CN103328537A

CN103328537A - Polyester quaternary ammonium salts

Info

Publication number: CN103328537A
Application number: CN2011800657431A
Authority: CN
Inventors: H·格林菲尔德; D·德福特; J·琼斯; D·J·莫尔顿
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2010-11-24
Filing date: 2011-11-21
Publication date: 2013-09-25
Anticipated expiration: 2031-11-21
Also published as: AU2011332104B2; CA2818753A1; CN103328537B; SG190372A1; WO2012071313A1; AU2011332104A1; KR20130117820A; BR112013012792A2; US20130239468A1; EP2643384A1

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 their purposes in fuel such as diesel oil fuel and oil fuel.The present invention relate to especially polyester quaternary ammonium salt in fuel as the purposes of purification agent and their preparation method.

Background of invention

Hydrocarbon-based fuel generally contains a large amount of settlings and forms material.When being used for oil engine (ICE), settling tends on the narrow area of the engine that contacts with fuel and forms on every side.In motor car engine, settling can form at engine intake valve, causes progression restriction and valve bonding to the gaseous fuel mixture flowing in combustion chamber.There is the common intake valve settling of two classes: resedimentation thing and thin settling.These dissimilar settlings affect the performance of fuel and engine in slightly different mode.The resedimentation thing be carbon containing and outward appearance for oil.They cause being restricted by the flow of valve, and this reduces again the peak power of engine, reduce fuel economy and improve discharging.Problem when thin settling tends to cause engine start also improves discharging.

Because engine becomes more responsive to settling, practice is to incorporate in the fuel composition purification agent with the formation that suppresses engine deposits and promote it to remove usually, improves thus motor performance and discharging.

The quaternized PIB/ amine that some poly-isobutyl-succinimide of known use is derivative and/or the acid amides dispersion agent/purification agent additive in the composition that acts as a fuel.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 can be by quaternizing agent such as propylene oxide alkylation, i.e. quaternised side tertiary amine point.The example of these additives is disclosed among the U.S. Patent application US2008/0307698.

Yet, above-mentioned advantage need to be provided, also demonstrate simultaneously the additive of viscosity characteristics and the material processing performance of improvement.This class improvement can allow that less diluent materials is used for containing in the normally used enriched material of commodity and additive-package and final fuel of these class A fuel A additives.If viscosity characteristics and material processing performance allow the composition that contains additive shift and process (be pumping, topple over, mixing etc.) and more typically heating material and/or and do not need special high viscosity equipment, then need less thinner.The thinner that the viscosity characteristics of improving and material processing performance are allowed minimizing uses, saves cost, reduces the environmental influence that therefore refuse also improves material.This also allows additive-package and midbody composite that use is denseer, and it can more effectively transport, and also reduces cost 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 the derivative quaternized purification agent of poly-isobutyl-succinimide is compared.Find now the quaternized salt of the new polyester of a class.The quaternized salt of these polyester has the polyester based alkyl and provides the quaternized purification agent that derives 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 detersive power and the thermostability performance identical with other quaternized purification agent, and viscosity characteristics and the material processing performance of above-mentioned improvement are provided.

The invention provides the composition that contains quaternized polyester salt, described quaternized polyester salt is derived from the polyester and the reaction that is suitable for uncle's amino is changed into the quaternizing agent of quaternary nitrogen of tertiary-amino-containing.Quaternizing agent can replace carbonic ether, alkyl epoxide or its combination for sulfuric acid dialkyl, benzyl halide, alkyl.Any described quaternizing agent, particularly alkyl epoxide can be used in combination such as acetic acid with acid.

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

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

The invention provides the method to the oil engine refuel, described method comprises step: feed in the oil engine at room temperature as the fuel of liquid and comprise the composition of one or more quaternized polyester salts described herein.

The present invention also provides the method for preparing the quaternary ammonium salt purification agent, and described method comprises step: the polyester that makes (a) tertiary-amino-containing; (b) be suitable for uncle's amino is changed into the quaternizing agent reaction of quaternary nitrogen.The optional bin cure acid dialkyl ester of quaternizing agent, benzyl halide, alkyl replace carbonic ether; Alkyl epoxide or its mixture with the acid combination.Described method produces quaternized dispersion agent described herein.

Detailed Description Of The Invention

Set forth each preferred feature of description and embodiment below by indefiniteness.

The 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 the 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 is changed into the reaction product of the quaternizing agent of quaternary nitrogen.The optional bin cure acid dialkyl ester of quaternizing agent, benzyl halide, alkyl replace carbonic ether; Alkyl epoxide or its mixture with the acid combination.

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 that contains uncle's amino.

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

R wherein ¹For hydrogen or contain the alkyl of 1-20 carbon atom, and R ²For containing the alkylene of 1-20 carbon atom.In some embodiments, R ¹Contain 1-12,2-10,4-8 or even 6 carbon atoms, R ²Contain 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-hydroxyl undecanoic acid or its combination.

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

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

Or

Wherein each definition provided above is still applicable.

