CN101407735A

CN101407735A - Mannich detergents for hydrocarbon fuels

Info

Publication number: CN101407735A
Application number: CNA2008101799143A
Authority: CN
Inventors: D·J·马尔菲尔; M·D·托马斯
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 2007-09-07
Filing date: 2008-09-05
Publication date: 2009-04-15
Also published as: DE102008046106A1

Abstract

New, highly effective substantially pure Mannich detergents for use in hydrocarbon fuels reduce engine deposits in spark and compression ignition internal combustion engines. The Mannich condensation reaction products are obtainable by reacting: (i) a polyamine having primary amino groups, (ii) a hydrocarbyl-substituted hydroxyaromatic compound, and (iii) an aldehyde, wherein the reaction is conducted at in a molar ratio of (i):(ii):(iii) of approximately 1:2:3 or 1:1:2. The Mannich detergent compounds may be dispersed in a liquid carrier to provide a fuel additive concentrate for hydrocarbon engine fuels which effectively control engine deposit formation in intake valves, port fuel injectors and combustion chambers.

Description

The mannich detergents that is used for hydrocarbon fuel

TECHNICAL FIELD OF THE INVENTION

[0001] the present invention relates to a kind of Mannich base condensed products of novelty and contain the sedimentary fuel composition of effective controlling combustion engine of described Mannich product.

The background technology of invention

[0002] if gasoline does not contain effective deposit-control additives, settling will form in internal combustion engines.Because most of base gasoline is defined as common specification, the performance of deposit-control additives is very important distinguish different gasoline types from performance standpoint.In recent years, considerable work was used for the additive that exploitation control (avoid or reduce) deposition generates, particularly in the fuel induction system of spark-ignition internal combustion engine.

[0003] effectively the sedimentary additive of controlling combustion engine has been the focus of a large amount of research activitiess in this area, yet further improvement is also expected.

Summary of the present invention

[0004] Mannich reaction products provided by the invention has de-sludging performance durable in hydrocarbon fuel, and the sedimentary control of improved spark or compression-ignition engine can effectively be provided.The clean cpd that is provided by Mannich condensation afterreaction product comprises: the polyamines that (i) has primary amine group, the (ii) hydroxy-aromatic compound that replaces of alkyl, (iii) aldehyde, wherein Mannich reaction is at whole (i): (ii): carry out under the mol ratio (iii) such as, the hydroxy-aromatic compound that polyamines (i) and alkyl replace (ii) reacts and obtains pure basically intermediate, and rear center body and aldehyde (iii) react and obtains Mannich reaction products as pure basically product.

[0005] important feature of the present invention be the control mannich condensation reaction to make reactor product be pure basically, particularly be easy to amplify at one and can be called in the process of " one kettle way (one pot) ".In spark ignition or compression internal combustion engine, Mannich reaction products provides to be not only and improves the sedimentary control of intake valve, also improves the deposition control in " colder " oil engine zone.For example, except intake valve, have been found that it stops up or direct injection device deposition, combustion chamber deposition and ingress port pollution etc. are effective in control (for example, avoid and/or reduce) port fuel-injectors.What Mannich reaction products of the present invention passed through and passed through does not still test about the industry deposition control performance of intake valve, also (promptly relevant for the industrial test of port fuel-injectors, ASTM D-6421, the PFI Equipment Test), compare simultaneously with the not mannich detergents by the PFI Equipment Test of contrast.

[0006] a kind of situation of the present invention, when 2.3 liters Ford Engine Block Test or, for example when the Intrepid Engine Block Test of Dodge, with other with other molar ratio (1: 1: 1,1: 2: 1, Deng) Mannich reaction products that obtains compares, Mannich reaction products provides identical at least or improved IVD performance.When obtaining the IVD performance that requires to improve, the PFI equipment performance that also is improved.

[0007] a kind of situation of the present invention, Mannich reaction products be pure basically and be not complicated polycomponent, uses when the different substantially molar ratio of this ratio carries out when Mannich reaction, and the mixture of multiple byproduct may obtain.

[0008] a kind of situation of the present invention, Mannich reaction products prepares in a reaction vessel, is meant the one kettle way reaction process sometimes.

[0009] in a kind of scheme, the polyamines with primary amine group that is used for Mannich reaction can be selected from the acyclic aliphatic polyamine that (A) has the aliphatic ring polyamines of primary amine group and (B) have primary amine group, or its combination.Preferably, here in the reaction process of Miao Shuing, primary amine is on adjacent carbon atom, or on the carbon atom that is separated by the methylene group, and the polyamines that provides is selected from and can forms 5 yuan or 6 yuan of heterocycles and have two nitrogen-atoms on ring.

[0010] in other a kind of scheme, Mannich reaction products obtains (i) 1 by the following substances reaction, 2-diamino hexahydroaniline, 1,3 diaminopropanes or 1, the 2-diaminoethanes is the cresols that replaces of polyisobutene and/or phenol and (iii) formaldehyde (ii), and wherein Mannich reaction is at (i): (ii): total mol ratio (iii) is approximately under 1: 2: 3 the situation carries out.

[0011] in other a kind of scheme, Mannich reaction products obtains (i) 1 by the following substances reaction, 2-diamino hexahydroaniline, 1,3 diaminopropanes or 1, the 2-diaminoethanes is the cresols that replaces of polyisobutene and/or phenol and (iii) formaldehyde (ii), and wherein Mannich reaction is at (i): (ii): total mol ratio (iii) is approximately under 1: 1: 2 the situation carries out.

[0012] Mannich reaction products can be disperseed to provide a kind of fuel additive concentrate that is used for the hydrocarbon automotive fuel in liquid carrier.In a kind of situation of this programme, exemplary fuel additive composition comprises (a) a kind of Mannich reaction products, it obtains the polyamines that (i) has primary amine group by the following substances reaction, it can form pure basically intermediate in mannich condensation reaction, described intermediate has 5 yuan or 6 member heterocyclic ring containing nitrogen segments, the (ii) hydroxy-aromatic compound that replaces of alkyl, (iii) formaldehyde, wherein (i) used in reaction: (ii): obtain pure basically intermediate thereby mol ratio (iii) guarantees that described polyamines (i) can (ii) react with the hydroxy-aromatic compound that alkyl replaces, and rear center body (iii) to react the Mannich reaction products that obtains with aldehyde be pure basically product; (b) liquid carrier.

