CN1112139A - Substituted polyoxyalkylene compounds - Google Patents

Abstract

The invention provides an alkyl compound R<1>-a-x-*-R<2> of the general formula I (the definitions of symbols in the general formula are consistent to the instruction book). The invention further provides a preparation process of the compound, which comprises a lubricating oil composition, a fuel composition, and a lubricating oil additive. The compound is performed as the use of a rust inhibitor and an operational method of a combustion engine.

Description

Substituted polyoxyalkylene compounds

The polyoxyalkylene compounds that the present invention relates to replace particularly, although be not unique, relates to this compound as rust-preventive agent, for example, and the rust-preventive agent in the lubricating oil composition.

Polyoxyalkylene compounds quite has been widely used as the additive of lubricating oil composition.For example, european patent application No.0 309 105(Exxon) nonionogenic tenside is disclosed, such as polyoxy sub alkyl polylol and ester thereof, point out that they are identical as the Ashless stain-resistant agent in the lubricating oil.Preferred polyhydric alcohols is prepared to segmented copolymer, so that compound has hydrophobic and hydrophilic two portions.The Pluronic(trade mark) polyvalent alcohol is claimed as and is particularly suitable for as rust-preventive agent.

U.S. Patent No. 3509052(Lubrizol) lubricating oil composition that comprises a kind of polyoxy sub alkyl polylol emulsifying agent (or its a kind of ester) is disclosed.Preferred polyhydric alcohols has hydrophobic and hydrophilic part.The Pluronic(trade mark) polyvalent alcohol is pointed out to be preferably.

U.S. Patent No. 3,784 474(Chevron) discloses a kind of comprising with polyoxy sub alkyl polylol, the lubricating oil composition of the rust-preventive agent of dibasic alcohol, ester or carbamate type.Preferred polyether polyols comprises epoxypropane polymer or segmented copolymer.The Pluronic(trade mark) polyvalent alcohol is disclosed as the commercial suitable polyvalent alcohol example that gets.Object lesson in the patent has been described the rust-preventive agent that utilizes oxygen propylidene and the unitary polyether polyols segmented copolymer preparation of oxygen ethylidene.

U.S. Patent No. 3,933 663(Chevron) discloses the lubricating oil composition of the compound that a kind of acid neutralization that comprises a poly-alkoxylation type of compounds quickens.Suitable compound is pointed out to comprise the trade mark such as Pluronics() some propylene oxide and the segmented copolymer of oxyethane.The structure of compound is pointed out as amphipathic.

U.S. Patent No. 3,957 854(Lubrizol) discloses oily moltenly, and with the carboxylicesters of a kind of polycarboxylic acid acylating agent and at least a polyoxy alkylidene alcohol preparation, this ester is a kind of segmented copolymer, includes hydrophobic and hydrophilic part.Suitable polyoxy alkylidene alcohol is pointed out as the Pluronic(trade mark) polyvalent alcohol.

U.S. Patent No. 4493776(Shell) disclose a kind of lubricating oil composition that comprises a kind of auxiliary and rust-preventive agent, it comprises at least a oxygen ethylidene ethanol that alkyl, aryl, alkaryl or aralkyl replace or the compound of oxygen propylidene propyl alcohol of being selected from; With a kind of mixture that is selected from the segmented copolymer of oxyethane that alkyl, aryl, alkaryl or aralkyl replace and propylene oxide.

U.S. Patent No. 5204 012(Ethyl Corportion) a kind of lubricating oil composition is disclosed, it comprises a kind of total acid value (TAN) scope about 10 to about 40, reacts the carboxylate for preparing by an ethylene oxide/propylene oxide segmented copolymer and a long-chain monocarboxylic acid.

The present invention is based on the poly (oxyalkylene) based compound of a series of replacement, when being used for, for example, during lubricating oil composition, has this discovery of beyond thought advantageous property.

According to the present invention, a kind of poly (oxyalkylene) based compound is provided, its general formula is:

R ¹-A-X-

-R ²（Ⅰ）

Wherein

R ¹Represent a hydrogen atom or a kind of in case of necessity substituted alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, alkaryl or heterocyclic group;

R ²Represent a kind of substituted in case of necessity alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, alkaryl, heterocyclic radical, alkoxyl group, aryloxy, alkylamino, dialkyl amido or fragrant amine groups; A represents a Sauerstoffatom (O-) or one-NH-group; And;

X represents the random copolymers of a polyoxy propylidene chain or an ethylene oxide/propylene oxide, and-Sauerstoffatom of X group is directly connected in R ²The CO-part.

People unexpectedly find, with other, for example, comprise with a Pluronic(trade mark) the polyoxyalkylene rust-preventive agent of the polyoxy alkylidene chain of the block copolymerization of polyvalent alcohol preparation relatively, the poly (oxyalkylene) based compound of formula I is the rust-preventive agent of favourable lubricating oil composition.Particularly, the poly (oxyalkylene) based compound of formula I can demonstrate the filling stability of improvement and/or have low acid number, also has satisfied rust inhibiting property simultaneously.

Usually, when any part described herein comprises an alkyl, when alkenyl or ethynylene group, this group can be linear or branching and preferably comprise 1-50 that be more preferably 1-25, the best is a 2-20 carbon atom.When any part described herein comprised an aryl, this group can be a substituted in case of necessity phenyl group.When any part comprised an aralkyl, this group can be a substituted in case of necessity phenmethyl.Preferably, phenyl or benzyl be non-replacement or replaced by an alkyl.When arbitrary part described herein comprised a cycloalkyl, this group can comprise 3-8, and more excellent is 3-6 carbon atom, as cyclopentyl or cyclohexyl.When arbitrary part comprised a heterocyclic group, this group can be any saturated or undersaturated ring system, as a C ₅-C ₇Ring system, comprise the heteroatoms that at least one is selected from oxygen, nitrogen and sulphur, 5 yuan and 6 yuan of rings are particularly preferred, as a tetrahydrofuran base, furyl, piperidyl, pyridyl, tetrahydro-thienyl or thiophenyl (thienyl).

The example of substituted radical comprises halogen atom (as the chlorine atom), nitro, hydroxyl, carboxyl, amino, cyano group, formyl radical, carbalkoxy, alkanoyl, alkyl sulfenyl, alkyl sulphonyl, alkane sulfo group, formamyl, alkylamino and polyoxy alkylidene group.When arbitrary aforesaid substituted radical comprised an alkyl or alkenyl part, this group can be linear or branching, and can comprise nearly 12, was preferably 6, particularly to 4 carbon atoms.

Be preferably R ¹Represent a hydrogen atom or a kind of substituted in case of necessity alkyl.

When A represents one-NH-group, R ¹Preferably represent the substituted alkyl of general formula II

H ₂N-（CHR ³） _r-CH ₂-〔O-CH ₂（CHR ³） _r〕 _s-（Ⅱ）

Each R wherein ³Represent a hydrogen atom or monomethyl group independently, the scope of r is from 1 to 3 and the scope from 1 to 200 of s.

In the general formula II, preferred r is 1, each R ³All represent monomethyl and s in the scope of 4-40.

When A represents a Sauerstoffatom, R ¹Preferably represent the alkyl of a non-replacement, particularly a kind of C ₄-C ₁₆Alkyl.Preferably, R ¹Represent a kind of alkyl of linearity.

Preferably, R ²Represent a substituted in case of necessity alkyl, phenyl or benzyl.

Work as R ²When representing a kind of substituted in case of necessity alkyl, this group preferably has at least 4 carbon atoms.The example of substituted alkyl comprises-(CH in case of necessity ₂) ₄COOH, the tertiary butyl, nonyl, the 1-ethyl pentyl group, its general formula is CH ₃(CH ₂) _n-the alkyl of linearity, wherein n represents 8-20, and the alkyl with general formula III:

（Ⅲ）

R wherein ⁴Representing a general formula is C _aH _2a+1-group; R ⁵Representing a general formula is C _bH _2b+1-group; R ⁶Representing a general formula is C _cH _2c+1-group; And a+b+c's and in the scope of 3-20, be preferably 3-8.

At R ²Represent under the situation of a substituted alkyl, alkyl can be replaced by a group with general formula IV:

R wherein ⁷Represent a hydrogen atom or a kind of substituted in case of necessity alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, alkaryl or heterocyclic group; A ' represents a Sauerstoffatom (O-) or one-NH-group; Reach the random copolymers chain that Y represents a polyoxy propylidene chain or an ethylene oxide/propylene oxide, and a Sauerstoffatom of Y group directly is bonded in carbonyl.Preferably, R ⁷And R ¹Represent same atom or group.Preferably, Y and X representative is with a part.Preferably A and A ' represent a Sauerstoffatom or one-NH-group.

Number-average molecular weight (the M of radicals X or Y _n) preferably in the scope of 300-5000, better scope is 300-3500, and particularly in the scope of 500-2500.Represent under the situation of a polyoxy propylidene chain in radicals X or Y, the number-average molecular weight of said chain can be in the scope of 300-3000.When radicals X or Y represented a random ethylene oxide/propylene oxide copolymer chain, number-average molecular weight can be in the scope of 1000-3000.

Radicals X or Y preferably comprise the oxyethane of ∝ wt% and the propylene oxide of (100-∝) wt%, and wherein the scope of ∝ is 0-60, and more preferably, the scope of ∝ is 0-30.

The total acid value of material (TAN) is the quantity of alkali, with in and the milligram number of the potassium hydroxide that all acidic components need in the 1g material explain.Preferably, the TAN with compound of formula I is lower than 5, is more preferably, and the TAN of the compound of said formula I is lower than 2.Particularly preferably be TAN and be lower than 0.5 compound.

The present invention expands to the preparation technology of the compound with formula I, and this technology comprises a compound with general formula V

R ¹-A-X-OH （Ⅴ）

R wherein ¹, A and X react with the compound with general formula VI: R as defined above ²

L ¹(VI)

R wherein ²As above-mentioned definition and L ¹It is a leavings group.

