be 1 to 6, and n can be 1 to 6.Alkyl R⁹To R¹⁴Each can stand alone as linear, branched, replace, ring-type, saturated, undersaturated, or comprise one or more hetero atom.Suitably alkyl can include but not limited to alkyl, aryl, alkylaryl, aryl alkyl, alkoxyl, aryloxy group, amino etc..Specially suitable alkyl can be linear or branched-alkyl.Dimethylamino propylamine can be included, but not limited to, e.g. with the representative example of amidatioon and the quaternized amine reactant to produce compound disclosed herein.

If described amine only comprises primary or secondary amino, then it can make at least one primary or secondary amino be alkylated to tertiary amino desirably before quaternized amides base amine.In one embodiment, primary amine and secondary amine or mixture and the alkylation of tertiary amine can be thorough or partially alkylated for tertiary amine, and alkoxylate is quaternary salt further.

Carboxylic acid

When tertiary amine also has primary or secondary amino, this tertiary amine can be by making amine and C₁To C₅₄Carboxylic acid reaction changes into amido amine.Described acid can be monoacid, dimeric dibasic acid or trimer acid.Described acid can be selected from formic acid, acetic acid, propanoic acid, butanoic acid, octanoic acid, capric acid, lauric acid, myristic acid, Palmic acid, stearic acid, arachidic acid, mountainAcid, lignoceric acid, cerinic acid, nutmeg olic acid, palmitoleic acid, hexadecenoic acid (sapienic acid), oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid (linoelaidic acid), alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexenoic acid and dimerization thereof and trimer acid.When reacting with amine, product can be C₁-C₅₄The substituted amido amine of-alkyl or alkenyl, such as C₁-C₅₄The substituted amidopropyldimethylamine of-alkyl or alkenyl.

Quaternizing agent

Suitably quaternizing agent can be selected from (+)-2,3-Epoxy-1-propanol, glycidyl ether, glycidyl esters, poly epihydric alcohol base ether, poly epihydric alcohol base ester and combinations thereof, and wherein the substituent group of glycidyl has averaged less than five each hetero atoms of carbon atom.The non-limiting example of the suitable glycidyl compound that can serve as quaternizing agent can be selected from:

Allyl glycidyl ether

1,4-butanediol diglycidyl ether

1,2-cyclohexane cyclohexanedimethanodibasic diglycidyl ester

Diglycidyl ether

N, N-diglycidyl-4-glycidyl-oxyaniline

Ethyl glycidyl ether

Furfuryl glycidyl base ether

Glycerol two contracting glyceryl ether

Glycerol triglycidyl group ether

(+)-2,3-Epoxy-1-propanol

Glycidyl isopropyl ether

Methyl propenoic acid glycidyl base ester

Glycidyl 4-methoxyphenyl ether

Glycidyl 2-methoxyphenyl ether

Glycidyl propargyl ether

1,6-HD diglycidyl ether

4,4' methylene bis (N, N-diglycidylaniline)

Neopentyl glycol diglycidyl ether

PEG diglycidyl ether

Poly-(propylene glycol) diglycidyl ether

Resorcinol diglycidyl ether

Trimethylolpropane tris glycidyl ether and the combination of above-mentioned two or more.

Quaternary ammonium salt from alkylamine can be prepared in one or two steps.Reaction can add carboxylic acid or alkyl phenol, to provide protonating agent the most if desired by making amine contact with glycidyl ether in reaction vessel and mix to carry out in reactant mixture.Carboxylic acid can be selected from any of above listed fatty acid, formic acid, acetic acid, propanoic acid, butanoic acid, polymeric acid and mixture thereof, such as polyolefin list or dicarboxylic acids, polymer polyol acid and mixture etc. thereof.Alkyl phenol protonating agent can be selected from polyisobutenyl phenol, dodecyl phenol, nonyl phenol etc. without limitation.When deployed, the mol ratio joining the protonating agent every mole epoxy equivalent in reactant mixture can be about 0.5:10, e.g., from about 2:5, or about 1:2 to about 2:1 every mole of epoxy equivalent of equimolar acid.In one embodiment, the anion of quaternary ammonium salt is carboxylate anion.