[0013] another scheme comprises the fuel that is used for spark ignition and compressor, various therein Mannich reaction products and/or the present invention's multifunctional additive for lubricating oils described herein mix, with a kind of control (for example, avoid or reduce) in the sedimentary method of a lot of positions of oil engine internal combustion engine valve, this oil engine position comprises one or more intake valves, port fuel-injectors, the gasoline direct injection device, the combustion chamber, the port fuel contamination, Deng, at the fuel composition burning and/or the operating internal-combustion engines of oil engine the application of the invention.Other scheme and characteristics of the present invention can become clearer by the description of specification sheets and claim.

The details of preferred version is described

[0014] Mannich reaction products.The sanitising agent compound here is useful as the deposit-control additives in the automotive fuel and comprises that simultaneously (i) has the polyamines of primary amine group, the (ii) hydroxy-aromatic compound that replaces of alkyl, the (iii) Mannich reaction products that obtains of aldehyde reaction, wherein reaction is at total (i): (ii): (iii) mol ratio (reactant) thus under carry out making, such as, polyamines (i) can (ii) react with the hydroxy-aromatic compound that alkyl replaces and obtain pure basically intermediate, and rear center body (iii) to react the Mannich reaction products that obtains with aldehyde be a kind of pure basically product.Preferably, (i): (ii): total mol ratio (iii) is approximately 1: 2: 3.

[0015] Mannich reaction products of the present invention is pure basically.For example, can obtain a kind of Mannich reaction products, preferably at least about 85% purity at least about 80% purity.On the principle, Mannich reaction products of the present invention can be at least about 90 purity that arrive at least about 95%.

[0016] aliphatie diamine and formaldehyde be reflected at Krassig, Makromol.Chem, 17:119 (1956) has description, has generated the al. as T.Araki et, at Macromolecules, 5 yuan of rings and 6 yuan of rings of describing among the 21:1995 (1988).

[0017] polyamines amine groups: using the polyamine reactant in Mannich reaction is polyamines, and this polyamines has suitable active amine groups in order to support Mannich reaction in a part.The reactive amines group can be primary amine or the secondary amine group in the molecule, although preferred primary amine group.Polyamines should be able to form pure basically 5 yuan or 6 yuan of nitrogenous cyclic intermediates (this intermediate has at least two nitrogen-atoms 5 yuan or 6 yuan of heterocycle segments on ring) by the hydroxy-aromatic compound reaction with the alkyl replacement, and this intermediate can react with the aldehyde of selecting successively and obtain pure basically Mannich reaction products.As a result, the polyamines of selection preferably includes diamines and is used for reducing, under unescapable situation, and side reaction and byproduct.Further preferred, in selected diamines, amine groups is a primary amine group, is connected with adjacent carbon atom respectively, or links with independent carbon atom that the methylene radical that is inserted into separates.

[0018] according to principle; here limit with preferred; typical aliphatics fat polyamine reactant may comprise have primary amine group alkenyl polyamine its carry out the physical space protection and avoid or can hinder the ability that it participates in mannich condensation reaction at least; suppose that the reactant of selecting is used for the productive target intermediate basically, promptly pure basically intermediate (this intermediate has at least two nitrogen-atoms 5 yuan or 6 yuan of heterocycle segments on ring).Described polyamines can be selected from by U.S. patent application No.11/336, on January 20th, 037,2006 described polyamines, all contents are combined in here as a reference.Amine groups secondary carbon(atom) or tertiary carbon atom common and in the polyamine compounds combine, and can support Mannich reaction.The reactive amines group can be primary amine or the secondary amine group in the molecule.Preferably, amine groups is a secondary amine, and the further preferred polyamines of selecting lacks promoting of other or can form the substituting group of byproduct in Mannich reaction, reaches and formation has 5 yuan or 6 yuan of heterocycles and encircles the corresponding to purpose of target with the pulsating pure basically intermediate of at least two nitrogen-atoms.

[0019] the suitable polyamines that is useful on the Mannich reaction does not here need amine groups, as primary amine group, is used for the physical space protection and avoids or can hinder the ability that it participates in mannich condensation reaction at least.

[0020] Shi Yi polyamines comprises the aliphatics cyclic polyamine, and polyamines cycloalkanes particularly is as polyamines hexanaphthene and certain low alkyl diamine.Pure basically 5 yuan or 6 yuan of cyclic intermediates (5 yuan or 6 yuan of heterocycle segments having at least two nitrogen-atoms on ring) that the selection of polyamines is to obtain expecting, it can be obtained pure basically Mannich reaction products by reaction successively.

[0021] the polyamines hexanaphthene can comprise 1,2-diamines hexanaphthene (" DAC "), and as an example, 1, the 2-diamino-cyclohexane for example, can be a mixture of isomers, as genial trans isomer.Independent or pure isomeric forms also can be used as reactant.

[0022] the aliphatics fat polyamine with primary amine group comprises quadrol and 1, the 3-diaminopropanes.These polyamines divide other to be used as pure basically 5 yuan or the 6 yuan of cyclic intermediates that form expectation.

[0023] hydroxy-aromatic compound of alkyl replacement.Be used to form hydroxy-aromatic compound that the typical alkyl of mannich detergents product of the present invention replaces by following formulae express:

[0024] wherein each R is H, C _1-4Alkyl, or hydrocarbyl substituent with molecular-weight average (Mw) scope about 300 to about 2,000, preferred especially about 500 to about 1,500, when by gel permeation chromatography (GPC) when determining, as limit at least one R be H simultaneously a R be described definite hydrocarbyl substituent.

[0025] typical hydrocarbyl substituent comprises polyolefin polymer, as polypropylene, and polybutene, polyisobutene, and ethylene.Other similar long chain hydrocarbon groups substituting groups also can use.Example comprises the multipolymer of butylene and/or iso-butylene and/or propylene, with one or more can with the monoolefine comonomer of its copolymerization (for example, ethene, the 1-amylene, the 1-hexene, the 1-octene, 1-decene, etc.) wherein copolymerization molecule contains at least 50% butylene and/or iso-butylene and/or propylene units by weight.Can be aliphatics and also can comprise non-aliphatic group with the monomer of propylene or this butene polymerization, for example, vinylbenzene, neighbour-vinyl toluene ,-vinyl toluene, Vinylstyrene and similar material thereof.Therefore, in any situation, being used to form the polymkeric substance of the hydroxy-aromatic compound that alkyl replaces and multipolymer is the aliphatic hydrocarbon polymkeric substance on substantially.The polyolefin polymer hydrocarbyl substituent can have at least 20%, and particularly at least 50% and more especially at least 70% olefinic double bonds is at the terminal position of the carbochain vinylidene isomer as high reaction activity.

[0026] polybutene is particularly useful.If there are not other special explanations here, term " polybutene " is used for common implication and comprises the polymkeric substance that makes from " pure " or " pure basically " 1-butylene or iso-butylene, and from the two or all three kinds 1-butylene, the polymkeric substance that the mixture of 2-butylene and iso-butylene makes.The commercial grade of described polymkeric substance can also comprise other alkene of negligible quantity.