Reaction preferably in aprotonic solvent neutralization in case of necessity in acid medium, in right-toluenesulphonic acids, or in an alkaline media, in alkaline carbonate or supercarbonate, or in the amine, as carrying out in a kind of trialkylamine or the pyridine.Under 40 ℃-180 ℃ of temperature ranges, reaction is easy to carry out.Reaction is preferably carried out under refluxing.

Select suitable L ¹, react and generate a kind of ester so that have the compound one of formula V and VI.L ¹Can represent a halogen atom, particularly a chlorine atom, perhaps monohydroxy group.Perhaps, the compound of said general formula VI can be represented an acid anhydrides, in this case, and L ¹Represent a R ²COO-group, and R ²As above definition.

In the compound of formula I, R ²Represent under the situation of an alkyl that is replaced by the group of above-mentioned general formula IV, the compound of said formula I can be reacted by the compound of at least a compound with general formula VII and V and prepare:

L wherein ²And L ³Can be identical or different and represent leavings group; And on behalf of a general formula, Z be-(CR ⁸R ⁹) _m-the divalence linearity or the ramose hydrocarbon moiety, wherein m is an integer, each R ⁸Represent a hydrogen atom or an alkyl independently, and each R ⁹Represent a hydrogen atom or an alkyl independently.

Select suitable L ²And L ³And reaction conditions, so that reacting, the compound one of general formula V and VII produces the compound with at least two ester groups of a formula I.L ²And L ³Can represent a halogen atom independently, a particularly chlorine atom, or monohydroxy.Preferably, L ²And L ³All represent monohydroxy.In this case, described compounds represented one dicarboxylic acid with general formula V is as adipic acid.

The general formula V, VI and VII are compound known, maybe can prepare by the method that is similar to already known processes.

For example, wherein A represents a Sauerstoffatom and R ¹Represent an alkyl, or wherein A represents one-NH-group and R ¹Represent the formula V compound of the substituted alkyl of an above-mentioned general formula II, can pass through the polymeric rings Ethylene Oxide, and oxyethane in case of necessity, what sell such as the Subsidiary Company of the Royal Dutch/Shell Group company, trade mark is a kind of pure initiator of " DOBANOL ", " DOBANOL " 25 initiators particularly, or have preparation easily under a kind of amine action of evocating of general formula (II ')

H ₂N-（CHR ³） _r-CH ₂-〔O-CH ₂-（CHR ³） _r〕 _s-NH ₂（Ⅱ′）

R wherein ³, r and s such as above-mentioned definition, this initiator can be from the Texaco Chemical Company, Bellaiye, Texas, U.S.A buys.

The general formula VI, R wherein ²Represent the alkyl of a branching, as a kind of alkyl of above-mentioned general formula III, and L ¹Represent monohydroxy compound to buy from Exxon company, trade mark be " CEKANOIC ", and as " CEKANOIC " 10 acid, and from the Subsidiary Company of the Royal Dutch/Shell Group, the purchase trade mark is the commodity of " VERSATIC ".As " VERSATIC " 5 acid and " VERSATIC " 10 acid.

The present invention expands to the compound a kind of compound of prepared in reaction together by general formula V and VI.

The present invention expands to the lubricating oil composition of the compound that comprises a large amount of (greater than 50wt%, based on the weight meter of whole composition) lubricating oil and a spot of formula I.

The lubricating oil that uses in composition of the present invention, its source can be natural, mineral, or synthetic.Natural lubricating oil comprises animal or plant oil, as Viscotrol C.Mineral oil comprises and comes from crude oil, the lubricating oil distillate of coal or resinous shale, and these cuts may pass through certain processing, as clay treatment, acid treatment, solvent treatment or hydrogen treatment.Synthetic lubricating oil comprises synthetic polymkeric substance or hydrocarbon polymer, the alkylene oxide polymer of modification and ester lubricant, and this is technical known.These lubricating oil are the crankcase oil of spark ignition and compression-ignition engine preferably, but also comprises hydraulic lubricant oil, metal processing oil solution, automatic switching finish and similar this type of finish.

Lubricating oil composition preferably comprises the compound of the formula I of 0.05-10wt%, and 0.1-5wt% is better, and 0.1-1wt% the best is according to the weight meter of whole composition.

Can comprise in the lubricating oil composition various other, known additives in the lubricating oil technology, such as viscosity index improver, as the line style of diene such as isoprene or divinyl or the polymkeric substance of star, or this diene and substituted cinnamic multipolymer in case of necessity.These multipolymers are suitable segmented copolymers, and preferably are hydrogenated to as making the saturated degree of most of olefinic unsaturated polymers.

Lubricating oil composition can further comprise a kind of ashless dispersant, and it is selected from the list of the molten chain alkyl replacement of oil or the salt of dicarboxylic acid or their acid anhydrides, acid amides, imide, azoles quinoline, and ester, or their mixture; Reach the aliphatic hydrocarbon that directly connects a polyamine species in the long-chain.Best ashless dispersant comprises the succinimide that polyolefine replaces.

Can add other suitable additive in the lubricating oil composition comprise ultimate pressure/wear preventive additive, such as the dithiophosphates of zinc or sodium, antioxidant, friction improver or containing metal washing composition are such as phenates, sulfonate, alkylsalicylate or naphthenate, all these washing composition can be overbasic.

According to the present invention, lubricating oil composition can prepare by be blended into a filling additive (concentrated solution) in lubricating base oil.A kind of like this filling additive includes a kind of lubricating oil usually as solvents/diluents, and one or more are in the additive that concentrates form.Therefore the present invention further provides a kind of lubricating oil filling additive, it comprises a thinner and based on whole filling additive, accounts for the compound of the above-mentioned formula I of 1-80wt%.

The compound that the present invention expands to formula I is used as rust-preventive agent.

The present invention further expands to the working method of the oil engine that prevents that iron rust from forming, and this method comprises with the lubricated said engine of above-mentioned lubricating oil composition.

The compound of formula I also can be used for fuel, for example gasoline, diesel oil fuel, kerosene and oil fuel.Suitably, the compound of formula I can be used as the carrier fluid of gasoline and diesel oil fuel oil filling additive.Correspondingly, the present invention expands to a fuel composition, and it comprises a kind of compound of a large amount of (based on whole composition meter greater than 50wt%) a kind of fuel and a spot of formula I.

Satisfactory fuel composition of the present invention also contains the soluble a spot of ashless dispersant of at least a hydrocarbon.As the compound of ashless dispersant, its feature normally is linked with the group of " polarity " on the relative high-molecular weight hydrocarbon chain." polarity " group contains one or more nitrogen element, oxygen element and phosphoric usually.Soluble molecular chain molecular weight is usually above those molecular weight with the ashless dispersant of metallic salt form use, but in some cases, their molecular weight is very approaching.

Usually, known any ashless dispersant can be used for fuel composition among the present invention in lubricant and fuel applications technology.

In one embodiment of the invention, dispersion agent is selected from the compounds that constitutes below:

(ⅰ) amine of at least a alkyl replacement, wherein hydrocarbyl substituent is aliphatic basically, and contains at least 8 carbon atoms;

(ⅱ) at least a acidylate, by the monocarboxylic acid acylating agent and at least a contain at least one-the aminocompound prepared in reaction of NH-group, the nitrogenous compound that contains the hydrocarbyl substituent group of one at least 10 aliphatic carbon atom, said acylating agent is by an imino-, amido, amidine or carboxyl ammonium key are bonded in said aminocompound;

(ⅲ) at least a by a phenol, aldehyde and have at least one-the nitrogenous condenses of the aminocompound condensation of NH-group;

(ⅳ) ester of the carboxylic acid of at least a replacement;

(ⅴ) at least a polymeric dispersant;

(ⅵ) the phenol dispersion agent of at least a hydrocarbon replacement; And

(ⅶ) at least a fuel is soluble, alcohol, alkoxy derivative phenol or amine.

For those professional and technical personnel, the hydrocarbon that is used for fuel composition of the present invention replaces amine to be known, and their existing argumentations in a series of patents.U.S. Patent No. 3,275 is arranged, 554,3,438,757,3,454,555,3,565,804,3,755,433 and 3,822,209 in these patents.These patent disclosures the amine that replaces of the suitable hydrocarbon that is used for the present invention, comprise their preparation method.

The amine that a kind of typical hydrocarbon replaces has general formula:

〔R ¹⁰R ¹¹N〕 _x〔-N（〔-UN-〕 _d〔-UQ〕 _e）〕 _YR ¹²H _1+2Y+dY-f（Ⅷ）

R wherein ¹⁰Be hydrogen, the alkyl of a kind of 1-10 carbon atom, or the hydroxy alkylene of 1-10 carbon atom; R ¹¹Be hydrogen atom, the alkyl of a kind of 1-10 carbon atom or a kind of 1-10 carbon atom, and can with R ¹⁰Form 5-6 unit with N and encircle the hydroxy alkylene that reaches until 12 carboatomic rings; U is the alkylidene group of a kind of 2-10 carbon atom, infers the hydrocarbon that holds trivalent nitrogen of any necessity herein, R ¹²It is the aliphatic hydrocarbon of a 30-400 carbon atom; Q is a piperazine structure; D is the integer of 0-10; E is the integer of 0-1; D+2e is the integer of 1-10; F is the integer of 1-5 and is an interior mean number of 1-4 scope, and is equal to or less than the nitrogen-atoms number in the molecule; X is the integer of 0-1; Y is the integer of 0-1; X+y equals 1.

