CN1081465A - The two-stroke cycle engine lubricant of forming by vegetables oil and complete additive - Google Patents

Abstract

The present invention relates to a kind of nitrogen-containing soluble organic composition.

Description

The two-stroke cycle engine lubricant of forming by vegetables oil and complete additive

The present invention relates to be dissolved in the complete additive of natural glycerin three esters to obtain nitrogen-containing soluble organic composition.Resulting composition can mix with fuel oil before use or in the use, is used for spark-ignition type two-stroke circulation engine.

In recent decades, the application that comprises the spark-ignition type two-stroke circulation engine of revolving cylinder engine (for example Wankel type) constantly increases.They have been used for power mower and other gardening equipments, power chain saw, pump, generator, outboard engine peculiar to vessel, snowmobile, motorcycle or the like at present.

Because the application of two-stroke cycle engine constantly increases, add that its working conditions is also more and more harsher, therefore the needs to lubricating oil also constantly increase, with this engine of sufficient lubrication.Have with the lubricated relevant problem of two-stroke cycle engine: ring sticking, get rusty, the lubrication failure of connecting rod and main bearing babbitting jig and on the internal surface of engine, generally generate carbon distribution and varnish deposit.Generate the paint film problem people is had a headache, can finally cause ring sticking, thereby the sealing function of piston ring was lost efficacy because on piston and cylinder wall, gather varnish deposit.And the inefficacy of sealing can cause cylinder compresses loss, and this is particularly harmful concerning the two-stroke cycle engine, because they are by suction new volume read-out to be introduced deflated cylinder.Therefore, the ring sticking meeting degenerates motor performance, and make fuel oil and (or) consumption of lubricant unnecessarily increases.Spark-plug fouling and engine passage blockage problem also are recurrent in the two-stroke cycle engine.

Made the professional who is familiar with present technique recognize that two-stroke cycle engine lubricant is a kind of dissimilar lubricant with the lubricated relevant specific question and the technology of two-stroke cycle engine.Can consult for example United States Patent (USP) 3,085,975; 3,004,837 and 3,753,905.

United States Patent (USP) 4,100,082(1978 July 11 were authorized people such as Clason) relate to the compositions of additives in the fuel that can be used for having the oil of lubricant viscosity and being generally liquid.More particularly, this patent relates to the compositions of additives of amino-phenol and some washing agent/dispersion agent composition, and relates to oil and the fuel that contains these compositions, and they are particularly useful concerning the two-stroke cycle engine.

United States Patent (USP) 4,663,063(1987 May 5 were authorized Davis) relate to the compositions of additives that can be used for lubricating composition, accounting for most in this lubricating composition is the oil with lubricant viscosity, small portion is above-mentioned compositions of additives.This lubricant can be used for the two-stroke circulation engine.More particularly, above-mentioned patent relates to such compositions of additives, and said composition contains by at least a and has one at least and contain the mixture of forming at least about the aminocompound of the alkylphenol of the alkyl of 10 aliphatic carbon atoms and at least a non-amino-phenol.Because the two-stroke cycle engine lubricant often mixes with fuel oil before use or in the use, so this patent also relates to two-stroke circulation fuel oil lubricant mixture.

United States Patent (USP) 4,708,809(1987 November 24 were authorized Davis) relate to by accounting for and mostly have the oil of lubricant viscosity and account for the lubricating composition that at least a alkylphenol of small portion is formed.This lubricant can be used for the two-stroke circulation engine.More particularly, this patent relates to containing and has at least one and contain alkylphenol at least about the alkyl of 10 aliphatic carbon atoms.Because the two-stroke cycle engine lubricant often mixes with fuel oil before use or in the use, so this patent also relates to two-stroke circulation fuel oil lubricant mixture.

The present invention relates to a kind of nitrogen-containing soluble organic composition, said composition is composed of the following components:

(A) at least a natural oil that contains animal oil or vegetables oil, this animal oil or vegetables oil contain the triglyceride level that following formula I is represented

R in the formula ¹, R ²And R ³Respectively be to contain the saturated of 8～24 carbon atoms or unsaturated aliphatic alkyl approximately, and

(B) (I) is a kind of comprises at least a washing agent/dispersion agent that an aliphatic carbon atom number is at least 10 substituent acidylate nitrogenous compound that has; this nitrogenous compound be by the carboxylic acid acylating agent and at least a contain at least one-aminocompound of NH base reacts and makes, described acylating agent is by tetrahydroglyoxaline key, imido base key, amido key, amidine key or an acyl-oxygen ammonium key and described aminocompound bonding mutually.

In another concrete scheme, the present invention comprises a kind of nitrogen-containing soluble organic composition composed of the following components:

(A) aforesaid natural oil

(B) at least a washing agent/dispersion agent that is selected from following compound:

(I) acylated above-mentioned nitrogenous compound,

The neutrality or the alkaline metal salt of (II) at least a organic sulfuric acid, phenol or carboxylic acid,

The amine that (III) at least a alkyl replaces, wherein hydrocarbyl substituent is essentially aliphatic hydrocarbyl and contains at least 12 carbon atoms, but is condition with the non-amino collection phenol of this amine,

(IV) at least a by phenol, aldehyde and contain at least one-nitrogenous condenses that the aminocompound of NH base generates: and

(C) the amino collection phenol represented of the formula II below at least a usefulness

R in the formula ⁴Base is for containing the saturated basically hydrocarbyl substituent of 10 aliphatic carbon atoms at least; A, b and c respectively are 1～3 times integer of contained fragrant check figure among the Ar, but are condition with the unsaturated valency that a, b, c sum are no more than Ar; The aromatics part of Ar for selecting for use 0-3 to be selected from the substituting group of low alkyl group, lower alkoxy, nitro, halogen atom or to adopt above-mentioned two or more substituent combination.

(A) natural oil

Implementing to use a kind of natural oil, this natural oil when of the present invention is triglyceride level animal oil or the vegetables oil that the formula I below a kind of usefulness is represented

In the formula, R ¹, R ²And R ³Respectively for containing the alkyl of 8～24 carbon atoms approximately." alkyl " this term is meant the base that contains the carbon atom that directly links to each other with the remainder of molecule here.In the context of the present invention, alkyl is mainly aliphatic hydrocarbyl, comprising:

(1) aliphatic hydrocarbyl, i.e. alkyl, for example heptyl, nonyl, undecyl, tridecyl, heptadecyl; The alkenyl that contains two keys, for example heptenyl, nonene base, undecenyl, tridecylene base, heptadecene base, heneicosene base; The alkenyl that contains two or three two keys, for example 8,11-17 carbon dialkylenes and 8,11,14-17 carbon trialkenyl.All isomer that also comprise these bases, but straight chain base preferably.

(2) aliphatic hydrocarbyl of Qu Daiing promptly contains the substituent base of nonhydrocarbon of the main hydrocarbon characteristic that can not change aliphatic hydrocarbyl in the present invention.Which substituting group the professional who is familiar with present technique understands suits, for example hydroxyl, carbalkoxy (particularly lower alkyl ester group) and alkoxyl group (particularly lower alkoxy), " rudimentary " this speech is meant the base of institute's carbon atom quantity no more than 7 here.

(3) assorted base, promptly those bases when mainly having aliphatic hydrocrbon characteristic of the present invention and the chain of forming by aliphatic carbon atom or encircle in contain the base of non-carbon atom.Which heteroatoms the professional who is familiar with present technique obviously understands is suitable for, and they comprise for example oxygen and sulphur.

Described alkyl can be saturated or unsaturated, or the mixture of the two.The triglyceride level that is more suitable for is R in the formula ¹, R ²And R ³The aliphatic group of representative contains the compound of 8～24 carbon atoms of having an appointment.Being used for typical triglyceride level of the present invention has Oleum Cocois, Thistle oil, high oleic safflower oil, sunflower oil, rape seed oil (both to comprise high erucic acid, also comprise low erucic acid), high oleic acid rape seed oil, high oleic sunflower oil, oleum gossypii seminis, peanut oil, Semen Maydis oil, high acid corn oil, Viscotrol C, Dow pond caul-fat (meadowfoam oil), Leix gram reins in and belongs to caul-fat, soya-bean oil, palm olein, palm-kernel oil, sesame oil, ringdove elecampane oil, and the animal oil and the fat that meet the structure formula I, for example lard and butter.Preferably use the vegetables oil triglyceride level.

Natural glycerin three esters chemically be not purified.That is to say, though soya-bean oil meets the R in the formula I ¹, R ²And R ³This parameter request that contains 8～24 carbon atoms approximately, but the mixture of the different lipid acid of carbonatoms in the triglyceride structure contained.Table 1 has been listed several natural oil compositions that belong to triglyceride level.

Be applicable to that more vegetables oil more of the present invention are: (the high oleic oleic acid content that is defined as is at least 70% for high oleic sunflower oil, high oleic acid rape seed oil, preferably be at least 80%), by Sunflower Receptacle (America Helianthus) obtain can be from SVO Enterprises, the Sunyl that EasHake, Ohio buy ^R70 or Sunyl ^R80 high oleic sunflower oils, high acid corn oil, soya-bean oil, Viscotrol C and ringdove elecampane oil.The ringdove elecampane oil is more suitable, because it is a kind of natural epoxidized oil.

Yet, natural non-epoxidized oil is carried out artificial epoxidation also belongs to scope of the present invention.That is to say, the natural oil and the peroxyacetic acid aqueous solution or hydrogen peroxide and acetic acid are reacted according to the known method of the professional who is familiar with present technique.The epoxide content of artificial epoxidised natural oil is with the degree of unsaturation of the triglyceride level of the completeness of epoxidation reaction and natural oil and different.This class epoxidized oil has such characteristic, and promptly its oxyethane oxygen level is at least 3%, is preferably 5～15%.Epoxidation natural oil-example is an epoxidized soybean oil, and is existing a kind of shown in following structural formula:

(B) washing agent/dispersion agent

In a concrete scheme, washing agent/dispersion agent is and (A) blended (B) (I).In another concrete scheme, washing agent/dispersion agent will be selected from (B) (I)～(B) (IV), and is and (A) and (C) blended.

In general, being used for washing agent/dispersion agent of the present invention is some materials of having done introduction for the professional Suo Shu Zhi And that is familiar with present technique in many books, article and patent.When speaking of the washing agent of some concrete kinds/dispersion agent, all to mention them below, mention their parts, they with this place the relevant disclosure of theme is discussed and is all incorporated into the reference of this specification sheets if just should understand when mentioning at this specification sheets.