Reaction can be carried out at e.g., from about 45 DEG C to about 70 DEG C at about 30 DEG C to about 90 DEG C.This reaction can be carried out by making the tertiary amino group of any amount react with the epoxide group that be enough to provide quaternary ammonium compound.In one embodiment, tertiary amino group can be about 2:1 to about 1:2 to the mol ratio of epoxide group.When the reactions are completed, can to remove volatile matter and unreacted reactant from product by reacting by heating product under vacuo.If desired, product can use mineral oil, diesel fuel, kerosene or unreactive hydrocarbons solvent dilution, to prevent product the most viscous.

One or more other optional compound may reside in fuel additive concentrate and/or the fuel composition of disclosed embodiment.Such as, fuel can comprise the cetane additive of convention amount, preservative, cold flow promoting agent (CFPP additive), pour-point depressant, solvent, demulsifier, lubricating additive, friction modifiers, amine stabiliser, combustion adjuvant, dispersant, antioxidant, heat stabilizer, conductivity promoting agent, metal deactivator, labeling dye, organic nitrate ignition accelerator, ring (cyclomatic) three carbonyl conjunction manganese compound etc..In some respects, compositions described here can comprise about 60 wt% or less, or in other side, one or more above-mentioned additives of about 50 wt% or less, gross weight based on multifunctional additive for lubricating oils.Similarly, fuel can comprise the conventional fuel blend components of appropriate amount, such as methanol, ethanol, dialkyl ether, 2-Ethylhexyl Alcohol etc..

Some aspects in disclosed embodiment, it is possible to use including aliphatic or alicyclic nitrate and comprise the organic nitrate ignition accelerator of at most about 12 carbon, wherein aliphatic or alicyclic group are saturated.The example of the organic nitrate ignition accelerator that can use is methyl nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate, nitric acid allyl ester, Butylnitrate ester, isobutyl nitrate, the secondary butyl ester of nitric acid, the nitric acid tert-butyl ester, amyl nitrate, isoamyl nitrate, 1-Methylbutyl nitrate, nitric acid 3-pentyl ester, the own ester of nitric acid, nitric acid heptyl ester, nitric acid 2-heptyl ester, n-octyl nitrate, isooctyl ester nitrate, nitric acid 2-Octyl Nitrite, nitric acid nonyl ester, decyl nitrate, nitric acid undecyl ester, nitric acid dodecyl ester, nitric acid ring pentyl ester, cyclohexyl nitrate, nitrate cyclohexyl, nitric acid cyclo-dodecyl ester, nitric acid 2-ethoxy ethyl ester, nitric acid 2-(2-ethoxy ethoxy) ethyl ester, nitric acid tetrahydrofuran ester etc..The mixture of this material can also be used.

The example of the suitable optional metals passivator that can be used for the application compositions is disclosed in the United States Patent (USP) 4 announced on November 13rd, 1984, in 482,357, the disclosure of which is incorporated by reference at this.This metal deactivator includes such as salicylidene-o-amino-phenol, two salicylidene ethylene diamines, two salicylidene trimethylene diamine and N, N'-bis-salicylidenes-1，2-diaminopropane.

When preparing the fuel composition of the application, additive can use with the amount that be enough to reduce or suppress the deposit in the fuel system of electromotor or combustor to be formed.In some respects, fuel can be formed containing control in a small amount or minimizing engine deposits, such as the above-mentioned product that the injector deposits in diesel engine is formed.Such as, based on active component basis, the quaternary ammonium salt amount that the diesel fuel of present disclosure can contain is about 5 mg to about 200 mg quaternary ammonium salt every kg fuel, e.g., from about 10 mg to about 100 mg quaternary ammonium salt every kg fuel, or about 30 mg to about 75 mg quaternary ammonium salt every kg fuel.Active component basis does not include when (i) produces and use, be combined with product and remain unreacted components in the product, (ii) if it has, in product forming process or afterwards, the weight of one or more solvents used in product manufactures.