Can and also have the nitrogenous or oxygen compound of uncle's amino with the acylating agent condensation; the example that maybe can be alkylated into the compound of this compounds includes but not limited to: the 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; the N-diethyl ethylenediamine; N; the N-dimethyl-ethylenediamine; N; N-dibutyl quadrol; N; N-diethyl-1; the 3-diaminopropanes; N; N-dimethyl-1; the 3-diaminopropanes; N; N; N'-trimethylammonium quadrol; N; N-dimethyl-N'-ethylethylenediamine; N; N-diethyl-N'-methyl ethylenediamine; N; N; N'-triethyl quadrol; the 3-dimethylamino propylamine; the 3-diethyl amino propylamine; the 3-dibutyl amino propyl amine; N; N; N'-trimethylammonium-1; the 3-propylene diamine; N; N; 2; 2-tetramethyl--1; the 3-propylene diamine; 2-amino-5-diethylamino pentane; N; N; N', N'-tetraethyl-diethylenetriamine; 3,3'-diamino-N-methyl-di-n-propylamine; 3; 3'-imino-two (N, N-dimethyl propylamine) or its combinations.In this class embodiment, the gained additive comprises quaternary ammonium amide salt, namely contains the purification agent of amide group and quaternary ammonium salt.

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

In some embodiments; another kind of can with acylating agent condensation and the nitrogenous or oxygen compound with uncle's amino after further alkylation; comprise alkanolamine; include but not limited to trolamine; N; N-dimethylamino propyl alcohol; N; N-diethylamino propyl alcohol; N; N-diethylamino butanols; tri-isopropanolamine; the 1-[2-hydroxyethyl] piperidines; 2-[2-(dimethyl amine) oxyethyl group]-ethanol; the N-ethyldiethanolamine; N methyldiethanol amine; N butyl diethanol amine; N; the N-DEAE diethylaminoethanol; N, the N-dimethylaminoethanol; 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol.In the embodiment of using alkanolamine wherein and/or analogous material, the 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, have and to comprise N with oxygen or the nitrogen-atoms of described sour condensation and the compound that further has uncle's amino, 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 class embodiment, be the tertiary-amino-containing polyesteramide for the preparation of the polyester of the tertiary-amino-containing of quaternized polyester salt.In in these embodiments some, then amine or amino alcohol and monomer reaction make resulting materials and other monomer polymerization, produce required polyesteramide, then can it is quaternized.

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

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

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

In these embodiments, quaternized polyester salt is used C substantially _1-22Or C _8-20The lipid 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 of the quaternized polyester salt of the present invention (Mn) can be 500-3000 or 700-2500.

The polyester that is used for the present invention can obtain by the mixture of one or more hydroxycarboxylic acids or hydroxycarboxylic acid and carboxylic acid is chosen wantonly to heat in the presence of esterifying catalyst.Hydroxycarboxylic acid can have formula HO-X-COOH, wherein X contains the saturated or unsaturated aliphatic group of the divalence of at least 8 carbon atoms, and wherein there are at least 4 carbon atoms between hydroxyl and the hydroxy-acid group, perhaps from this hydroxycarboxylic acid and the mixture of the carboxylic acid of hydroxyl not.This reaction can be carried out under 160-200 ℃ temperature until obtain the desired molecule amount.Can measure the acid number of product after the esterification process, in some embodiments, required polyester has the acid number of 10-100mg KOH/g or 20-50mg KOH/g.The indication acid number scope of 10-100mg KOH/g is equivalent to the number-average molecular weight of 5600-560.The water that forms in the esterification can be removed from reaction medium, and this can be easily by making nitrogen gas stream pass through reaction mixture, perhaps by in the presence of solvent such as toluene or dimethylbenzene, reacting, and when forming, distill water and carry out.

Then the gained polyester can be separated in a usual manner; Yet, when reaction its exist can not be harmful to the organic solvent used subsequently in the presence of when carrying out, can use the solution of gained polyester.

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

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

Can be preferably carboxylic acid saturated or the unsaturated lipid compounds of group together with the carboxylic acid that hydroxycarboxylic acid uses to obtain these polyester, particularly contain alkyl and the alkenyl-carboxylic of the chain with 8-20 carbon atom.As the example of this class acid, can mention lauric acid, palmitinic acid, stearic acid and oleic acid.

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

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

Fully do not contain and mean component of the present invention and mainly formed by the material that is different from above-mentioned alkyl and replaces acylating agent so that relate to indistinctively the additive derived from this class reagent that these reagent and the present composition do not comprise significant quantity in reacting.In some embodiments, component of the present invention or the present composition can comprise less than this class reagent of 10 % by weight or derived from the additive of this class reagent.In other embodiments, MAD can be 5,3,2,1 or even 0.5 or 0.1 % by weight.One of purpose of these embodiments is so that get rid of reagent such as polyisobutylene succinic anhydride from the present invention reaction, so, also so that get rid of quaternized salt detergent additives derived from reagent such as polyisobutylene succinic anhydride.Focus of the present invention is polyester or hyper-dispersant, quaternary ammonium salt detergent additives.

B. quaternizing agent

The quaternized salt purification agent of the present invention forms when above-mentioned on-quaternised purification agent and quaternizing agent reaction.Suitable quaternizing agent comprises that selected sulfuric acid dialkyl, benzyl halide, alkyl replace carbonic ether; Alkyl epoxide or its mixture with the acid combination.

In one embodiment, quaternizing agent can comprise alkylogen, for example muriate, iodide or bromide; Alkyl sulfonate esters; Sulfuric acid dialkyl, for example methyl-sulfate; Sultones; Alkyl phosphate; Phosphoric acid C for example _1-12The trialkyl 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 be derived from the sulfuric acid dialkyl, and for example methyl-sulfate, N-oxide compound, sultone are such as third and butyl sultone; Alkyl, acyl group or aralkyl halide such 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 optional is further replaced by alkyl or alkenyl.