(B) nitrogenous compound of (I) acidylate

Many aliphatic carbon atom numbers that contain are 10 R ⁹Substituting group and be that to react the acidylate nitrogenous compound that makes by carboxylic acid acylating agent and a kind of aminocompound be known for the professional who is familiar with present technique.In these were formed, acylating agent was by tetrahydroglyoxaline imido base key, amido key, amidine key or an acyl-oxygen ammonium key and described aminocompound bonding.Contain 10 (preferably 30) aliphatic carbon atoms substituting group can or molecule by in the carboxylic acid acylating agent's deutero-part, perhaps molecule by aminocompound deutero-part in.But preferably in the acylating agent part.Acylating agent can not wait to the substituent acylating agent of high molecular aliphatic series that contains carbonatoms 5000,10,000 or 20,000 from formic acid and acylated derivatives thereof.Aminocompound can be about 30 aliphatic substituent amine to containing carbonatoms from ammonia itself.Relevant R ⁹More detailed condition be discussed below.

A quasi-representative acidylate aminocompound that can be used for making composition of the present invention is those by containing that carbonatoms is at least that 10 aliphatic substituent acylating agent reacts with the nitrogen compound that contains one-NH base at least and the compound that makes.Generally, acylating agent is monocarboxylic acid or polycarboxylic acid (or reactive suitable with it), for example succsinic acid of Qu Daiing or propionic acid; Aminocompound is the mixture of polyamines or several polyamine species, and most typical is ethylene polyamine.Aliphatic substituent R in this class acylating agent ⁹Often contain at least about 50～400 carbon atoms.The aliphatic series substituent R ⁹Be C by homopolymerization or copolymerization _2-101-alkene is derived, or the mixture of the two.General R ⁹Derive by ethene, propylene, butylene and composition thereof.Usually derive by the polymeric iso-butylene.The example of aminocompound that can be used for making acylated compounds of the present invention is as follows:

(1) polyalkylene polyamine of representing with following general formula III

R in the formula ⁸Respectively be hydrogen atom, low alkyl group, rudimentary hydroxyalkyl or C _1-12Alkyl, but with at least one R ⁸Must be that hydrogen atom is a condition; N is 1～10 integer; U is C _2-10Alkylidene group

(2) polyamine of representing with following general formula IV that contains heterocyclic substituent

R in the formula ⁸The same with the definition of U, m is 1～10 integer, m ¹Be 1～10 integer, Y is Sauerstoffatom or bivalent sulfur atom or N-R ⁸Base;

(3) aromatic polyamine of representing with following general formula V

Ar is for containing the virtue nuclear of 6～20 carbon atoms, each R approximately in the formula ⁸Definition the same, Y is about 2～8.

The object lesson of polyalkylene polyamine (1) has quadrol, four (ethene) five amine, three (trimethylene) tetramine, 1,2-two amido propylene etc.The object lesson that contains the polyamine (2) of heterocyclic substituent has N-2-aminoethyl piperazine, N-2 and N-3 aminopropyl morpholine, N-3-(dimethylamino) the propyl group piperazine etc.The object lesson of aromatic polyamine (3) has the phenylenediamine of various isomeries, the naphthylene diamine of various isomeries etc.

Existing many patents have been introduced useful acylated nitrogen compound, and these patents comprise United States Patent (USP) 3,172,892; 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; And 3,804,763.The typical case of this class acidylate nitrogenous compound is represented as by containing mixture that carbonatoms is about poly-(iso-butylene) substituent succinyl oxide acylating agent (for example acid anhydride, acid, ester etc.) of 50～400 and several ethylene polyamines (contain about 3～7 amino nitrogen atom and about 1～6 ethylidene unit in the ethylene polyamine, got by ammonia and ethylene chloride condensation) and reacts and make.Extensively open in view of this class acidylate aminocompound, do not need here its characteristic and preparation method are done further discussion.And but acidylate aminocompound of the U.S. Patent Publication pointed out above and preparation method thereof quoted and incorporate this specification sheets into.

The acylated nitrogen compound that another kind belongs to this class is that aliphatic monocarboxylic acid that the amber acid or anhydride peace treaty by above-mentioned alkylene amines and above-mentioned replacement contains 2～22 carbon atoms reacts and the compound that makes.In these acylated nitrogen compounds, succsinic acid and monocarboxylic mol ratio be about 1: 0.1～and 1: 1.Typical monocarboxylic acid is formic acid, acetic acid, 12 (alkane) acid, butyric acid, oleic acid, stearic acid, the stearic acid isomer cuts that is called Unimac 5680, toluic acid etc.United States Patent (USP) 3,216,936 and 3,250,715 have done more detailed introduction to these compounds, here the disclosure of the relevant this respect of these patents are quoted and are incorporated into.

Also having a kind of acylated nitrogen compound that can be used for making composition of the present invention is to be reacted and the compound that makes by aliphatic monocarboxylic acid who contains 12-30 carbon atom approximately and above-mentioned alkylene amines (being generally ethylene polyamine, propylene polyamines or trimethylene polyamines of containing 2～8 amino and composition thereof).The aliphatic monocarboxylic acid is generally the linear aliphatic carboxylic acid that contains 12～30 carbon atoms and the mixture of side chain aliphatic carboxylic acid.A kind of widely used acylated nitrogen compound is reacted by above-mentioned alkylene polyamine and aliphatic acid mixture (being made up of the straight-chain acid of about 5～30 molecular fractions and the branched acids of about 70～95 molecular fractions) and the compound that makes.The mixture that extensively is called Unimac 5680 in trade is arranged in the mixture that can buy on market.These mixtures are United States Patent (USP) 2,812,342 and 3,260, and the by product of the dimerisation of 671 unsaturated fatty acidss of being introduced.

Branched chain fatty acid can comprise that also those its side chains do not belong to the lipid acid of alkyl, for example phenyl stearic acid, cyclohexyl stearic acid and chloro stearic acid.About the existing a large amount of introduction of side chain aliphatic carboxylic acid/alkylene polyamine product in the present technique field.For example United States Patent (USP) 3,110, and 673; 3,251,853; 3,326,801; 3,337,459; 3,405,064; 3,429,674; 3,468,639; 3,857,791.Here with the content quotation about lipid acid/polyamines condenses and the application in lubricating oil composition thereof of these patent disclosures, incorporate into.

(B) neutrality or the alkaline metal salt of (II) organic sulfuric acid, carboxylic acid or phenol

Not strict to the requirement of making the selected metal of these salt, in fact any metal all can use.But consider availability, cost and maximum efficiency, some metal is more commonly used.These metals comprise basic metal and alkaline-earth metal (be I A family and II A family metal, but do not comprise francium and radium).II B family metal and polyvalent metal (for example aluminium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel and copper) also can use.Often use the salt of the ionic mixture that contains two or more above-mentioned metal.

These salt can be neutral or alkaline.In neutral salt, the content of metallic cation only is enough to make the acidic-group neutralization in the salt anionic; In basic salt, then contain excessive metallic cation, often be referred to as high alkalinity salt or hyperalkaline salt.

These alkalescence and neutral salt can be the organic vitriolic salt of oil soluble.The organic vitriolic example of oil soluble has sulfonic acid, thionamic acid, thiosulfonic acid,-sulfinic acid, sulfenic acid, partial ester sulfuric acid, sulfurous acid and thiosulfuric acid.Be generally carbocyclic ring or aliphatic sulfonate.

Carbocyclic ring sulfonic acid comprises monocycle or polycyclic aromatic or cycloaliphatic compounds.Most of oil-soluble sulfonic acid salt can be represented with following formula VI and formula VII:

In the formula, M is above-mentioned metallic cation or hydrogen; T is-nucleolus, for example benzene, naphthalene, anthracene, phenanthrene, diphenylene-oxide, thianthrene, phenothioxin, dibenzothiophene, thiodiphenylamine, phenyl ether, diphenyl sulfide, pentanoic, hexanaphthene, petronaphthalene, naphthane, pentamethylene etc.; R in the formula VI is an aliphatic group, for example alkyl, alkenyl, alkoxyl group, alkoxyalkyl, carbalkoxy alkyl etc.; X is at least 1, and R _X+ T contains 15 carbon atoms at least altogether approximately.R in the formula VII ¹⁰Be at least about the aliphatic group that contains 15 carbon atoms, M is metallic cation or hydrogen.R ¹⁰The example of base has alkyl, alkenyl, alkoxyalkyl, carbalkoxy alkyl etc.R ¹⁰Object lesson be by ceresine, saturated paraffin and unsaturated paraffin and polyolefine (polymkeric substance of alkene such as C2, C3, C4, C5, C6) the deutero-base that contains 15～7000 or more carbon atoms approximately.T, R and R in formula VI and the formula VII ¹⁰Also can contain other the inorganic or organic substituents except that above-named, for example hydroxyl, thin base, halogen atom, nitro, amino, nitroso-group, sulfide, disulphide etc.In the formula VI, x, y, z and b all are at least 1, and a, b and d also are at least 1 in the formula VII equally.

Below be the object lesson that belongs to the oil-soluble sulfonic acid in top formula VI and the VII scope, and should to understand these examples be the salt that can be used for those sulfonic acid of the present invention in order to illustrate.In other words, also to be interpreted as be explanation to its corresponding neutral salt and basic salt to the purpose of enumerating every kind of sulfonic acid.This class sulfonic acid is mahogany acid; Bright stock sulfonic acid; By Saybolt viscosity is about 200 seconds lubricating oil distillate deutero-sulfonic acid under about 100 seconds to 210 under 100; Ceresine sulfonic acid; For example a wax of benzene, naphthalene, phenol, phenyl ether, curing naphthalene, pentanoic, thiophene, α-Lv Dainai or many wax substituted sulfonic acid and many sulfonic acid; Other substituted sulfonic acids such as alkyl benzene sulphonate (ABS) (wherein alkyl contains 8 carbon atoms at least), hexadecyl phenol monosulphide sulfonic acid, two-hexadecyl thianthrene disulfonic acid, dilauryl betanaphthyl sulfonic acid, dioctyl nitro-naphthalene-monosulfonic acid, and an alkarylsulphonic acid (dodecylbenzene " residue material (being bottom product) " sulfonic acid for example.

An alkarylsulphonic acid is by with propylene tetramer or isobutylene trimer alkylation and introduce 1,2,3 or the substituent benzenesulfonamide derivative of higly branched chain C12 more on phenyl ring.The dodecylbenzene residue mixture of (mainly be-(dodecyl) benzene and two-(dodecyl) benzene) can be used as the byproduct in the household detergent manufacturing processed and obtains.By the residue material that generates in linear alkylbenzene sulfonate (LAS) manufacturing processed carry out alkylation and similar product also can be used for making the used sulfonate of the present invention.