The additive of the application, including above-mentioned quaternary ammonium salt, and the optional additive for preparing fuel of the present invention, respectively or can be blended with various sub-combinations and enter in Base Diesel machine fuel.In some embodiments, the additive component of the application can be blended while using multifunctional additive for lubricating oils and enter in diesel fuel, because this point utilizes when being in the form of multifunctional additive for lubricating oils, the combination of each composition the intermiscibility obtained and convenience.The use of concentrate can also reduce the blended time and reduce the probability that deviation is blended.

The fuel of the application goes for the operation of Diesel engine.Electromotor includes stationary engine (electromotor used in such as TRT, pumping plant etc.) and free-standing electromotor (electromotor of the prime mover being used for example as in automobile, truck, road grading equipment, military vehicle etc.).Such as, fuel can include any and all midbarrel fuels, diesel fuel, biorenewable fuel, biodiesel fuel, fatty acid alkyl esters, gas is to liquid (gas-to-liquid, GTL) fuel, jet fuel, alcohol, ether, kerosene, synthetic fuel, such as Fischer-Tropsch fuel, liquefied petroleum gas, fuel oil (bunker oils), coal to liquid (coal To liquid, CTL) fuel, biomass to liquid (biomass To liquid, BTL) fuel, high bituminous fuel, derived from the fuel (natural, that purify and petroleum coke (petcoke)) of coal, genetic engineering bio-fuel and crops and the extract from it, and natural gas.As used herein, " biorenewable fuel " is understood to mean that any fuel derived from the resource being different from oil.This resource includes but not limited to Semen Maydis, Semen setariae, Semen sojae atricolor and other crops；Grass, such as switchgrass, Miscanthus and Hybrid Grass；Algae, zostera marina, vegetable oil；Natural fat；With its mixture.In one aspect, biorenewable fuel can include monohydric alcohol, such as, include 1 to about 5 carbon atom those.The suitably non-limiting example of monohydric alcohol includes methanol, ethanol, propanol, n-butyl alcohol, isobutanol, the tert-butyl alcohol, amylalcohol and isoamyl alcohol.

Therefore, each side of the application relates to the method reducing the injector deposits amount of electromotor, and described electromotor has at least one combustor and one or more direct fuel ejector being connected with combustion chamber fluid.In yet another aspect, quaternary ammonium salt described here or the fuel containing described quaternary ammonium salt can be with poly-alkyl-butanimides ,-Mannich (Mannich) compound ,-acid ,-amide,-ester, and-amide/acid and-acid/ester combine.

In some respects, described method includes, via Diesel engine ejector, being sprayed in combustor by the compression ignition fuel based on hydrocarbon comprising the quaternary ammonium salt of present disclosure, and lighting this compression ignition fuel.In some respects, described method can also be included in diesel fuel and mix at least one above-mentioned optional supplementary element.

In one embodiment, the diesel fuel of the application can be substantially free of, such as without poly-alkyl-butanimide, and-mannich compound ,-acid ,-amide,-ester ,-amide/acid and-acid/ester.For the purpose of the application, term " is substantially free of " and is defined as forming ejector cleannes or deposit there is no the concentration that can measure impact.

Embodiment

Following example illustrate the exemplary of present disclosure.These embodiments and the application it at, except as otherwise noted, all parts and percentages are by weight.Wish that purpose only for the purpose of illustration provides these embodiments, rather than be used for limiting the scope of the present invention disclosed herein.

