CN103328537B - Polyester quaternary ammonium salts - Google Patents

Abstract

The invention relates to polyester quaternary ammonium salts, including amine, amide, and ester salts, processes for making them, and their use as additives, including their use in fuels, such as diesel fuel and fuel oils. The invention particularly relates to the use of polyester quaternary ammonium salts as detergents in fuels and the methods of making them.

Description

Polyester quaternary ammonium salt

Invention field

The present invention relates to polyester quaternary ammonium salt, comprise amine, acid amides and ester salt, its preparation method, and they are as the purposes of additive, comprise them at fuel as the purposes in diesel oil fuel and oil fuel.The present invention particularly polyester quaternary ammonium salt in fuel as the purposes of purification agent and their preparation method.

background of invention

Hydrocarbon-based fuel generally forms material containing a large amount of settling.When in oil engine (ICE) time, settling to tend on the narrow area of the engine contacted with fuel and around formed.In motor car engine, settling can be formed on engine intake valve, causes the progression restriction to gaseous fuel mixture flowing in combustion chamber and valve bonding.There is the common inlet valve deposits of two classes: resedimentation thing and thin settling.These dissimilar settlings affect the performance of fuel and engine in a slightly different way.Resedimentation thing be carbon containing and outward appearance be oil.The flow that they result through valve is restricted, and this reduces again the peak power of engine, reduces fuel economy and improves discharge.Thin settling tends to problem when causing engine start and improves discharge.

Because engine becomes more responsive to settling, usually practice to be incorporated to by purification agent in fuel composition to suppress the formation of engine deposits and to promote that it removes, and improves motor performance and discharge thus.

The quaternized PIB/ amine that some poly-isobutyl-succinimide of known use derives and/or acid amides dispersion agent/purification agent are as the additive in fuel composition.Poly-isobutyl-succinimide also can be described as polyisobutenyl succinimide.These quaternized dispersion agent/purification agents are derived from traditional PI B/ amine and/or acid amides fuel dope compound, and described compound has by quaternizing agent as propylene oxide alkylation, i.e. quaternised side tertiary amine point.The example of these additives is disclosed in U.S. Patent application US2008/0307698.

But, need to provide above-mentioned advantage, also demonstrate the viscosity characteristics of improvement and the additive of material processing performance simultaneously.This kind of improvement can allow that less diluent materials is for containing in normally used enriched material and additive-package in the commodity of these class A fuel A additives and final fuel.If viscosity characteristics and material processing performance allow composition transfer containing additive and process (i.e. pumping, topple over, mixing etc.) and need not more typically heating material and/or and do not need special high viscosity equipment, then need less thinner.The viscosity characteristics improved and material processing performance allow the environmental influence that the thinner of minimizing uses, cost-saving, therefore reduction refuse also improves material.This also allows the additive-package that use is denseer and midbody composite, and it can more effectively transport, and also reduces costs and environmental influence.

summary of the invention

The present invention relates to the new purification agent of a class, described purification agent provides and traditional PI B/ amine purification agent, comprises the obvious improvement that quaternized purification agent that poly-isobutyl-succinimide derives is compared.The quaternized salt of the new polyester of present discovery one class.The quaternized salt of these polyester has polyester based alkyl and provides the quaternized purification agent derived with poly-isobutyl-succinimide to compare viscosity characteristics and the material processing performance of improvement with associated materials.The quaternized salt of polyester of the present invention provides the detersive power and thermostability performance that purification agent quaternized with other is identical, and provides viscosity characteristics and the material processing performance of above-mentioned improvement.

The invention provides the composition containing quaternized polyester salt, described quaternized polyester salt derived from tertiary-amino-containing polyester be suitable for uncle's amino to change into the reaction of the quaternizing agent of quaternary nitrogen.Quaternizing agent can be dialkyl sulfate, benzyl halide, alkyl replacement carbonic ether, hydrocarbyl epoxides or its combination.Any described quaternizing agent, particularly hydrocarbyl epoxides can use with acid such as acetic acid combinations.

The invention provides quaternized polyester salt, wherein for polyester in its preparation this as the aliphatic carboxylic acid containing at least one hydroxyl with have and can have the reaction product of the compound of tertiary amino further with the oxygen of described sour condensation or nitrogen-atoms.The present invention further provides the polyesteramide that pet reaction thing is tertiary-amino-containing.

The present invention further provides fuel composition, described fuel composition comprises quaternized polyester salt described herein and is at room temperature the fuel of liquid.Also other fuel dope can be there is.

The invention provides to the method for oil engine refuel, described method comprises step: feeding in internal combustion engine is at room temperature fuel and the composition comprising one or more quaternized polyester salts described herein of liquid.

The present invention also provides the method preparing quaternary ammonium salt purification agent, and described method comprises step: the polyester making (a) tertiary-amino-containing; (b) quaternizing agent reaction uncle's amino being changed into quaternary nitrogen is suitable for.Quaternizing agent is optional replaces carbonic ether from dialkyl sulfate, benzyl halide, alkyl; The hydrocarbyl epoxides combined with acid or its mixture.Described method produces quaternized dispersion agent described herein.

detailed Description Of The Invention

Set forth below by indefiniteness and describe each preferred feature and embodiment.

polyester quaternary ammonium salt purification agent

Polyester quaternary salt purification agent of the present invention comprises quaternized polyesteramine, acid amides and ester salt.This additive also can be described as season polyester salt.Additive of the present invention can be described as the polyester of tertiary-amino-containing and is suitable for uncle's amino to change into the reaction product of the quaternizing agent of quaternary nitrogen.Quaternizing agent is optional replaces carbonic ether from dialkyl sulfate, benzyl halide, alkyl; The hydrocarbyl epoxides combined with acid or its mixture.

A. on-quaternised polyester

Polyester for the preparation of the tertiary-amino-containing of additive of the present invention also can be described as the on-quaternised polyester containing tertiary amino.

In some embodiments, polyester is aliphatic carboxylic acid containing at least one hydroxyl and has and can have the reaction product of the compound of tertiary amino further with the oxygen of described sour condensation or nitrogen-atoms.Can be used for above-mentioned polyester standby in suitable fat carboxylic acid can be expressed from the next:

Wherein R ¹for hydrogen or the alkyl containing 1-20 carbon atom, and R ²for the alkylene containing 1-20 carbon atom.In some embodiments, R ¹containing 1-12,2-10,4-8 or even 6 carbon atoms, R ²containing 2-16,6-14,8-12 or even 10 carbon atoms.

In some embodiments, the aliphatic carboxylic acid for the preparation of polyester is 12-oxystearic acid, ricinolic acid, sabinic acid, 5-hydroxy-dodecanoic acid, 5-hydroxydecanoic acid, 4-hydroxydecanoic acid, 10-hydroxyundecanoic acid or its combination.

In some embodiments, have can with the oxygen of described sour condensation or nitrogen-atoms and the compound further with tertiary amino be expressed from the next:

Wherein R ³for the alkyl containing 1-10 carbon atom; R ⁴for the alkyl containing 1-10 carbon atom; R ⁵for the alkylene containing 1-20 carbon atom; And X ¹for O or NR ⁶, wherein R ⁶for hydrogen or the alkyl containing 1-10 carbon atom.In some embodiments, R ³containing 1-6,1-2, or even 1 carbon atom, R ⁴containing 1-6,1-2, or even 1 carbon atom, R ⁵containing 2-12,2-8 or even 3 carbon atoms, and R ⁶containing 1-8 or 1-4 carbon atom.In in these embodiments some, formula (II) becomes:

or

Wherein each definition provided above is still suitable for.