With by product in the washing composition manufacturing processed and for example SO ₃React with the method for making sulfonate and for the professional who is familiar with present technique, all know.For example can consult Kirk-Othmer " Encyclopedia of Chemical Technology " book second edition, " sulfonate " literary composition of the 291st page of grade of the 19th volume (by John Wiley ﹠ Sons, N.Y. published in 1969).About other introductions of neutral and alkaline sulfonate and manufacture method thereof can be consulted following United States Patent (USP): 2,174,110; 2,174,506; 2,174,508; 2,193,824; 2,197,800; 2,202,781; 2,212,786; 2,213,360; 2,228,598; 2,233,676; 2,239,974; 2,263,312; 2,276,090; 2,276,097; 2,315,514; 2,319,121; 2,321,022; 2,333,568; 2,333,788; 2,335,259; 2,337,552; 2,346,568; 2,366,027; 2,374,193; 2,383,319; 3,312,618; 3,471,403; 3,488,284; 3,595,790; With 3,798,012.Here with its disclosed in this respect content quotation and incorporating into.

Also comprise aliphatic sulfonic acid, for example the paraffin sulfonic acid that replaces of paraffin sulfonic acid, unsaturated paraffin sulfonic acid, hydroxyl, six propene sulfonic acids, four amylene sulfonic acid, polyisobutylene sulphonic acid (polyisobutene wherein contain 20～7000 or more carbon atom), chloro paraffin sulfonic acid, nitro paraffin sulfonic acid etc.; Cyclic aliphatic sulfonic acid, for example the cyclohexyl sulfonic acid that replaces of oil cycloalkanes sulfonic acid, dodecyl cyclopentyl sulfonic acid, lauryl cyclohexyl sulfonic acid, two-(diisobutyl) cyclohexyl sulfonic acid a, wax or many wax etc.

Here with appending claims in when referring to sulfonic acid or its salt, all use " mahogany acid " or " sulfonated petro-leum " such term to comprise that all are by petroleum products deutero-sulfonic acid or its salt.Particularly a valuable class mahogany acid is the russet sulfonic acid (being to gain the name because of its russet) that obtains as making the byproduct in the oil white oil process with sulfuric acid process.

In general, the I A of above-mentioned synthetic sulfonic acid and mahogany acid belongs to, II A belongs to and II B belongs to the metal neutral salt and basic salt all can be used for enforcement of the present invention.

Can make the carboxylic acid that is applicable to neutral salt of the present invention and basic salt by it and comprise aliphatic series, cyclic aliphatic and one dollar aromatic carboxylic acid and polycarboxylic acid, for example the aromatic carboxylic acid of the cyclohexylenedinitrilotetraacetic acid of the chaulmoogric acid of naphthenic acid, alkyl or alkenyl replacement, alkyl or alkenyl replacement, alkyl or alkenyl replacement.Described aliphatic acid generally contains 8 carbon atoms at least, preferably contains 12 carbon atoms at least.Usually its carbonatoms approximately is no more than 400.In general, if aliphatic carbochain is branched, the oil soluble of acid is better under certain carbon content.This cyclic aliphatic and aliphatic carboxylic acid can be saturated or unsaturated.Object lesson has the mixture of two or more carboxylic acid that can buy on toxilic acid, docosoic that 2 ethyl hexanoic acid, alpha-linolenic acid, propylene tetramer replace, Unimac 5680, n-nonanoic acid, capric acid, Zoomeric acid, linolic acid, lauric acid, oleic acid, ricinolic acid, 11 (alkane) acid, dioctyl Cyclopentane carboxylic acid, tetradecanoic acid, dilauryl+hydrogen naphthalene monocarboxylic acid, stearyl octahydro indene carboxylic acid, palmitinic acid, the market, for example tall oil acid, magenta acid (rosein acid) etc.

Being more suitable in the oil soluble carboxylic acid of making used salt of the present invention is the oil-soluble aromatic carboxylic acid.This class acid can be represented with following general formula VIII:

R in the formula ¹¹For carbonatoms is at least 4, but no more than 400 aliphatic hydrocarbyl, a is 1～4 integer, and Ar is a multivalence aromatic hydrocarbon ring, respectively contains about 14 carbon atoms, and X respectively is sulphur or Sauerstoffatom, and m is 1～4 integer, its condition is R ¹¹Must make R with α ¹¹Base on average provides at least 8 aliphatic carbon atoms for each acid molecule of formula VIII representative.Example with the aromatic ring of variable Ar representative has by deutero-multivalence aromatic bases such as benzene, naphthalene, anthracene, phenanthrene, indenes, fluorenes, biphenyl.Generally use Ar ^*The base of representative is the multivalence ring by benzene or naphthalene deutero-such as phenylene and naphthylidene, for example methylphenylene, oxyethyl group phenylene, nitro phenylene, sec.-propyl phenylene, hydroxyl phenylene, dredge basic phenylene, N, N-diethylamino phenylene, chloro phenylene, dipropoxy naphthylidene, triethyl naphthylidene with and similarly trivalent, tetravalence, pentavalent ring.

R ¹¹Base is generally pure alkyl, is preferably alkyl or alkenyl.But R ¹¹Base can contain a small amount of substituting group, for example phenyl, cycloalkyl (for example cyclohexyl, cyclopentyl etc.), and keeping R basically ¹¹Also can contain non-alkyl under the prerequisite of the hydrocarbon characteristic of base, for example nitro, amino, halogen atom (for example chlorine, bromine etc.), lower alkoxy, low alkyl group sulfydryl, the (thio group (fracture basic (interrupting groups) promptly=S), promptly=O), of oxygen substituting group, for example-NH-,-O-,-S-etc.As long as R ¹¹Any non-carbon atom contained in the base is no more than R ¹¹About 10% of base gross weight, R ¹¹Base just can keep hydrocarbon characteristic required for the present invention.R ¹¹The example of base have butyl, isobutyl-, amyl group, octyl group, nonyl, dodecyl, docosyl, tetracontyl, 5-chloro hexyl, 4-oxyethyl group amyl group, 4-hexenyl, 3-cyclohexyl octyl group, 4-(right-chlorine is than phenyl) octyl group, 2,3,5-trimethylammonium heptyl, 4-ethyl-5-Methyl Octyl, and by polymeric alkene deutero-substituting group, these polyolefinic examples have the ethylene-propylene copolymer of chloroprene rubber, polyethylene, polypropylene, polyisobutene, ethylene-propylene copolymer, chlorinated olefin polymer, oxidation.Equally, Ar ^*Base also can contain all non-hydrocarbon substituents, and for example lower alkoxy, low alkyl group are dredged base, nitro, halogen atom, carbonatoms and be less than 4 alkyl or alkenyl, hydroxyl, thin base etc.

Particularly effective with this class carboxylic acid that following formula IX is represented:

R in the formula ¹¹, X, Ar ^*, m and a definition cotype VIII, P is 1～4 integer, is generally 1 or 2.In this class carboxylic acid, this class oil soluble carboxylic acid of representing with following formula X particularly effectively:

In the formula, R ¹²For containing 4 but be no more than the aliphatic hydrocarbyl of about 400 carbon atoms at least, a is 1～3 integer, and b is 1 or 2, c be 0,1 or 2(be preferably 1), its condition is R ¹²Must make acid molecule in the aliphatic hydrocrbon substituting group of each acid molecule contain aliphatic carbon atom mean number with a is at least about 12.The Whitfield's ointment of aliphatic hydrocrbon replacement particularly effectively in this class oil soluble carboxylic acid, each the aliphatic hydrocrbon substituting group on this Whitfield's ointment on average contains about 16 carbon atoms at least, and each molecule contains 1～3 substituting group.Salt is with following such Whitfield's ointment preparation, and promptly the aliphatic hydrocrbon substituting group on this Whitfield's ointment is to be derived and its average carbon atom number is about 30～400 by polymeric alkene (particularly rudimentary 1-monoolefine of polymeric such as polyethylene, polypropylene, polyisobutene, ethylene/propene copolymer etc.).

The carboxylic acid that meets above-mentioned formula VIII～IX has been well-known in the present technique field or can have prepared with technical known method.The preparation method of these carboxylic acids of representing with above general formula and neutral and basic metal is well-known, at for example United States Patent (USP) 2,197,832; 2,197,835; 2,252,662; 2,252,664; 2,714,092; Open in 3,410,798 and 3,595,791.

Being used for another kind of neutrality of the present invention and alkaline carboxylate salt is the alkenyl succinate deutero-of being represented by following general formula XI:

R in the formula ¹¹Definition cotype VIII.This class salt and preparation method thereof is in United States Patent (USP) 3,271,130; In 3,567,637 and 3,632,510 introduction is arranged, quoted here and incorporate into.

Other United States Patent (USP)s of preparation method of introducing the basic salt of above-mentioned sulfonic acid, carboxylic acid and any two or more these sour mixture specially have: 2,501,731; 2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,777,874; 3,027,325; 3,256,186; 3,282,835; 3,384,585; 3,373,108; 3,365,396; 3,342,733; 3,320,162; 3,312,618; 3,318,809; 3,471,403; 3,488,284; 3,595,790 and 3,629,109.Here incorporate disclosed in this respect content of these patents and the disclosed concrete alkaline metal salt that is suitable for into this specification sheets.

The neutral salt of phenol and basic salt (being commonly referred to phenates) also can be used for composition of the present invention, they also be for the professional who is familiar with present technique known.Can represent with following general formula XII in order to the phenol that generates these phenates

R in the formula ¹¹, n, Ar ^*, X and m meaning and preferentially select that all the formula VIII with top is identical.The same example of formula VIII also is suitable for.

Usually an obtainable class phenates is to be made by the following represented phenol of general formula X III:

A is 1～3 integer in the formula, and b is 1 or 2, and z is 0 or 1, R ¹³For on average containing the saturated substantially hydrocarbyl substituent of 30～400 aliphatic carbon atoms, R approximately ¹⁴System is selected from low alkyl group, lower alkoxy, nitro and halogen.

Being used for the special phenates of a class of the present invention is the sulfuration phenates that II A belongs to alkalescence (being high alkalinity etc.) metal, with a kind of vulcanizing agent (for example halogenide of sulphur, sulphur or sulfide or sulfhydrate salt) above-mentioned phenol sulfuration is made.The method of making this class sulfuration phenates is in United States Patent (USP) 2,680,096; In 3,036,971 and 3,775,321 introduction is arranged, here its disclosure is in this respect quoted and incorporated into this specification sheets.

Other available phenates are to be made by the phenol by alkylidene group (for example methylene radical) bonding.Its method is to make monocycle or encircle phenol more and generally react with aldehydes or ketones under the situation that has acidity or basic catalyst to exist.The phenol of this class bonding and sulfuration phenates in 038, particularly have detailed introduction all at United States Patent (USP) 3,350 in its 6～8 hurdle, here its disclosure is in this respect quoted and incorporated into this specification sheets.

Certainly, above-mentioned organic sulfuric acid, carboxylic acid and two or more neutrality of phenol and the mixture of basic salt also can be used for composition of the present invention.Usually neutral and basic salt is sodium salt, lithium salts, magnesium salts, calcium salt or barium salt, comprises the mixture of any above-mentioned two or more salt.