[0027] polyisobutene also is useful especially.What is called contains the high-activity polyisobutylene that relative high-content has the polymer molecule of terminal vinylidene group, for example, at least 20% comprises alkyl vinylidene isomer in the two keys of whole terminal olefins in the polyisobutene, preferably at least 50% and more preferably at least 70%, form by described method, for example, at U.S. patent No.4,152,499 and W.German Offenlegungsschrift2904314 in describe, be the polyolefine that preferably is used to form the aromatic hydroxyl reactant that alkyl replaces.Also being fit to make what be used for forming aromatic hydroxyl reactant that long-chain of the present invention replaces is that number-average molecular weight is 500 to 3000 ethylene,, wherein, the chain of the polymkeric substance at least about 30% comprises the ethylidene of terminal unsaturation.

[0028] in a kind of scheme, a R is H in the hydroxy-aromatic compound that alkyl replaces, and a R is C _1-4Alkyl and a R are hydrocarbyl substituents with molecular-weight average about 300 to about 2000.By the hydroxy-aromatic compound that only has the replacement in Mannich reaction site takes place, for example, have only an ortho position or a position do not have substituted (for example, R=H wherein), with combining of amine groups, but be all primary amine groups on the polyamines described herein, the oil engine deposition of oil engine different positions can effectively be avoided or reduce to resulting mannich detergents product.

[0029] in a specific scheme, alkylation by neighbour-cresols and high-molecular weight hydrocarbyl polymers can obtain the hydrocarbyl substituent hydroxy-aromatic compound, and for example the hydrocarbyl polymers group of molecular-weight average about 300 to about 2000 provides the cresols that alkyl replaces.In a more specific scheme, the cresols that the polyisobutylene alkylate of neighbour-cresols and molecular-weight average about 300 to about 2000 provides polyisobutene to replace.In a scheme the most specific, the cresols (PIB-cresols) that polyisobutene (PIB) alkylation of ortho-cresol and molecular-weight average about 500 to about 1500 provides polyisobutene to replace.

[0030] in the specific scheme of another one, the hydroxy-aromatic compound that alkyl replaces can obtain providing the alkyl fortified phenol by the alkylation of neighbour-phenol and high-molecular weight hydrocarbyl polymers, for example, the hydrocarbyl polymers group of molecular-weight average about 300 to about 2000.In a specific scheme, the cresols that the polybutene alkylation of neighbour-cresols and molecular-weight average about 500 to about 1500 provides polybutene to replace.

[0031] still, anyly in mannich condensation reaction, be easy to the hydroxy-aromatic compound that the alkyl that reacts replaces and use.Hydrocarbyl substituent can contain some residual unsaturatess, but usually, is saturated basically.

[0032] alkylated reaction of hydroxy-aromatic compound normally carries out in the presence of alkylation catalyst, for example Lewis acid catalyst (for example, BF ₃Or AlCl ₃), temperature range is about 30 to about 200 ℃.For the polyolefine that uses as hydrocarbyl substituent, its polymolecularity scope is preferably from about 1 to about 4, preferably from about 1 to about 2, is measured by GPC.The alkylating proper method of hydroxy-aromatic compound is known in this area among the present invention.GB1 for example, 159,368 and U.S. patent Nos.4,238,628; Instructed in 5,300,701 and 5,876,468.

[0033] aldehyde.The aldehyde that typically is used to prepare the Mannich base product comprises fatty aldehyde and aromatic aldehyde.Fatty aldehyde comprises C ₁To C ₆Aldehyde, formaldehyde for example, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, and hexanal.The available aromatic aldehyde comprises, for example, and phenyl aldehyde and salicylic aldehyde.Operable heterocyclic aldehydes described herein is furfural and thiophene aldehyde, etc.The reactant (formaldehyde-producing reagent) that generates formaldehyde is as Paraformaldehyde 96, or hydration formaldehyde solution also is useful as formalin.Most preferably formaldehyde and formalin.

[0034] Mannich reaction products is synthetic.In order to prepare Mannich product of the present invention, polyamines, the scope of the service temperature of the hydroxy-aromatic compound that alkyl replaces and the Mannich reaction of aldehyde is described with reference to U.S. application 11/336,037.Suitable temperature range can be from about 40 ℃ to about 200 ℃.Yet reaction also can be carried out at low temperatures, for example also advocates under 30 ℃.This reaction can be carried out (diluent free or solvent) or carry out in solvent or thinner in main body.Water can separate out and can remove by constant boiling point rectifying in reaction process.For example, during the water of separating out in removing reaction process, temperature can increase usually, for example 150 ℃.The conventional reaction times is from about 3 to about 4 hours, although owing to need or want seeking time changeable, also can apply for 11/336,037 according to the U.S. of while pending trial.

[0035] exemplary process can (ii) join under the situation that forms mixture in the reaction vessel with suitable aromatic solvent at the hydroxy-aromatic compound that alkyl is replaced and begin reaction.(The suitable solvent also comprises non-aromatic base solvent, and heptane for example in this case, can some difference according to those skilled in the art's the temperature of understanding), mixture was mixed, for example by stirring, under inert environments, for example at the N with suitable SCFH ₂Under the atmosphere.Nominally suitable SCFH scope is 0.1 to 0.2SCFH.Preferably mixture be in homogeneous phase and the appropriateness temperature under add polyamines (I), for example about 40 ℃ to about 45 ℃.The hydroxy-aromatic compound that preferred alkyl replaces (ii) is about 2: 1 with the molar ratio of polyamines (i).The intermediate that obtains is pure basically, can use without necessary trouble or expensive process or separation.The aldehyde of selecting, for example formaldehyde is added.The present invention is preferred, and the aldehyde of interpolation amount (iii) makes (i): (ii): mol ratio (iii) is approximately 1: 2: 3.Temperature raises, and for example arrives about 45 to about 50 ℃.Temperature is increased to and is lower than 100 ℃, and for example about 80 ℃, and container keeps about 30 to assign to 60 fens under described temperature with its contents.Use Dean-Si Tuoke water trap (Dean Stark trap) or the equipment that is equal to carry out rectifying then, temperature is set to the temperature of rising, scope is 130 to about 150 ℃, for example about 145 ℃, rectifying begins to advocate when making the temperature of reaction mixture arrive about 95 to 105 ℃ over time.When rectifying begins, inert atmosphere air-flow (N for example ₂Atmosphere) rise to about 0.1SCFH to about 1.0SCFH, for example 0.5SCFH is as example.Temperature keeps the competent time on the temperature of selected rising, can be additional about 2 hours to about 2.5 hours.After the rectifying, in reactor product, can add the multifunctional additive for lubricating oils (being called additive-package sometimes) that required added solvent obtains comprising Mannich reaction products.For example, thus multifunctional additive for lubricating oils can make enriched material by the solvent of add selecting comprises about 25% solvent.Described enriched material can carry out quality control testing and suitable engine testing easily.