Can have the nitrogenous of tertiary amino or oxygen compound with acylating agent condensation and also, the example that maybe can be alkylated into the compound of this compounds includes but not limited to: 1-amino piperidine, 1-(2-amino-ethyl) piperidines, 1-(3-aminopropyl)-2-pipecoline, 1-methyl-(4-methylamino) piperidines, 4-(1-pyrrolidyl) piperidines, 1-(2-amino-ethyl) tetramethyleneimine, 2-(2-amino-ethyl)-1-crassitude, N, N-diethyl ethylenediamine, N, N-dimethyl-ethylenediamine, N, N-dibutyl quadrol, N, N-diethyl-1,3-diaminopropanes, N, N-dimethyl-1,3-diaminopropanes, N, N, N'-trimethylammonium quadrol, N, N-dimethyl-N'-ethylethylenediamine, N, N-diethyl-N'-methyl ethylenediamine, N, N, N'-triethylethylenediamine, 3-dimethylamino propylamine, 3-diethyl amino propylamine, 3-dibutyl amino propyl amine, N, N, N'-trimethylammonium-1,3-propylene diamine, N, N, 2,2-tetramethyl-1,3-propane diamine, 2-amino-5-diethylaminopentane, N, N, N', N'-tetraethyl-diethylenetriamine, 3,3'-diamino-N-methyl-di-n-propylamine, 3,3'-imino-two (N, N-dimethyl propylamine) or its combination.In this kind of embodiment, gained additive comprises quaternary ammonium amide salt, namely contains the purification agent of amide group and quaternary ammonium salt.

Nitrogenous or oxygen compound can comprise the heterogeneous ring compound that aminoalkyl group replaces further, such as 1-(3-aminopropyl) imidazoles and 4-(3-aminopropyl) morpholine.

In some embodiments, another kind of can have the nitrogenous of tertiary amino or oxygen compound after further alkylation with acylating agent condensation, comprise alkanolamine, include but not limited to trolamine, N, N-dimethyl amino propanol, N, N-Ndiethylaminopropanol, N, N-diethylamino butanols, tri-isopropanolamine, 1-[2-hydroxyethyl] piperidines, 2-[2-(dimethyl amine) oxyethyl group]-ethanol, N-ethyldiethanolamine, N methyldiethanol amine, N butyl diethanol amine, N, N-DEAE diethylaminoethanol, N, N-dimethylaminoethanol, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol.In the embodiment using wherein alkanolamine and/or analogous material, gained additive comprises ester quat salt, namely contains the purification agent of ester group and quaternary ammonium salt.

In one embodiment, nitrogenous or oxygen compound is tri-isopropanolamine, 1-[2-hydroxyethyl] piperidines, 2-[2-(dimethylamino) oxyethyl group]-ethanol, N-ethyldiethanolamine, N methyldiethanol amine, N butyl diethanol amine, N, N-DEAE diethylaminoethanol, N, N-dimethylaminoethanol, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol or its combination.

In some embodiments, having can with the oxygen of described sour condensation or nitrogen-atoms and the compound further with tertiary amino comprises N, N-diethyl ethylenediamine, N, N-dimethyl-ethylenediamine, N, N-dibutyl quadrol, N, N-dimethyl-1,3-diaminopropanes, N, N-diethyl-1,3-diaminopropanes, N, N-dimethylaminoethanol, N, N-DEAE diethylaminoethanol or its combination.

Quaternized polyester salt can be quaternized polyesteramide salt.In this kind of embodiment, the polyester for the preparation of the tertiary-amino-containing of quaternized polyester salt is tertiary-amino-containing polyesteramide.In in these embodiments some, amine or amino alcohol and monomer reaction, then make resulting materials and other monomer polymerization, produces required polyesteramide, then can be quaternized by it.

In some embodiments, quaternized polyester salt comprises the positively charged ion that following formula represents:

Wherein R ¹for hydrogen or the alkyl containing 1-20 carbon atom, and R ²for the alkylene containing 1-20 carbon atom; R ³for the alkyl containing 1-10 carbon atom; R ⁴for the alkyl containing 1-10 carbon atom; R ⁵for the alkylene containing 1-20 carbon atom; R ⁶for hydrogen or the alkyl containing 1-10 carbon atom; N is the number of 1-20 or 1-10; R ⁷for hydrogen, alkyl carbonyl containing 1-22 carbon atom, or the alkyl containing 1-22 carbon atom; And X ²for the group derived from quaternizing agent.In some embodiments, R ⁶for hydrogen.

As above, in some embodiments, R ¹containing 1-12,2-10,4-8 or even 6 carbon atoms, and R ²containing 1 or even 2-16,6-14,8-12 or even 10 carbon atoms, R ³containing 1-6,1-2 or even 1 carbon atom, R ⁴containing 1-6,1-2 or even 1 carbon atom, R ⁵containing 2-12,2-8 or even 3 carbon atoms, and R ⁶containing 1-8 or 1-4 carbon atom.In in these embodiments any one, n can be 2-9 or 3-7, and R ⁷6-22 or 8-20 carbon atom can be contained.R ⁷it can be acyl group.

In these embodiments, quaternized polyester salt uses C substantially _1-22or C _8-20lipid acid end-blocking.The example of appropriate acid comprises oleic acid, palmitinic acid, stearic acid, erucic acid, lauric acid, 2 ethyl hexanoic acid, 9,11-linolic acid, 9,12-linolic acid, 9,12,15-linolenic acid, sylvic acid or its combination.

The number-average molecular weight (Mn) of the quaternized polyester salt of the present invention can be 500-3000 or 700-2500.

Obtain by the mixture of one or more hydroxycarboxylic acids or hydroxycarboxylic acid and carboxylic acid is optionally heated under the existence of esterifying catalyst for the polyester in the present invention.Hydroxycarboxylic acid can have formula HO-X-COOH, wherein X is saturated containing the divalence of at least 8 carbon atoms or unsaturated aliphatic group, and wherein there are at least 4 carbon atoms between hydroxyl and hydroxy-acid group, or from the mixture of this hydroxycarboxylic acid with the not carboxylic acid of hydroxyl.This reaction can be carried out until obtain molecular weight at the temperature of 160-200 DEG C.Can measure the acid number of product after esterification process, in some embodiments, required polyester has the acid number of 10-100mg KOH/g or 20-50mg KOH/g.The instruction acid value of 10-100mgKOH/g is equivalent to the number-average molecular weight of 5600-560.The water formed in esterification can be removed from reaction medium, and this can conveniently by making nitrogen gas stream by reaction mixture, or by reacting under the existence of solvent as toluene or dimethylbenzene, and distill water when being formed and carry out.

Then gained polyester can be separated in a usual manner; But, when react its existence can not be harmful to carry out under the existence of the organic solvent applied subsequently time, the solution of gained polyester can be used.

In described hydroxycarboxylic acid, the group that X represents can contain 12-20 carbon atom, optionally wherein there is 8-14 carbon atom between carboxylic acid and hydroxyl.In some embodiments, hydroxyl is secondary hydroxyl.

The specific examples of this kind of hydroxycarboxylic acid comprises the mixture of ricinolic acid, 9-and 10 hydroxy stearic acid (by oleic acid sulfuration, thereafter be hydrolyzed and obtain), with 12-oxystearic acid, and especially except 12-oxystearic acid, the commercially available hydrogenated castor oil fatty of the stearic acid containing minor amount and palmitinic acid.

The carboxylic acid that can use to obtain these polyester together with hydroxycarboxylic acid is preferably carboxylic acid that is saturated or unsaturated lipid compounds of group, particularly containing the alkyl of chain and the alkenyl-carboxylic with 8-20 carbon atom.As the example of this kind of acid, lauric acid, palmitinic acid, stearic acid and oleic acid can be mentioned.

In one embodiment, polyester is the business 12-oxystearic acid of about 1600 derived from number-average molecular weight.Polyester such as this polyester is described in greater detail in british patent specification Nos.1373660 and 1342746.

In some embodiments, the component for the preparation of above-mentioned additive does not fully contain, does not substantially contain, or the alkyl not containing polyester even completely replaces acylating agent and/or do not replace two acylating agents, such as polyisobutylene succinic anhydride containing the alkyl of polyester.In some embodiments, these reagent got rid of are the reaction product of following component: long chain hydrocarbon, the polyolefine that usual and cholesterol carboxylic acid reaction thing reacts, such as (i) α, β-cholesterol C ₄-C ₁₀dicarboxylic acid, such as fumaric acid, methylene-succinic acid, toxilic acid; (ii) derivative of (i), the acid anhydride of such as (i) or C ₁-C ₅the monoesters that alcohol is derivative or diester; (iii) α, β-cholesterol C ₃-C ₁₀monocarboxylic acid is as vinylformic acid and methacrylic acid; Or the derivative of (iv) (iii), the such as C of (iii) ₁-C ₅alcohol derived ester, with general formula (R ⁹) (R ¹⁰) C=C (R ¹¹) (CH (R ⁷) (R ⁸)) represent containing any compound of ethylene linkage, wherein R ⁹and R ¹⁰be hydrogen or hydrocarbyl group independently of one another; R ¹¹, R ⁷and R ⁸be hydrogen or hydrocarbyl group independently of one another and preferably at least one is the alkyl containing at least 20 carbon atoms.In one embodiment, the alkyl of eliminating replaces acylating agent is dicarboxylic acid acylating agent.In in these embodiments some, it is polyisobutylene succinic anhydride that the alkyl of eliminating replaces acylating agent.