(B) amine of (III) alkyl replacement

Being used to prepare the amine that the alkyl of composition of the present invention replaces is well-known for the professional who is familiar with present technique, and many patents have been done introduction to it.United States Patent (USP) 3,275 is wherein arranged, 554; 3,438,757; 3,454,555; 3,565,804; 3,755,433; With 3,822,209.Here disclosed alkylamine of the present invention and its preparation method of being applicable to of these patents quoted and incorporated into this specification sheets.

Can be used for alkylamine of the present invention and comprise the monoamine of representing with following general formula X IV:

The example of this class monoamine has:

Many (propylene) amine

N, N-dimethyl-N-many (ethylene/propene) amine

(monomer mole ratio is 50: 50)

Many (iso-butylene) amine

N, N-two (hydroxyethyl)-N-many (iso-butylene) amine

Many (iso-butylene/1-butylene/2-butylene) amine

(monomer mole ratio is 50: 25: 25)

The N-(2-hydroxypropyl)-N-many (iso-butylene) amine

Many (the 1-butylene)-aniline of N-

Many (the iso-butylene)-morpholines of N-

Can be used for forming the amine that the alkyl of composition of the present invention replaces and comprise that some is not included in the N-amino-alkyl morpholine in the above-mentioned general formula X IV.The hydrocarbyl amino morpholine that this class alkyl replaces can be represented with following general formula X V:

R in the formula ⁷For containing the aliphatic hydrocarbyl of 30～400 carbon atoms approximately, A is the hydroxy alkylene of hydrogen or the alkyl that contains 1～10 carbon atom or 1～10 carbon atom, and U is the alkylidene group that contains 2～10 carbon atoms.The polyamines that hydrocarbyl amino morpholine that these alkyl replace and formula X V are represented all belongs to the amine that the typical alkyl that is used to prepare composition of the present invention replaces.

(B) the nitrogenous condenses of (IV) phenol, sulphur and aminocompound

Phenol/aldehyde/aminocompound the condenses that can be used for preparing composition of the present invention comprises that those belong to the compound of Mannich condensate.Usually they are that to have a hydrogen atom at least by at least a phenol that replaces such as alkyl (for example alkylphenol, alkyl wherein contains about 30～400 carbon atoms at least) and so on be that the active dydrogen compounds that combines with an aromatic carbon atom and at least a aldehyde material (commonly used is formaldehyde or formaldehyde precursor) that maybe can produce aldehyde and at least a amino that contains at least one NH base or polyamino compound react simultaneously or sequentially and make.Described aminocompound comprises that to contain carbonatoms be 1～30 hydrocarbyl substituent or contains uncle's monoamine or the secondary monoamine that carbonatoms is about the hydrocarbyl substituent that 1～30 hydroxyl replaces.Another kind of aminocompound commonly used is the polyamines of introducing when the acidylate nitrogenous compound is discussed.

The example of monoamine has methyl ethyl-amine, methyl octadecylamine, aniline, diethylamine, diethanolamine, dipropyl amine, or the like.Following United States Patent (USP) has been done detailed introduction to the Mannich condensate that can be used for preparing composition of the present invention.

United States Patent (USP)

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

3,036,003??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??3,539,633

Since these patent disclosures the manufacturing of relevant Mannich condensate and the content of the application facet in lubricating oil thereof, therefore quoted here and incorporated into this specification sheets.

The condenses that is made by the sulfur-bearing reactant also can be used for composition of the present invention.This class sulfur-bearing condenses is in United States Patent (USP) 3,368,972; 3,649,229; 3,600,372; Done introduction in 3,649,659 and 3,741,896.Since these patent disclosures the sulfur-bearing Mannich condensate, therefore quoted here and incorporated into this specification sheets.The condenses that generally is used to prepare composition of the present invention be by have contain approximately 6～400(more commonly used be 30～250) phenol of the alkyl substituent of individual carbon atom makes.These condensess commonly used are by formaldehyde or C _2-7Aliphatic aldehyde and a kind ofly make at the used aminocompound of preparation acidylate nitrogenous compound described in (B) (I).

These condensess that are more suitable for are to react by the aminocompound of the aldehyde of the phenolic compound of about 1 mole of part and about 1～2 mole of part and about 1～5 equivalent part (1 equivalent aminocompound equals its molecular weight by the quantity divided by contained=NH base) to make.This class condensation reaction condition is well-known for the professional who is familiar with present technique, and is proved by these patents above-mentioned.Since these patent disclosures reaction conditions, therefore quoted and incorporated into this specification sheets.

Particularly be applicable to that a class condensation product of the present invention is that 644(1974 filed an application March 15 with United States Patent (USP) sequence number 451 for example) in disclosed " two-step approach " condenses of making.In brief, the preparation method of these nitrogenous compounds is as follows: (1) makes at least a carbonatoms that contains be at least about 30 to aliphatic series or the substituent hydroxy aromatic compound of cyclic aliphatic and a kind of lower aliphatic C until about 400 _1～7Aldehyde or its invertible polymer react approximately being no more than in the presence of the alkaline reagents (for example alkali metal hydroxide) under 150 ℃ the temperature; (2) the intermediate reaction mixture that above-mentioned reaction is generated neutralizes substantially; And (3) make the intermediate that neutralized and at least aly contain a compound that contains the amino of one-NH base at least and react.

Preferably these two steps condensess are made by following several compounds: (a) have the phenol that carbonatoms is about 30～250 hydrocarbyl substituent, this substituting group is by the polymer-derived of propylene, 1-butylene, 2-butylene or iso-butylene; (b) formaldehyde or its invertible polymer (for example trioxane, polyoxymethylene) or the suitable thing of its function (for example methylal) and (C) a kind of alkylene polyamine, for example ethylene polyamine of nitrogen-atoms number between 2 and 10.The further details of the condenses that is more suitable for about this class can be consulted the United States Patent (USP) sequence number of pointing out above 451,644.Since this patent disclosure two step condensess, therefore quoted and incorporated into this specification sheets.

(C) amino phenol

The aromatics part A r of formula I can be Dan Fanghe (for example benzene nucleus, pyridine nucleus, thiophene nuclear, 1,2,3,4-naphthane nuclear etc.) or polynuclear aromatic part.This multinuclear part can be the type of condensing, and promptly wherein having a virtue nuclear at least is to condense at two places and another virtue nuclear, and for example the situation of naphthalene, anthracene, azanaphthalenes etc. comes to this.Another kind of situation is that this polynuclear aromatic part can be a bonding type, wherein has two nuclears (monokaryon or multinuclear) at least by the mutual bonding of bridged bond.This class bridged bond can be selected from carbon-to-carbon singly-bound, ehter bond, ketonic bond, sulfide bond, the polysulfide key that contains 2～6 sulphur atoms, acyl key, sulfonyl key, methene key, alkylene base key, two (low alkyl group) methene key, low-grade alkylidene ehter bond, alkylidene group ketonic bond, low-grade alkylidene sulfide linkage, contain the mixture of the low-grade alkylidene polysulfide key of 2～6 carbon atoms, amino key, polyamino key and this class divalence bridged bond.In some cases, 1 above bridged bond can be arranged between the aromatics among the Ar.For example, fluorenes nuclear has two by a methene key and covalent linkage and mutually benzene nucleus of key.This endorsing to regard as has 3 nuclears, is virtue nuclear but have only two nuclears.But general Ar carbon atoms (if low alkyl group or alkoxy substituent are arranged then add these substituting groups) only in virtue nuclear self.

Virtue among Ar nuclear (condense, bonding or both have concurrently) number in decision formula II a, b and the integer of c aspect can play very big effect.For example, when Ar only contains when nuclear virtue, a, b and c respectively be 1～4, when Ar contains two virtue nuclears, and a, b and c can respectively be 1～8, promptly near 3 times (fragrant check figure is 2 in naphthalene) of contained fragrant check figure.If Ar partly has 3 virtue nuclears, a, b and c can respectively be 1～12 integer.For example, when Ar is-biphenyl or naphthyl moiety, a, b and c can respectively be 1～8 integer.Obviously, the value of a, b and c is restricted, and promptly its summation can not surpass unsaturated total valence mumber of Ar.

The monocycle virtue is endorsed being to use general formula ar(Q) Ar part that m represents, the ar representative contains the monocycle virtue nuclear (for example benzene) of 4～10 carbon atoms in the formula, and each Q respectively represents a low alkyl group, lower alkoxy, nitro or halogen atom, and m is 0～3.In this specification sheets and appended claim, used " rudimentary " speech is meant the base that contains 7 or be less than 7 carbon atoms, for example low alkyl group and lower alkoxy.Halogen atom comprises fluorine, chlorine, bromine and iodine atom; General halogen atom is fluorine and chlorine atom.

The object lesson of monocycle Ar part has:

Me is a methyl in the formula, and Et is an ethyl, and Pr is a n-propyl, and Nit is a nitro.

If Ar is a multinuclear condensed ring aromatic part, it can represent with following general formula,

The definition of ar, Q and m is the same in the formula, m ¹Be 1～4 and represent a pair of key that condenses, this condenses key condenses two rings, so that two carbon atoms become the part of each ring in adjacent two rings.The object lesson of condensed ring aromatic part has:

If aromatics part A r is a bonding polynuclear aromatic part, the general formula below it is available is represented:

W is 1～about 20 integer in the formula, the definition of ar is the same, but all must have 3 unsaturated valencys (being free valency) at least in the ar base, and Q and m's is described as defined above, each Lng is bridged bond, respectively is selected from the carbon-to-carbon singly-bound, (for example-O-), ketonic bond (for example for ehter bond ), sulfide bond (for example-S-), contain 2～6 sulphur atoms the polysulfide key (for example-S _2～6-), sulphonyl key (for example-S(O)-), sulfonyl key (for example-S(O) ₂-), the low-grade alkylidene key (for example-CH ₂-,-CH ₂-CH ₂-,

Deng), two (low alkyl group)-methene keys (CR for example ⁰ ₂), the low-grade alkylidene ehter bond (for example-CH ₂O-,-CH ₂O-CH ₂-, CH ₂-CH ₂O-,-CH ₂CH ₂OCH ₂CH ₂-,

Deng), low-grade alkylidene sulfide bond (for example one or more in the low-grade alkylidene ehter bond-O-for-key that the S-atom replaces), low-grade alkylidene polysulfide key (for example one of them or more than one-O-is-S _2～6The basic replacement), amino key (for example

,-CH ₂N-,

,

, wherein alk is a low-grade alkylidene etc.), the polyamino key (for example

, wherein unsaturated free N valency is H atom or R ⁰Base institute combination) and mixture (each R of these bridged bonds ⁰For-low alkyl group).One or more ar bases in the bonding aromatics part also may for example be condensed nuclear in the above

Replace.