For this general formula is described, must understand R ¹²Be connected on the unsaturated nitrogen valence link in the molecular formula bracket with the H atom.Therefore, for example, general formula comprises time generic molecular formula, wherein R ¹²Be connected on the tail end nitrogen-atoms, and the inferior generic molecular formula of isomery, wherein R ¹²Be connected in the nitrogen-atoms of non-tail end.Do not connect R ¹²Nitrogen-atoms can connect a hydrogen atom or a R ¹⁰R ¹¹The N substituting group.

Useful in the present invention and be contained in the amine that the alkyl in the above-mentioned general formula VIII replaces and comprise monoamine, such as poly-(propylene) amine, N, N-dimethyl-n gathers (ethylene/propene) amine (monomer mole ratio 50: 50), poly-(iso-butylene) amine, N, poly-(iso-butylene) amine of two (the hydroxyethyl)-N-of N-, poly-(iso-butylene/1-butylene/2-butylene) amine (monomer mole ratio 50: 25: 25), the N-(2-hydroxyethyl)-poly-(iso-butylene) amine of N-, the N-(2-hydroxypropyl)-and poly-(iso-butylene) amine of N-, poly-(1-butylene) aniline of N-and poly-(iso-butylene) morpholine of N-; And poly-(iso-butylene) quadrol of polyamine such as N-, N-gathers (propylene) trimethylene diamines, and N-gathers (1-butylene)-diethylenetriamine, N ' N '-poly-(iso-butylene) tetren, N, N-dimethyl-N '-poly-(propylene) and 1,3-propylene diamine.

The amine that useful alkyl replaces in fuel composition of the present invention also comprises some amino of the N-with general formula IX-alkyl morpholine:

R ¹²N（R ¹⁰）UM （Ⅸ）

R wherein ¹²Be the aliphatic hydrocarbon group of a kind of 30-400 carbon atom, R ¹⁰Be hydrogen atom, the hydroxy alkylene of the alkyl of a kind of 1-10 carbon atom or a kind of 1-10 carbon atom, U is the alkylidene group of a kind of 2-10 carbon atom, and M is a kind of morpholine structure.The polyamine that hydrocarbyl amino morpholine that these alkyl replace and general formula VIII are described is the typical alkyl replacement amine that is used for preparing the present composition.

For the professional and technical personnel, by a kind of carboxylic acid acylating agent and the aminocompound prepared in reaction and the substituent a series of acidylates of hydrocarbon skeleton that contain at least 10 aliphatic carbon atoms, nitrogenous compound is known.Acylating agent passes through an imino-, amido, and amidine or carboxyl ammonium key are connected in aminocompound.The hydrocarbon skeleton substituting group of at least 10 aliphatic carbon atoms both can be in molecule carboxylic acid acylating agent's deutero-part, also can be in molecule aminocompound deutero-part, yet, preferably in the acylating agent part.Acylating agent can change to from formic acid and acylated derivatives thereof have high molecular, carbonatoms is until 5000,10000 or 20000 aliphatic substituent acylating agent.Aminocompound can change to the aliphatic substituent amine that contains until 30 carbon atoms from ammonia itself.

Useful typical series acidylate, nitrogenous compound is to react those nitrogenous compounds that make by aliphatic substituent a kind of acylating agent and a kind of a kind of nitrogen compound that is characterized as in the molecule at least one-NH-group that contains one at least 10 carbon atom in the present composition.Typically, acylating agent will be a list or poly carboxylic acid (or its suitable reactant), and such as a kind of succsinic acid or propionic acid of replacement, reaching aminocompound will be the mixture of a kind of polyamine or polyamine, the most typically, be the mixture of ethylidene polyamine.Amine also can be the polyamines that a kind of hydroxyalkyl replaces.Aliphatic substituting group in such acylating agent preferably on average at least 30 or 50 reaches up to 400 carbon atoms.

The illustrative hydrocarbon skeleton substituting group that comprises at least 10 aliphatic carbon atoms is positive decyl, dodecyl, tetrapropylene base, Octadecane base, oil base, chlorooctadecane base and triacontyl.Usually, the hydrocarbon skeleton substituting group be the homopolymer of the monoene of 2-10 carbon atom and diene or multipolymer (as, multipolymer, terpolymer) prepare, such as ethene, propylene, butene-1, iso-butylene, divinyl, isoprene, 1-be alkene and 1-octene.These alkene are typical 1-monoolefines.These substituting groups also can derive from this homopolymer and multipolymer halogenated (as, chloro or bromo) analogue.In any case, substituting group can make from other method, such as high molecular monomer alkene (as, 1-40 carbenes) and the analogue of chlorination and hydrochlorinate, the analogue of aliphatic series petroleum fractions, particularly paraffin and cracked and chlorating analogue and hydrochlorinate, white oil, synthetic alkene such as those Ziegler-Natta explained hereafter as, the method that poly-(ethene lubricating grease) and other those professionals know.Nonsaturation in any substituting group can be by reducing or cancellation according to technical known technology hydrogenation.

The term " hydrocarbon skeleton " that is used for this specification sheets is meant that a group has a carbon atom to be directly connected in the rest part of molecule and has the hydrocarbon feature that is dominant in hydrocarbon skeleton substitution compound class of the present invention.Therefore, can contain a non-hydrocarbyl group in per ten carbon atoms of hydrocarbon skeleton group, condition is the hydrocarbon feature that this hydrocarbyl group can not change the principal character of group significantly.The professional should recognize these groups.It comprises, for example, and hydroxyl, halogeno-group (particularly chloro base and fluoro base), alkoxyl group, alkyl thiol and alkyl sulfide oxygen groups.In any case, frequently, the hydrocarbon skeleton substituting group is pure alkyl and does not contain so non-hydrocarbyl group.

The hydrocarbon skeleton substituting group is saturated basically, and that is exactly that per 10 C-C singly-bounds contain no more than 1 carbon-to-carbon unsaturated bond.Frequently, the unsaturated link(age) that contains no more than 1 the non-fragrance of carbon-to-carbon in per 50 C-Cs.

In nature, the hydrocarbon skeleton substituting group also is aliphatic substantially, and that is exactly, and in substituting group in per 10 carbon atoms, containing no more than one has 6 or the group of the non-aliphatic series of carbonatoms (cycloalkyl, cycloalkenyl group or aryl) still less.In any case, this substituting group often is to contain no more than 1 so non-aliphatic group in per 50 carbon atoms, and under many circumstances, does not contain so non-aliphatic group; That is exactly that typical substituting group is pure aliphatic series.Typically these pure aliphatic substituting groups are alkyl or kiki alkenyl group.

Comprise on average more than 30 carbon atoms, the saturated substantially substituent object lesson of hydrocarbon skeleton as follows: the mixture that gathers (ethylene/propene) group of 35-70 carbon atom, the mixture of poly-(ethylene/propene) group of the oxidation of 35-70 carbon atom or mechano-degradation, mixture of poly-(propylene/1-is alkene) group of 80-150 carbon atom and mixture with polyisobutylene group of an average 50-75 carbon atom.

Substituent source preferably is a polyisobutenyl, and it is under the katalysis of lewis acid catalyst such as aluminum chloride or boron trifluoride, and polymerization has the C of the iso-butylene content of the butene content of 35-70wt% and 30-60wt% ₄Refining liquid flows and gets.These polyisobutene mainly contain structure ₃) ₂CH ₂-different propylene repeating unit (greater than always repeating unitary 80%).

The example of aminocompound of compound that is used to prepare acidylate is as follows: (1) has the polyalkenes polyamine of general formula ⅹ:

（R ¹⁴） ₂N〔P-N（R ¹⁴）〕 _tR ¹⁴（ⅹ）

Each R wherein ¹⁴Be a hydrogen atom independently, contain that its restricted condition is at least one R until an alkyl of 30 carbon atoms or the alkyl of hydroxyl replacement ¹⁴Be hydrogen atom, t is the integer of 1-10, and P is a C _1-18Alkylidene group;

(2) polyamine that replaces of the carboxyalkyl of polyamine as the aforementioned wherein;

(3) wherein as the aforementioned the polyamine and the heterocyclic substituent that replace of the heterocyclic radical of polyamine derive from, for example, piperazine, tetrahydroglyoxaline, pyrimidine or morpholine; And

(4) have the aromatic polyamine of general formula XI:

Ar（NR ¹⁴ ₂） _z（Ⅺ）

Wherein Ar is the aromatic nucleus of a 6-20 carbon atom, each R ¹⁴As above-mentioned definition and z is 2-8.

The object lesson of the polyalkylene polyamine of general formula X has quadrol, four (ethylidene), five amine, three (trimethylene)-tetramines and 1,2-propylene diamine.

The object lesson of the polyamine that hydroxyalkyl replaces comprises the N-(2-hydroxyethyl) quadrol, N, N '-two-(2-hydroxyethyl) quadrol and N-(3-hydroxyl butyl) tetramethylene-diamine.

The object lesson of the polyamine of heterocyclic substituted is the N-2-aminoethyl piperazine, N-2-and N-3-aminopropyl morpholine, the N-3-(dimethylamino) propyl group piperazine, 2-heptyl-3-(2-aminopropyl) tetrahydroglyoxaline, 1, two (2-aminoethyl) piperazines of 4-, the 1-(2-hydroxyethyl) piperazine and 2-heptadecyl-1-(2-hydroxyethyl)-tetrahydroglyoxaline.

The object lesson of aromatic polyamine is the phenylenediamine of various isomeries and the naphthylene diamine of various isomeries.

Many patents have been described the nitrogen compound of useful acidylate, comprise United States Patent (USP) NOS.3, and 172,892,3,219,666; 3,272,746,3,310,492,3; 341,542,3,444,170,3,455; 831,3,455,832,3,576; 743,3,630,904,3,632; 511,3,804,763 and 4,234,435.The acidylate nitrogenous compound of this quasi-representative is by the polyisobutylene-substituted succinic anhydride acylating agent; wherein the polyisobutene substituting group contains 50 to 400 carbon atoms, with every kind of ethylidene polyamines contain 3-7 amino nitrogen atom the ethylidene polyamine mixture reaction and make.