Fully not containing meaning to relate to these reagent indistinctively during instant component makes to react primarily of the material composition being different from above-mentioned alkyl and replacing acylating agent and the present composition does not comprise the additive derived from this kind of reagent of significant quantity.In some embodiments, instant component or the present composition can comprise and be less than this kind of reagent of 10 % by weight or the additive derived from this kind of reagent.In other embodiments, MAD can be 5,3,2,1 or even 0.5 or 0.1 % by weight.One of object of these embodiments makes to get rid of reagent as polyisobutylene succinic anhydride from the present invention's reaction, so, also make to get rid of derived from the quaternized salt detergent additives of reagent as polyisobutylene succinic anhydride.Focus of the present invention is polyester or hyper-dispersant, quaternary ammonium salt detergent additives.

B. quaternizing agent

The present invention's quaternized salt purification agent is formed when above-mentioned on-quaternised purification agent and quaternizing agent react.Suitable quaternizing agent comprises selected dialkyl sulfate, benzyl halide, alkyl replacement carbonic ether; The hydrocarbyl epoxides combined with acid or its mixture.

In one embodiment, quaternizing agent can comprise alkylogen, such as muriate, iodide or bromide; Alkyl sulfonate esters; Dialkyl sulfate, such as methyl-sulfate; Sultones; Alkyl phosphate; Such as phosphoric acid C _1-12trialkyl ester; Di(2-ethylhexyl)phosphate C _1-12alkyl ester; Boric acid ester; Boric acid C _1-12alkyl ester; Alkyl nitrite; Alkyl nitrate ester selected; Dialkyl carbonate; Chain acid alkyl ester; Phosphorodithioic acid O, O-C _1-12alkyl ester or its mixture.

In one embodiment, quaternizing agent can derived from dialkyl sulfate, and such as methyl-sulfate, N-oxide compound, sultone are as third and butyl sultone; Alkyl, acyl group or aralkyl halide are as methyl and ethyl chloride, bromine or iodine, or benzyl chloride, and alkyl (or alkyl) replaces carbonic ether.If alkylogen is benzyl chloride, then aromatic ring is optionally replaced by alkyl or alkenyl further.

The alkyl (or alkyl) that alkyl replaces carbonic ether can contain 1-50,1-20,1-10 or 1-5 the every group of carbon atom.In one embodiment, alkyl replaces carbonic ether and contains two alkyl, and described alkyl can be identical or different.The example that suitable alkyl replaces carbonic ether comprises methylcarbonate or diethyl ester.

In another embodiment, quaternizing agent can be the hydrocarbyl epoxides that is shown below combined with acid:

Wherein R ¹, R ², R ³and R ⁴can be H or the alkyl containing 1-50 carbon atom independently.The example of hydrocarbyl epoxides comprises: ethylene oxide, propylene oxide, oxybutylene, Styrene oxide 98min. and combination thereof.In one embodiment, quaternizing agent does not comprise any Styrene oxide 98min..

In some embodiments, the acid used together with hydrocarbyl epoxides can for the component of separating, such as acetic acid.In other embodiments, such as, when alkyl acylating agent is dicarboxylic acid acylating agent, do not need acid constituents separately.In this kind of embodiment, purification agent by will substantially not containing or even not prepare as the combinations of reactants of acetic acid containing acid constituents separately, and instead, relies on the acid groups of alkyl acylating agent.In other embodiments, a small amount of acid constituents can be there is, but be <0.2 or even <0.1 equimolar acid every mole of alkyl acylating agent.These acid also can use together with other quaternizing agent above-mentioned, comprise alkyl and replace carbonic ether and hereinafter described associated materials.

In some embodiments, quaternizing agent of the present invention does not comprise any containing the substituting group more than 20 carbon atoms.In other words, in some embodiments, make gained additive Identification of Soluble Organic and therefore do not provided by quaternizing agent for the long substituting group of the object of the invention, but producing additive by above-mentioned on-quaternised purification agent.

In certain embodiments, have amine official can purification agent and the mol ratio of quaternizing agent be 1:0.1-2, or 1:1-1.5, or 1:1-1.3.

In another embodiment, quaternizing agent can be the ester that can form the carboxylic acid of quaternary ammonium salt with reactive tertiary amine, or the ester of poly carboxylic acid.Generally speaking, this kind of material can be described as the compound with following structure:

R ¹⁹-C(=O)-O-R ²⁰(IX)

Wherein R ¹⁹for the alkyl, alkenyl, aryl or the alkylaryl that optionally replace, and R ²⁰for the alkyl containing 1-22 carbon atom.

Suitable compound comprises the carboxylicesters of the pKa with 3.5 or less.In some embodiments, compound is be selected from the ester of carboxylic acid replacing aromatic carboxylic acid, alpha-hydroxy carboxylic acid compounds and poly carboxylic acid.In some embodiments, compound is the ester replacing aromatic carboxylic acid, therefore R ¹⁹for substituted aryl.R can for having substituted aryl, the phenyl or naphthyl of 6-10 carbon atom.R suitably can be selected from carbon alkoxyl group, nitro, cyano group, hydroxyl, SR by one or more " or NRR " group replace, wherein R " and R " can be the alkyl of hydrogen or optional replacement, alkenyl, aryl or carbon alkoxyl group separately independently.In some embodiments, R " and R " be hydrogen or the optional substituted alkyl containing 1-22,1-16,1-10 or even 1-4 carbon atom independently of one another.

In some embodiments, the R in above formula ¹⁹for being selected from hydroxyl, carbon alkoxyl group, nitro, cyano group or NH by one or more ₂group replace aryl.R ¹⁹can be polysubstituted aryl, such as trihydroxy-phenyl, but also can be monosubstituted aryl, such as orthosubstituted aryl.R ¹⁹can be selected from and be selected from OH, NH ₂, NO ₂or the group of COOMe replaces.Suitably, R ¹⁹for hydroxyl substituted aryl.In some embodiments, R ¹⁹for 2-hydroxy phenyl.R ²⁰can be alkyl or alkylaryl, such as, contain alkyl or the alkylaryl of 1-16 carbon atom or 1-10 or 1-8 carbon atom.R ²⁰can be methyl, ethyl, propyl group, butyl, amyl group, benzyl or its isomer.In some embodiments, R ²⁰for benzyl or methyl.In some embodiments, quaternizing agent is wintergreen oil.

In some embodiments, quaternizing agent is the ester of alpha-hydroxy carboxylic acid compounds.This compounds be applicable to herein is described in EP1254889.The example of the suitable combination thing of the residue containing alpha-hydroxy carboxylic acid compounds comprises: the methyl of (i) 2-hydroxy-iso-butyric acid-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, benzyl-, phenyl-and allyl ester; (ii) 2-hydroxy-2-methyl butyric acid methyl-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, benzyl-, phenyl-and allyl ester; (iii) 2-hydroxyl-2 Ethylbutanoic acid methyl-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, benzyl-, phenyl-and allyl ester; (iv) lactic acid methyl-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, benzyl-, phenyl-and allyl ester; (v) oxyacetic acid methyl-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, allyl group-, benzyl-and phenylester.In some embodiments, quaternizing agent comprises 2-hydroxy-methyl isobutyl acid.

In some embodiments, quaternizing agent comprises the ester of poly carboxylic acid.In this definition, we mean the carboxylic acid comprising dicarboxylic acid and have more than 2 acid structure divisions.In some embodiments, ester is the alkyl ester of the alkyl had containing 1-4 carbon atom.Suitable example comprises diester or three esters of the diester of oxalic acid, the diester of phthalic acid, the diester of toxilic acid, the diester of propanedioic acid or citric acid.