The alkyl (or alkyl) that alkyl replaces carbonic ether can contain the every group of 1-50,1-20, a 1-10 or 1-5 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 for the alkyl epoxide that is shown below of acid combination:

R wherein ¹, R ², R ³And R ⁴Can be H or the alkyl that contains 1-50 carbon atom independently.The example of alkyl epoxide 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 of using with the alkyl epoxide can be the component of separating, for example acetic acid.In other embodiments, for example when alkyl acylating agent is the dicarboxylic acid acylating agent, do not need acid constituents separately.In this class embodiment, purification agent can prepare by will be substantially not containing or even not contain acid constituents separately such as the combinations of reactants of acetic acid, and instead, relies on the acid groups of alkyl acylating agent.In other embodiments, can have a small amount of acid constituents, but be＜0.2 or even＜every mole of alkyl acylating agent of 0.1 equimolar acid.These acid also can be used with above-mentioned other quaternizing agent, comprise that alkyl replaces carbonic ether and associated materials hereinafter described.

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

In certain embodiments, having the purification agent of amine official energy and the mol ratio of quaternizing agent is 1:0.1-2, or 1:1-1.5, or 1:1-1.3.

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

R ¹⁹-C(=O)-O-R ²⁰(IX)

R wherein ¹⁹Be optional alkyl, alkenyl, aryl or the alkylaryl that replaces, and R ²⁰For containing the alkyl of 1-22 carbon atom.

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

In some embodiments, the R in the following formula ¹⁹For by one or more hydroxyl, carbon alkoxyl group, nitro, cyano group or NH of being selected from ₂The aryl that replaces of group.R ¹⁹Can be polysubstituted aryl, trihydroxy-phenyl for example, but also can be single substituted aryl, for example ortho position substituted aryl.R ¹⁹Can be selected from being selected from OH, NH ₂, NO ₂Or the group of COOMe replaces.Suitably, R ¹⁹Be the hydroxyl substituted aryl.In some embodiments, R ¹⁹Be the 2-hydroxy phenyl.R ²⁰Can be alkyl or alkylaryl, for example 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 ²⁰Be 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 that is applicable to herein is described among the EP1254889.The example of suitable combination thing that contains the residue of alpha-hydroxy carboxylic acid compounds comprises: (i) methyl of 2-hydroxy-iso-butyric acid-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, benzyl-, phenyl-and allyl ester; (ii) methyl of 2-hydroxy-2-methyl butyric acid-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, benzyl-, phenyl-and allyl ester; (iii) methyl of 2-hydroxyl-2 Ethylbutanoic acid-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, benzyl-, phenyl-and allyl ester; (iv) methyl of lactic acid-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, benzyl-, phenyl-and allyl ester; (v) methyl of oxyacetic acid-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, allyl group-, benzyl-and phenylester.In some embodiments, quaternizing agent comprises the 2-hydroxy-methyl isobutyl acid.

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

In some embodiments, quaternizing agent is the carboxylicesters that has less than 3.5 pKa.Compound comprises in this class embodiment more than an acid groups therein, 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.

In the above-mentioned quaternizing agent any comprises the alkyl epoxide, can be used in combination with acid.Suitable acid comprises carboxylic acid, such as acetic acid, propionic acid, 2 ethyl hexanoic acid etc.

The composition that contains the quaternized purification agent of polyester

The quaternized salt purification agent of the present invention can be used as additive in each based composition, comprise 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 is used for to oil engine or naked flame burning device refuel.These compositions also can contain one or more other additives.These optional additives are described in hereinafter.In some embodiments, the fuel that is applicable among the present invention comprises any commercially available fuel, and in some embodiments, any commercially available diesel oil fuel and/or biofuel.

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

The fuel that is applicable among the present invention is excessively not limited.Generally speaking, suitable fuel is usually in envrionment conditions, and for example room temperature (20-30 ℃) is down liquid or is liquid usually under operational condition.Fuel can be hydrocarbon fuel, nonhydrocarbon fuel or its mixture.

Hydrocarbon fuel can be petroleum fractions, comprises such as the defined gasoline of ASTM specification D4814 or such as the defined diesel oil fuel of ASTM specification D975.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 can for example comprise preparing by method such as Fischer-Tropsch method for the hydrocarbon by the preparation of natural gas synthetic oil 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 than heavy fuel oil, for example No. 5 and No. 6 oil fuel, and it is also referred to as residual fuel oil, heavy fuel oil and/or furnace oil.This class A fuel A can use separately or and other, usually mix to form than light fuel and have more low viscous mixture.Also comprise the bunker fuel that is generally used in the ship engine.The fuel of these types has high viscosity and can be solid under envrionment conditions, but heating and feed the engine of its refuel or burner in the time be liquid.

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

The mixture of hydrocarbon and nonhydrocarbon fuel can comprise for example gasoline and methyl alcohol and/or ethanol, diesel oil fuel and ethanol, and diesel oil fuel and transesterify vegetables oil such 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 still less, 5000ppm or still less, 1000ppm or still less, 350ppm or still less, 100ppm or still less, 50ppm or still less or 15ppm or sulphur content still less.

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

B. additive concentrate compositions

Multifunctional additive for lubricating oils is the composition of thinner that contains one or more additives and also can contain fuel, oil or some types of a tittle.Then can be used as usual way adds in other composition these enriched materials to process and to provide additive, generation final composition such 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 above-mentioned fuel, solvent, thinning oil or analogous material.These compositions also can comprise one or more hereinafter described other additives.