The nitrogenous compound that belongs to the another kind of acidylate of this class is to obtain with the mono carboxylic acid of aliphatic series reaction that contains 2-22 carbon atom by the succsinic acid of above-mentioned alkylenamines and above-mentioned replacement or acid anhydrides.In the acylated nitrogen compound of these types, succsinic acid to the scope of the mol ratio of monocarboxylic acid 1: 0.1-1: between 1.Typical monocarboxylic acid is a formic acid, acetate, and dodecylic acid, butyric acid, oleic acid, stearic acid is called as the cuts and the toluic acid of the stearic acid isomer of Unimac 5680.These materials are at United States Patent (USP) NOS.3.216, have obtained describing more fully in 936 and 3,250,715.

The nitrogen compound that also has the acidylate that is used for fuel composition of the present invention of another type; it is the fatty monocarboxylic acid and the aforementioned alkylenamines of 12-30 carbon atom; be typically; the ethylidene that contains 2-8 amine groups, the reaction product of propylidene or trimethylene polyamine and composition thereof.The fat monocarboxylic acid normally comprises the straight chain of 12-30 carbon atom and the mixture of branched chain aliphatic carboxylic acid.The nitrogenous compound of the widely used acidylate of one class is to make by the mixture reaction of aforementioned alkylidene group polyamine with the lipid acid of the branched chain resin acid of straight-chain acid with 5-30 molar percentage and 70-95 molar percentage.Be that those are the Unimac 5680 of people known to extensively in the mixture of these commercial gained in trade, these mixtures are as United States Patent (USP) NOS.2, the by product of the dimerization reaction of 812,342 and 3,260, the 671 undersaturated lipid acid of describing.

Branched chain lipid acid can comprise that also those side chains are not the lipid acid of alkyl in nature, such as the phenyl of having found and cyclohexyl stearic acid and chloro stearic acid.Branched chain aliphatic carboxylic acid/alkylidene group polyamine product, for example, in United States Patent (USP) NOS. 3,110,673,3,251,853,3,326,801,3,337,459,3,405,064, be described in 3,429,674,3,468,639 and 3,857,791.

Phenol/ester/aminocompound condenses as the dispersion agent in the fuel composition of the present invention comprises that those are commonly referred to as the condenses of Mannich condensate.Normally, these condensess are by with at least a active hydrogen compounds, wherein have at least a hydrogen atom to be bonded on the aromatic carbon atom, the phenol that replaces such as hydrocarbon (as, a kind of alkylphenol, wherein the average carbon atom number of alkyl is 12-400 at least, is preferably 30-400), maybe can generate the material (being typically the formaldehyde parent) of aldehyde and at least a amino that contains at least one NH group or polyamino compound simultaneously or react successively and make with at least a aldehyde.These aminocompounds comprise the uncle or the secondary monoamine of the hydrocarbon substituent that the alkyl of the hydrocarbon substituent that contains 1-30 carbon atom or 1-30 carbon atom replaces.The typical aminocompound of another type is the polyamine of describing when the nitrogenous compound of acidylate is discussed.

Typical monoamine comprises methylethyl amine, methyl octadecane amine, aniline, diethylamide, diethanolamine and dipropylamine.Following patent includes a large amount of description for the Mannich condenses: United States Patent (USP) NOS.2,459,112,3,413,347,3,558,743,2,962,442,3,442,808,3,586,629,2,984,550,3,448,047,3,591,598,3,036,002; 3,454,497,3,600,372,3,166,516,3,459,661,3,634,515,3,236,770,3,461,172,3,649,229,3,355,270,3,493,520,3,697,574,3,368,972 and 3,539,633.

The condenses that is made by the sulfur-bearing reagent also can be used for fuel composition of the present invention.This sulfur-bearing condenses is at United States Patent (USP) NOS.3, is described in 368,972,3,649,229,3,600,372,3,649,659 and 3,741,896.These patents have also disclosed the Mannich condenses of sulfur-bearing.The sulfur-bearing condenses that is generally used for preparing composition of the present invention is from containing 6-400 carbon atom, the phenol of the alkyl substituent of the more typical 30-250 of a being carbon atom and making, and these typical sulfur-bearing condensess are from formaldehyde or C _2-7Aliphatic aldehyde and a kind of aminocompound, those aminocompounds of all nitrogenous compounds that is used to prepare acidylate as described above and making.

These preferred condensess be by with the aldehyde group of 1mol oxybenzene compound group and 1-2mol and the normal aminocompound group of 1-5 (the monovalent aminocompound be it molecular weight divided by in the molecule-number of NH-group) reaction produces, for the professional and technical personnel, the condition that this condensation reaction is carried out is known.

The nitrogenous condensation product that is used for fuel composition of the present invention of special recommendation is that those pass through (1) with at least a at least 30 carbon atoms and aliphatic series or the substituent hydroxyaromatic compounds of cyclic aliphatic and a kind of C of 400 carbon atoms at the most of containing _1-7Aldehyde or its reversible polymer of lower aliphatic, in alkaline reactive medium,, reacting under 150 ℃ the temperature at the most such as the metal hydroxides of an alkalescence; (2) the such intermediate reaction mixture that forms of basic neutralization; And (3) with the neutral intermediate product and at least a contain at least one-compound of the amino of NH-group reacts and makes.

Preferablely be, these condensess are the substituent phenol of hydrocarbon skeleton that 30-250 carbon atom arranged with (a), and said substituting group is to derive from propylene, 1-butylene, a kind of polymkeric substance of 2-butylene or iso-butylene reaches (b) formaldehyde, or its reversible polymer, (as ， trioxane, Paraformaldehyde 96), or the suitable compound of its functional group, (as, methylol) and (c) a kind of alkylene polyamine are such as the ethylidene polyamine of 2-10 nitrogen-atoms and make.

The ester that is used as dispersion agent in fuel composition of the present invention is the derivative of the carboxylic acid of replacement, and wherein substituting group is aliphatic substantially, is saturated basically, comprises at least 30, is preferably at least 50, at the most the hydrocarbon skeleton group of 750 fatty carbon atoms.Term used herein " hydrocarbon skeleton group " is meant the rest part that is directly connected in molecule of a carbon atom and the group that mainly has the hydrocarbon feature in the foregoing group of the present invention.Such group comprises following group:

(1) hydrocarbyl group; They are aliphatic groups that those professionals know, the aliphatic group that aromatic series and alicyclic (andalicyclic) replace, and similar group.

(2) hydrocarbyl group of Qu Daiing; They are to contain the substituent group of nonhydrocarbon, and in the foregoing group of the present invention, non-hydrocarbon substituent does not change the main hydrocarbon feature of group.Those professionals will recognize suitable substituents; The substituent example of nonhydrocarbon is a halogenic substituent, nitro, hydroxyl, alkoxyl group, carbalkoxy and alkyl sulfenyl.

(3) heteroatom group: they are in the previously described group of the present invention, mainly are the group of hydrocarbon feature on feature, contain the atom that is different from carbon atom in chain or the ring, are different from chain or ring that carbon atom constitutes.For those professionals, suitable heteroatoms is conspicuous, for example, comprises nitrogen, oxygen and sulphur.

Usually, contain no more than about three substituting groups or heteroatoms in the hydrocarbon skeleton group in per 10 carbon atoms, and preferably no more than 1.

The carboxylic acid that replaces normally contains alkylating agent alkylation unsaturated acid or derivatives thereof that satisfactory hydrocarbon skeleton rolls into a ball such as acid anhydrides and prepares with a kind of.Suitable unsaturated acid and derivative thereof comprise vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, furoate clothing, furoate clothing acid anhydride, citraconic acid, citraconic anhydride, methylfumaric acid, propene dicarboxylic acid, chloromaleic acid, equisetic acid, Ba Dousuan, methylcrotonic acid, Sorbic Acid, 3-is olefin(e) acid, 10-decylenic acid and 2-amylene-1,3, the 5-tricarboxylic acid.Special recommendation be undersaturated dicarboxylic acid and their derivative, particularly toxilic acid, fumaric acid and maleic anhydride.

Suitable alkylating agent comprises and contains 2-10 carbon atom and the normally monomeric homopolymer of polymerizable olefin and the multipolymer of 2-6 carbon atom, and contains the derivative of polar substituent.Such polymkeric substance on substantially be saturated (as, they contain no more than about 5% ethylene linkage) and be substantially aliphatic (as, they contain at least 80% and 95%(weight at least preferably) the unit that derives from aliphatic monoene).The monomeric example that is used to produce this polymkeric substance is ethene, propylene, 1-butylene, 2-butylene, iso-butylene, 1-octene and 1-decene.Some undersaturated unit can come from conjugated diolefine such as 1,3-butadiene and isoprene; Unconjugated diene is such as 1,4-hexadiene, 1,4-cyclohexadiene, 5-ethylidene-2-norbornene and 1,6-octadiene; With triolefin such as 1-isopropylidene-3a, 4,7,7a-tetrahydro-indenes, 1-isopropylidene dicyclopentadiene and 2-(2-methylene radical-4-methyl-3-pentenyl) (2.2.1)-dicyclo-5-heptene.

At first the polymer class of Tui Jianing comprises those terminal olefines such as propylene, 1-butylene, and iso-butylene and 1-be alkene synthetic polymkeric substance.Special recommendation is mainly by iso-butylene unit synthetic polybutene in this base polymer.Secondly the polymer class of recommending is by ethene, a kind of C _3-8A-monoene and a kind of polyenoid synthetic terpolymer that is selected from the compounds that non-conjugated diene (non-conjugated diene is special recommendation) and triolefin form are formed.The example of these terpolymers is E.I.duPont de Nemours ﹠amp; " Ortholeum 2052 " that Company produces, it is a kind of terpolymer, the vinyl group that contains 48 molar percentages, 1 of the propylene group of 48 molar percentages and 4 molar percentages, 4-hexadiene group, logarithmic viscosity number is under 1.35(30 ℃, and the 8.2g polymkeric substance is dissolved in the tetracol phenixin of 10ml).