In some embodiments, quaternizing agent is the carboxylicesters with the pKa being less than 3.5.Compound comprises in this kind of embodiment of more than one acid groups wherein, and we mean to relate to the first dissociation constant.Quaternizing agent can be selected from the ester of carboxylic acid, described carboxylic acid be selected from following one or more: oxalic acid, phthalic acid, Whitfield's ointment, toxilic acid, propanedioic acid, citric acid, nitrobenzoic acid, benzaminic acid and 2,4,6-trihydroxybenzoic acid.In some embodiments, quaternizing agent comprises dimethyl oxalate, 2-nitrobenzene methyl and wintergreen oil.

Any one in above-mentioned quaternizing agent, comprises hydrocarbyl epoxides, can combinationally use with acid.Suitable acid comprises carboxylic acid, such as acetic acid, propionic acid, 2 ethyl hexanoic acid etc.

containing the composition of the quaternized purification agent of polyester

The present invention's quaternized salt purification agent can be used as additive in each based composition, comprises fuel composition and additive concentrate compositions.

A. fuel composition

The quaternized purification agent of the present invention can be used as additive in fuel composition.Fuel composition of the present invention comprises above-mentioned quaternized detergent additives and liquid fuel, and for giving oil engine or open flame burner refuel.These compositions also can contain one or more other additives.These optional additives are described in hereinafter.In some embodiments, the fuel be applicable in the present invention comprises any commercial fuel, and in some embodiments, any market available diesel oil fuel and/or biofuel.

Next the description of the fuel type be applicable in the present invention is related to and can be present in the present invention containing the fuel in the composition of additive and the fuel that can add wherein containing the composition of additive and/or fuel additive concentrate.

The fuel be applicable in the present invention is unduly limited.Generally speaking, suitable fuel, usually in envrionment conditions, such as, is liquid under room temperature (20-30 DEG C) or is usually liquid in the operating condition.Fuel can be hydrocarbon fuel, nonhydrocarbon fuel or its mixture.

Hydrocarbon fuel can be petroleum fractions, comprise as ASTM specification D4814 the gasoline that defines or as ASTM specification D975 the diesel oil fuel that defines.In one embodiment, liquid fuel is gasoline, and in another embodiment, liquid fuel is white gasoline.In another embodiment, liquid fuel is diesel oil fuel.Hydrocarbon fuel for the hydrocarbon prepared by natural gas synthetic oil method, can be comprised and such as being prepared by method such as Fischer-Tropsch method, and the hydrocarbon of optional hydroisomerization.In some embodiments, the present invention is fuel used is diesel oil fuel, biodiesel fuel or its combination.

Suitable fuel also comprises comparatively heavy fuel oil, and such as No. 5 and No. 6 oil fuel, it is also referred to as residual fuel oil, heavy fuel oil and/or furnace oil.This class A fuel A can be used alone or and other, usually compared with light fuel mixing with formed there is more low viscous mixture.Also comprise the bunker fuel be generally used in ship engine.The fuel of these types has high viscosity and at ambient conditions can for solid, but is liquid when heating and feed in the engine of its refuel or burner.

Nonhydrocarbon fuel for containing oxygen composition, can be commonly referred to oxygenate, and described oxygenate comprises alcohol, ether, ketone, the ester of carboxylic acid, itroparaffin or its mixture.Nonhydrocarbon fuel can comprise methyl alcohol, ethanol, methyl tertiary butyl ether, methylethylketone, ester-exchanged oil and/or from the fat of plant and animal as coleseed methyl esters and soy methyl ester, and Nitromethane 99Min..

The mixture of hydrocarbon and nonhydrocarbon fuel can comprise such as gasoline and methyl alcohol and/or ethanol, diesel oil fuel and ethanol, and diesel oil fuel and transesterify vegetables oil are as coleseed methyl esters and other biologically-derived fuel.In one embodiment, liquid fuel is the emulsion of water in hydrocarbon fuel, nonhydrocarbon fuel or its mixture.

In several embodiments of the present invention, liquid fuel can have based on weight 50,000ppm or less, 5000ppm or less, 1000ppm or less, 350ppm or less, 100ppm or less, 50ppm or less or 15ppm or less sulphur content.

Liquid fuel of the present invention is present in fuel composition with the primary amount being usually greater than 95 % by weight, in other embodiments, being greater than 97 % by weight, being greater than 99.5 % by weight, being greater than 99.9 % by weight or be greater than 99.99 % by weight and exist.

B. additive concentrate compositions

Multifunctional additive for lubricating oils is containing one or more additives and also can contains the composition of the thinner of the fuel of a tittle, oil or some types.Then can be used as usual way adds to process and to provide additive in other composition by these enriched materials, generation final composition is as above-mentioned fuel composition.

Additive concentrate compositions of the present invention contains one or more above-mentioned quaternized purification agent and optional diluent, and described thinner can be any one above-mentioned fuel, solvent, thinning oil or analogous material.These compositions also can comprise one or more hereinafter described other additives.

C. other additive optional

The present composition comprises above-mentioned quaternized purification agent, and also can comprise one or more other additives.Other performance additive this kind of adds in any described composition by the application that can be depending on results needed and composition use.

Although other performance additive any described herein can be used in any present composition, other additive is used in particular for fuel composition below: antioxidant, corrosion inhibitor, purification agent and/or be different from above-mentioned those dispersant additives, cold flow improver, suds suppressor, demulsifying compound, lubricant, metal deactivators, valve seat decline additive, biocide, static inhibitor, deicing agent, liquid agent, combustion improving agent, sealing swelling agent, wax control polymers, scale inhibitor, gas hydrate inhibitor or its any combination.

Suitable antioxidant comprises such as hindered phenol or derivatives thereof and/or diarylamine or derivatives thereof.Suitable purification agent/dispersant additives comprises such as polyetheramine or nitrogenous purification agent, include but not limited to PIB amine purification agent/dispersion agent, succinimide purification agent/dispersion agent, with other quaternary ammonium salt purification agent/dispersion agent, comprise the derivative quaternized PIB/ amine of poly-isobutyl-succinimide and/or acid amides dispersion agent/purification agent.Suitable cold flow improver comprises the multipolymer of such as maleic anhydride and cinnamic esterified copolymer and/or ethene and vinyl-acetic ester.Suitable demulsifying compound comprises such as poly-alkoxylation alcohol.Proper lubrication agent comprises such as aliphatic carboxylic acid.Suitable metal deactivators comprises such as aromatic triazole or derivatives thereof, includes but not limited to benzotriazole.Suitable valve seat decline additive comprises such as alkali metal sulfosuccinates.Suitable suds suppressor and/or defoamer comprise such as organo-siloxane, such as polydimethylsiloxane, PES-4, polydiethylsiloxane, polyacrylic ester and polymethacrylate, trimethylammonium-Trifluoro-propyl methylsiloxane etc.Suitable liquid agent comprises such as mineral oil and/or poly-(alpha-olefin) and/or polyethers.Combustion improving agent comprises such as octane and cetane number improver.

Other performance additive that can be present in the present composition also comprises diester, diamide, esteramides and ester imide friction improver, it is by dicarboxylic acid (as tartrate) and/or tricarboxylic acid (as citric acid) and amine and/or alcohol, optionally reaction and preparing under the existence of known esterifying catalyst.Usually these friction improvers derived from tartrate, citric acid or derivatives thereof can derived from amine and/or branching alcohol, and produce friction improver, described friction improver itself has the branched hydrocarbyl radical of the significant quantity be present in its structure.Example for the preparation of the suitable branching alcohol of this kind of friction improver comprises 2-Ethylhexyl Alcohol, different tridecyl alcohol, Guerbet alcohol and composition thereof.