The object lesson of bonding part has:

General all these Ar partly remove R ,-OH and-NH ₂Outer other substituting groups that do not contain of base (with any bridging group).Owing to reasons such as cost, availability, performances, this Ar partly is generally benzene nucleus or the naphthalene nuclear that benzene nucleus, low-grade alkylidene are made bridged bond.Therefore, typical A r one has the benzene nucleus of 3～5 unsaturated valencys or naphthalene nuclear, and it is saturated to make wherein 1 or 2 unsaturated valency can be hydroxyl institute, and remaining unsaturated valency is as far as possible in the ortho position or the contraposition of hydroxyl.Preferably Ar one has the benzene nucleus of 3 unsaturated valencys at least, so that 1 unsaturated valency can be saturated by hydroxyl, other 2 or 3 unsaturated valencys are then in the ortho position or the contraposition of hydroxyl.

Basic saturated hydrocarbyl R ⁹

Amino-phenol of the present invention contain one directly and aromatics part A r bonded, at least about the saturated substantially monovalence alkyl R that contains 10 aliphatic carbon atoms ⁹, this R ⁹Approximately be no more than 400 aliphatic carbon atom basic can containing.Each aromatic kernel in aromatics part A r an above R can be arranged ⁹Base, but no more than 2 or 3 usually.The R that exists ⁹The sum of base is by the value representation of " a " in the formula II.Generally, the aliphatic carbon atom number of this alkyl is at least about 30, and more common is at least about 50, but approximately is no more than 750, more commonly approximately is no more than 300.

Generally, alkyl R ⁹Be that homopolymer or interpolymer (for example multipolymer, terpolymer) by monoolefine that contains 2～10 carbon atoms and diolefine (for example ethene, propylene, butene-1, iso-butylene, divinyl, isoprene, 1-hexene, 1-octene etc.) makes.Usually these alkene are 1-monoolefines, for example the homopolymer of ethene.The R base also can be derived by halo (for example chloro or the bromo) analogue of this homopolymer or interpolymer.But R ⁹Base can be made by other sources, these sources as high molecular weight chains olefinic monomer (for example 1-40 carbenes) and chloro analogue thereof and hydrogen chloro analogue, aliphatic petroleum fractions (particularly paraffin and cracked thereof and chloro analogue and chlorine chloro analogue), white oil, synthetic alkene (for example using the Ziegler-Natta manufactured) and be other sources of being familiar with known to the professional of present technique as many ethene fat.Make R according to technical known method before the denitrification step that will introduce below ⁹Base hydrogenation can make R ⁹The degree of unsaturation of base reduces or eliminates.

The group that terminology used here " alkyl " representative contains a carbon atom that directly links to each other with the rest part of molecule and mainly has hydrocarbon characteristic of the present invention.Therefore, per 10 carbon atoms can contain 1 non-alkyl in the alkyl, and its condition is the main hydrocarbon characteristic that this non-alkyl can not change this group significantly.Be familiar with the present technique professional and can know that all this class base comprises for example hydroxyl, halogen atom (particularly chlorine and fluorine), alkoxyl group, alkyl thiol, alkyl sulfide oxygen base (alkyl sulfoxy) etc.Yet alkyl R is alkyl fully usually, does not contain these non-alkyl.Alkyl R ⁹Basically be saturated.What is called is saturated basically to be meant that this alkyl whenever contains 10 carbon-to-carbon singly-bounds and only contains 1 carbon-to-carbon unsaturated bond.General this alkyl whenever contains 50 C-Cs and only contains 1 non-aromatics unsaturated link(age) of carbon-to-carbon.

The alkyl of amino phenol of the present invention also mainly has aliphatic characteristic, promptly whenever contains 10 carbon atoms in the R base, only contains 1 its carbonatoms and be 6 or be less than 6 non-aliphatic series part (cycloalkyl, cycloalkenyl or aryl) but R usually ⁹Per 50 carbon atoms only contain 1 non-aliphatic group of this class in the base, and do not contain this non-aliphatic group in many cases, and promptly the typical R base is aliphatic fully.Commonly used these are the R of aliphatic series fully ⁹Base is alkyl or alkenyl.Substantially saturated alkyl R ⁹Object lesson as follows

Four (propylene) base

Three (iso-butylene) base

Tetracontyl

The henpentacontane base

Poly-(ethylene/propene) based mixtures that contains 35～70 carbon atoms approximately

Contain the oxidative degradation of 35～70 carbon atoms or poly-(ethylene/propene) based mixtures of mechano-degradation approximately

Poly-(propylene/1-hexene) based mixtures that contains 80～150 carbon atoms approximately

Poly-(iso-butylene) based mixtures that contains 20～32 carbon atoms approximately

Poly-(iso-butylene) based mixtures that on average contains 50～75 carbon atoms

R ⁹The source that is more suitable for of base is poly-(iso-butylene), and it is to be that 35～75%(is heavy by butene content), iso-butylene content is that 15～60%(is heavy) C ₄Refinery's oil stream carries out polymerization and gets in the presence of Lewis acid catalyst (for example aluminum chloride or boron trifluoride).These polybutene mainly contain following configuration isobutylene repeat units (greater than the repeating unit sum 80%)

Can make alkyl R with the known many methods of the professional who is familiar with present technique ⁹Be connected on the aromatics part A r of amino phenol of the present invention.A kind of method that particularly is suitable for is the Friedel-Crafts reaction, and this method is that a kind of alkene polymkeric substance of olefinic bonds (for example contain-) or its halo or hydrogen halo analogue and acid are reacted.This reaction is that the existence at Lewis acid catalyst (for example boron trifluoride and the complex compound formed with ether, phenol, hydrogen fluoride etc. thereof, aluminum chloride, aluminum bromide, zinc dichloride etc.) takes place down.The method and the condition of carrying out this reaction are well-known for the professional who is familiar with present technique.For example can consult the 894th～895 page of discussion that is entitled as in " Alkylation of Phenols " (alkylation of phenol) literary composition of " Kirk-Othmer Encyclopedia of Chemical Technology " (second edition, the 1st volume) that Interscience Publishers company (branch of John Wiley and Company) published in New York in 1963.The professional who is familiar with present technique also can remember at an easy rate other be suitable for equally and easily method with alkyl R ⁹Be connected on the aromatics part A r.

Be appreciated that from the formula II amino phenol of the present invention contains every kind of substituting group as follows at least: the R of hydroxyl, above-mentioned definition ⁹The base and-primary amine groups-NH ₂Every kind of above-mentioned base all must be connected on the carbon atom as the part of the virtue nuclear in the Ar part, still, if virtue nuclear more than one is arranged in the Ar part, so above-mentioned various bases do not need to be connected on the same aromatic ring.

In the concrete scheme that is more suitable for, amino phenol of the present invention contains above substituent each 1 (be a, b and c respectively are 1), but only contains 1 aromatic ring (preferably benzene).The amino phenol that this class is more suitable for can be represented with following formula X VI

R in the formula ⁹Base is for containing 30～400 basic saturated hydrocarbyls that are in the aliphatic carbon atom of hydroxyl ortho position or contraposition, R approximately ⁶Be low alkyl group, lower alkoxy, nitro or halogen atom, E is 0 or 1.General E is 0, R ⁹For saturated substantially, be the alkyl of aliphatic series fully.It usually is to be in-alkyl or the alkenyl of the substituent contraposition of OH.Amino often has only one in the amino phenol that these are more suitable for, for-NH ₂, but also can have two.

In another concrete scheme that particularly is fit to of the present invention, used amino phenol is represented with following formula X VII:

R in the formula ⁹Be C by homopolymerization or copolymerization _2～101-alkene deutero-on average contains 30～400 aliphatic carbon atoms approximately; R ⁶Described as defined above with E.General R ⁹Be by ethene, propylene, butylene, and composition thereof deutero-.Normally by polymeric iso-butylene deutero-.Past often R ⁹At least about containing 50 aliphatic carbon atoms, and E is 0.

Amino phenol of the present invention can make by many synthetic routes, and these routes are different on used reaction type and use order.For example, available alkylating agent (for example polymeric alkene) makes aromatic hydrocarbon (for example benzene) alkylation, to generate alkylating aromatics intermediate.Make this intermediate nitrated then, for example generate many nitro intermediate.Then make these many nitro intermediate be reduced into diamines, make its diazotization again, and react so that one of them amino changes into hydroxyl, thereby required amino phenol is provided with water.Another kind method is by making a nitro in many nitro intermediate change into hydroxyl with the alkali congruent melting, thereby obtains hydroxyl-4-nitro alkyl aromatic substance, makes it to reduce again and obtains required amino phenol.

Another route available for preparing amino phenol of the present invention is to make the phenol alkylation to generate alkylating phenol with the olefinic alkylating agent.Then that this alkylating phenol is nitrated with m-nitrophenol in generating, then wherein at least a portion nitroreduction becomes amino, and the professional who make it change into required amino phenol, to be familiar with present technique knows makes the alkylating method of phenol shown in the literary composition noted before in Kirk-Othmer " the Encyclopedia of Chemical Technology " book.It also is known making the nitrated method of phenol.For example can consult the literary composition that the 888th page of grade of Kirk-Othmer " Encyclopedia of Chemical Technology " (second edition the 13rd volume) is entitled as " Nitrophenols ", and the P.R.D.De La Mare that publishes of New York Academic Press nineteen fifty-nine and disquisition " the Aromatic Substitution of J.H.Ridd; Nitration and Halogenation "; " the Nitration and Aromatic Reactivity " of J.G.Hogget, London, Cambridge University Press, 1961; And Henry Feuer chief editor's The Chemistry of the Nitro and Nitroso Groups ", Interscience Publishers N.Y.1969.

Aromatic hydroxy compound can use the mixture of nitric acid, nitric acid and the acid such as sulfuric acid or boron trifluoride, nitrogen tetraoxide, nitronium tetrafluoroborate and acyl group nitric ether nitrated.Generally, concentration is a kind of suitable nitrating agent for for example about 30～90% nitric acid.Basically being the inert liquid diluent can help the carrying out that react by the situation that contacts of improving reagent with solvent (for example acetic acid or butyric acid).Making nitrated condition of hydroxy aromatic compound and concentration also has been well-known in the present technique field.For example, reaction can extremely be carried out under about 150 ℃ temperature at about-15 ℃, general nitrated should carrying out under about 25～75 ℃.

Be used for making and treat that the nitrated required nitrating agent consumption of nitrated hydroxyaromatic intermediate contained each mole virtue nuclear is different with the concrete kind of nitrating agent, generally be about 0.5～4 mole.If at Ar virtue nuclear more than 1 is arranged partly, the nitrating agent consumption can increase pro rata according to contained fragrant check figure.For example, one mole is used for naphthyl aromatics intermediate of the present invention and contains and be equivalent to two " monocycle " virtue nuclear, about 1～4 mole of nitrating agent of so general use.When making nitrating agent with nitric acid, every mole of virtue nuclear uses about 1.0～3.0 molar nitric acids.The carrying out of promotion or accelerated reaction can be used the nitrating agent (for each " monocycle " virtue nuclear) with molar excess if desired.