Comparative example 1

Quaternary ammonium salt is prepared by according to the method for United States Patent (USP) 8,147,569.To according to United States Patent (USP) 8,147, the PIBSI (polyisobutenyl succinic anhydride (PIBSA) of 1:1 and the product of dimethylaminopropyl amine (DMAPA)) (249 grams) of 569 preparations and the mixture of aromatic solvent aromatic hydrocarbon (70 grams) add acetic acid (17.3 grams), 1,2-epoxy butane (34.6 grams), isopropanol (64 grams) and 2-Ethylhexyl Alcohol (18 grams).Mixture is heated 1 hour at 50 DEG C, then heats 2 hours 15 minutes at 55 DEG C, heat 2 hours at 60 DEG C, and heat 5 hours at 65 DEG C.Under reduced pressure remove volatile matter at 65 DEG C, obtain the product as the brown gummy oil containing quaternary ammonium salt.

Comparative example 2

Quaternary ammonium salt is prepared by according to the method for U.S. Publication 2012/0138004.According to the step of " preparation materials A ", by PIBSA (PIB Mn= 950,225 grams) and the mixture of aromatic solvent (91 grams) be heated to 45 DEG C.Add DMAPA (23.4 grams) through 10 minutes, keep mixture temperature not to be increased beyond 60 DEG C.Find reactant mixture very thickness and be difficult to stir.Mixture is stirred 2 hours at 60 DEG C.Then 2-Ethylhexyl Alcohol (68 grams) and 1,2-epoxy butane (33.4 grams) are joined in product.Gained mixture is heated 1 hour at 55 DEG C, heats 1 hour at 60 DEG C, heat 2 hours at 62.5 DEG C, and heat 1 hour at 65 DEG C.Under reduced pressure remove volatile matter, obtain the quaternary ammonium salt product as brownish oil.

Inventive embodiments 1

By polyisobutenyl succinic anhydride (PIBSA) (139.07 grams, average MW=980 g/mol, 0.142 mole), 500 equipped with agitator put into by 14.39 grams of dimethylamino propylamines (DMAPA, 0.141 mole) and 66.35 grams of Aromatic 150 solvents In mL reaction flask.Heat the mixture to 70 DEG C, and keep 2 hours in this temperature with constant agitation.Products therefrom it is believed that and is mainly made up of polyisobutenyl DMAPA amide/acid (PDa).

By poly-(propylene glycol) diglycidyl ether (PPGDE) (45.00 grams, MW= 640,0.070 moles) and 51.94 grams of 2-Ethylhexyl Alcohols join in the same flask comprising above-mentioned PDa product.Heat the mixture to 55 DEG C, and keep 4 hours in this temperature with constant agitation.From carbon-H NMR spectroscopy, primary product believed as:

。

Inventive embodiments 2

Under an inert atmosphere by oleyl amides base diemethylamine (183 grams), isopropylglycidyl ether (IPGE, 58 grams), the mixture of oleic acid (141 grams) and 2-Ethylhexyl Alcohol (80 grams) heats 4.5 hours at 60 DEG C.Mixture is reheated 2 hours at 65 DEG C, obtains the product as brownish oil.

Inventive embodiments 3

It is similar to inventive embodiments 2 and prepares product, except using the PDa (302 grams of active matters) from inventive embodiments 1 to replace oleyl amides base diemethylamine.This mixture also comprises 2-Ethylhexyl Alcohol (59 grams) and isopropylglycidyl ether (IPGE) (32 grams).By mixture 55 DEG C of reaction heating 2 hours, heat 1.5 hours at 60 DEG C subsequently, heat 2 hours at 65 DEG C, obtain the product as viscous oil.

Inventive embodiments 4

Tertiary amine is prepared, except using C according to inventive embodiments 1₂₀-C₂₄Alkenyl succinic anhydride replaces PIBSA, and reaction temperature is reduced to 65 DEG C.Amine (250 grams) in aromatic solvent (72 grams) is joined in (+)-2,3-Epoxy-1-propanol (36 grams) and 2-Ethylhexyl Alcohol (86 grams).Mixture is heated 2 hours at 55 DEG C, heats 3 hours at 60 DEG C subsequently, heat 2.5 hours at 65 DEG C, obtain the product as oil.