Other performance additive can comprise the nitrogenous purification agent/dispersion agent of high TBN, such as succinimide, and it is Hydrocarbyl-substituted succinic acid anhydrides and the condensation product gathering (alkylene amines).Succinimide purification agent/dispersion agent is described in United States Patent (USP) 4,234,435 and 3,172, in 892 more completely.Another kind of ashless dispersant is react by alkyl acylating agent and multi-aliphatic alcohol such as glycerine, tetramethylolmethane or Sorbitol Powder the high-molecular weight ester prepared.This kind of material is described in greater detail in United States Patent (USP) 3, and 381, in 022.Another kind of random dispersion agent is Mannich base.These are for the material that formed as formaldehyde condensation by higher molecular weight alkyl substituted phenol, alkylene polyamine and aldehyde and be described in greater detail in United States Patent (USP) 3,634, in 515.Other dispersion agent comprises polymeric dispersant additive, it typically is containing polar functional to give the hydrocarbyl polymers of polymer dispersed force characteristic.Amine is generally used for preparing the nitrogenous dispersion agent of high TBN.Can use one or more poly-(alkylene amines), and these can comprise poly-(vinyl-amine) that one or more have 3-5 ethylene units and 4-6 nitrogen unit.This kind of material comprises Triethylenetetramine (TETA) (TETA), tetren (TEPA) and penten (PEHA).This kind of material is usually used as containing a large amount of ethylene units and nitrogen-atoms, and various isomerization structure, and the mixture comprising the various isomer of various ring texture is commercially available.Poly-(alkylene amines) also can comprise in industry as the residual known relatively high molecular weight amines of vinyl-amine still.

Also can by dispersion agent by reacting and aftertreatment with any one in plurality of reagents.Be urea in these, thiocarbamide, dimercaptothiodiazole, dithiocarbonic anhydride, aldehyde, ketone, carboxylic acid, alkyl replace succinyl oxide, nitrile, epoxide, boron compound and phosphorus compound.The reference describing this process in detail lists in United States Patent (USP) 4,654, in 403.

The present composition can comprise the detergent additives being different from the quaternized salt additives of the present invention.Purification agent the most frequently used in engine lubrication field obtains great majority or its basicity all or TBN by basic nitrogen compound (usually based on this metalloid as the metal hydroxides of calcium, magnesium or sodium, oxide compound or carbonate).This kind of metallic high alkaline purification agent, also referred to as high alkalinity or hyperalkaline salt, is generally single phase homogeneous Newtonian systems, it is characterized in that metal content exceedes and exists for neutralizing according to metal with the stoichiometry of the concrete acidic organic compound of metal reaction.Overbased material is prepared by mixture reaction usually in the reaction medium of a kind of inert organic solvents for acid organic substrate (such as mineral oil, petroleum naphtha, toluene, dimethylbenzene) of the metal base of acid material (usual mineral acid or low-grade carboxylic acid, preferably carbon dioxide) and acidic organic compound (also referred to as matrix), stoichiometric excess usually.Usually also there is a small amount of promotor as phenol or alcohol, and a small amount of water in some cases.Acid organic substrate has the carbon atom of enough numbers usually to be provided in the solubleness in oil.

This kind of conventional overbased material and their preparation method are well known to those skilled in the art.Describe prepare sulfonic acid, carboxylic acid, phenol, phosphonic acids metal-salt and in these two or more patent of technology of mixture any comprise United States Patent (USP) 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; With 3,629,109.Salixarate purification agent is described in United States Patent (USP) 6, and 200, in 936.

Antioxidant comprises phenolic antioxidants, and it can comprise the butyl fortified phenol containing 2 or 3 tertiary butyls.Contraposition also can be occupied by the group of alkyl or bridging two aromatic rings.Rear a kind of antioxidant is described in greater detail in United States Patent (USP) 6,559, in 105.Antioxidant also comprises aromatic amine, such as nonylated diphenylamine.Other antioxidant comprises olefine sulfide, titanium compound and molybdenum compound.U.S. Patent No. 4,285,822 such as disclose containing the lubricating oil composition containing molybdenum and sulphur composition.Certainly, the typical amount of antioxidant depends on concrete antioxidant and its independent effect, but illustrative total amount can be 0.01-5, or 0.15-4.5, or 0.2-4 % by weight.In addition, can exist more than a kind of antioxidant, and these some be combined in its combine total effect aspect can for synergy.

Viscosity modifier (sometimes also referred to as viscosity index improver or viscosity modifier) can comprise in the compositions of the present invention.Viscosity modifier is generally polymkeric substance, comprises polyisobutene, polymethacrylate (PMA) and polymethacrylate, hydrogenated diene polymer, alkyl styrenes, esterification styrene-maleic anhydride copolymer, hydrogenation alkenyl aromatic hydrocarbon conjugated diene copolymer and polyolefine.PMA is prepared by the mixture of the methacrylate monomer with different alkyl.Alkyl can for the straight or branched group containing 1-18 carbon atom.Most PMA is viscosity modifier and pour point reducer.

The multi-functional viscosity modifier also with dispersion agent and/or antioxidant property is known and can optionally uses.Dispersant viscosity modifiers (DVM) is an example of this kind of multifunction additive.DVM is prepared by a small amount of nitrogen containing monomer and alkyl methacrylate copolymerization usually, produce have dispersion force, viscosity modified, pour point decline and dispersion force some combination additives.Vinyl pyridine, NVP and methacrylic acid N, N'-dimethylamino ethyl ester are the example of nitrogen containing monomer.The polyacrylic ester obtained by polymerization or the copolymerization of one or more alkyl acrylates is also used as viscosity modifier.

In some embodiments, anti-wear agent can comprise phosphorous wear-resistant/extreme pressure agent, such as metal thiophosphate, phosphoric acid ester and salt thereof, phosphorus-containing carboxylic acid, ester, ether and acid amides; And phosphorous acid ester.In certain embodiments, phosphorus anti-wear agent can exist to provide the amount of 0.01-0.2 or 0.015-0.15 or 0.02-0.1 or 0.025-0.08 % by weight phosphorus.Usually, anti-wear agent is zinc dialkyl dithiophosphate (ZDP).For the typical ZDP that can contain 11%P (based on without oil), suitable amount can comprise 0.09-0.82 % by weight.Non-phosphorous anti-wear agent comprises boric acid ester (comprising boration epoxide), dithio carbamate compounds, molybdate compound and olefine sulfide.In some embodiments, fuel composition of the present invention containing phosphorous wear-resistant/extreme pressure agent.

Any other performance additive above-mentioned can be added in the present composition.Each directly can be added in additive of the present invention and/or composition, but usually they be mixed to form compositions of additives or enriched material with additive, then by itself and fuel mix to produce fuel composition.These various types of compositions are described in greater detail in above.In the present composition, the amount of other additive can be 1-10 % by weight usually, or 1.5-9.0%, or 2.0-8.0%, allly all states based on without oil meter.

the preparation method of quaternary ammonium salt purification agent

The invention provides the preparation method of quaternized amides and/or ester purification agent, wherein method comprises: the polyester making (a) tertiary-amino-containing; (b) be suitable for quaternizing agent reaction uncle's amino being changed into quaternary nitrogen, obtain quaternized dispersion agent thus.

As mentioned above, quaternizing agent is optional replaces carbonic ether from dialkyl sulfate, benzyl halide, alkyl; The hydrocarbyl epoxides combined with acid or its mixture.

The inventive method also can be described as the method preparing quaternized purification agent, and described method comprises step: (1) is by the polyester of (a) tertiary-amino-containing, (b) quaternizing agent and optional (c) protonic solvent mixing; (2) mixture is heated to the temperature of 50-130 DEG C; (3) keep reaction to completing; Obtain quaternized purification agent thus.In one embodiment, react be less than 80 DEG C or be less than 70 DEG C temperature under carry out.In other embodiments, reaction mixture is heated to the temperature of about 50 to 120 DEG C, 80 DEG C or 70 DEG C.In other embodiments again, temperature of reaction can be 70-130 DEG C.In other embodiments, temperature of reaction can be 50-80 DEG C or 50-70 DEG C.

In some embodiments, the inventive method does not add any acid reaction, such as acetic acid.In these embodiments, obtain salt product, although there is not acid reaction separately.

As mentioned above, in some embodiments, the polyester of on-quaternised tertiary-amino-containing is aliphatic carboxylic acid containing at least one hydroxyl and has and can have the condensation product of the compound of tertiary amino further with the oxygen of described sour condensation or nitrogen-atoms, obtains the polyester of tertiary-amino-containing thus.In some embodiments, having can with the oxygen of described sour condensation or nitrogen-atoms and the compound further with tertiary amino is amino containing uncle and uncle or secondary amino group diamines.