The carboxylic acid that replaces and the preparation method of derivative thereof know in professional skill field, need not encyclopaedize.For example, referring to United States Patent (USP) NOS3,272,746,3,522,179 and 4,234,435.Polymkeric substance can equal the mol ratio of unsaturated acid or derivatives thereof, is greater than or less than 1, decides according to the product type that needs.

Ester is the carboxylic acid and ester that oxy-compound becomes of aforesaid those replacements, and oxy-compound can be aliphatic compound, such as monohydroxy with polyhydric alcohol, or aromatic compound such as phenol and naphthols.The example of aromatic oxy-compound comprises phenol, 2-Naphthol, naphthyl alcohol, cresylol, Resorcinol, pyrocatechol, P, P '-dihydroxybiphenyl, the 2-chlorophenol, 2,4-dibutyl phenol, the phenol that the propylene tetramer replaces, two dodecyl phenols, 4,4 '-the methylene radical bis-phenol, alpha-decyl-2-Naphthol, the phenol that polyisobutene (molecular weight 1000) replaces, the condensation product of heptylphenol and formaldehyde, the condensation product of octyl phenol and acetone, two (hydroxyphenyl) oxide compound, two (hydroxyphenyl) sulfide, two (hydroxyphenyl) disulphide, 4-cyclohexyl phenol.Phenol and the alkylated phenol that contains until 3 alkyl substituents are reasonable.Each alkyl substituent can contain 100 or more carbon atom.

But esterification becomes the aliphatic alcohol of ester preferably to contain 40 aliphatic carbon atoms at the most.They can be single hydroxyl alcohols, such as methyl alcohol, ethanol, isooctyl alcohol, dodecanol, ring is alcohol, cyclopentanol, V-1326, hexatriacontane alcohol, neo-pentyl alcohol, isobutyl alcohol, phenylcarbinol, beta-phenyl ethanol, 2-heptaline, β-chloro ethanol, the monomethyl ether of ethylene glycol, the single-butyl ether of ethylene glycol, single propyl ether of diethylidene glycol, the monododecyl ether of triethylene glycol, the monoleate of ethylene glycol, the monostearate of diethylidene glycol, 2-amylalcohol, the trimethyl carbinol, 5-bromo-dodecanol, the dioleate of nitro-stearyl alcohol and glycerol.Polyhydroxy-alcohol preferably contains 2-10 hydroxyl.They can from, for example, ethylene glycol, diethylidene glycol, triethylene glycol, four ethylidene glycols, dipropylidene diol, three propylidene glycol, two butylidene glycol, three butylidene glycol, and other the aklylene glycol that contains the 2-8 carbon atom is exemplified.Other useful polyhydroxy-alcohol comprises glycerol, the monoleate of glycerol, the monostearate of glycerol, the monomethyl ether of glycerol, tetramethylolmethane, 9,10-dihydroxystearic acid, 9, the methyl esters of 10-dihydroxystearic acid, 1,2-butyleneglycol, 2,3-hexylene glycol, 2,4-hexylene glycol, Penacol, 1,2,3,4-butantetraol, arabitol, sorbyl alcohol, mannitol, 1,2-cyclohexandiol and xylyl alcohol.Carbohydrate is such as sucrose, and shallow lake sugar and Mierocrystalline cellulose also can be used for into ester in the present invention.Carbohydrate can glucose, fructose, and sucrose, rhamnosyl, seminose, Glycerose and semi-lactosi are as an example.

The poly-hydroxy alcohols of special recommendation is that those contain at least three hydroxyls, some hydroxyls with the monocarboxylic acid that contains 8-30 carbon atom, such as sad, oleic acid, stearic acid, linolic acid, dodecylic acid, or the polyhydroxy-alcohol of loose oar oleic acid esterification.The example of the polyhydroxy-alcohol of such partial esterification is the monoleate of sorbyl alcohol, two stearates of sorbyl alcohol, the monoleate of glycerol, the monostearate of glycerol, two dodecylates of 1.

Ester also can derive from undersaturated alcohol, such as allyl alcohol, and styryl carbinol, propargyl ethanol, the pure and mild oleyl alcohol of 1-cyclohexene-3-.Also have another kind to be used for the present invention, the alcohols that can esterification becomes ester, form by ether alcohol and amino alcohol, comprise, for example, alkylidene oxide, the oxidation arylidene, amino-alkylidene group and amino-arylidene replace contains one or more oxyalkylene groups, oxidation arylidene, the alcohol of amino-alkylidene group or amino-arylidene.Their example has cellosolvo, carbitol, phenoxyethyl alcohol, heptan (base) phenyl-(inferior oxygen propyl group) ₆-H, octyl group-(oxyethylene) ₃₀-H, phenyl-(inferior oxygen octyl group) ₂-H, the glycerol that single (heptan (base) phenyl-Ya oxygen propyl group) replaces, poly-(styrene oxide), amino-ethanol, 3-amino-ethyl amylalcohol, two (hydroxyethyl) amine, P-amino-phenol, tripropanolamine, N-hydroxyethyl-ethylenediamine and N, N, N ', N '-tetrahydroxy-trimethylene diamines.For great majority, contain the ether alcohol of 150 oxyalkylenes at the most, wherein alkylidene group to contain 1-8 carbon atom be preferably.

Ester can be the diester or the acid ester of succsinic acid, that is, the polyhydric alcohol or the phenol of partial esterification promptly contain the ester of alcohol freely or phenolic hydroxyl group.The mixture of the ester of above-mentioned explanation equally also is included in the scope of the invention.

Succinate can prepare by SOME METHODS.Preferably can make things convenient for and can produce the method for the ester with advantageous property, be to comprise a kind of suitable alcohol or phenol and a kind of succinyl oxide reaction that is replaced by hydroxyl basically.Esterification is preferably carried out under 150 ℃-300 ℃ temperature normally more than 100 ℃.

The retortable removal of by product water that in esterification reaction process, generates.Esterification can be carried out in solvent to promote to mix and be easy to controlled temperature.It also can promote water to remove from reaction mixture.Useful solvent comprises dimethylbenzene, toluene, diphenyl ether, chlorinated benzene and mineral oil.

The improvement of top technology comprises the succinyl oxide that replaces replacement with corresponding succsinic acid.Yet in temperature more than 100 ℃, the acid anhydrides reaction easily takes place in succsinic acid, therefore changes into their acid anhydrides, and then by the esterification with pure reaction reaction.From this point, in this technology, the performance of succsinic acid and its acid anhydrides is suitable basically.

The succsinic acid reactant that uses and the relative proportion of hydroxy reaction are to a great extent according to hydroxy number in the type of desired product and the hydroxy reaction molecule.For example, generate the half ester of succsinic acid, that is, have only in two acid groups one esterified, the succsinic acid that comprises every mole of replacement reacts with one mole single hydroxyl alcohol, and the acid of necessary every mole of diester that generates succsinic acid is with two moles alcohol.On the other hand, six moles succsinic acid of one mole hexavalent alcohol and as much generates a kind of ester, and wherein each hydroxyl in Chun six alcoholic extract hydroxyl groups carries out esterification with a carboxyl of the succsinic acid of two carboxyls.Therefore, used succsinic acid is decided by hydroxy number in the hydroxy reaction molecule to the maximum ratio of polyhydroxy-alcohol.With regard to purpose of the present invention, found that the ester that succsinic acid reactant by waiting molal quantity and hydroxy reaction reaction obtain has good character.Therefore be preferred.

In some cases, at catalyzer such as sulfuric acid, pyridine hydrochloride, hydrochloric acid, Phenylsulfonic acid, m-toluene sulfonic acid, it is favourable carrying out esterification under phosphoric acid or other the known esterifying catalyst catalysis.The amount of the catalyzer in the reaction system can be low to moderate the weight of 0.01%(with respect to reaction mixture), 0.1%-5% normally.

Succinate can be by the succsinic acid that will replace or acid anhydrides and an epoxy compounds or epoxy compounds and water the alternative method of mixture reaction obtain.Such response class is similar to the reaction with acid or acid anhydrides and ethylene glycol.For example, can prepare this product by succsinic acid and the 1mol reacting ethylene oxide that will replace.Equally, product also can obtain by succsinic acid and the 2mol reacting ethylene oxide that will replace.The epoxide that is used for this reaction that other can get generally includes, for example, and propylene oxide, Styrene oxide 98min., ethyl oxyethane, dimethyl ethylene oxide, Epicholorohydrin.Oxide cyclohexane, 1, the hot alkylene oxide of 2-, epoxidised soybean oil, 9, the methyl esters of 10-epoxystearic acid and the monoepoxide of divinyl.For most of epoxide, epoxide is that alkylidene group is the alkylene oxide of 2-8 carbon atom; Or epoxidised fatty acid ester, wherein fatty acid-based have at the most 30 carbon atoms and ester group and derive from and have the lower alcohol of 8 carbon atoms at the most.