[0036] an important characteristic of the present invention relative molar ratio that is primitive reaction thing in the Mannich reaction.Usually, polyamines (i): the hydroxy-aromatic compound that alkyl replaces (ii): aldehyde total molar ratio (iii) for example makes, polyamines (i) can (ii) react with the hydroxy-aromatic compound that alkyl replaces and obtain pure basically intermediate, and rear center body can (iii) react with aldehyde and obtains Mannich reaction products as pure basically product.Preference is as (i): (ii): total mol ratio (iii) is approximately 1: 2: 3.Mol ratio of the present invention is approximately 1: 2: 3 and means+and/-5%, for example, divide other, ratio is 1 (+/-5%) (+/-5%) rub than 3 (+/-5%) that rubs than 2 that rubs.1: 2: 3 molar ratio is that preferably wherein to use approximate equimolar three kinds of Mannich reaction reactants be not preferred.If per 1 mole of oxy-compound reacts with being less than 1 polyamines that rubs and/or being less than 1 aldehyde that rubs, some reactants are hydroxy-aromatic compound for example, can keep the active meeting of unreacted state and Mannich product to reduce, basically purity can reduce, and can show low IVD performance and the lower performance in the PFI testing of equipment.So far, considered to be higher than 1: 1: 1 ratio, for example, per 1 hydroxy-aromatic compound that rubs uses and to be higher than 1 polyamines that rubs and/or to be higher than 1 aldehyde that rubs, and the byproduct of not expecting may form or a large amount of unreacted polyamines or aldehyde can be present in maybe must remove from reaction mixture in the final product and causes raw-material waste.The total molar reactive thing ratio that uses current regulation to be approximately 1: 2: 3 uses simultaneously to be selected from based on the polyamines of explaining standard here and can obtain pure basically the have superior active ability and the Mannich reaction products of physicals.

Therefore [0037] when reacting, current molar ratio is relatively easily kept and is controlled, and can help to avoid the wrong-way in the industrial production.When operation reaction in a big factory reactor, have the possibility that is easy to return volatile reactants (polyamines and formaldehyde) loss, owing to enter reactor head by evaporation, carry secretly from reaction mixture in purifying gas flow such as the water and remove, wait usually and may take place.Thereby compensate any described loss make liquid reaction mixture contain reactant according to molar ratio of the present invention be feasible with attractive because can access pure basically Mannich reaction products.Because relative molar ratio can be controlled, and reactor product is not complicated mixture when reaction is carried out with molar ratio of the present invention, but pure basically reactor product, so when the postreaction process of the costliness of having avoided not setting, reaction can move on a large scale when having reduced the reactant loss.Therefore it is reasonable and practical should synthesizing.

[0038] additive condenses and fuel composition.Mannich product of the present invention preferably with liquid carrier, inductor or liquid agent are used in combination.Described carrier can be different type, and for example liquid gathering-α-ethylene oligomerization body, liquid polyolefine (for example, polypropylene, polybutene, polyisobutene, or it is similar), liquid hydrogen treatment polyolefine (for example, hydrogen treatment polypropylene, the hydrogen treatment polybutene, the hydrogen treatment polyisobutene, or it is similar), mineral oil, liquid poly-(oxyalkylene) compound, liquid alcohol or polyol, liquid ester and similar liquid carrier or solvent.The mixture of two or more these carriers or solvent can be used.

[0039] carrier.Mannich product of the present invention preferably with liquid carrier, inductor or liquid agent are used in combination.Described carrier can be different type, and for example liquid gathering-α-ethylene oligomerization body, liquid polyolefine (for example, polypropylene, polybutene, polyisobutene, or it is similar), liquid hydrogen treatment polyolefine (for example, hydrogen treatment polypropylene, the hydrogen treatment polybutene, the hydrogen treatment polyisobutene, or it is similar), mineral oil, liquid poly-(oxyalkylene) compound, liquid alcohol or polyol, liquid ester and similar liquid carrier or solvent.The mixture of two or more these carriers or solvent can be used.

[0040] the specific liquid carrier that is used for mannich detergents described herein comprises 1) mixture of mineral oil or mineral oil, particularly viscosity index is lower than about 120,2) a kind of or mixture, particularly molecular-weight average of poly-alpha-olefin oligomer about 500 to 1500,3) polyester, poly-(oxyalkylene) compound that particularly has the scope about 500 to about 1500 of molecular-weight average, 4) one or more liquid poly-alkylenes, or 5) 1), 2), 3), and/or 4) arbitrary mixture.Although without limits, these carriers have the performance of certain desired.

[0041] mineral oil vehicle used herein comprises the content of wax, contains naphthalene and contains the oil of pitch, can obtain from different petroleum crude oils and handles by suitable mode.For example, mineral oil can be solvent extraction or hydrotreated oils.Regeneration mineral oil also can use.Hydrotreated oils is most preferred.Preferred 40 ℃ of following viscosity of mineral oil of using are for being lower than about 1600SUS, and more preferably descending at 40 ℃ is about 300 and 1500SUS.Content of wax mineral oil most preferably 40 ℃ of about 475SUS of following range of viscosities arrives about 700SUS.For obtain that best result needs most to be that the viscosity index of mineral oil is lower than about 100, more preferably less than about 70 and most preferred range be from about 30 to about 60.

[0042] operable poly-alpha-olefin (PAO) carrier comprises the hydrotreatment and the poly-alpha olefins oligopolymer of hydrotreatment not, for example, hydrogenation or hydrogenated products not, the elementary tripolymer of 'alpha '-olefin monomers, the tetramer and pentamer, monomer whose contains 6 to 12, is generally 8 to 12 and 10 carbon atoms most preferably from about.It synthesizes the Processing at Hydrocarbon, February nineteen eighty-two, the 75th page and U.S. patent Nos.3,763,244; 3,780,128; 4,172,855; 4,218,330; With 4,950, open in 822.Usual method consists essentially of the catalytic oligomerization of short linear alpha-olefin (suiting to obtain) from the catalytic treatment of ethene.Usually viscosity (measuring down for the 100 ℃) scope that has as the poly-alpha-olefin of carrier is 2 to 20 centistoke (unit of kinematic viscosity) departments (cSt).Preferably, the viscosity that has of poly-alpha-olefin at least 8cSt and most preferably from about 10cSt under 100 ℃.Especially the poly-alpha-olefin that needs (PAO) comprises polybutene with molecular-weight average about 500 to about 1500 and more preferably polyisobutene and/or have the polyisobutene of the hydrotreatment of molecular-weight average about 500 to about 1500.