Additive of the present invention can obtain under the existence of protonic solvent.Suitable protonic solvent comprises the solvent with the specific inductivity being greater than 9.In one embodiment, protonic solvent comprises the compound containing 1 or more hydroxyl (-OH) functional group, and can comprise water.

In one embodiment, solvent is glycol and glycol ethers.Containing 2-12 carbon atom, or 4-10, or the glycol of 6-8 carbon atom and oligopolymer (such as dipolymer, trimer and tetramer) thereof are suitable for usually.Illustrative glycol comprises ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, BDO, 2-methyl-l, ammediol, neopentyl glycol, triglycol, polyoxyethylene glycol etc. and oligopolymer thereof and polymeric derivative and mixture.Illustrative glycol ethers comprises the C of propylene glycol, ethylene glycol and oligopolymer thereof ₁-C ₆alkyl oxide as methyl, ethyl, propyl group, butyl or hexyl two-, three-and Tetraglycol 99 ether.Suitable glycol ethers comprises the ether of dipropylene glycol, tripropylene glycol, glycol ether, triglycol; Ethyl diethylene glycol ethers, butyldiglycol ether, methoxy triglycol, ethoxy triglycol, butoxy triglycol, methoxyl group Tetraglycol 99, butoxy Tetraglycol 99.

The solvent be applicable in the present invention also comprises C _1-20alcohol, comprises branched hydrocarbyl radical alcohol.The example of suitable alcohols comprises 2-isoocanol, 2-methyl-decanol, 2-ethylpentanol, 2-Ethylhexyl Alcohol, 2-ethyl nonyl alcohol, 2-propyl enanthol, 2-butanols enanthol, 2-butyl octanol, isooctyl alcohol, dodecanol, hexalin, methyl alcohol, ethanol, the third-1-alcohol, 2-methyl propan-2-ol, 2-methyl-prop-1-alcohol, fourth-1-alcohol, fourth-2-alcohol, amylalcohol and isomer thereof, and composition thereof.In one embodiment, solvent of the present invention is 2-Ethylhexyl Alcohol, 2-ethyl nonyl alcohol, 2-propyl enanthol or its combination.In one embodiment, solvent of the present invention comprises 2-Ethylhexyl Alcohol.

Solvent can be the mixture of any commercially available alcohol or this kind of alcohol, and comprises the mixture of this kind of alcohol and alcohol and water.In some embodiments, water is the exclusive solvents used.In some embodiments, the amount of the water of existence can be more than 1 % by weight of solvent mixture.In other embodiments, solvent mixture can contain trace water, and wherein water-content is for being less than 1 or 0.5 % by weight.

Alcohol can be aliphatic, alicyclic, aromatics or heterocycle, comprise alicyclic alcohol that aliphatic series replaces, heterocyclic alcohol that aromatic alcohol that aliphatic series replaces, aliphatic series replace, the fatty alcohol of alicyclic replacement, the aromatic alcohol of alicyclic replacement, the heterocyclic alcohol of alicyclic replacement, the fatty alcohol of heterocyclic substituted, the alicyclic alcohol of heterocyclic substituted and heterocyclic substituted aromatic alcohol.

Be reluctant bound by theory, think and need polar aprotic solvent (it can comprise water) to promote that acid is dissociated into ion and proton.When first the purification agent with amine official energy reacts with quaternizing agent, need dissociation protonated with the ion that will be formed.When quaternizing agent is alkyl epoxide, gained ion is unstable alkoxide ion.Dissociation also provides the counter ion of the acid groups from additive, and described additive is used for the quaternary ammonium ion formed in stable reaction, produces more stable product.

industrial application

In one embodiment, the inventive method produces quaternary ammonium salt purification agent.Quaternary ammonium salt purification agent can be used as the additive in the fuel of oil engine and/or open flame burner.

Oil engine comprises spark ignition and compression ignition engine; Double stroke or Otto cycle; By direct injection, indirect injection, port injection and carburetor supply liquid fuel; Common rail and Integral injector system; Gently (such as passenger vehicle) and heavy (such as commercial truck) engine; With the engine with hydrocarbon and nonhydrocarbon fuel and composition thereof refuel.Engine can for being incorporated to a part for the comprehensive discharge system of this class component; Egr system; Aftertreatment, comprises three-way catalyst, oxide catalyst, NOx absorption agent and catalyzer, optional catalysis and the on-catalytic particle trapper using fuel based catalyzer; Vario valve timing; With injection timing and rate shape.

The open flame burner of burning can for assembling be with any naked flame burning equipment of combustion of liquid fuel.These comprise family expenses, commercial and industrial burner.Industrial burner comprises those that need preheating suitably to be processed by fuel and to be atomized.Also comprise oil burning apparatus, fuel electric generating apparatus, fired heater and boiler, and for ship and marine use, comprise the boiler in deep-draft vessel.Comprise the boiler for power generation assembly, utility device and large-scale fixing and ship engine.Flaming fuel combustion appliance can be incinerator, such as rotary kiln incinerator, spouting of liquid kiln, fluidized-bed kiln, cement kiln etc.Also comprise steel and aluminum forging furnace.Naked flame burning equipment can be equipped with flue gas recirculation system.

As used herein, term " hydrocarbyl substituent " or " alkyl " use with its conventional meaning well known to those skilled in the art.Specifically, it refers to have the carbon atom that is connected directly between on molecule rest part and mainly has the group of hydrocarbon character.The example of alkyl comprises: hydrocarbon substituent, i.e. aliphatic series (such as alkyl or alkenyl), alicyclic (such as cycloalkyl, cycloalkenyl group) substituting group, with aromatics-, aliphatic series-and the aromatic substituent of alicyclic replacement, and wherein ring completes the cyclic substituents of (such as two substituting groups form ring together) by another part of molecule; The hydrocarbon substituent replaced, namely contains the substituting group of the non-hydrocarbon (such as halogen (especially chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group and sulfinyl (sulfoxy)) not changing substituent main hydrocarbon character in the context of the present invention; Assorted substituting group, namely in the context of the present invention, while there is main hydrocarbon character in the ring be made up of carbon atom or chain containing the substituting group being different from carbon.Heteroatoms comprises sulphur, oxygen, nitrogen, and comprises substituting group as pyridyl, furyl, thienyl and imidazolyl.Generally speaking, for every 10 carbon atoms, in alkyl, have no more than 2, preferably no more than 1 substituents; Usually, there is not substituents in alkyl.As used herein, term " alkyl carbonyl " or " alkyl carbonyl substituting group " mean the alkyl containing carbonyl.

More known above-mentioned materialss may interact in final preparaton, make the component of final preparaton may be different from those originally adding.Such as, metal ion (such as purification agent) can migrate to other acid or anionic site of other molecule.The product formed thus, comprises the product formed through using the present composition with its intended use and may be not easy to describe.But all this kind of improvement and reaction product include within the scope of the invention; The present invention includes by the composition of preparation by said components mixing.

Embodiment

The present invention is set forth further by following examples.Although provide this embodiment to set forth the present invention, they are not intended to limit it.

embodiment A-on-quaternised polyesteramide (preparation material)

On-quaternised polyesteramide is prepared by making 6 moles of 12-oxystearic acids and the reaction of 1 mole of dimethylamino propylamine in the jacketed reaction container being equipped with agitator, condenser, the fresh feed pump be connected in auxiliary adding tube, nitrogen pipeline and thermopair/temperature controlling system, wherein reacts and to carry out at about 130 DEG C and to keep about 4 hours.Then reaction mixture being cooled to about 100 DEG C and adding butanols zirconium with such amount makes catalyzer be formed the reaction mixture of 0.57 % by weight.Reaction mixture be heated to about 195 DEG C and keep about 12 hours.Cool and collect products therefrom.

embodiment B-quaternized polyesteramide salt purification agent (embodiment of the present invention)