As substituting of succsinic acid or acid anhydrides, the etheride of the succsinic acid of lactonic acid or replacement can be used for above-mentioned technology.Such etheride can be two acylbromides, diacid chloride, single acyl chlorides and single acylbromide.The succinyl oxide and the acid that replace can be passed through, and for example, maleic anhydride and a high molecular weight olefin or the halon that obtains such as the aforesaid olefin polymer of chlorination are reacted and prepare.Reaction only comprises heats reactant under preferable 100-250 ℃ temperature.The product that obtains by such reaction is a kind of alkenyl succinic anhydrides.Alkenyl is hydrogenatable to be alkyl.Acid anhydrides used water or liquid stream are handled and are hydrolyzed into corresponding acid.The another kind of useful method for preparing succinyl oxide or acid anhydrides is with methylene-succinic acid or acid anhydrides and a kind of alkene or a kind of chlorating hydrocarbon, common at 100-250 ℃ the temperature range internal reaction and make.Succinyl-halogenide can by with acid or their acid anhydrides and a kind of acyl halogenating agent such as phosphorus tribromide, five phosphorus oxide, or thionyl chloride is reacted and prepared.These methods and other the method for preparing the amber compounds are known in production technique, do not need further to elaborate at this.

Also can further obtain preparing the method for the ester that is used for fuel composition of the present invention.For example, ester can be by generating the list or the dibasic acid esters of toxilic acid with toxilic acid or acid anhydrides and such as the reaction of setting forth previously, then with this ester and a kind ofly make such as the alkene of setting forth previously or halohydrocarbons reaction.They also can be by first esterification itaconic anhydride or acid, subsequently with intermediate product ester and a kind of alkene or a kind of halohydrocarbon, with previously described the same terms under reaction and preparing.

A large amount of dissimilar polymeric dispersants is recommended to be used for the lubricating oil preparation, and this polymeric dispersant is useful in fuel composition of the present invention.Usually, this additive is stated as in the lubricating oil preparation and is used as the viscosity index improver with dispersing characteristic.Polymeric dispersant normally has long carbochain and contains " polarity " group and give the polymkeric substance or the multipolymer of dispersing characteristic.The example of polar group comprises amino, amido, imino-, hydroxyl and ether group.For example, polymeric dispersant can be the methacrylic ester of attached polar functionalities or the multipolymer of acrylate, contains the ethylene/propene copolymer or the vinyl acetate/fumarate multipolymer of polar group.

Many such polymkeric substance formerly have in the technical literature and are described, for example at United States Patent (USP) NOS.4, in 402,844,3,356,763 and 3,891,721.

A large amount of polymeric dispersants can prepare on polyolefin backbone by the grafting polar monomer.For example, United States Patent (USP) NOS.3,687,849 and 3,687,905 have set forth with maleic anhydride and have been grafted on the polyolefin backbone as a grafted monomer.Toxilic acid or ester acid anhydride are satisfactory especially grafted monomer, because this monomer is relatively cheap, provide an economy, the carboxyl by further reaction toxilic acid or acid anhydrides and for example nitrogen compound or oxy-compound and the dispersion agent nitrogen compound is incorporated into operational path in the polymkeric substance.United States Patent (USP) NO.4,160, but set forth the graft copolymer that obtains by the monomeric monomer system graft reaction that will comprise toxilic acid or acid anhydrides and at least a other different addition copolymerization in 739; This grafted monomer system carries out afterreaction with polyamine then.Can be α with the monomer of toxilic acid or acid anhydrides copolymerization, β-monoene belongs to the undersaturated monomer that can fully be dissolved in the reaction medium and toxilic acid or acid anhydrides are had reactive behavior, so that relatively large toxilic acid or acid anhydrides enter into the grafted polymerisate.Correspondingly, suitable monomer comprises the ester of vinylformic acid and methacrylic, acid amides and nitrile, and do not contain the monomer that free acid radical is rolled into a ball.The monomeric graftomer that is incorporated into of heterocyclic can be set forth by a technology, this technology comprises the alkyl ester of the first step with acrylic or methacrylic acid, contain in vinylbenzene and one on the copolymer skeleton of hydrogenant segmented copolymer of conjugated diolefine of 4-6 carbon atom separately or with the vinylbenzene graft polymerization, to generate initial graftomer, in second step, polymerisable heterocyclic monomer, separately or with a hydrophobic vinyl ester copolymerization in initial graft copolymer to generate second kind of graft copolymer.

Other patent of describing the graftomer of the dispersion agent that is used as fuel composition of the present invention comprises United States Patent (USP) NOS.3,243,481,3,475,514,3,723,575,4,026,167,4,085,055,4,181,618 and 4,476,283.

Another kind of is so-called " star " type polymkeric substance and multipolymer as the polymeric dispersant in the present composition.Such polymkeric substance is at United States Patent (USP) such as US4, sets forth in 346,193,4,141,847,4,358,565,4,409,120 and 4,077,893.

Be used for the phenol dispersion agent that the alkyl of fuel composition of the present invention replaces and comprise the oxybenzene compound that hydrocarbon replaces, wherein the hydroxyl substituting group has one is enough to make oxybenzene compound to dissolve in molecular weight in the fuel.Usually, hydrocarbon substituent will be one saturated basically, and the hydrocarbon skeleton group of at least 30 carbon atoms is arranged.Oxybenzene compound will be represented by following chemical formula:

（R ¹⁵） _g-Ar ¹-（OH） _h（Ⅻ）

R wherein ¹⁵Be a saturated basically hydrocarbon skeleton substituting group that average 30 to 400 aliphatic carbon atoms are arranged, reaching g and h all is 1,2 or 3.Ar ¹Be aromatics part such as a benzene nucleus, the benzene nucleus that naphthalene nuclear or key connect.In case of necessity, the top phenates of chemical formula XII representative can contain other substituting group such as rudimentary alkyl, rudimentary alkoxyl group, nitro, amino and halogenic substituent group.This substituent preferred example is nitro and amine groups in case of necessity.

Saturated substantially hydrocarbon skeleton radicals R in the chemical formula XII ¹⁵Can contain up to 750 aliphatic carbon atoms, although it often has the maximum value of average 400 carbon atoms.In some cases, R ¹⁵The minimum value that one 50 carbon atoms are arranged.Should be noted that phenolic compound is at aromatic portion Ar ¹In each virtue endorse and contain more than a R ¹⁵Group.

Usually, hydrocarbon skeleton substituent group R ¹⁵Derive from the list of 2-10 carbon atom or diene all or multipolymer (as, copolymer, terpolymer), such as ethene, propylene, butene-1, iso-butylene, divinyl, different propylene, 1-be alkene and 1-octene.Typically, these alkene are 1-monoolefines.R ¹⁵Group also can derive from all this or multipolymer the halo analogue (as, chloro or bromo).In any case, R ¹⁵Group can otherwise make, analogue such as monomer family macromolecule amount alkene (as 1-40 carbenes) and its chlorination and hydrochlorinate, the petroleum fractions of aliphatic series, the analogue of paraffin and its cracking and chlorating analogue and its hydrochlorinate particularly, white oil, the alternate manner that synthetic alkene such as those alkenes by the Ziegler-Natta explained hereafter (as, polyethylene fat) and professional and technical personnel know.R ¹⁵In any unsaturation key can be according to known technology in the technology, hydrogenation before the denitrification step of after this describing and obtain reduction or cancellation.

Concrete saturated substantially hydrocarbon skeleton R ¹⁵The example of group is as follows: tetracontyl, the henpentacontane base, the mixture of poly-(ethylene/propene) group of 35-70 carbon atom, the mixture of poly-(ethylene/propene) group of the 35-70 of an oxidation or mechano-degradation carbon atom, the mixture of poly-(propylene/1-is alkene) group of 80-150 carbon atom, have the mixture of the polyisobutylene group of 20-32 carbon atom, and have the mixture of the polyisobutylene group of an average 50-75 carbon atom.

Radicals R ¹⁵Preferable source be polyisobutene, it is by under lewis acid catalyst such as aluminum chloride or boron trifluoride katalysis, polymerization contains the C of the iso-butylene of the butylene of 35-75 weight percentage and 30-60 weight percentage ₄Refining liquid flows and obtains.These polyisobutene mainly contain (the total repetition unit greater than 80%) structure ₃) ₂CH ₂-isobutylene repeat units.

The technology that can know by a series of professional and technical personnel is with the hydrocarbon skeleton radicals R ¹⁵Be connected in aromatic portion Ar ¹

In an embodiment preferred, the phenols dispersion agent that is used for fuel composition of the present invention is that wherein substituting group in case of necessity is one or more nitryl group as the nitrophenols of the hydrocarbon replacement of chemical formula XII representative.Nitrophenols can be produced easily by nitrated suitable phenol, typically, can have at least 30 by nitrated, preferably the alkylphenol of the alkyl of at least 50 carbon atoms and generate nitrophenols.The preparation that is used for the nitrophenols that a series of alkyl of fuel composition of the present invention replace is in U.S. Patent No. 4,347, is described in 148.

In another embodiment preferred, the hydrocarbon fortified phenol dispersion agent that is used for the present invention is that wherein substituting group in case of necessity is one or more amino such as the amino-phenol of the hydrocarbon replacement of chemical formula XII representative.These amino-phenols can be by nitrated above-described suitable hydroxyaromatic compounds and subsequently nitroreduction are become amino and produce easily.Typically, contain at least 30 and be preferably the alkyl of at least 50 carbon atoms or the alkylphenol of alkenyl generates useful amino-phenol by nitrated and reduction.In the present invention as the preparation of a large amount of hydrocarbon substituted-amino phenol of dispersion agent in U.S. Patent No. 4,320, be described in 021.

In fuel composition of the present invention, be used as the soluble alcohol of fuel in addition of dispersion agent, the alkoxy derivative of phenol and amine.This derivative of many types can be utilized, as long as derivative is that fuel is soluble.This derivative must be water-insoluble then better except fuel is solvable.Correspondingly, in preferred embodiments,, be characterized in that its HLB value is 1-13 as the soluble alkoxy derivative of fuel of dispersion agent.