C. choose other additive wantonly

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

Although any other performance additive described herein can be used in any present composition, following other additive is used in particular for fuel composition: 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 polymkeric substance, scale inhibitor, gas hydrate inhibitor or its any combination.

Suitable antioxidant comprises for example hindered phenol or derivatives thereof and/or diarylamine or derivatives thereof.Suitable purification agent/dispersant additives comprises for example 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 derivative quaternized PIB/ amine and/or the acid amides dispersion agent/purification agent of poly-isobutyl-succinimide.Suitable cold flow improver comprises for example multipolymer of maleic anhydride and cinnamic esterified copolymer and/or ethene and vinyl-acetic ester.Suitable demulsifying compound comprises for example poly-alkoxylation alcohol.The proper lubrication agent comprises for example aliphatic carboxylic acid.Suitable metal deactivators comprises for example aromatic triazole or derivatives thereof, includes but not limited to benzotriazole.Suitable valve seat decline additive comprises for example basic metal sulfosuccinate.Suitable suds suppressor and/or defoamer comprise for example organo-siloxane, such as polydimethylsiloxane, PES-4, polydiethylsiloxane, polyacrylic ester and polymethacrylate, trimethylammonium-three fluoro-propyl group methylsiloxane etc.Suitable liquid agent comprises for example mineral oil and/or poly-(alpha-olefin) and/or polyethers.Combustion improving agent comprises for example 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 (such as tartrate) and/or tricarboxylic acid (such as citric acid) and amine and/or alcohol, chooses reaction in the presence of known esterifying catalyst wantonly and prepares.Usually these friction improvers derived from tartrate, citric acid or derivatives thereof can produce friction improver derived from amine and/or branching alcohol, and described friction improver itself has the branched hydrocarbyl radical that is present in the significant quantity in its structure.Example for the preparation of the suitable branching alcohol of this class 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, succinimide for example, and it is the alkyl substituted succinyl oxide and the condensation product of poly-(alkylene amines).Succinimide purification agent/dispersion agent is described in United States Patent (USP) 4,234 more completely, in 435 and 3,172,892.The high-molecular weight ester of another kind of ashless dispersant for preparing by alkyl acylating agent and multi-aliphatic alcohol such as glycerine, tetramethylolmethane or Sorbitol Powder reaction.This class material is described in greater detail in United States Patent (USP) 3,381, in 022.Another kind of random dispersion agent is Mannich base.These are for the material that forms by higher molecular weight alkyl substituted phenol, alkylene polyamine and aldehyde such as formaldehyde condensation and be described in greater detail in United States Patent (USP) 3,634, in 515.Other dispersion agent comprises the polymeric dispersant additive, it typically is to contain 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 that one or more have poly-(vinyl-amine) of 3-5 ethylidene unit and 4-6 nitrogen unit.This class material comprises Triethylenetetramine (TETA) (TETA), tetren (TEPA) and penten (PEHA).This class material is usually as containing a large amount of ethylidene unit and nitrogen-atoms, and various isomerization structure, comprises that the mixture of various isomer of various ring texturees is commercially available.Poly-(alkylene amines) also can comprise in the industry as the residual known relatively high molecular weight amines of vinyl-amine still.

Also can with dispersion agent by with plurality of reagents in any reaction and aftertreatment.Be succinyl oxide, nitrile, epoxide, boron compound and the phosphorus compound of urea, thiocarbamide, dimercaptothiodiazole, dithiocarbonic anhydride, aldehyde, ketone, carboxylic acid, alkyl replacement in these.Describe the reference of this processing in detail and list in United States Patent (USP) 4,654, in 403.

The present composition can comprise the detergent additives that is different from the quaternized salt additives of the present invention.The most frequently used purification agent obtains great majority or all its basicity or TBN by basic nitrogen compound metal hydroxides, oxide compound or the carbonate of this metalloid such as calcium, magnesium or sodium (usually based on) in the engine lubrication field.This metalloid high alkaline detergent is also referred to as high alkalinity or hyperalkaline salt, is generally single-phase even newton's system, it is characterized in that metal content surpasses to be used for according to metal with the stoichiometry of the concrete acidic organic compound of metal reaction that neutralization exists.Overbased material prepares at the mixture reaction of the reaction medium of a kind of inert organic solvents for acid organic substrate (for example mineral oil, petroleum naphtha, toluene, dimethylbenzene) usually by the excessive metal base of acid material (usually mineral acid or low-grade carboxylic acid, preferably carbon dioxide) and acidic organic compound (being also referred to as matrix), stoichiometry usually.Usually also there are a small amount of promotor such 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 at the solubleness in the oil.

The conventional overbased material of this class and their preparation method are well known to those skilled in the art.The metal-salt of preparation sulfonic acid, carboxylic acid, phenol, phosphonic acids is described and in these any two or more patent of technology of mixture 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.The Salixarate purification agent is described in United States Patent (USP) 6,200, in 936.

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

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

The multi-functional viscosity modifier that also has dispersion agent and/or antioxidant property is known and can chooses use wantonly.Dispersant viscosity modifiers (DVM) is an example of this class multifunction additive.DVM prepares by a small amount of nitrogen containing monomer and alkyl methacrylate copolymerization usually, and generation has dispersion force, viscosity modified, pour point descends and the additive of some combinations of dispersion force.Vinyl pyridine, NVP and methacrylic acid N, N'-dimethylamino ethyl ester are the example of nitrogen containing monomer.The polyacrylic ester that is obtained by polymerization or the copolymerization of one or more alkyl acrylates is also as viscosity modifier.