Inventive embodiments 5

It is similar to inventive embodiments 4 and prepares product, except using from the PDa of inventive embodiments 1 as tertiary amine.Product is brownish oil.

In the examples below, industrial standard diesel engine fuel injector as described below is used to test, CEC F-98-08 (DW10), Diesel engine is carried out injector deposits test.DW10 test is carried out with B10 fuel (soy methyl ester, SME).

Diesel engine test procedure

The DW10 test developed by Coordinating European Council (CEC) is for proving that fuel causes the tendency of fuel injector dirty, and is also used for proving that some fuel additive prevents or controls the ability of these deposits.Additive evaluation uses the CEC of the co-rail diesel engine nozzle coking test for directly injection The code of F-98-08.Engine dynamometer testboard carries out the Peugeot DW10 Diesel engine of ejector coking test for installing.Electromotor is 2.0 liters of electromotors of four cylinders.Each combustor has four valves, and fuel injector is DI piezoelectric injector, has Euro V classification.

Core protocol steps includes making electromotor operating circulate through 8 hours and allow electromotor to immerse the time quantum that (soak) (engine cut-off) specifies.Above-mentioned sequence is repeated four times.At the end of per hour, it is thus achieved that the power measurement values of electromotor, electromotor runs under rated condition simultaneously.The difference of the rated power that the ejector dirty tendency of fuel is observed by test loop and between end characterizes.

The fuel of previously test is rinsed in test from electromotor before preparing to be included in removal ejector.Check, cleaning is tested ejector, and is reinstalled within the engine.If selecting new ejector, the newest ejector stands break-in in 16 hours circulation.It follows that use required test loop program to start electromotor.Once electromotor heating, measures power with 4000 RPM and full load, and the full power after checking cleaning ejector is recovered.If power measurement values is within prescribed limit, start test loop.Table 1 below provides the performance being used for evaluating the DW10 coking cycle of the fuel additive according to present disclosure.

Table 1 - DW10 Coking cycle 1 Hour performance

。

In the PC-10 diesel fuel (basic fuel) comprising zinc neodecanoate, nitric acid 2-Octyl Nitrite and fatty acid ester friction modifiers, above-mentioned Engine Block Test step is used to test various fuel additives.Start by " pollution " stage not having additive only basic fuel to form, subsequently for " cleaning " stage being made up of the basic fuel containing additive.All operations carry out 8 hours polluting and 8 hours cleanings, except as otherwise noted.Use " pollution " power measurement values at the end of the stage and " cleaning " power measurement values at the end of the stage to calculate power and recover percentage ratio.Power recovers percentage ratio and is determined by following formula

Power recovers percentage ratio=(DU-CU)/DU x 100

Wherein DU is not have under additive the power loss percentage ratio at the end of the pollution stage, and CU is containing the power percentage at the end of cleaning stage under fuel additive, and power is measured according to CEC F98-08 DW10 test.Result is given in Table 2.

Table 2

。

B10 fuel (soy methyl ester) is used to carry out other CEC F98-08 DW10 test.Result is shown in table 3 below.

Table 3

。

Shown in inventive embodiments 4-8 in the upper table of contrast and comparative example 1-2, for the fuel injector that cleaning is dirty, compositions prepared in accordance with the present invention is equivalent to the conventional quarternary ammonium salt compound in petroleum diesel fuel, and the conventional quarternary ammonium salt compound being better than in biodiesel fuel.

It should be noted that singulative " ", " a kind of " and " described " include plural referents, unless be explicitly and clearly limited to an indicant as used in this specification and claims.It is thus possible, for instance " antioxidant " includes the antioxidant that two or more are different.As used herein, term " includes " and grammatical variants is intended that nonrestrictive, and therefore in list, the narration of object is not precluded from other similar object, and it can substitute listed object or increase in listed object.