The professional and technical personnel knows, and the fuel-soluble of alkoxy derivative and water insolubility can be by selecting alcohol, and phenol or amine are selected special alkoxide reactant, and select and alcohol, phenol, or the amount of the alkoxide reactant of amine reaction is controlled.Correspondingly, the alcohol that is used to produce oxyalkylated derivative is hydrocarbon skeleton base alcohol.And amine is the amine that above-described alkyl replaces.Phenol can be the phenol that phenol or hydrocarbon replace, and hydrocarbon substituent can contain few to 1 carbon atom.

Alkoxy derivative can by alcohol, the mixture reaction of phenol or amine and epoxide or epoxide and water and and produce.For example, derivative can be by alcohol, and the reaction of phenol or amine and equimolar amount or excessive oxyethane is produced.Other can with alcohol, phenol, or the epoxide of amine reaction comprise as, propylene oxide, Styrene oxide 98min., 1,2-butylene oxide ring, 2,3-butylene oxide ring, Epicholorohydrin, epoxy-cyclohexane, 1,2-octylene oxide.Preferably, epoxide is the alkene oxygen that alkylidene group contains the 2-8 carbon atom.As above mentioned, require and preferred and alcohol, the amount of the alkene oxygen of phenol or amine reaction is unlikely that derivative is had is water-soluble.

Be commercial available below, can be used as the example of the alkene oxygen derivative of fuel composition dispersion agent of the present invention: Ethomeen S/12, tertiary amine oxirane condensation product (HLB, 4.15 of Armeen; Armak Industries) and Plurafac A-24, the oxygen ethylization straight chain alcohol (HLB5.0) of BASF Wyandotte Industries.The soluble alcohol of other suitable fuel, the alkoxy derivative of phenol and amine are conspicuous for the professional.

In a particularly preferred embodiment, and then with regard to the compound of formula I, can add in the fuel composition of the present invention and contain succinimide derivatives that a spot of polyolefine replaces as ashless dispersant, wherein polyolefinic number-average molecular weight is in the scope of 800-5000, and is preferred 1000 to 5000, and preferable is at least 1750,1800 or 1850 and be at most 4000,3500,3000 or 2500, the amine that generates succinimide is preferably C _1-30Amine, particularly C _4-12The amine that contains 3-7 nitrogen-atoms, as diethylenetriamine, Triethylenetetramine (TETA), tetramethylene pentamine, penten, six ethylidene, seven amine, tri propylidene tetramine and 2 kinds top or the mixture of various kinds of amine.

The preferable range of the amount of the soluble ashless dispersant of hydrocarbon that adds is 30-500ppmw based on the total composition meter, preferably 100-300ppmw.

Fuel composition can additionally comprise (as the surrogate as succinimide derivatives) as the carbamate that the oily molten polyamine described among European patent EP-A-290088 or the N-that describes as European patent EP-A-414 963 replace, add in each case with patent in the same amount described.

Can further comprise as European patent EP-A-290 in the fuel composition, a kind of basic metal of 088 a kind of succinic acid derivative of describing or the salt of alkaline-earth metal is as the flame velocity improving agent, add with patent in the same amount described.

Except component described above, fuel composition also can comprise other additive.Therefore, it can comprise a kind of lead compound as a kind of antiknock dope, and correspondingly, according to the present invention, fuel composition comprises two kinds of leaded and white gasolinees.Fuel composition also can comprise antioxidant such as phenol, as 2,6-DI-tert-butylphenol compounds, or phenylenediamine are as N, N '-two sec-butyl p-phenylenediamine, or be different from the antiknock dope of lead compound, or the polyethers amino additive, as U.S. Patent No. 4,477,261 and European patent EP-A-151 621 in the polyethers amino additive described.

According to the present invention, in fuel composition, used fuel is gasoline preferably, i.e. main ebullient hydrocarbon-based fuel in 30-230 ℃ of gasoline boiling range.Such matrix fuel can comprise saturated, alkene and mixture aromatic hydrocarbon.It can derive from straight-run spirit, mixture, the hydrocarbon feed of thermo-cracking or catalytic pyrolysis, the petroleum fractions of hydrocracking or the hydrocarbon of catalytic modification of the synthetic aromatic hydrocarbon of producing.The octane value of matrix fuel is unessential and is generally more than 65.In gasoline, alcohol, ether, ketone or ester can replace the hydrocarbon of a great deal of.Naturally, matrix fuel is that requirement is substantially anhydrous, because water will hinder its smooth burning.

The present invention sets forth by following embodiment, and the number-average molecular weight of quoting among the embodiment (Mn) unless otherwise indicated, is that standard substance is measured by gel permeation chromatography (GPC) with polystyrene and polypropylene glycol.

The following term of using among the embodiment is explained as follows:

Polyoxyethylene glycol I-a kind of C ₁₂-C ₁₅The initial number-average molecular weight (Mn) of linear alcohol is 1500 homopolymer of propylene oxide;

Polyoxyethylene glycol II-a kind of C ₁₄-C ₁₅The initial number-average molecular weight of linear alcohol is 1500 homopolymer of propylene oxide;

The initial number-average molecular weight (Mn) of polyoxyethylene glycol III-a kind of butanols is the random copolymers of 85wt% propylene oxide/15wt% oxyethane of 2000.

The initial number-average molecular weight (Mn) of polyoxyethylene glycol IV-a kind of butanols is the random copolymers of 85wt% propylene oxide/15wt% oxyethane of 2000.

The initial number-average molecular weight of polyoxyethylene glycol V-a kind of polyoxyethylene glycol be 50wt% propylene oxide/50wt% ethylene oxide moiety of 2000 random/multipolymer of part block.

Polyoxyethylene glycol VI-a kind of C ₁₂-C ₁₅The homopolymer of propylene oxide of the number-average molecular weight (Mn) 500 that linear alcohol is initial.

" VERSATIC " 5(trade mark) Subsidiary Company of acid (2, the 2-neopentanoic acid)-the Royal Dutch/Shell Group sells.

" VERSATIC " 10(trade mark) acid-have a mixture of the branched carboxylic acids of general formula (III ')

R wherein ⁴Representing a general formula is C _αH _{2 α+1}-group; R ⁵Represent a general formula C _bH _2b+1-group; R ⁶Represent a general formula C _cH _2c+1-group; And a+b+c=8, it can be bought commodity and obtain from the Subsidiary Company of the Royal Dutch/Shell Group.

The segmented copolymer of the ethylene oxide/propylene oxide/ethylene oxide of a polyoxyethylene glycol PE6100-number-average molecular weight (Mn) 2000 (measuring method the unknown of Mn), this material obtains from Wyandottchemical Company corresponding to " PLURONIC " (trade mark) PL-61 polyol.

The segmented copolymer of the ethylene oxide/propylene oxide/ethylene oxide of a polyoxyethylene glycol PE8100-number-average molecular weight (Mn) 2600 (measuring method the unknown of Mn).This material obtains from Wyandott Chemical Company corresponding to " PLURONIC " (trade mark) PL-81 polyvalent alcohol.

Embodiment 1

Polyoxyethylene glycol I and " VERSATIC " 10(trade mark) sour ester (compound of formula I, wherein R ¹Be C ₁₂-C ₁₅Alkyl, A is-O-that X is a polyoxy propylidene chain and a R ²Be the group of general formula III, wherein a+b+c=8) preparation.

With Anhydrous potassium carbonate (34.5g, 0.25M) under stirring at room (20 ℃) add the polyoxyethylene glycol I (300g in the three-necked flask at the bottom of the garden, 0.21M) toluene (150ml) solution in, then add " VERSATIC " 10(trade mark) chloride derivative of acid (47.6g, 0.25M).Overhead is installed on the flask, a thermometer and a condenser, and immerse in the oil bath.Mixture refluxed 16 hours under 120-130 ℃ temperature.The primary reaction mixture is cooled to room temperature and filters by a sintered glass funnel.Excessive solvent is removed under vacuum then.Then with crude product and yellow soda ash (50g, 0.3M) and water (5ml) stirred together 8 hours.Mixture is used toluene (150ml) dilution then and is filtered.The solution that obtains is gone up dry in anhydrous sodium sulphate (50g), filter and concentrated solution and make required product (315g, 95% yield) under vacuum.

Embodiment 2-19

By with the similar method of embodiment 1 technology, listed polyoxyethylene glycol in the table and carboxylic acid derivative are reacted, and further produce compound according to formula I of the present invention.

Embodiment 20

Adipic acid ester (a kind of compound of formula I, the wherein R of preparation polyoxyethylene glycol I ¹Be C ₁₂-C ₁₅Alkyl, A is-O-that X is polyoxy propylidene chain and R ²Be-(CH ₂) ₄C(O)-Y-A '-R ⁷Group, wherein R ⁷, A and Y and corresponding R ¹, A and X have same definition)

Under the nitrogen atmosphere condition, polyoxyethylene glycol I (300g in three-necked bottle at the bottom of the garden that Dean one Rodney Stark water trap is installed, 0.2M) and adipic acid (15.5g, and stirring adding toluene (150ml) and right-toluenesulphonic acids in mixture 0.1M) (9.5g, 0.05M).The mixture of gained stirred 16 hours down nitrogen atmosphere, 130 ℃, and room temperature (20 ℃) is preceding being cooled to, with the 1M potassium hydroxide aqueous solution (3 * 200ml) washings, with the aqueous sodium persulfate solution washing of 10%w/v (5 * 200ml), at anhydrous sodium sulphate (Na ₂SO ₄) go up drying, filter and vapourisation under reduced pressure.Then crude product and yellow soda ash (50g, 0.3M) and water (5ml) stirred together 8 hours.Mixture dilutes with toluene (150ml) and filters then.Resulting solution is with anhydrous sodium sulphate (50g) drying, filters and concentrated solution and make required product (248g, 80% yield) under vacuum.