For making the hydroxyaromatic intermediate nitrated, generally need 0.25～24 hour, but the nitrating mixture reaction longer time (for example 96 hours) may be suited.

The method that makes aromatic nitro compound be reduced into corresponding amine also is well-known.For example can consult Kirk-Othmer " Encyclopedia of Chemical Technology ", second edition, being entitled as of the 2nd volume 76-99 page or leaf " Amination by Reduction " (" amination of being undertaken by reduction ") literary composition.Generally can in the presence of metal catalyst (for example oxide compound of palladium, platinum and platinum, nickel, copper chromite etc.), carry out this reduction reaction with hydrogen, carbon monoxide or hydrazine.In these catalytic reduction reactions, can use the promotor of the oxyhydroxide of basic metal for example or alkaline-earth metal or amine (comprising amino phenol) and so on.

Also can be by using the reducing metal to finish reduction reaction in the presence of acid (for example hydrochloric acid).Typical reducing metal is zinc, iron and tin; Also can use these metal-salts.

Also can make nitroreduction in the Zinin reaction, the 455th page of grade of " Organic Reactions " (organic reaction) the 20th volume that John Wiley ﹠ Sons N.Y.1973 publishes discussed the problem of this respect.Generally, Zinin reaction relates to usefulness-divalent sulphur compound (for example alkali metalsulphide, polysulfide and sulfhydrate) and makes nitroreduction.

Can make nitroreduction by electrolytic action, for example can consult, above-mentioned " Amination by Reduction " literary composition.

Common amino phenol of the present invention makes the nitrophenol reduction with hydrogen under the situation that above-mentioned metal catalyst exists.This reduction reaction is generally carried out (being typically under about 50 °～150 ℃) under about 15～250 ℃, and the pressure of hydrogen is about 0～2000Psi(gauge pressure), typically be about 50～250Psi(gauge pressure), the reduction reaction time is about 0.5～50 hour usually.For ease of the carrying out of reaction, can use inert liquid diluent and solvent, for example ethanol, hexanaphthene etc. basically.The amino phenol product obtains with well-known technology (for example distill, filtration, extraction etc.).

Reduction reaction is performed until and is generally about 80% at least about 50%(in the nitro intermediate mixture) nitro when changing into amino till.The typical itineraries that the present invention who introduces previously prepares amino phenol can reduce:

(I) is nitrated with the compound that at least a nitrating agent is represented the formula X VII below at least a usefulness, contains first reaction mixture of nitro intermediate with generation:

R in the formula ⁴For containing the basic saturated hydrocarbyl of 10 aliphatic carbon atoms at least; A and c respectively are the integer of 1～3 times of contained fragrant check figure in Ar ', and its condition is the unsaturated valency that the summation of a, b and c is no more than Ar '; Ar ' is for containing 0～3 aromatics part of selecting substituting group (be selected from low alkyl group, lower alkoxy, nitro and halogen atom or two or more described select for use substituent combination) for use, but must meet following condition, promptly (a) Ar ' have the hydrogen atom that 1 carbon atom direct and a part of examining as virtue directly links to each other at least; And (b) when Ar ' when only containing 1 hydroxyl and 1 the substituent benzene of R, this R substituting group will be in the ortho position or the contraposition of described hydroxyl substituent;

(II) will become amino at least about 50% nitroreduction in above-mentioned first reaction mixture.

Usually this means and become amino at least about 50% nitroreduction in the mixture of a kind of compound that following general formula X IX is represented or several compounds

R in the formula ⁴For containing the basic saturated hydrocarbyl of 10 aliphatic carbon atoms at least; A, b and c respectively are 1 integer until 3 times of contained fragrant check figures in Ar, and the summation that its condition is a, b and c is no more than the unsaturated valency of Ar; Ar is for containing 0～3 aromatics part of selecting substituting group (be selected from low alkyl group, lower alkoxy, halogen atom or two or more described select for use substituent combination) for use; But must meet following condition, promptly when Ar when only containing 1 hydroxyl and 1 substituent benzene nucleus of R, R ⁴Substituting group will be in the ortho position or the contraposition of described hydroxyl substituent.

Of the present invention contain component (A) and (B) (I) or (A), (B) and composition (C) be applicable to the two-stroke cycle engine.When said composition comprises (A) and (B) when (I), the weight ratio of these components is about 97: 3 to about 80: 20; What be more suitable for is 95: 5～about 85: 15, is preferably about 93: 7～88: 12.When said composition comprises (A), (B) and (C) time, the shared weight part of these components is as follows:

Component is general better best

(A)??70-94??76-94??80-90

(B)??5-18??3-12??5-10

(C)??1-12??1-7.5??3-6

Component of the present invention generates solution according to above-mentioned scope blend.Should be appreciated that except that said components, in two-stroke circulation composition, also can contain other components.

Following specific description embodiment has introduced how to prepare and has comprised (B) of the present invention and (C) washing agent/dispersion agent and the amino phenol of component.In these embodiment and this specification sheets and appended claim, all percentage ratios, umber and proportional numers all refer to weight unless expressly stated otherwise.Unless expressly stated otherwise,, temperature all refers to ℃.

Embodiment 1A

A kind of polyisobutene by 4578 parts of polyisobutene substituted phenols (being about 1000(with number-average molecular weight records in assay method with vapor infiltration) carried out the boron trifluoride catalytic alkylation effect of phenol and make), the mixture heating up to 60 formed with alcohol (Textile spirits) of 3052 parts of thinner mineral oil and 725 parts of weavings is ° so that it is even.After being cooled to 30 ℃, the solution of 319.5 part of 16 volumetric molar concentration nitric acid in 600 parts of water is added in this mixture.Must cool off, make the temperature of this mixture keep below 40 °.The reaction mixture restir after 2 hours, is moved to aliquot (3710 parts) in second reaction vessel.In addition the solution of 127.8 part of 16 volumetric molar concentration nitric acid in 130 parts of water is added down at 25-30 °, so that this second section is handled.This reaction mixture was stirred 1.5 hours, be stripped to 220 °/30 millibars then.Filter the oil solution that the back obtains required intermediate (I A).

Embodiment I B

The mixture of 810 parts of described intermediate oil solutions of embodiment 1A, 405 parts of Virahols and 405 parts of toluene is packed in the autoclave of a suitable size.After adding 0.81 part of platinum-oxide catalyst, autoclave found time and purge four times, to remove residual air with nitrogen.When the reactant in the autoclave is stirred, hydrogen is fed in the autoclave, pressure is the 29-55psi(gauge pressure) and be heated to 27～92 °, heated altogether 13 hours.Find time and purge four times to remove the hydrogen of remaining surplus with nitrogen.Make then reaction mixture by diatomite to filter, filtrate carried out stripping and obtain the oil solution of required amino-phenol.This solution contains 0.578% nitrogen.

Embodiment 2

The mixture of 906 parts of alkyl benzene sulphonate (ABS) oil solutions (molecular-weight average that records with the vapor infiltration platen press is 450), 564 parts of mineral oil, 600 parts of toluene, 98.7 parts of magnesium oxide and 120 parts of water was blown 7 hours with carbonic acid gas under 78～85 °, air blowing speed be about 3 cubic feet of carbonic acid gas/hour.In whole carbonation process, reaction mixture is constantly stirred.After the carbonation, reaction mixture is stripped to 165 °/20 millibars ， And elimination residues.Filtrate is required metal than the oil solution that is about 3 high-alkali sulfonic acid magnesium.

Embodiment 3

Prepared a kind of polyisobutene at succinyl oxide, its method is that chloro polyisobutene (average chlorinity is 4.3%, on average contains 82 carbon atoms) is reacted under about 200 ° with maleic anhydride.The saponification value of gained polyisobutenyl succinyl oxide is 90.In the mixture of forming by 1246 parts of this succinyl oxides and 1000 parts of toluene, adding 76.6 parts of barium oxide under 25 °.With this mixture heating up to 115 ℃, dripped 125 parts of water with 1 hour time.Mixture is refluxed down at 150 ℃.All reacted until all barium oxide and to have finished.Stripping and filtration back acquisition barium content are 4.71% filtrate.

Embodiment 4

(its molecular weight is about 950 with 1500 parts of chloro polyisobutene, chlorinity is 5.6%), the mixture heating up of 285 parts of alkylene polyamines with the average composition that is equivalent to tetraethylene pentamine on stoichiometric calculation and 1200 parts of benzene is to refluxing, the temperature of chien shih mixture is slowly brought up to 170 ° and is removed benzene simultaneously during then with 4 hours.After the mixture cooling, with isopyknic by hexane and raw spirit by 1: 1 ratio preparation and must mixed solution dilute.With mixture heating up to refluxing and adding 10% aqueous sodium carbonate of 1/3 volume.Make mixture cooling and phase-splitting after the stirring.Wash organic phase with water, and to carry out stripping so that being provided, required nitrogen content is 4.5% polyisobutene polyamines.

Embodiment 5

The polyisobutene that with 140 parts of toluene and 400 parts of saponification values is 109 polyisobutenyl succinyl oxide (being about 850(vapor infiltration platen press by molecular weight records) makes) and 63.6 parts its on average forms the mixture heating up to 150 formed at vinyl-amine mixture suitable aspect the stoichiometric calculation ℃ with tetraethylene pentamine, simultaneously except that anhydrating/the methylbenzene azeotropic mixture.Under reduced pressure this reaction mixture is heated to 150 ℃ then, stops distillation until toluene.The nitrogen content of remaining acylated polyamine is 4.7%.

Embodiment 6

Down in the industrial diethylenetriamines of heating slowly added 6820 part Unimac 5680s at 1133 parts in 110～150 ° with 2 hour time.This mixture was kept 1 hour down at 150 °, and then be heated to 180 ° with 1 hour time.Use 0.5 hour time with mixture heating up to 205 ° at last, in whole heat-processed with the nitrogen blowing mixt to remove volatile matter.Mixture was kept under 205～230 ° 11.5 hours altogether, under 230 °/20 millibars it is carried out stripping then, to produce required acylated polyamine, it is that nitrogen content is 6.2% residue.