[0043] polyethers that can be used as carrier is molecular-weight average poly-(oxyalkylene) compound between about 500 to about 1500, especially can comprise poly-(oxyalkylene) compound that is dissolvable in water fuel, and it can be by following formulae express:

[0044]R ₁-(R ₂-O) _n-R ₃

[0045] R wherein ₁Hydrogen normally, alkoxyl group, cycloalkyloxy, hydroxyl, amino, alkyl (for example, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, etc.), ammonia substituted hydrocarbon radical, or hydroxyl substituted hydrocarbon radical group, R ₂Be alkylene with 2-10 carbon atom (preferred 2-4 carbon atom), R ₃Hydrogen normally, alkoxyl group, cycloalkyloxy, hydroxyl, amino, alkyl are (for example, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, etc.), the ammonia substituted hydrocarbon radical, or hydroxyl substituted hydrocarbon radical group, wherein n is that 1 to 500 integer preferable range is numbers (normally mean number) of the inferior-oxyl of repetition for from 3 to 120 expressions.Has a plurality of-R ₂In the compound of-O-group, R ₂Can be that identical or different alkylene is rolled into a ball and ought can be arranged arbitrarily or entirely not simultaneously.Preferred poly-(oxyalkylene) compound is the one matter that contains repeating unit, and this repeating unit is by pure and mild one or more epoxy alkane, and preferred a kind of epoxy alkane reaction obtains.

[0046] as the average molecular weight range of poly-(oxyalkylene) compound of carrier fluid preferably from about 500 to about 3000, more preferably from about 750 to about 2500 and most preferably from about 1000 to about 2000.

[0047] the subunit group of useful poly-(oxyalkylene) compound is made up of a kind of poly-(oxyalkylene) one matter (monool) with alkyl terminal, as at U.S. patent No.4,877, the 6th hurdle in 416, the 20th row is pointed in the 7th hurdle the 14th row and the document quoted in this paragraph, and the full content of described paragraph and described document draws at this and is reference.

[0048] the subunit group of preferred poly-(oxyalkylene) compound comprises poly-(oxyalkylene) one matter (monool) of a kind of alkyl or its mixture, and it is that 40 ℃ of following viscosity are at least about 70 centistoke (unit of kinematic viscosity) departments (cSt) and the 100 ℃ of following viscosity liquid that dissolves in gasoline at least about 13cSt in pure state.In these compounds, by a kind of have at least about 8 carbon atoms and more preferably from about 10 one matters (monools) that form to the propoxylation of the alkanol of about 18 carbon atoms or its mixture be particularly preferred.

[0049] poly-(oxyalkylene) carrier that is used for the present invention practice preferably the viscosity under its pure state under 40 ℃ at least about 60cSt (more preferably under 40 ℃ at least about 70cSt) and under 100 ℃ at least about 11cSt (more preferably under 100 ℃ at least about 13cSt).In addition, poly-(oxyalkylene) compound that is used for the present invention practice preferably the viscosity under its pure state be not higher than about 400cSt under 40 ℃ and under 100 ℃, be not higher than about 50cSt.More preferably, its viscosity is being no more than about 300cSt and is being no more than about 40cSt under 100 ℃ under 40 ℃.The viscosity that most preferred poly-(oxyalkylene) compound has is being no more than about 200cSt and is being no more than about 30cSt under 100 ℃ under 40 ℃.

[0050] preferred poly-(oxyalkylene) compound is the derivative of poly-(oxyalkylene) glycol compound and monoether, it satisfies above-mentioned viscosity requirement and contains by alcohol or polyalcohols and epoxy alkane, for example, propylene oxide and/or contain or do not contain the butylene oxide ring of oxyethane, the repeating unit that reaction forms, the product that the oxyalkylene group of at least 80 moles of % derives from 1,2 epoxy prapane in the molecule particularly.About preparing for example Kirk-Othmer of these details references that gather (oxyalkylene) compounds, Encyclopedia ofChemical Technology, the 3rd edition, 18 volumes, 633-645 page or leaf (copyright 1982byjohn wiley﹠amp; Sons) and incorporated by reference here, remove the Kirk-Othmer encyclopedia and the document wherein quoted is previous is used for reference here.U.S. patent Nos.2,425,755; 2,425,845; 2,448,664; With 2,457,139 have also described these processes, also that full content is incorporated by reference here.

[0051] poly-(oxyalkylene) one matter (monools) of a kind of alkyl or its mixture are contained in the subunit group of particular preferred poly-(oxyalkylene) compound, and it is at the liquid that dissolves in gasoline that is at least about 70 centistoke (unit of kinematic viscosity) departments (cSt) under 40 ℃ and is at least about 13cSt under 100 ℃ in viscosity under the pure state.Typically under these temperature the maximum value of viscosity for not to be higher than about 400cSt under 40 ℃ and under 100 ℃, not to be higher than about 50cSt.More preferably, their viscosity is being no more than about 300cSt and is being no more than about 40cSt under 100 ℃ under 40 ℃.The viscosity that most preferably poly-(oxyalkylene) compound has is being no more than about 200cSt and is being no more than about 30cSt under 100 ℃ under 40 ℃.In these compounds, particularly preferably be by a kind of and have at least about 8 carbon atoms and more preferably have about 10 one matters (monools) that form to the propoxylation of the alkanol of about 18 carbon atoms or its mixture.

[0052] the oxyalkylene units part (for example, methyl dimethoxy base ethylidene unit and/or ethyl dimethyl ethylidene unit) that contains capacity according to poly-(oxyalkylene) compound of the present invention comes feasible poly-(oxyalkylene) compound to have the gasoline solubility.

[0053] another kind of carrier fluid is a for example polypropylene of liquid poly-alkylene, polybutene, polyisobutene, polypenthylene, the multipolymer of propylene and butylene, the multipolymer of butylene and iso-butylene, the multipolymer of the multipolymer of propylene and iso-butylene and propylene, butylene and iso-butylene, or its mixture.Other useful poly-alkylene comprise the polypropylene of hydrotreatment, the polybutene of hydrotreatment, the polyisobutene of hydrotreatment, or its similar substance.Preferred poly-alkylene carrier fluid comprises that molecular weight distribution is lower than 1.4 polybutene such as U.S. patent No.6, described in 048,373.The common use of the material of this common type and other carrier fluid is at for example U.S. patent No.5, describes to some extent in 089,028 and 5,114,435, and its disclosed content is incorporated by reference here.