For this specification and the purpose of claims, except as otherwise noted, the number of all expression quantity, percentage ratio or ratio and other numerical value that use in description and claims is interpreted as being modified by term " about " in all instances.Therefore, unless indicated to the contrary, the numerical parameter enumerated in the following description and appended dependent claims is approximation, and it can be changed according to the desired properties attempting to be obtained by present disclosure.At least, and rather than try to limit the application of the principle of the coordinate of right, each numerical parameter at least should be according to the numerical value of the significant digits reported and by applying the common method of rounding up to explain.

Although it have been described that detailed description of the invention, but the most not or unpredictable to replacement scheme, improve, change, improve and substantially equivalent thing can be made by applicant or other those skilled in the art.Therefore, submission and the claims that can be modified be intended to include all such replacement schemes, improve, change, improve and substantially equivalent thing.

Therefore, it is disclosed embodiments below.

Scheme 1. is for the fuel additive of fuel injection Diesel engine, comprise quaternary ammonium salt, this quaternary ammonium salt comprises the alkylamine of at least one tertiary amino derived from (a), b () is selected from the epoxide of (+)-2,3-Epoxy-1-propanol, glycidyl ether, glycidyl esters, poly epihydric alcohol base ether, poly epihydric alcohol base ester and combinations thereof, wherein the substituent group of glycidyl has averaged less than five each hetero atoms of carbon atom, and the reaction of (c) optionally proton donor.

The fuel additive of scheme 2. scheme 1, wherein said proton donor is selected from carboxylic acid and alkyl phenol.

The fuel additive of scheme 3. scheme 1, wherein said alkylamine is selected from acylated amine and amido amine.

The fuel additive of scheme 4. scheme 2, wherein said proton donor is selected from fatty acid, formic acid, acetic acid, propanoic acid, butanoic acid, polyisobutenyl succinic acid, amide/acid or acid/ester and polymeric acid and the carboxylic acid of mixture thereof.

Scheme 5. fuel composition, comprises the fuel additive of the scheme 1 of about 5 to about 200 ppm, gross weight based on described fuel composition.

Scheme 6. diesel fuel composition, comprises the diesel-dope of the scheme 1 of about 10 to about 100 ppm, gross weight based on described fuel composition.

Scheme 7. improves the method for the injector performance of fuel injection Diesel engine, run based on fuel composition including making described electromotor, described fuel composition comprises major amount of fuel and quaternary ammonium salt based on described fuel composition gross weight by weight about 5 to about 200 ppm, this quaternary ammonium salt comprises the alkylamine of at least one tertiary amino derived from (a), b () is selected from (+)-2,3-Epoxy-1-propanol, glycidyl ether, glycidyl esters, poly epihydric alcohol base ether, the epoxide of poly epihydric alcohol base ester and combinations thereof, wherein the substituent group of glycidyl has averaged less than five each hetero atoms of carbon atom, (c) reaction of optional proton donor.

The method of scheme 8. scheme 7, wherein said electromotor includes that direct fuel sprays Diesel engine.

The method of scheme 9. scheme 7, wherein said alkylamine is selected from acylated amine and amido amine.

The method of scheme 10. scheme 7, wherein said fuel composition comprises about 10 to about 200 The quaternary ammonium salt of ppm, gross weight based on described fuel composition.

The method of scheme 11. scheme 7, wherein said fuel comprises biodiesel fuel.

Scheme 12. makes the method that direct fuel injection Diesel engine runs, burn within the engine including making fuel composition, described fuel composition comprises major amount of fuel and quaternary ammonium salt based on described fuel composition gross weight by weight about 5 to about 200 ppm, this quaternary ammonium salt comprises the alkylamine of at least one tertiary amino derived from (a), b () is selected from (+)-2,3-Epoxy-1-propanol, glycidyl ether, glycidyl esters, poly epihydric alcohol base ether, the epoxide of poly epihydric alcohol base ester and combinations thereof, wherein the substituent group of glycidyl has averaged less than five each hetero atoms of carbon atom, (c) reaction of optional proton donor.