Embodiment 7

22 part of 37% formalin (being equivalent to 8 parts of aldehyde) is added drop-wise in the mixture of being made up of 50 parts of polypropylene fortified phenols (molecular weight that records with the vapor infiltration platen press is about 900), 500 parts of mineral oil (the solvent treatment paraffinic based oil that a kind of viscosity under 100 is 100SUS) and 130 part of 9.5% dimethylamine agueous solution (being equivalent to 12 parts of amine) with 1 hour time.In the interpolation process, temperature of reaction rises to 100 ° and kept 3 hours slowly under this temperature, use the nitrogen blowing mixt simultaneously.100 parts of toluene and 50 parts of mixed butyl alcohols are added in the cooled reaction mixture.Wash organic phase three times with water until being neutral, 200 °/5-10 millibar is filtered and be stripped to organic phase with the litmus paper test.Remaining is the final product oil solution that contains 0.45% nitrogen.

Embodiment 8

90 ℃ down preparation be that 105 polyisobutene (molecular weight 1000) replaces succinyl oxide and 23 parts of mixtures that Unimac 5680 is formed by 140 parts of (weight) mineral oil, 174 parts of saponification values.In this mixture, added 17.6 parts of polyalkylene amine mixt (be equivalent to tetraethylene pentamine its total composition) with 1.3 hour time down in 80～100 ℃.This reaction is heat release.Reach 3 hours with the nitrogen blowing mixt down at 225 ℃, air blowing speed is 5 Pounds Per Hours, after this obtains 47 parts of moisture gold-plating fluids.This mixture was descended dry 1 hour at 225 ℃, be cooled to 110 ℃ and filtration then, generate the oil solution of required the finished product.

The present invention also considers to use other additives in lubricating oil composition of the present invention.These other additives comprise those typical additives types, and for example antioxidant, extreme-pressure additive, corrosion inhibitor, pour point reducer, colour stabilizer, antifoams and other generally are the known additives material concerning the personnel that are familiar with the lubricating oil composition compounding process.

Dyestuff can be used for identifying purpose and in order to show whether two-stroke circulation fuel oil contains lubricant.In some product, add the coupler that resembles organic surface active agent and so on, with the solubleness of improving component and the water tolerance that improves fuel oil/lubricant mixture.

In some special applications, wear-resistant and lubricity improver is used in for example racing car and in order to obtain very high fuel oil/lubricant ratios.Sometimes use scavenging agent or improve the additive of combustion chamber deposit, with the extending plug life-span with remove carbon deposits.Halogenated compound and (or) phosphorus containg substances can be applicable to this respect.

Various types of rust-preventive agent and corrosion inhibitor can add in the two-stroke turning oil composition.Sometimes for aesthetic consideration, use spices or reodorant.

Lubricant, for example synthetic polymer (for example the number-average molecular weight with vapor infiltration platen press or gel permeation chromatography is about 500～10,000 polyisobutene), polyol ether (for example poly-(oxygen ethene-oxypropylene) ether) and ester oil (for example above-mentioned ester oil) also can be used for oil compositions of the present invention.The natural oil cut, for example bright stock heavy (making the sticking product that generates in the process of lubricating oil at the oil of routine) also can be used for this purpose.General their consumptions in two-stroke turning oil account for 3～20% of total oil compositions

Thinner, petroleum naphtha or also can add oil compositions of the present invention for example about 38～90 ℃ of following ebullient low-molecular-weight esters (for example Stoddard solvent), typical consumption is 5～25%.When using thinner, it can direct substitution (A), i.e. 10 parts (A) available 10 parts of thinners replacement.

The table II is introduced several illustrative biological degradation two-stroke cycle engine oil lubrication composition of the present invention.

The table II

Washing agent-dispersion agent embodiment 1

The amino-phenol of embodiment natural oil consumption, weight part embodiment consumption

A??Sunyl?80??85??6??7.5??7.5

B??Sunyl?80??90??6??10.0??…

C soya-bean oil 80 6 10.0 10.0

D high acid corn oil 96 2 1.0 3.0

E ringdove elecampane oil 89 4 3.5 7.5

F Viscotrol C 92 3 2.0 6.0

G soya-bean oil 82 5 3.0 15.0

The high oleic acid rape seed oil 96 5 1.0 3.0 of H

I high oleic safflower oil 88 6 4.0 8.0

In some two-stroke cycle engine, lubricating oil can directly inject the inlet duct float chamber with fuel oil, perhaps injects fuel oil before fuel oil is about to enter the combustion chamber.Two-stroke lubrication by oil circulation agent of the present invention can be used for this class engine.

The people who is familiar with this respect technology knows that the two-stroke circulating oil often is introduced directly in the fuel oil to form the mixture of lubricating oil and fuel oil, then with this mixture importing engine cylinder.This series lubricant agent-fuel oil mixture belongs within the scope of the present invention.In this class lubricating oil-fuel oil mixture, general per 1 part of lubricating oil contains about 15-250 part fuel oil, and typical situation is that per 1 part of lubricating oil contains about 50-100 part fuel oil.

The fuel oil that is used for the two-stroke cycle engine is well-known for the person skilled in the art, in general, the contained major portion of such fuel oil is liquid fuel normally, for example hydrocarbon petroleum overhead product fuel oil (for example engine gasoline of ASTM Specification D-439-73 definition).This class fuel oil also can contain non-hydrocarbon materials, for example (for example methyl alcohol, ethanol, diethyl ether, methyl ethyl ether, Nitromethane 99Min.s) such as alcohol, ether, organic nitro-compounds, they are with the same also within the scope of the invention by plant or mineral source (for example corn, clover, resinous shale and coal) deutero-liquid fuel.The example of these fuel mixtures has the combination etc. of combination, gasoline and the Nitromethane 99Min. of gasoline and alcoholic acid combination, diesel oil and ether.What particularly be fit to is gasoline, and to distillate be 60 ° to the ASTM boiling point 10%, at 90% mixture that distillates the hydrocarbon that is about 205 ℃.

Two-stroke circulation fuel oil also contains known other additives of person skilled in the art, comprise octane promoter (for example lead tetraalkyl compound), plumbous scavenging agent (halogenated paraffin for example, as ethylene dichloride, ethylene dibromide), octane value growth promoter (methyl-tertbutyl ether (MTBE) for example, ethyl-tertbutyl ether (ETBE) and aromatic substance, for example dimethylbenzene and toluene), dyestuff, antioxidant (for example 2, the 6-tertiary butyl-4-methylphenol), rust-preventive agent (for example alkylated succinic acid and acid anhydride), fungistat, gum inhibitor, metal deactivator, demulsifying compound, the casing top half lubricant, deicing agent etc.

One example of lubricant-fuel composition that the present invention is included be with gasoline with above the described lubricant mixture of Embodiment C in (25～200 weight part): the mixture of the ratio composition of 1 weight part.

The concentrate that contains solubility nitrogenous compound of the present invention also belongs within the scope of the present invention.These concentrates generally comprise one or more above-mentioned natural oils that account for 20～80% and the nitrogenous composition of one or more solubilities that accounts for 20～80%.Person skilled in the art's easy to understand, this class concentrate also can comprise one or more above-mentioned all kinds supplementary additives.

Most of all is to compare with a kind of reference oil with gratifying quality in the test aspect the two-stroke cycle applications.For example, in Yamaha CE50S lubricity test, its objective is that the reduction that will make torque is less than or equals reference oil (this numerical value is more little, lubricated good more).

Embodiment J

Prepared fuel oil: the mixture of lubricating oil=150: 1, its method is that 100 parts of embodiment A products (lubricating oil) are added in 15,000 parts of gasoline (fuel oil).Torque in Yamaha CE50S reduces to 4.75, and benchmark two-stroke circulation composition is at fuel oil: the torque of lubricating oil=150: 1 o'clock reduces to 6.26.

Although the invention has been described in conjunction with the concrete scheme that is more suitable for of the present invention, be appreciated that the person skilled in the art can see its various improvement significantly after reading this specification sheets.Therefore it should be understood that a disclosed explanation will comprise those these improvement within the appending claims scope here.

Claims (58)

1, a kind of nitrogen-containing soluble organic composition composed of the following components:

(A) at least a natural oil that contains animal oil or vegetables oil, this animal oil or vegetables oil contain the triglyceride level that following formula is represented

R in the formula ¹, R ²And R ³Respectively be to contain the saturated of 8～24 carbon atoms or unsaturated aliphatic alkyl approximately, and

(B) (I) is a kind of comprises at least a washing agent/dispersion agent that an aliphatic carbon atom number is 10 substituent acidylate nitrogenous compound that has; this nitrogenous compound be by the carboxylic acid acylating agent and at least a contain at least one-aminocompound of NH base reacts and makes, described acylating agent is by imido base key, amido key, amidine key or an acyl-oxygen ammonium key and described aminocompound bonding.

2, the described composition of claim 1, wherein natural oil contains a vegetable oil.

3, the described composition of claim 2, wherein vegetables oil comprises that soya-bean oil, rape seed oil, high oleic acid rape seed oil, sunflower oil, high oleic sunflower oil, Oleum Cocois, Semen Maydis oil, peanut oil, Thistle oil, palm olein, high acid corn oil, palm-kernel oil, Dow pond caul-fat (meadowfoam oil), Leix gram are reined in and belongs to caul-fat and ringdove elecampane oil.

4, the described composition of claim 1, wherein natural oil is a kind of animal oil that contains lard or tallow oil.

5, the described composition of claim 1, wherein R ¹, R ²And R ³Respectively contain about 12～22 carbon atoms.

6, the described composition of claim 3, wherein vegetables oil comprises high oleic sunflower oil, high oleic safflower oil, high acid corn oil or high oleic acid rape seed oil.

7, the described composition of claim 1; wherein washing agent/dispersion agent is at least aly to have an aliphatic carbon atom number and be at least 10 substituent acidylate nitrogenous compound; this nitrogenous compound be by the carboxylic acid acylating agent and at least a contain at least one-aminocompound of NH base reacts and makes, described acylating agent is by imido base key, amido key, amidine key or an acyl-oxygen ammonium key and described aminocompound bonding.

8, the described composition of claim 7, the wherein alkylene polyamine of aminocompound for representing with following general formula

U is the alkylidene group that contains 2～10 carbon atoms in the formula, each R ⁸Respectively be hydrogen atom, low alkyl group or rudimentary hydroxyalkyl, but 1 R will be arranged at least ⁸Must be hydrogen atom, n be 1～10.

9, the described composition of claim 8, wherein acylating agent is monocarboxylic acid or polycarboxylic acid, or the suitable thing of its reactant, contains a carbonatoms and is at least about 30 aliphatic hydrocarbyl substituting group.

10, the described composition of claim 9 wherein replaces base system by C _2-10The homopolymer of 1-monoene or multipolymer or the mixture of the two make.

11, the composition of claim 10, wherein homopolymer or multipolymer are the homopolymer or the multipolymers of ethene, propylene, 1-butylene, 2-butylene, iso-butylene or its mixture.

12, the composition of claim 8, wherein acylating agent is at least a monocarboxylic acid or the suitable thing of its reactant, contains 12～30 carbon atoms of having an appointment.