[0054] in some cases, Mannich base sanitising agent/dispersion agent can synthesize in carrier fluid.In other situation, synthetic sanitising agent/dispersion agent mixes with an amount of carrier fluid in advance.If desired, sanitising agent/dispersion agent can form in The suitable solvent or carrier fluid then and mix with the identical or different carrier fluid of additional content.

[0055] use ratio with respect to the liquid carrier of Mannich base for when fuel composition consumes in engine in preferred additives bag of the present invention and fuel composition, the intake valve spatter property when intake valve spatter property and use do not contain the same combination of liquid carrier is compared and is increased.Therefore; under normal conditions; in the Mannich base forming process or after forming; but carrier fluid that before carrier fluid adds, is adopted and weight ratio based on the Mannich base sanitising agent/dispersion agent of activeconstituents; for example do not comprise solvent, if solvent is arranged; usually arrived in about 2.0: 1 scope at about 0.3: 1, and preferable range is about 0.5: 1 to about 1.5: 1.

[0056] common multifunctional additive for lubricating oils of the present invention comprises from about 12 to about 69wt%, preferably from about 22 to about 50wt% the Mannich base sanitising agent/dispersion agent based on activeconstituents.Multifunctional additive for lubricating oils also can comprise carrier fluid, and its content is decided by required carrier and Mannich base sanitising agent/dispersant ratio.

[0057] when forming fuel composition of the present invention, Mannich product and carrier fluid (having or do not have other additive) adopt enough consumptions to reduce or avoid sedimentary formation in the oil engine.Therefore, this fuel contains the intake valve deposition of deposition and the most particularly spark-ignition internal combustion engine of a spot of Mannich base sanitising agent/dispersion agent that can control and reduce the oil engine formation of deposits and according to the above ratio liquid carrier fluid, particularly inlet system.Usually fuel of the present invention comprises aforesaid based on activeconstituents, and the amount of Mannich base sanitising agent/dispersion agent is to be about 10 to about 200ptb from about 5 to about 300ptb (the weight pounds of per thousand barrels of volume of fuel additives) and preferable range.In a kind of use liquid carrier fluidic preferred fuel composition, every weight part mannich detergents/dispersion agent (based on activeconstituents), the total amount that exists of carrier fluid is preferably from about 0.3 to about 2.0 weight parts, more preferably every weight part mannich detergents/dispersion agent, the amount of carrier fluid are to about 1.0 weight parts from about 0.4.

[0058] other additive.Other selectable additives, for example, one or more dissolve in the oxidation inhibitor of fuel, demulsifying compound, antirust or sanitas, metal passivator, combustion improver, pure cosolvent, the octane improving agent, purification agent for treating waste gas, friction modifiers, slip additive, auxiliary sanitising agent/dispersant additives, biocide, anti static additive, flow improver, the gasoline de-misting agent, the crashworthiness agent, anti-icer, the damaged agent of anti-valve (door) seat, combustion improving agent, sign (markers), staining agent and multifunction additive (for example, methyl ring five or two eneyne manganese, three carbonyls and/or other ring-type five or two eneyne manganese tri carbonyl compounds) also can be included in fuel of the present invention and the additive condenses.No matter select which kind of component for use in the composition of the present invention, the amount of every kind of composition should satisfy it at least can demonstrate its function corresponding at the final fuel composition.

[0059] in preferred embodiment, multifunctional additive for lubricating oils contains at least a boiling point in addition and is lower than about 200 ℃ unreactive hydrocarbons solvent.

[0060] basic fuel.The basic fuel that is used to form fuel of the present invention be arbitrarily with all basic fuels that spark-ignition internal combustion engine is manipulated that is suitable for, for example unleaded engine and aviation spirit, with so-called reformed gasoline, its hydrocarbon that contains the gasoline boiling range usually simultaneously is for example pure with the mixed composition that dissolves in fuel oxidation, ether and other suitable oxygen-containing organic compound.Preferred mixture comprises the alkanol methyl alcohol for example that dissolves in fuel, ethanol and their higher material of the same clan, and the ether that dissolves in fuel methyl tributyl ether for example, ethyl tributyl ether, methyl three amyl ethers and consanguinity compound, and the mixture of these materials.Oxide compound, when using, the amount in basic fuel is lower than about 25 volume % usually, and preferred amount makes that the content range of the oxygen that provides is about 0.5 to about 5 volume % in total fuel.But when necessary, suitably or under the situation about needing, the scope that breaks away from this component when practical application of the present invention also allows.

[0061] being used to form the additive of preferred fuel of the present invention can be individually or be mixed into basic fuel with other the subgroup form of closing.But, preferably use additive condenses of the present invention to mix all components simultaneously, because the compatible advantage that component mutually combines and provided under the multifunctional additive for lubricating oils form has been provided like this.Use enriched material also to shorten mixing time and the wrong possibility of reduction mixing.

[0062] control of formation of deposits in the oil engine.Fuel dope of the present invention can effectively be controlled the deposition in (for example stop and/or remove) spark ignition and compression (for example diesel oil) oil engine.Control typically refers to the formation of low deposition but present extraly fuel dope can stop and remove deposition.Although the research of this area has trended towards mainly paying close attention to intake valve deposition, and pay close attention to the combustion chamber deposition to a certain extent, yet that fuel dope of the present invention has been found to be is more general.They not only can be used to stop/remove intake valve deposition, and also being found it is effectively on control so-called " colder " oil engine area deposition, for example port fuel-injectors especially.Another application is to stop the gasoline direct injection device to stop up.

[0063] owing to can limit air-flow and change the interior flow pattern of cylinder, the deposition that forms on intake valve and the port can reduce power of IC engine.The processing property of cold start-up and preheating also may be subjected to the influence of reverse side, and waste discharge may increase.Other valve deposition problems of intake valve comprise that valve adheres to and the valve sintering.Fuel dope of the present invention is effective when the deposition of these types of control.

[0064] combustion chamber is another internal combustion engine component of paying close attention to formation of deposits.Owing to can increase temperature of combustion and compression ratio, the deposition of combustion chamber may increase the demand (ONR) of octane value.If because the sedimentary formation in combustion chamber causes the ONR of oil engine to increase too much, recommended gasoline AKI may not avoid knocking or follow the power loss of pinking compression in having the equipment of detonation sensor.It is the extra oil engine deposition problems that occurs in some oil engines that combustion chamber deposit disturbs (CCDI) and combustion chamber deposit to peel off (CCDF).CCDI shows it as cold oil engine collision noise, comes from some designs, and top land contacts with the sedimentary physics of the oil engine at cylinder top.CCDF produces when combustion chamber deposit is peeled off and be present between valve face and the valve seat, because the valve seal difference causes compression pressure to reduce.Fuel dope of the present invention is effective when the deposition of these types of control.