In some embodiments, anti-wear agent can comprise phosphorous wear-resistant/extreme pressure agent, for example metal thiophosphate, phosphoric acid ester and salt thereof, phosphorus-containing carboxylic acid, ester, ether and acid amides; And phosphorous acid ester.In certain embodiments, the phosphorus anti-wear agent can exist with the amount that 0.01-0.2 or 0.015-0.15 or 0.02-0.1 or 0.025-0.08 % by weight phosphorus are provided.Usually, anti-wear agent is zinc dialkyl dithiophosphate (ZDP).For containing the 11%P typical ZDP of (based on without oil), appropriate vol can comprise the 0.09-0.82 % by weight.Non-phosphorous anti-wear agent comprises boric acid ester (comprising the boration epoxide), dithio carbamate compounds, molybdate compound and olefine sulfide.In some embodiments, fuel composition of the present invention not phosphorous wear-resistant/the extreme pressure agent.

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

The preparation method of quaternary ammonium salt purification agent

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

As mentioned above, the optional bin cure acid dialkyl ester of quaternizing agent, benzyl halide, alkyl replace carbonic ether; Alkyl epoxide or its mixture with the acid combination.

The inventive method also can be described as the method for the quaternized purification agent of preparation, and described method comprises step: (1) mixes polyester, (b) quaternizing agent and optional (c) protonic solvent of (a) tertiary-amino-containing; (2) with the temperature of mixture heating up to 50-130 ℃; (3) keep reaction to finishing; Obtain thus quaternized purification agent.In one embodiment, the reaction less than 80 ℃ or less than 70 ℃ temperature under carry out.In other embodiments, reaction mixture is heated to approximately the temperature of 50 to 120 ℃, 80 ℃ or 70 ℃.In other embodiments again, temperature of reaction can be 70-130 ℃.In other embodiments, temperature of reaction can be 50-80 ℃ or 50-70 ℃.

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

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

Additive of the present invention can obtain in the presence of protonic solvent.Suitable protonic solvent comprises the solvent that has greater than 9 specific inductivity.In one embodiment, protonic solvent comprises and contains 1 or the poly-hydroxy (OH) compound of functional group, and can comprise water more.

In one embodiment, solvent is two pure and mild glycol ethers.Contain 2-12 carbon atom, or 4-10, or the glycol of 6-8 carbon atom and oligopolymer (for example dipolymer, trimer and tetramer) thereof are usually applicable.The illustrative glycol comprises ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, BDO, 2-methyl-l, ammediol, neopentyl glycol, triglycol, polyoxyethylene glycol etc. and oligopolymer and polymeric derivative and mixture.The illustrative glycol ethers comprises the C of propylene glycol, ethylene glycol and oligopolymer thereof ₁-C ₆Two of alkyl oxide such as methyl, ethyl, propyl group, butyl or hexyl-, 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, methoxyl group triglycol, oxyethyl group triglycol, butoxy triglycol, methoxyl group Tetraglycol 99, butoxy Tetraglycol 99.

The solvent that is applicable among 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, 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 class alcohol, and the mixture that comprises the pure and mild alcohol of this class and water.In some embodiments, the unique solvent of water for using.In some embodiments, the amount of the water of existence can be more than 1 % by weight for solvent mixture.In other embodiments, solvent mixture can contain trace water, and wherein water-content is less than 1 or 0.5 % by weight.

Alcohol can be for aliphatic, alicyclic, aromatics or heterocycle, comprises the alicyclic alcohol that aliphatic series replaces, the aromatic alcohol that aliphatic series replaces, heterocyclic alcohol, 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 the aromatic alcohol of heterocyclic substituted of aliphatic series replacement.

Be reluctant bound by theoryly, thinking needs polar aprotic solvent (it can comprise water) to promote acid to be dissociated into ion and proton.When the purification agent with amine official energy at first reacts with quaternizing agent, need to be from solution so that the ion that forms is protonated.In the situation that quaternizing agent is alkyl epoxide, the gained ion is unsettled alkoxide ion.Also provide counter ion from the acid groups of additive from solution, described additive is used for the quaternary ammonium ion that stable reaction forms, and produces more stable product.

Industrial application

In one embodiment, the inventive method produces the quaternary ammonium salt purification agent.The quaternary ammonium salt purification agent can be used as the additive for the fuel of oil engine and/or naked flame burning device.

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; Be total to rail and Integral injector system; Gently (for example passenger vehicle) and heavy (for example commercial truck) engine; With the engine with hydrocarbon and nonhydrocarbon fuel and composition thereof refuel.Engine can be the part of the comprehensive discharge system that incorporates this class component into; Egr system; Aftertreatment comprises three-way catalyst, oxide catalyst, NOx absorption agent and catalyzer, optional catalysis and the on-catalytic particle trapper that uses the fuel based catalyzer; Vario valve regularly; With injection timing and speed moulding.

The naked flame burning device of burning can be any naked flame burning equipment of assembling with combustion of liquid fuel.These comprise family expenses, commercial and industrial burner.Industrial burner comprises needs preheating fuel is suitably processed and those of atomizing.Also comprise oil burning apparatus, fuel electric generating apparatus, fired heater and boiler, and be used for ship and marine use, comprise the boiler in the deep-draft vessel.Comprise boiler and large-scale fixing and ship engine for power generation assembly, utility device.The 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 the stack gas recirculation system.