13, the composition of claim 12, wherein acylating agent is fatty monocarboxylic acid or the suitable thing of its reactant, contains carbochain straight chain and side chain.

14, the composition of claim 13, wherein aminocompound is at least about the mixture of the ethylene polyamine, propylene polyamines or trimethylene polyamines or these polyamines that contain 2～8 amino.

15, the composition of claim 1, wherein A and B(I) weight ratio in about 97: 3～about 80: 20 scope.

16, a kind of nitrogen-containing soluble organic composition composed of the following components:

(A) at least a natural oil that contains animal oil or vegetables oil, this animal oil or vegetables oil contain the triglyceride level that following formula is represented

R in the formula ¹, R ²And R ³Respectively for containing the saturated of 8～24 carbon atoms or unsaturated aliphatic alkyl approximately

(B) at least a washing agent/dispersion agent that is selected from following compound

(I) at least a to be had an aliphatic carbon atom number and is at least 10 substituent acidylate nitrogenous compound, this compound be by the carboxylic acid acylating agent and at least a contain at least one-aminocompound of NH base reacts and makes, described acylating agent is by imido base key, amido key, amidine key or an acyl-oxygen ammonium key and described aminocompound bonding;

The neutrality or the alkaline metal salt of (II) at least a organic sulfuric acid, phenol or carboxylic acid;

The amine that (III) at least a alkyl replaces, wherein hydrocarbyl substituent is essentially aliphatic hydrocarbyl and contains at least 12 carbon atoms, but this amine must not be amino-phenol (B);

(IV) at least a by phenol, aldehyde and contain at least one-nitrogenous condenses that the aminocompound of NH base generates; With

(C) amino-phenol represented of the general formula below at least a usefulness

R in the formula ⁴For containing the basic saturated hydrocarbyl substituting group of 10 aliphatic carbon atoms at least; A, b and c respectively are 1～3 times integer of contained fragrant check figure among the Ar, but are condition with the unsaturated valency that a, b, c sum are no more than Ar; Ar is for can select for use 0～3 to be selected from the substituting group of low alkyl group, lower alkoxy, nitro, halogen atom or to adopt above-mentioned two or more substituent combination.

17, the composition of claim 16, wherein natural oil comprises a vegetable oil.

18, the composition of claim 17, wherein vegetables oil comprises that soya-bean oil, rape seed oil, high oleic acid rape seed oil, sunflower oil, high oleic sunflower oil, Oleum Cocois, peanut oil, Thistle oil, high oleic safflower oil, palm olein, Semen Maydis oil, high acid corn oil, palm-kernel oil, Dow pond caul-fat (meadowfoam oil), Leix gram are reined in and belongs to caul-fat and ringdove elecampane oil.

19, the composition of claim 16, wherein natural oil is the animal oil that comprises lard or tallow oil.

20, the composition of claim 16, wherein R ¹, R ²And R ³Respectively contain about 12～22 carbon atoms.

21, the composition of claim 18, wherein vegetables oil comprises high oleic sunflower oil, high oleic safflower oil, high acid corn oil or high oleic acid rape seed oil.

22, the composition of claim 16, wherein R ⁴Contain and approximately be no more than 750 carbon atoms, the substituting group of not selecting for use links to each other with Ar.

23, the composition of claim 22, wherein R ⁴Be alkyl or alkenyl.

24, the composition of claim 16, wherein R ⁴Contain 30～750 aliphatic carbon atoms approximately, and be by C _2-10The homopolymer of alkene or multipolymer make.

25, the composition of claim 24, wherein said ethylene series is selected from ethene, propylene, butylene and composition thereof.

26, the composition of claim 16, wherein a, b and c respectively are 1, do not have and select for use substituting group to link to each other with Ar, and Ar is-benzene nucleus.

27, the composition of claim 26, wherein R ⁴Be at least about and contain 30 carbon atoms, approximately be no more than the alkyl or the alkenyl of 750 carbon atoms at the most, and be by C _2-10The homopolymer of 1-monoolefine or multipolymer deutero-.

28, the composition of claim 16, amino-phenol wherein can be represented by the formula

R in the formula ⁵For on average containing the basic saturated hydrocarbyl substituting group of 30～400 aliphatic carbon atoms, R approximately ⁶System is selected from low alkyl group, lower alkoxy, nitro and halogen atom; Z is 0 or 1

29, the composition of claim 28, wherein R ⁵Being aliphatic hydrocarbyl fully, at least about containing 50 carbon atoms, and is by being selected from C _2-10The polymkeric substance of 1-monoolefine or multipolymer (and composition thereof) make.

30, the composition of claim 29, wherein z is 0.

31, the composition of claim 16, wherein washing agent/dispersion agent is (II), is at least a neutrality or the alkaline metal salt of organic sulfuric acid, phenol or carboxylic acid.

32, the composition of claim 31, wherein washing agent/dispersion agent is at least a alkaline metal salt of a kind of organic sulfonic acid or phenol.

33, the composition of claim 32, wherein metal is at least a basic metal or alkaline-earth metal.

34, the composition of claim 32, wherein washing agent/dispersion agent is at least a alkaline earth metal sulfonate.

35, the composition of claim 34, wherein sulfonate is alkyl substituted benzene sulfonate, alkyl wherein is at least about containing 8 carbon atoms.

36, the composition of claim 35, wherein amino-phenol is represented with following formula

R in the formula ⁵For on average containing the basic saturated hydrocarbyl substituting group of 30～400 aliphatic carbon atoms, R approximately ⁶System is selected from low alkyl group, lower alkoxy, nitro and halogen atom; Z is 0 to be 1

37, the composition of claim 16, wherein washing agent/dispersion agent is (III), contains the amine of a hydrocarbyl substituent at least.

38, the composition of claim 37, wherein amine is the monoamine that following general formula is represented

AXNR ⁷

39, the composition of claim 37, wherein the amine of alkyl replacement is the ammonia alkyl morpholine that replaces with the alkyl that following general formula is represented

R in the formula ⁷For containing the aliphatic hydrocarbyl of 30～400 carbon atoms approximately, A is hydrogen, contain the alkyl of 1～10 carbon atom or contain the hydroxy alkylene of 1～10 carbon atom; U is the alkylidene group that contains 2～10 carbon atoms.

40, the composition of claim 39, amino-phenol is wherein represented with following general formula:

R in the formula ⁹For on average containing the basic saturated hydrocarbyl substituting group of 30～400 aliphatic carbon atoms approximately; R ⁶System is selected from low alkyl group, lower alkoxy, nitro and halogen atom; Z is 0 or 1.

41, the composition of claim 16; wherein washing agent/dispersion agent is (I); at least aly have an aliphatic carbon atom number and be at least 10 substituent acidylate nitrogenous compound; this compound be by the carboxylic acid acylating agent and at least a contain at least one-aminocompound of NH base reacts and makes, described acylating agent is by imido base key, amido key, amidine key or an acyl-oxygen ammonium key and described aminocompound bonding.

42, the composition of claim 41, wherein aminocompound is the alkylene polyamine that following general formula is represented

U is the alkylidene group that contains 2～10 carbon atoms in the formula, each R ⁸Each represents hydrogen atom, low alkyl group or lower alkyl alkyl, but 1 R is arranged ⁸It must be hydrogen atom; N is 1～10.

43, the composition of claim 42, wherein acylating agent is monocarboxylic acid or polycarboxylic acid, or the suitable thing of its reactant, contains 1 carbonatoms and is at least about 30 aliphatic hydrocrbon substituting group.

44, the composition of claim 43 wherein replaces base system by C _2～10The homopolymer of 1-monoolefine or multipolymer or its mixture make.

45, the composition of claim 44, wherein homopolymer or multipolymer are homopolymer or multipolymer or its mixture of ethene, propylene, 1-butylene, 2-butylene, iso-butylene.

46, the composition of claim 45, wherein amino-phenol is represented with following formula

R in the formula ⁵For on average containing the basic saturated hydrocarbyl substituting group of 30～400 aliphatic carbon atoms approximately, be in the ortho position or the contraposition of hydroxyl; R ⁶System is selected from low alkyl group, lower alkoxy, nitro and halogen atom; Z is 0 or 1.

47, the composition of claim 42, wherein acylating agent is at least a monocarboxylic acid or the suitable thing of its reactant, contains 12～30 carbon atoms.

48, the composition of claim 47, wherein acylating agent is fatty monocarboxylic mixture or the suitable thing of its reactant, contains straight chain carbochain and side chain carbochain.

49, the composition of claim 48, wherein aminocompound is at least about ethylene polyamine, propylene polyamines or the trimethylene polyamines that contains 2～8 amino, perhaps is the mixture of these polyamines.

50, the composition of claim 49, wherein amino-phenol is represented with following formula

R in the formula ⁵For on average containing the basic saturated hydrocarbyl substituting group of 30～400 aliphatic carbon atoms approximately; R ⁶System is selected from low alkyl group, lower alkoxy, nitro and halogen atom; Z is 0 or 1.

51, the composition of claim 16, wherein washing agent/dispersion agent is (IV), phenol, aldehyde and contain at least one-the nitrogenous condenses of the aminocompound of NH base.

52, the composition of claim 51, wherein phenol is the phenol that alkyl replaces, this alkyl is at least about containing 30 carbon atoms.

53, the composition of claim 52, wherein aldehyde is formaldehyde or the suitable thing of its reactant.

54, the composition of claim 53, wherein aminocompound is represented with following formula

U is the alkylidene group that contains 2～10 carbon atoms in the formula; Each R ⁸Respectively be hydrogen atom, low alkyl group or rudimentary hydroxyalkyl, but 1 R will be arranged at least ⁸Be necessary for hydrogen atom; N is 1～10.

55, the composition of claim 54, wherein the preparation method of condenses makes phenol be no more than in the presence of alkaline catalysts under 150 ℃ the temperature earlier to react with aldehyde, the intermediate reaction mixture that will so generate then neutralization, making at last, neutral intermediate reaction mixture and at least a aminocompound that contains 1-NH base at least react.

56, the composition of claim 51, wherein amino-phenol is represented with following formula:

R in the formula ⁵For on average containing the basic saturated hydrocarbyl substituting group of 30～400 aliphatic carbon atoms approximately; R ⁶System is selected from low alkyl group, lower alkoxy, nitro and halogen atom; Z is 0 or 1.

57, the composition of claim 55, wherein amino-phenol is represented with following formula

R in the formula ⁵For on average containing the basic saturated hydrocarbyl substituting group of 30～400 aliphatic carbon atoms approximately; R ⁶System is selected from low alkyl group, lower alkoxy, nitro and halogen atom; Z is 0 or 1.

58, the composition of claim 16 contains 70～94 weight parts (A), about 5～18 weight parts (B) and about 1～12 weight part (C).