Quaternized polyesteramide salt purification agent is prepared by making the 2-Ethylhexyl Alcohol of the on-quaternised polyesteramide of 600g embodiment A, 120g, 18.5g acetic acid and 32.3ml propylene oxide react in the jacketed reaction container being equipped with agitator, condenser, the fresh feed pump be connected in auxiliary adding tube, nitrogen pipeline and thermopair/temperature controlling system, wherein reacts and to carry out at about 75 DEG C and to be fed in reaction vessel by propylene oxide through about 3.5 hours.Then reaction mixture is kept about 3 hours at such a temperature.Cool and collect 760g product, TAN, FTIR and ESI-MS analyze and are confirmed that it is about 80 % by weight quaternized polyesteramide salt purification agents, and all the other materials are mainly on-quaternised polyesteramide.The material collected have TAN, 23.82mg KOH/g of 1.26mg KOH/g TBN, at 100 DEG C kinematic viscosity (as measured by ASTM D445), the 1574cm of 28.58cSt ^-1place IR acetic ester peak value, and be 1.22% nitrogen.

embodiment C-on-quaternised polyesteramide (preparation material)

On-quaternised polyesteramide reacts by making 1300g ricinolic acid and 73.5g dimethylamino propylamine in the jacketed reaction container being equipped with agitator, condenser, the fresh feed pump be connected in auxiliary adding tube, nitrogen pipeline and thermopair/temperature controlling system and prepares, wherein react and carry out at about 130 DEG C, dropwise added amine through about 8 minutes, and reaction mixture is kept about 4 hours.Then reaction mixture be cooled to about 100 DEG C and add 7.8g butanols zirconium.Reaction mixture be heated to about 195 DEG C and keep about 17 hours.Products therefrom is filtered, cools and collect.Collect 1301g product, it has the TAN of 0mg KOH/g and is presented at 1732cm by IR ^-1ester peak value, the 1654cm at place ^-1the acid amides peak value at place, but at 1700cm ^-1place does not have sour peak value.

embodiment D-quaternized polyesteramide salt purification agent (embodiment of the present invention)

Quaternized polyesteramide salt purification agent is prepared by making the 2-Ethylhexyl Alcohol of the on-quaternised polyesteramide of 600g Embodiment C, 123g, 18.9g acetic acid and 33.1ml propylene oxide react in the jacketed reaction container being equipped with agitator, condenser, the fresh feed pump be connected in auxiliary adding tube, nitrogen pipeline and thermopair/temperature controlling system, wherein react and carry out at about 75 DEG C, and through about 3.5 hours, propylene oxide is fed in reaction vessel.Then reaction mixture is kept about 3 hours at such a temperature.Cool and collect 751g product, TAN, FTIR and ESI-MS analyze and turn out to be it for about 70 % by weight quaternized polyesteramide salt purification agents, and all the other materials are on-quaternised polyesteramide mainly.Collect material have TAN, 23.14mg KOH/g of 0mg KOH/g TBN, at 100 DEG C 47.0cSt kinematic viscosity (as measured by ASTM D445), at 1574cm ^-1the IR acetic ester peak value at place.

embodiment E-on-quaternised polyisobutene purification agent (comparative example)

On-quaternised polyisobutene list succinimide purification agent is by being equipped with agitator, condenser, be connected to the fresh feed pump in auxiliary adding tube, 100pbw polyisobutylene succinic anhydride (itself is prepared with 1:1.2 molar ratio reaction by 1000 number-average molecular weight high vinylidene polyisobutylenes and maleic anhydride) is made in the jacketed reaction container of nitrogen pipeline and thermopair/temperature controlling system, 13pbw tetren reacts and prepares, wherein acid anhydride is preheated to about 80 DEG C, through about 8 hours, amine is added in system, wherein reaction mixture temperature is remained on less than 120 DEG C.Then reaction mixture is heated to 170 DEG C, then coupling vacuum stripping.Cool and collect gained on-quaternised polyisobutene list succinimide purification agent.

embodiment F-quaternized polyisobutene purification agent (comparative example)

Quaternized polyisobutenyl succinimide purification agent is by being equipped with agitator, condenser, be connected to the fresh feed pump in auxiliary adding tube, 100pbw polyisobutylene succinic anhydride (itself is prepared with 1:1.2 molar ratio reaction by 1000 number-average molecular weight high vinylidene polyisobutylenes and maleic anhydride) is made in the jacketed reaction container of nitrogen pipeline and thermopair/temperature controlling system, 10.9pbw dimethylamino propylamine reacts and prepares, wherein acid anhydride is preheated to about 80 DEG C, through about 8 hours, amine is added in system, wherein reaction mixture temperature is remained on less than 120 DEG C.Then reaction mixture be heated to 150 DEG C and keep 3 hours, producing on-quaternised polyisobutenyl succinimide purification agent.Then 40.6pbw2-ethylhexanol, 1pbw water, 5.9pbw acetic acid are added in on-quaternised polyisobutenyl succinimide purification agent.In maintenance after 3 hours, add 8.5pbw propylene oxide, reaction is kept about 6 hours at 75 DEG C.Cool and collect the quaternized polyisobutenyl succinimide purification agent of gained.

xUD-9 testing of engine

Peugot XUD-9 engine in indirect injection engine. in this experiment, measure the % residual flow in fuel injector when off-test, wherein higher % residual flow is wanted, as the instruction reducing the formation of syringe settling.XUD-9 testing of engine is separately carried out based on the fuel composition containing Embodiment B, the fuel composition containing embodiment F and the fuel composition containing embodiment E.Each composition uses identical basic fuel and contains the additive to be assessed of 71ppm.Known basic fuel provides when testing separately the % residual flow being less than 20%.Acquired results is as follows:

Table 1-XUD-9 testing of engine result

Fuel sample	The additive of assessment	% residual flow
			1	Embodiment of the present invention B	84
2	Comparative example F	100
			3	Comparative example E	36

Result display embodiment of the present invention B additive and the quaternized polyisobutenyl succinimide purification agent of embodiment F approximately equally wellly and show more much betterly than the on-quaternised polyisobutenyl succinimide purification agent of embodiment E.All embodiments all show better than independent basic fuel, but the additive of Embodiment B and F is more remarkable than basic fuel to be showed better.

As discussed herein, hereafter prove further, when then technician considers outstanding viscosity and the material processing performance of embodiment of the present invention B, the comparable XUD-9 testing of engine performance provided by embodiment of the present invention B and comparative example F is important.

dW-10 testing of engine

DW-10 shaker test uses the F-98-08 test protocols of CEC (Coordinating EuropeanCouncil, CEC), and it uses Peugeot DW-10 engine.This is light-duty direct injection common rail testing of engine, and described experimental measurement engine power loss, it relates to fuel detergent additive effect.Lower power loss value shows good purification agent performance.Test engine is the representative of commercially available new engine.

Each composition uses identical basic fuel and contains the additive to be assessed based on active substance 71ppm.Acquired results is as follows:

Table 2-DW-10 testing of engine result

Fuel sample	The additive of assessment	% variable power under EOT
			4	Without-independent basic fuel	-5.1%
5	Embodiment of the present invention B	+2.1%
			6	Embodiment of the present invention D	+1.1%

7	Comparative example E	-3.4%
			8	Comparative example F	+2.0%

The quaternized polyisobutenyl succinimide purification agent of result display embodiment of the present invention B and D additive and embodiment F approximately equally wellly and show more much betterly than the on-quaternised polyisobutenyl succinimide purification agent of embodiment E.All embodiments all show better than independent basic fuel, but the additive of Embodiment B, D and F is more remarkable than basic fuel to be showed better.

As discussed herein, hereafter prove further, when then technician considers outstanding viscosity and the material processing performance of embodiment of the present invention B and D, the comparable DW-10 testing of engine performance provided by embodiment of the present invention B, D and comparative example F is important.

viscosity and material processing performance

Material processing performance is by considering the kinematic viscosity of material, and remarkably influenced material can how easily in commodity and/or need to add to make the amount of the abundant accessible thinner of material, increase total method cost, complicacy and waste and assess.Generally speaking, the viscosity at 100 DEG C is lower, and material processing performance is better.In order to suitably compare, the kinematic viscosity of material with identical activity substance content, namely should compare with the analogous material of the thinning oil of identical amount and existence.