As used herein, term " hydrocarbyl substituent " or " alkyl " use with its meaning commonly used well known to those skilled in the art.Particularly, it refers to have the carbon atom that directly is connected on the molecule rest part and the group that mainly has hydrocarbon character.The example of alkyl comprises: hydrocarbon substituent, namely aliphatic series (for example alkyl or alkenyl), alicyclic (for example cycloalkyl, cycloalkenyl group) substituting group, and aromatics-, aliphatic series-and the aromatic substituent of alicyclic replacement, and wherein encircle the cyclic substituents of finishing (for example two substituting groups form ring together) by another part of molecule; The hydrocarbon substituent that replaces namely contains the substituting group of the non-hydrocarbyl group (for example halogen (especially chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group and sulfinyl (sulfoxy)) that does not change substituent main hydrocarbon character in the context of the invention; Assorted substituting group namely in the context of the invention, contains the substituting group that is different from carbon in the ring that is being comprised of carbon atom or the chain when having main hydrocarbon character.Heteroatoms comprises sulphur, oxygen, nitrogen, and comprises substituting group such as pyridyl, furyl, thienyl and imidazolyl.Generally speaking, for per 10 carbon atoms, in alkyl, exist no more than 2, preferred no more than 1 non-hydrocarbon substituent; Usually, there is not non-hydrocarbon substituent in the alkyl.As used herein, term " alkyl carbonyl " or " alkyl carbonyl substituting group " mean to contain the alkyl of carbonyl.

More known above-mentioned materialss may interact in final preparaton so that the component of final preparaton may from originally add those are different.For example, metal ion (for example purification agent) can migrate to other acidity or the anionic site of other molecule.The product that forms thus comprises that the product that forms through be intended to the purposes use present composition with it may be not easy to describe.Yet all these classes improve and reaction product includes within the scope of the invention; The present invention includes by said components being mixed the composition for preparing.

Embodiment

The present invention further sets forth 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)

The on-quaternised polyesteramide is being by being equipped with agitator, condenser, being connected in the auxiliary jacketed reaction container that adds fresh feed pump, nitrogen pipeline and thermopair/temperature controlling system on the pipe 6 moles of 12-oxystearic acids and 1 mole of dimethylamino propylamine reaction are prepared, and wherein reacts and approximately carrying out under 130 ℃ and keeping approximately 4 hours.Then reaction mixture is cooled to approximately 100 ℃ and add the butanols zirconium so that catalyzer consists of the reaction mixture of 0.57 % by weight with such amount.Reaction mixture is heated to approximately 195 ℃ and kept approximately 12 hours.Cooling is also collected products therefrom.

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

Quaternized polyesteramide salt purification agent is being by being equipped with agitator, condenser, being connected in the auxiliary jacketed reaction container that adds fresh feed pump, nitrogen pipeline and thermopair/temperature controlling system on the pipe on-quaternised polyesteramide of 600g embodiment A, 2-Ethylhexyl Alcohol, 18.5g acetic acid and the reaction of 32.3ml propylene oxide of 120g are prepared, and wherein reacts and approximately carrying out under 75 ℃ and through approximately propylene oxide being fed in the reaction vessel in 3.5 hours.Then reaction mixture is remained under this temperature approximately 3 hours.Cooling is also collected the 760g product, and TAN, FTIR and ESI-MS analyze and be confirmed that it is the approximately quaternized polyesteramide salt of 80 % by weight purification agent, and all the other materials are mainly the on-quaternised polyesteramide.The material of collecting has the TBN of TAN, the 23.82mg KOH/g of 1.26mg KOH/g, at kinematic viscosity (as measuring by ASTM D445), the 1574cm of 100 ℃ of lower 28.58cSt ^-1The IR of place acetic ester peak value, and be 1.22% nitrogen.

Embodiment C-on-quaternised polyesteramide (preparation material)

The on-quaternised polyesteramide is by being equipped with agitator, condenser, being connected in the auxiliary jacketed reaction container that adds fresh feed pump, nitrogen pipeline and thermopair/temperature controlling system on the pipe 1300g ricinolic acid and the reaction of 73.5g dimethylamino propylamine are prepared, wherein react and approximately carrying out under 130 ℃, through approximately dropwise adding amine in 8 minutes, and reaction mixture was kept approximately 4 hours.Then reaction mixture is cooled to approximately 100 ℃ and add 7.8g butanols zirconium.Reaction mixture is heated to approximately 195 ℃ and kept approximately 17 hours.Products therefrom is filtered, and cooling is also collected.Collect the 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 ^-1The place does not have sour peak value.

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

Quaternized polyesteramide salt purification agent is by being equipped with agitator, condenser, being connected to and assisting the on-quaternised polyesteramide that makes the 600g Embodiment C in the jacketed reaction container that adds fresh feed pump, nitrogen pipeline and thermopair/temperature controlling system on the pipe, 2-Ethylhexyl Alcohol, 18.9g acetic acid and the reaction of 33.1ml propylene oxide of 123g to prepare, wherein react and approximately carrying out under 75 ℃, and through approximately propylene oxide being fed in the reaction vessel in 3.5 hours.Then reaction mixture is remained under this temperature approximately 3 hours.The 751g product is also collected in cooling, and TAN, FTIR and ESI-MS analyze and turn out to be it and be the about quaternized polyesteramide salt of 70 % by weight purification agent, and all the other materials mainly are the on-quaternised polyesteramides.The material of collecting has the TBN of TAN, the 23.14mg KOH/g of 0mg KOH/g, in the kinematic viscosity (as measuring by ASTM D445) of 100 ℃ of lower 47.0cSt, at 1574cm ^-1The IR acetic ester peak value at place.