Embodiment 21

Preparation polyoxyethylene glycol II and " VERSATIC " 5(trade mark) sour ester (a kind of compound of formula I, wherein R ¹Be C ₁₄-C ₁₅Alkyl, A are-O-that X is a polyoxy propylidene chain and a R ²Be the tertiary butyl)

The anhydride ester derivs of the polyoxyethylene glycol II in a round-bottomed flask (150g adds " VERSATIC " 5(trade mark 0.1M) and in the mixture of pyridine (150ml)) acid (46.5g, 0.25M).The mixture of gained refluxed 14 hours, before being cooled to room temperature, injecting water (400ml) and added 60-80 petroleum spirit extraction (3 * 200ml).Organic phase washes (3 * 200ml) with water.At anhydrous sodium sulphate (Na ₂SO ₄) go up drying, filter and vapourisation under reduced pressure.Crude product then with yellow soda ash (50g, 0.3M) and water (5ml) stirred together 8 hours.Use toluene (150ml) to dilute this mixture and filtration again.The solution of gained is gone up dry in anhydrous sodium sulphate (50g), filter and concentrated solution and make required product (119g, 75% yield) under vacuum

Embodiment 22

The poly-ethanol VI of preparation and " VERSATIC " 10(trade mark) sour ester (a kind of compound of formula I, wherein R ¹Be C ₁₂-C ₁₅Alkyl, A are-O-that X is a polyoxy propylidene chain and a R ²Be a group of general formula III, wherein a+b+c=8)

At room temperature, polyoxyethylene glycol VI in a three-necked round bottom flask (150g, stir 0.25M) and in the solution of toluene (150ml) add triethylamine (35.4g, 0.35M), add " VERSATIC " 10(trade mark then) and the chloride derivative of acid (66.7g, 0.35M).One overhead is installed on the flask, a thermometer and a condenser, and flask immersed in the oil bath.Mixture refluxed 7 hours under about 120-130 ℃ temperature.The primary reaction mixture is cooled to room temperature then, wash with water (3 * 200ml), at anhydrous sodium sulphate (Na ₂SO ₄) go up drying, filter and the vapourisation under reduced pressure solvent.Crude product then with yellow soda ash (50g, 0.3M) and water (5ml) stirred together 8 hours.Mixture dilutes with toluene (150ml) and filters then.The solution of gained is gone up dry in anhydrous sodium sulphate (50g), filter and concentrated solution and make required product (150g, 80% yield) under vacuum.

Comparative example C ₁-C ₄

By with the similar method of embodiment 1 technology, list in the reaction of polyoxyethylene glycol in the table 2 and carboxylic acid derivative and the poly (oxyalkylene) based compound of producing generation is used for and compound of the present invention relatively.

Comparative example C5

Two-oleic acid ester of preparation polyoxyethylene glycol PE6100

Under nitrogen atmosphere, in three-necked flask at the bottom of the garden,, stir adding right-toluenesulphonic acids (0.6g) and oleic acid (120g, 3 equivalents) in the toluene of 0.15M (200ml) solution to polyoxyethylene glycol PE6100(300g.One overhead and a Dean one Rodney Stark water trap are installed on the flask.Mixture was 119 ℃ of reflux 8 hours.The component to 150 of heating in the flask ℃ and remove toluene, and to pass to flow velocity be 1, the nitrogen gas stream of 500cc/min.

Comparative example C6

Two-oleic acid ester of preparation polyoxyethylene glycol PE8100

Under nitrogen atmosphere, in three-necked flask at the bottom of the garden,, stir adding right-toluenesulphonic acids (0.3g) and oleic acid (87g, 3 equivalents) in toluene 0.108M) (400ml) solution to polyoxyethylene glycol PE8100(300g.One overhead and a Dean-Stark trap are installed on the flask.Mixture was 118 ℃ of reflux 7 hours.The component to 150 of heating in the flask ℃ and remove toluene, and to pass to flow velocity be 1, the nitrogen gas stream of 500cc/min.

Evaluation to the poly (oxyalkylene) based compound

Below the compound of embodiment 1-22 and comparative example C1-C6 is estimated, be the results are shown in table 3,4 and 5.

(i) total acid value (TAN)

The TAN value of material is the amount of alkali, with in and in the 1g material milligram number (mg KOH) of the required potassium hydroxide of all acid content represent.The TAN value is to obtain by standard method of test ASTM D664-81.

(ii) the kinematic viscosity of 40 ℃ and 100 ℃ is to determine according to standard method of test ASTM D445.

(iii) viscosity index is to calculate according to standard method of test ASTM D2270-86.

(iv) fill the stability test background

Standard lubricant filling additive contains one or more metallo-detergents especially, and filling additive is divided into two classes: monometallic (as having only calcium) prescription and composition metal (as Ca and Mg) prescription.Ideally, any potential rust-preventive agent should either way can work at monometallic and composition metal prescription.

Test procedure

Sample is by at embodiment 1-16, and every kind of compound of 18-22 and comparative example C1-C5 is added with concentration 3wt% in two kinds of commercial lubricant filling additives of containing metal washing composition one or both and prepares.A kind of filling additive is monometallic class (having only Ca), and another kind is composition metal type (Ca and Mg).Sample is placed maximum three months also relative stabilities of test sample down at 60 ℃.

Table 3 and table 4 have been listed the result of sample according to precipitation (D) or muddy (H).Used term " TD " and " VSH " expression " traces of precipitated " and " very slight muddiness " in the table.Also after each mensuration, write down " storage period " in the table

(v) neutralization ratio is than testing background

U.S. Patent No. 3,933 662(Chevron) has been described in a kind of the passing through and velocity test, think can and engine, the mode that the result of getting rusty as classification II B engine test is associated and determine the method for selected rust-preventive agent quality.This method comprises the oil phase tart water that neutralizes with alkalescence, and detects the neutral process with the PH meter.

Test procedure

Add in two kinds of above-described lubricant filling additive samples with concentration 3wt% in every kind of compound of embodiment 1-22 and comparative example C1-C6 and fill stability test.Resulting concentrated solution is then with 10%(weight) concentration and " HVI " 60(trade mark) (a kind of base oil of high viscosity index (HVI) of transparent cleaning, the kinematic viscosity in the time of 100 ℃ are 4.4-4.9mm to base oil ²/ s(ASTM D445) and minimum flash point be 204 ℃ (ASTM D92) and " HVI " 115(trade mark) (a kind of transparent cleaning high viscosity index (HVI) base oil, kinematic viscosity is 8.2-9.2mm in the time of 100 ℃ to matrix oil ²/ s(ASTM D445) and minimum flash point be 232 ℃ of (ASTM D92) blend, " HVI " 60(trade mark in the mixture) and " HVI " 115(trade mark) weight ratio of base oil is 5: 1.Resulting lubricating oil is tested as follows then.

An one combination PH electrode and an overhead is housed on the flask at the bottom of-the 250ml three neck gardens.Flask immerses one 50 ℃ fixedly in the constant temperature oil bath of liquid level.With hydrochloric acid (0.01M; 30ml) add in the flask and allow it reach steady temperature (30min).Detected oil (20ml) joins in the flask with a syringe then, measures pH value after 10 minutes.

Table 3 and table 4 have been listed resulting pH value.

It will be appreciated that from table 3 and table 4, in and the velocity test result show that the compound (according to the compound of formula I of the present invention) of embodiment 1-22 will have the iron rust fixed performance that is comparable to Embodiment C 1-C6 compound, filling the stability test result clearly illustrates that, the weighting agent of the present invention that contains the compound of formula I has good storage stability, and those to contain comparative example compound person be less stable.

(vi) classification IID engine test procedure

In being used as described above and compare test and prepare contain embodiment 1,4, a series of oil of 7 and 14 compound, test in the test of classification IID engine is with the fixing character of the iron rust of estimating these compounds.In this test, 8.5 or above digitized representation qualified.Resulting the results are shown in the following table 5.

Claims (11)

1, a kind of poly (oxyalkylene) based compound of formula I

Wherein

R ¹Represent the substituted in case of necessity alkyl of a hydrogen atom or, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, alkaryl or heteroatomic ring substituting group;

R ²Represent a substituted in case of necessity alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, alkaryl, heterocyclic radical, alkoxyl group, aryloxy, alkylamino, dialkyl amido or virtue are amino;

A represents a Sauerstoffatom (O-) or one-NH-group; And

X represents the random copolymers chain of a polyoxy propylidene chain or an ethylene oxide/propylene oxide, and a Sauerstoffatom of radicals X directly is bonded in R ²A CO part.

2, compound according to claim 1, wherein R ¹Representative-C ₄-C ₁₆Alkyl substituent.

3, compound according to claim 1 and 2, wherein R ²Represent substituted in case of necessity alkyl, phenyl or a tolyl substituting group.

4, according to the described compound of aforementioned each claim, wherein the scope of the number-average molecular weight of radicals X is 300-3500.

5, according to the described compound of aforementioned each claim, wherein the total acid value of the compound of said formula I (TAN) is lower than 5.

6, a kind of preparation method of the compound of formula I, this method comprises the compound R with the general formula V ¹-A-X-OH V

R wherein ¹, the definition in the claim of A and X such as any front, with the compound reaction of general formula VI,

R wherein ²As the definition in the claim of any front, and L ¹It is a leavings group.

7, a kind of lubricating oil composition comprises a large amount of lubricating oil and a spot of compound as the described formula I of each claim among the claim 1-5.

8, a kind of fuel composition comprises a large amount of fuel and a spot of compound as the described formula I of each claim among the claim 1-5.

9, among the claim 1-5 compound of the described formula I of each claim as the application of rust-preventive agent.

10, a kind of lubricating oil concentrated solution, it comprises a kind of thinner and based on whole concentrated solution meter, add-on is the compound as the described formula I of the arbitrary claim of 1-5 of 1-80wt%.

11, prevent a kind of working method that oil engine gets rusty, this method comprises to be used according to the lubricated said engine of a kind of lubricating oil composition of claim 7.