For this reason, the viscosity of testing example B, D and F under its Initial Active content.For Embodiment B and D, about 85% active substance, and for embodiment F, about 75% active substance.Also all based on the viscosity of weight testing example B and D under 75% active substance, contrast with embodiment F better to allow.The active substance sample reduced is by mixing embodiment additive with appropriate 2-Ethylhexyl Alcohol and preparing.Then ASTM D445 is used to measure the viscosity of these mixtures.Below acquired results is shown in:

Table 3-viscosity data

Result display embodiment of the present invention B has kinematic viscosity significantly lower at 100 DEG C compared with comparative example F with D, wherein under the activity substance content of 75%, considers sample.These results show that sample of the present invention has significantly better material processing performance and easilier use to compare higher concentration with the additive of F with comparative example E and do not have process problem.

embodiment G-quaternized polyesteramide salt purification agent (embodiment of the present invention)

Quaternized polyesteramide salt purification agent is prepared by making the on-quaternised polyesteramide of 3501g embodiment A, 80.4g acetic acid, 24.5g water and 141.3ml propylene oxide react in the jacketed reaction container being equipped with agitator, condenser, the fresh feed pump be connected in auxiliary adding tube, nitrogen pipeline and thermopair/temperature controlling system, wherein react and carry out at about 75 DEG C, and through about 4 hours, propylene oxide is fed in reaction vessel, mild stirring simultaneously.Then reaction mixture is kept about 3 hours at such a temperature.Cool and collect 3710.5g product, TAN, FTIR and ESI-MS analyze and are confirmed that it is >90 % by weight quaternized polyesteramide salt purification agent, and all the other materials are on-quaternised polyesteramide mainly.Collect material have TAN, 27.76mg KOH/g of 0mg KOH/g TBN, at 100 DEG C 327.4cSt kinematic viscosity (as measured by ASTM D445), at 1575cm ^-1the IR acetic ester peak value at place, and be 1.42% nitrogen.

embodiment H-quaternized polyesteramide salt purification agent (embodiment of the present invention)

Quaternized polyesteramide salt purification agent is prepared by making the on-quaternised polyesteramide of 3401g Embodiment C, 107.3g acetic acid, 32.0g water and 1875.1ml propylene oxide react in the jacketed reaction container being equipped with agitator, condenser, the fresh feed pump be connected in auxiliary adding tube, nitrogen pipeline and thermopair/temperature controlling system, wherein react and carry out at about 75 DEG C, and through about 3.5 hours, propylene oxide is fed in reaction vessel, mild stirring simultaneously.Then reaction mixture is kept about 3 hours at such a temperature.Cool and collect 3687.8g product, TAN, FTIR and ESI-MS analyze and are confirmed that it is >90 % by weight quaternized polyesteramide salt purification agent, and all the other materials are on-quaternised polyesteramide mainly.Collect material have TAN, 26.4mg KOH/g of 0mg KOH/g TBN, at 100 DEG C 201.3cSt kinematic viscosity (as measured by ASTM D445), at 1574cm ^-1the IR acetic ester peak value at place, and be 1.33% nitrogen.

By reference above-mentioned each file is incorporated to the present invention.Except in embodiment, or outside clearly stating in addition, all quantity describing the amount of material, reaction conditions, molecular weight, carbonatoms etc. are in this manual to be understood that is modified by wording " about ".Unless otherwise indicated, all quantity of the amount or ratio that describe material are in this manual based on weight.Except as otherwise noted, each chemical mentioned herein or composition should be understood to the commercial grade material that can contain isomer, by product, derivative and usually be to be understood that other this kind of material be present in commercial grade.But except as otherwise noted, the amount of each chemical composition is expressed as to eliminate and usually can be present in any solvent in commercial materials or thinning oil.Be to be understood that the upper and lower bound of amount described herein, scope and ratio can combine independently.Similarly, the scope of each element of the present invention can use with the scope of other element any or together with measuring with amount.As used herein, the material comprising and do not affect the fundamental sum new features of composition considered substantially is allowed in statement " substantially by ... composition ".

Claims (12)

1. comprise the composition of quaternized polyesteramide salt, it comprises the reaction product of following component:

A. the polyesteramide containing tertiary amino; With

B. quaternizing agent, wherein said quaternizing agent be selected from combinationally use with acid ethylene oxide, propylene oxide, oxybutylene, Styrene oxide 98min. or its combine, dimethyl oxalate, 2-nitrobenzene methyl, and wintergreen oil.

2. composition according to claim 1, wherein said polyesteramide comprises the reaction product of following component: the aliphatic carboxylic acid containing at least one hydroxyl, and have can with the compound of the nitrogen-atoms of described sour condensation, wherein said compound contains tertiary amino.

3. composition according to claim 2, wherein said aliphatic carboxylic acid is expressed from the next:

Wherein R ¹for hydrogen or the alkyl containing 1-20 carbon atom, and R ²for the alkylene containing 1-20 carbon atom; And

Wherein have can with the nitrogen-atoms of described sour condensation and the compound further with tertiary amino be expressed from the next:

Wherein R ³for the alkyl containing 1-10 carbon atom; R ⁴for the alkyl containing 1-10 carbon atom; R ⁵for the alkylene containing 1-20 carbon atom; And X ¹for NR ⁶, wherein R ⁶for hydrogen or the alkyl containing 1-10 carbon atom.

4. composition according to claim 1, wherein said quaternized polyesteramide salt comprises the positively charged ion that following formula represents:

Wherein R ¹for hydrogen or the alkyl containing 1-20 carbon atom, and R ²for the alkylene containing 1-20 carbon atom; R ³for the alkyl containing 1-10 carbon atom; R ⁴for the alkyl containing 1-10 carbon atom; R ⁵for the alkylene containing 1-20 carbon atom; R ⁶for hydrogen or the alkyl containing 1-10 carbon atom; N is the number of 1-10; R ⁷for hydrogen, alkyl carbonyl containing 1-22 carbon atom, or the alkyl containing 1-22 carbon atom; And X ²for the group derived from quaternizing agent.

5. composition according to claim 2, it is wherein said that have can with the nitrogen-atoms of described sour condensation and the compound further with tertiary amino comprises N, N-diethyl ethylenediamine, N, N-dimethyl-ethylenediamine, N, N-dibutyl quadrol, N, N-dimethyl-1,3-diaminopropanes, N, N-diethyl-1,3-diaminopropanes or its combination.

6. composition according to claim 2, the wherein said aliphatic carboxylic acid containing at least one hydroxyl comprises: 12-oxystearic acid; Ricinolic acid; Sabinic acid; 5-hydroxy-dodecanoic acid; 5-hydroxydecanoic acid; 4-hydroxydecanoic acid; 10-hydroxyundecanoic acid; Or its combination.

7. composition according to claim 1, it comprises metal deactivators, purification agent, dispersion agent, viscosity modifier, friction improver, dispersant viscosity modifiers, extreme pressure agent, anti-wear agent, antioxidant, corrosion inhibitor, suds suppressor, demulsifying compound, pour point reducer, sealing swelling agent, wax control polymers, scale inhibitor, gas hydrate inhibitor or its any combination further.

8. composition according to claim 1, it comprises overbased metal-containing detergents, zinc dialkyl dithiophosphate or its combination further.

9. composition according to claim 1, it comprises further is at room temperature the fuel of liquid.

10. give the method for oil engine refuel, it comprises:

A. feed in described oil engine:

I. be at room temperature the fuel of liquid; With

Ii. comprise the composition of quaternized polyesteramide salt, described quaternized polyesteramide salt comprises the reaction product of following component: the polyesteramide of (a) tertiary-amino-containing; (b) quaternizing agent, wherein said quaternizing agent be selected from combinationally use with acid ethylene oxide, propylene oxide, oxybutylene, Styrene oxide 98min. or its combine, dimethyl oxalate, 2-nitrobenzene methyl, and wintergreen oil.

The method of the quaternized polyesteramide salt purification agent of 11. preparation, it comprises:

I. the polyesteramide of (a) tertiary-amino-containing is made; (b) quaternizing agent reaction, wherein said quaternizing agent be selected from combinationally use with acid ethylene oxide, propylene oxide, oxybutylene, Styrene oxide 98min. or its combine, dimethyl oxalate, 2-nitrobenzene methyl, and wintergreen oil;

Obtain quaternized dispersion agent thus.

12. methods according to claim 11, wherein the polyesteramide of tertiary-amino-containing is prepared by the following method, and described method comprises:

I. make the aliphatic carboxylic acid of (a) (i) containing at least one hydroxyl and (a) (ii) have can with the nitrogen-atoms of described sour condensation and the compound further with tertiary amino react;

Obtain the polyesteramide of tertiary-amino-containing thus.