Embodiment E-on-quaternised polyisobutene purification agent (Comparative Examples)

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

Embodiment F-quaternized polyisobutene purification agent (Comparative Examples)

Quaternized polyisobutenyl succinimide purification agent is by being equipped with agitator, condenser, be connected to the auxiliary fresh feed pump that adds on the pipe, make 100pbw polyisobutylene succinic anhydride (itself is prepared with the 1:1.2 molar ratio reaction by 1000 number-average molecular weight high vinylidene polyisobutylenes and maleic anhydride) 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 approximately 80 ℃, through approximately 8 hours with amine adding system in, wherein reaction mixture temperature is remained on below 120 ℃.Then reaction mixture is heated to 150 ℃ and kept 3 hours, produces on-quaternised polyisobutenyl succinimide purification agent.Then 40.6pbw2-ethylhexanol, 1pbw water, 5.9pbw acetic acid are added in the on-quaternised polyisobutenyl succinimide purification agent.After keeping 3 hours, add the 8.5pbw propylene oxide, will react 75 ℃ of lower maintenances approximately 6 hours.Cooling is also collected the quaternized polyisobutenyl succinimide purification agent of gained.

The XUD-9 testing of engine

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

Table 1-XUD-9 testing of engine result

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

The result shows the approximately the same good ground of the quaternized polyisobutenyl succinimide purification agent of embodiment of the invention B additive and embodiment F and shows than the on-quaternised polyisobutenyl succinimide purification agent of embodiment E much betterly.All embodiment show better than independent basic fuel, yet the additive of Embodiment B and F is than the remarkable better performance of basic fuel.

As discussed herein, further proof hereinafter, when then the technician considered the outstanding viscosity of embodiment of the invention B and material processing performance, the comparable XUD-9 testing of engine performance that is provided by embodiment of the invention B and Comparative Examples F was important.

The DW-10 testing of engine

The DW-10 shaker test is used the F-98-08 test protocols of CEC (Coordinating European Council, CEC), and it uses Peugeot DW-10 engine.This is altogether rail testing of engine of light-duty direct injection, described experimental measurement engine power loss, and it relates to the fuel detergent additive and renders a service.Lower power loss value shows preferably purification agent performance.Test engine is the representative of commercially available new engine.

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

Table 2-DW-10 testing of engine result

The fuel sample	The additive of assessment	% variable power under the EOT
			4	Nothing-independent basic fuel	-5.1%
5	Embodiment of the invention B	+2.1%
			6	Embodiment of the invention D	+1.1%

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

The result shows the approximately the same good ground of the quaternized polyisobutenyl succinimide purification agent of embodiment of the invention B and D additive and embodiment F and shows than the on-quaternised polyisobutenyl succinimide purification agent of embodiment E much betterly.All embodiment show better than independent basic fuel, yet the additive of Embodiment B, D and F is than the remarkable better performance of basic fuel.

As discussed herein, further proof hereinafter, when then the technician considered the outstanding viscosity of embodiment of the invention B and D and material processing performance, the comparable DW-10 testing of engine performance that is provided by embodiment of the invention B, D and Comparative Examples F was important.

Viscosity and material processing performance

The material processing performance can pass through to consider the kinematic viscosity of material, and how the remarkably influenced material can easily be used for commodity and/or need to add so that the amount of the abundant accessible thinner of material, the total method cost of increase, complicacy and waste are assessed.Generally speaking, the viscosity under 100 ℃ is lower, and the material processing performance is better.For suitable comparison, the kinematic viscosity of material should with identical activity substance content, namely compare with the thinning oil of same amount and the analogous material that exists.

For this reason, the viscosity of test implementation example B, D and F under its initial activity substances content.For Embodiment B and D, about 85% active substance, and for embodiment F, approximately 75% active substance.Also all based on the viscosity of the routine B of weight test implementation under 75% active substance and D, contrast with embodiment F to allow better.The active substance sample that reduces prepares by the embodiment additive is mixed with an amount of 2-Ethylhexyl Alcohol.Then use ASTM D445 to measure the viscosity of these mixtures.Below acquired results is shown in:

Table 3-viscosity data

The result shows that embodiment of the invention B and D have and compares with Comparative Examples F 100 ℃ of lower significantly lower kinematic viscosity, wherein considers sample under 75% activity substance content.These results show that sample of the present invention has significantly better the material processing performance and easilier uses and do not have a processing problem to compare higher concentration with the additive of Comparative Examples E and F.

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

Quaternized polyesteramide salt purification agent is by being equipped with agitator, condenser, being connected to and assisting the on-quaternised polyesteramide, 80.4g acetic acid, 24.5g water and the reaction of 141.3ml propylene oxide that make the 3501g embodiment A in the jacketed reaction container that adds fresh feed pump, nitrogen pipeline and thermopair/temperature controlling system on the pipe to prepare, wherein react and approximately carrying out under 75 ℃, and through approximately propylene oxide being fed in the reaction vessel in 4 hours, mild stirring simultaneously.Then reaction mixture is remained under this temperature approximately 3 hours.Cooling is also collected the 3710.5g product, and TAN, FTIR and ESI-MS analyze and be confirmed that it is〉the quaternized polyesteramide salt of 90 % by weight purification agent, all the other materials mainly are the on-quaternised polyesteramides.The material of collecting has the TBN of TAN, the 27.76mg KOH/g of 0mg KOH/g, in the kinematic viscosity (as measuring by ASTM D445) of 100 ℃ of lower 327.4cSt, at 1575cm ^-1The IR acetic ester peak value at place, and be 1.42% nitrogen.