The method of scheme 13. scheme 12, wherein said alkylamine is selected from acylated amine and amido amine.

The method of scheme 14. scheme 12, wherein said proton donor is selected from fatty acid, formic acid, acetic acid, propanoic acid, butanoic acid, polyisobutenyl succinic acid, amide/acid or acid/ester and polymeric acid and the carboxylic acid of mixture thereof.

The method of scheme 15. scheme 12, wherein said fuel comprises biodiesel fuel.

Claims

1. for the fuel additive of fuel injection Diesel engine, comprise quaternary ammonium salt, this quaternary ammonium salt comprises the alkylamine of at least one tertiary amino derived from (a), b () is selected from the epoxide of (+)-2,3-Epoxy-1-propanol, glycidyl ether, glycidyl esters, poly epihydric alcohol base ether, poly epihydric alcohol base ester and combinations thereof, wherein have averaged less than five carbon atoms relative to the substituent group of each hetero atom glycidyl, and the reaction of (c) optionally proton donor.

2. the fuel additive of claim 1, wherein said proton donor is selected from carboxylic acid and alkyl phenol.

3. the fuel additive of claim 1, wherein said alkylamine is selected from acylated amine and amido amine.

4. the fuel additive of claim 2, wherein said proton donor is selected from fatty acid；Formic acid；Acetic acid；Propanoic acid；Butanoic acid；Polyisobutenyl succinic acid, amide/acid or acid/ester；And polymeric acid；And the carboxylic acid of mixture.

5. fuel composition, comprises the fuel additive of the claim 1 of 5 to 200 ppm, gross weight based on described fuel composition.

6. diesel fuel composition, comprises the diesel-dope of the claim 1 of 10 to 100 ppm, gross weight based on described fuel composition.

7. the method improving the injector performance of fuel injection Diesel engine, run based on fuel composition including making described electromotor, described fuel composition comprises major amount of fuel and quaternary ammonium salt based on described fuel composition gross weight by weight 5 to 200 ppm, this quaternary ammonium salt comprises the alkylamine of at least one tertiary amino derived from (a), b () is selected from (+)-2,3-Epoxy-1-propanol, glycidyl ether, glycidyl esters, poly epihydric alcohol base ether, the epoxide of poly epihydric alcohol base ester and combinations thereof, wherein have averaged less than five carbon atoms relative to the substituent group of each hetero atom glycidyl, (c) reaction of optional proton donor.

8. the method for claim 7, wherein said electromotor includes that direct fuel sprays Diesel engine.

9. the method for claim 7, wherein said alkylamine is selected from acylated amine and amido amine.

10. the method for claim 7, wherein said fuel composition comprises the quaternary ammonium salt of 10 to 200 ppm, gross weight based on described fuel composition.

The method of 11. claim 7, wherein said fuel comprises biodiesel fuel.

12. make the method that direct fuel injection Diesel engine runs, burn within the engine including making fuel composition, described fuel composition comprises major amount of fuel and quaternary ammonium salt based on described fuel composition gross weight by weight 5 to 200 ppm, this quaternary ammonium salt comprises the alkylamine of at least one tertiary amino derived from (a), b () is selected from (+)-2,3-Epoxy-1-propanol, glycidyl ether, glycidyl esters, poly epihydric alcohol base ether, the epoxide of poly epihydric alcohol base ester and combinations thereof, wherein have averaged less than five carbon atoms relative to the substituent group of each hetero atom glycidyl, (c) reaction of optional proton donor.

The method of 13. claim 12, wherein said alkylamine is selected from acylated amine and amido amine.

The method of 14. claim 12, wherein said proton donor is selected from fatty acid；Formic acid；Acetic acid；Propanoic acid；Butanoic acid；Polyisobutenyl succinic acid, amide/acid or acid/ester；And polymeric acid；And the carboxylic acid of mixture.

The method of 15. claim 12, wherein said fuel comprises biodiesel fuel.