[0065] fuel injector and vaporizer also are to pay close attention to the parts that formation of deposits takes place.Be positioned at the deposition of the medium and small fuel channel of injector, for example injector pivot deposition may be slowed down the mobile and transformation injection types of fuel, and it can influence power conversely, fuel economy, and cornering ability.Deposition may cause similar problem in carburettor, because the carburetion machine also uses little ditch and hole to come metering fuel.Fuel dope of the present invention is effective when the deposition of these types of control.

[0066] just as described, fuel dope of the present invention is effective when the deposition in controlled chilling oil engine zone.For example, on behalf of another deposition, end points fuel injector (PFI) deposition may influence the oil engine zone of engine performance conversely.PFI deposition can, for example, in the thermoosmosis process that oil engine has been turned off, form.The gasoline residue of staying the injector top exposes at high temperature time to be longer than gasoline and to flow through conventional time of injector, and it causes the degraded of gasoline to cause sedimentary formation.These depositions can fuel limitation flow and hinder or the mode of jam-pack petrol injector top metering orifice is destroyed spray pattern by part.Fuel dope of the present invention is effectively avoiding formation of deposits or forming aspect a small amount of deposition, for example can reduce sedimentary amount in some cases.Therefore fuel dope of the present invention is effective when control may appear at the sedimentation type of cooling internal combustion engines parts.

[0067] following example is to be used to further specify, and does not limit the scheme consistent with the present invention.Here the percentage ratio that describe and use, ratio, part and amount are not having all to be meant quality under the situation of specified otherwise.

Embodiment

[0068] purpose of the following embodiment of existence is for illustrating and being not limited only to this.

[0069] carries out model reaction with helping the reactor product that obtains according to the present invention is analyzed.2, and the 4-xylenol (2,4-DMPh) hydroxy-aromatic compound that replaces as alkyl is useful, because the analysis of reactor product is easier, with analytical technology, and for example NMR and mass spectrum, easier operation is confirmed can getable impurity according to the present invention.Model reaction such as embodiment 1,2 and 3 are described.

[0070] Embodiment 1:

[0071] a kind of model Mannich reaction products is by vinyl diamines (" EDA "), and is a kind of 2, the 4-xylenol (2,4-DMPh) and formaldehyde (" FA ") reaction make.Be used in the EDA of Mannich reaction: 2, the molar ratio of 4-DMPh: FA is about 1.0: 2.0: 3.0.EDA, 2, the reaction of 4-DMPh and FA is carried out in a round-bottomed bottle (" RBF ") in ensuing mode, this round-bottomed bottle equipment mechanical stirring, nitrogen feed mouth, Dean-Si Tuoke water trap (Dean Stark trap), and heating jacket.Solvent (for example toluene) and 2,4-DMPh introduces RBF, and mixture stirs (nitrogen protection, about 0.1SCFH) at low temperatures in inert atmosphere.When being heated to about 80 ℃, mixing material is stirred and mixes this component, simultaneously at nitrogen (N ₂) protection under.EDA joins RBF.Gentle thermopositive reaction when rising to about 55 ℃, temperature takes place.FA slowly adding and RBF and wherein component be heated and know that temperature reaches about 80 ℃.Temperature kept about 1 hour.Temperature rises to 145 ℃ and is used to use Dean-Si Tuoke water trap (Dean Stark trap) to distill.Distillation began to carry out about 30 minutes, when near approximately 95-105 ℃ of temperature.When the distillation beginning, nitrogen gas stream is adjusted to 0.5SCFH.Temperature remain on 145 ℃ extra approximately 2 to 2.5 hours.Vacuum separation can be carried out.

[0072] instrumental analysis (for example NMR and mass spectrum) shows that this product has and is higher than 80% purity, can obtain the purity at least about 85%.

[0073] stays the product gross weight in the reaction flask according to distillation back (and vacuum separation, if operation), calculate and the solvent that adds a kind of additional quantity of needs is made the finished product mixture and contained 25% solvent.

[0074] embodiment 2

[0075] the model Mannich reaction products that obtains with embodiment 1 similar methods, difference is 1,3-two amido propane use as polyamines.Instrumental analysis (for example NMR and mass spectrum) shows that this product has about 95% purity.

[0076] embodiment 3

[0077] the model Mannich reaction products that obtains with embodiment 1 similar methods, difference is 1,2-diamines basic ring hexylamine uses as polyamines.

[0078] the model Mannich reaction products of embodiment 1-3 is pure basically in for example polyamines: 2, and the molar ratio of 4-DMPh: FA is 1: 1: 1 or the product that obtained in 1: 1: 2 o'clock.

[0079] based on the data of model, Mannich reaction products of the present invention can be the purity at least about 80%, usually above at least about 85% purity, for example, although be theoretic, the available purity of Mannich reaction products of the present invention from least about 90 at least about 95%.

[0080] embodiment 4

[0081] a kind of Mannich reaction products that obtains is described by following reaction formula:

[0082] similar to the mode of embodiment 1 and as the routine described of [0032]-[0033] synthetic, wherein the molar ratio of quadrol and PIB-cresols and formaldehyde is to be similar to 1: 2: 3 when reaction is carried out.PIB-cresols is by being approximately 900 polyisobutene and neighbour-cresols alkylation and forming with containing molecular-weight average.The purity that the Mannich reaction products that obtains has is higher than 80%.

[0083] embodiment 5

[0084] a kind of Mannich reaction products that obtains is described by following reaction formula:

[0085] similar to the mode of embodiment 1 and as the routine described of [0032]-[0033] synthetic when reaction is carried out wherein 1, the molar ratio of 2-diamines hexanaphthene and PIB-cresols and formaldehyde is to be similar to 1: 2: 3.PIB-cresols is by being approximately 900 polyisobutene and neighbour-cresols alkylation and forming with containing molecular-weight average.The purity that the Mannich reaction products that obtains has is higher than 80%.

[0086] embodiment 6

[0087] a kind of Mannich reaction products that obtains is described by following reaction formula:

[0088] similar to the mode of embodiment 1 and as the routine described of [0032]-[0033] synthetic when reaction is carried out wherein 1, the molar ratio of 3-diamines propane and PIB-cresols and formaldehyde is to be similar to 1: 2: 3.PIB-cresols is by being approximately 900 polyisobutene and neighbour-cresols alkylation and forming with containing molecular-weight average.The purity that the Mannich reaction products that obtains has is higher than 80%.