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

Quaternized polyesteramide salt purification agent is by being equipped with agitator, condenser, being connected to and assisting the on-quaternised polyesteramide, 107.3g acetic acid, 32.0g water and the reaction of 1875.1ml propylene oxide that make the 3401g Embodiment C in the jacketed reaction container that adds fresh feed pump, nitrogen pipeline and thermopair/temperature controlling system on the pipe to prepare, wherein react and approximately carrying out under 75 ℃, and through approximately propylene oxide being fed in the reaction vessel in 3.5 hours, mild stirring simultaneously.Then reaction mixture is remained under this temperature approximately 3 hours.Cooling is also collected the 3687.8g product, and TAN, FTIR and ESI-MS analyze and be confirmed that it is〉the quaternized polyesteramide salt of 90 % by weight purification agent, all the other materials mainly are the on-quaternised polyesteramides.The material of collecting has the TBN of TAN, the 26.4mg KOH/g of 0mg KOH/g, in the kinematic viscosity (as measuring by ASTM D445) of 100 ℃ of lower 201.3cSt, at 1574cm ^-1The IR acetic ester peak value at place, and be 1.33% nitrogen.

Incorporate above-mentioned each file into the present invention by reference.Except among the embodiment, or outside offering some clarification in addition, all quantity of describing in this manual the amount, reaction conditions, molecular weight, carbonatoms etc. of material are to be understood that by wording " approximately " modifies.Unless otherwise indicated, all quantity of the amount of material or ratio are described in this manual based on weight.Except as otherwise noted, each chemical or the composition mentioned of this paper should be understood to contain isomer, by product, derivative and usually is to be understood that the commercial grade material that is present in other this class material in the commercial grade.Yet except as otherwise noted, the scale of each chemical composition is shown has got rid of any solvent or the thinning oil that usually can be present in the commercial materials.The upper and lower bound that is to be understood that amount described herein, scope and ratio can make up independently.Similarly, the scope of each element of the present invention and amount can be used with scope or the amount of any other element.As used herein, statement " substantially by ... form " allow the material of the fundamental sum new features of the composition that comprises that not substantially impact is considered.

Claims

1. the composition that comprises quaternized polyester salt, it comprises the reaction product of following component:

A. the polyester that contains uncle's amino; With

B. be suitable for uncle's amino is changed into the quaternizing agent of quaternary nitrogen.

2. according to claim 1 composition, wherein said polyester comprises the reaction product of following component: contain the aliphatic carboxylic acid of at least one hydroxyl, and have can with the oxygen of described sour condensation or the compound of nitrogen-atoms, wherein said compound contains uncle's amino.

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

R wherein ¹For hydrogen or contain the alkyl of 1-20 carbon atom, and R ²For containing the alkylene of 1-20 carbon atom; And

Wherein have and can be expressed from the next with oxygen or the nitrogen-atoms of described sour condensation and the compound that further has uncle's amino:

R wherein ³For containing the alkyl of 1-10 carbon atom; R ⁴For containing the alkyl of 1-10 carbon atom; R ⁵For containing the alkylene of 1-20 carbon atom; And X ¹Be O or NR ⁶, R wherein ⁶For hydrogen or contain the alkyl of 1-10 carbon atom.

4. according to claim 1 composition, wherein said quaternized polyester salt comprises quaternized polyesteramide salt, wherein the polyester for the preparation of the tertiary-amino-containing of described quaternized polyester salt is the polyesteramide of tertiary-amino-containing.

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

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

6. according to claim 2 composition, wherein said have and can comprise N with oxygen or the nitrogen-atoms of described sour condensation and the compound that further has uncle's amino, 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.

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

8. according to claim 1 composition, wherein said quaternizing agent comprises ethylene oxide, propylene oxide, oxybutylene, Styrene oxide 98min. or its combination, wherein quaternizing agent and acid are used in combination.

9. according to claim 1 composition, it further comprises metal deactivators, be different from those 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 polymkeric substance, scale inhibitor, gas hydrate inhibitor or its any combination of claim 1.

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

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

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

A. in described oil engine, feed:

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

Ii. the composition that comprises quaternized polyester salt, described quaternized polyester salt comprises the reaction product of following component: (a) polyester of tertiary-amino-containing; (b) be suitable for uncle's amino is changed into the quaternizing agent of quaternary nitrogen.

13. prepare the method for quaternary ammonium salt purification agent, it comprises:

I. make the polyester of (a) tertiary-amino-containing; (b) be suitable for uncle's amino is changed into the quaternizing agent reaction of quaternary nitrogen; Obtain thus quaternized dispersion agent.

14. method according to claim 14, wherein the polyester of tertiary-amino-containing prepares by the following method, and described method comprises:

I. make (a) (i) contain the aliphatic carboxylic acid of at least one hydroxyl and (a) (ii) have and can and further have the compound reaction of uncle's amino with oxygen or the nitrogen-atoms of described sour condensation;

Obtain thus the polyester of tertiary-amino-containing.