[0089] embodiment 7

[0090] the model Mannich reaction products that obtains with embodiment 4 similar methods, difference is that alkyl hydroxyl substituted aromatic compound is a PIB-phenol.This PIB-phenol is essentially para-orientation, and for example, phenol is replaced by the PIB segment of reactive behavior in contraposition.The purity that the Mannich reaction products that obtains has is at least about 80%.

[0091] embodiment 8

[0092] the model Mannich reaction products that obtains with embodiment 5 similar methods, difference is that alkyl hydroxyl substituted aromatic compound is PIB-phenol (identical with the PIB-phenol of embodiment 7).The purity that the Mannich reaction products that obtains has is at least about 80%.

[0093] embodiment 9

[0094] the model Mannich reaction products that obtains with embodiment 6 similar methods, difference is that alkyl hydroxyl substituted aromatic compound is a PIB-phenol, wherein the PIB segment in contraposition and in than embodiment 7 the pulsating activity of PIB of PIB-phenol low.The purity that the Mannich reaction products that obtains has is at least about 80%.

[0095] embodiment 10

[0096] from embodiment 4,5,6,7,8 and 9 distillation reaction product is used to make exemplary multifunctional additive for lubricating oils.After the distillation, according to the product gross weight of staying in the reaction flask, the added solvent that adds a kind of needs is made the mixture that contains 25% solvent with the finished product mixture, calculates and adjusts according to the reactor product of embodiment 4-9.Additional if desired suitable component can be included in the multifunctional additive for lubricating oils.

[0097] embodiment 11

[0098] similar to the mode of embodiment 1, with polyamines: the hydroxy-aromatic compound that alkyl replaces: the molar ratio of aldehyde is 1: 1: 1,1: 1: 2, came preparing product in 1.17: 1: 1.29 and 10: 1: 1.2, and wherein EDA is a polyamines.Use the mode identical with embodiment 1, contrast product is passed through polyamines: the hydroxy-aromatic compound of alkyl replacement: the molar ratio of aldehyde is that about 1: 1: 1 and about 1: 1: 2 ratio are prepared from, wherein 1, and 3-diamines propane is polyamines.Similar to the mode of embodiment 1, pass through polyamines: the hydroxy-aromatic compound that alkyl replaces: the molar ratio of aldehyde is to compare in about 1: 1: 1, and mode is identical with embodiment 1, wherein 1, and 2-diamines hexanaphthene is a polyamines.No matter yes or no can be used different solvents, different solvents can not influence final synthetic mixture (reactor product), and therefore, it is suitable doing contrast with Mannich reaction products according to the present invention.

[0099] contrast product is to contain the complex mixture that is present in the Mannich reaction products in the mixture.This complex mixture can not purify easily and obtain pure basically Mannich reaction products.Therefore this Mannich reaction products (compound) is a kind of composition of complex mixture.Therefore this Mannich reaction products (compound in the mixture) is very impure, and its purity is quite low in theory, and it is reasonable expectation that its purity (mixture, reactor product) for example is lower than about 50%.

[00100] contrasts with it, in a kind of situation of the present invention, a kind of Mannich reaction products is not have byproduct and unreacted starting material basically, can be defined as basically pure, it can be expected reliable consistent composition of additive-package (enriched material) of actual Mannich reaction products (compound) concentration as containing.Mean that also a kind of fuel can more reliable formation contains the Mannich reaction products (compound) of the amount of expectation.Can show that also this Mannich reaction products can prepare on a large scale easily in " one kettle way ", compare with the method for the manufacturing mannich condensation reaction product of routine, this method has the potential loss of low material in building-up process and low potential reaction substrate concentration changes (fluctuating).

[00101] performance test.It is as follows that Mannich reaction products of the present invention and correlated Mannich reaction products all can carry out different performance tests:

[00102] I:Intrepid IVD vehicle testing: intake valve deposition (IVD).It is similar to the BMW IVD test (ASTM D 5500) of standard that this oil engine cleaning is estimated the IVD test, and difference is that the DodgeIntrepid engine has replaced the BMW engine, uses chassis DYNO dynamometer machine to replace the distance of mileage.

[00103] II:ASTM D-6421, PFI rig test: the test of end points fuel stage, wherein " pass " rate is lower than 10% leak stopping rate;

[00104] III:ASTM D-5598, Chrysler turbocharger PFI test: end points fuel injector (PFI) engine testing.

[00105] IV:CRC Ford 2.3L IVD test.

[00106] V:Mercedes M102E 2.3L IVD tests and explains European IVD test procedure.

[00107] end points fuel injector (" PFI ") is to such an extent as to test can be corrected recursive.

[00108] these tests provide the direct measuring method that has deposit deposits yields level at special mannich detergents.

[00109] described for the processing ratio and the result of the typical IVD test (2.3L Ford test) of two kinds of typical Mannich reaction products of the present invention by following table 1.Table 3 is the baseline fuel (Citgo RUL fuel) that does not contain Mannich reaction products of the present invention.The test operation time is 100 hours.

[00110] table 1

FORD?2.3LIVD@RICHMOND

100 hours. the result

The CRC test procedure

Test Deposition, mg

Sequence number Additive PTB IVD CCD

1 does not have 537.9 1,487.7

2 embodiment 5 60.0 34.3 1,543.8

3 embodiment 6 56.4 39.2 1,356.4

[00111] product of embodiment 5 is a kind of additive (30.4% solids content) in test 2.The additive binding substances that uses is 1 part of sanitising agent (Mannich) and 0.8 part of carrier (making the polypropylene oxide polymkeric substance by propylene oxide being added alkylphenol in this case) normally.

[00112] product of embodiment 6 is multifunctional additive for lubricating oils (30.4% solids content) in test 3.Operate in the same way with the additive in test 2.

[00113] the new fuel injector of testing of bringing into use.

[00114] You consumption can be examined and guarantee that this internal combustion engine operation is normal, in addition, is not that this test needs.

[00115] CCD (mgs) refers to the combustion chamber deposition and is the total amount of CHD (cylinder top deposition) and PTD (top land deposition).

[00116] term PTB is meant the poundage of the additive of per 1000 barrels of fuel.

[00117] be used for being described in a test rate and the result's table 2 below of correction PFIrig test of two kinds of typical Mannich reaction products in the fuel (carry out twice, test 5 and 7). (ASTM D-6421 PFI test is revised by substituting different injectors).

[00118] table 2

PFI Rig Test (correction)

Test The % loss of flow

Test # Additive Ratio (PTB) @44 circulate (on average)

4 embodiment 5 80 7.7

5 do not have 19.7

6 embodiment 6 80 8.1

7 do not have 12.8

[00119] identical fuel is used in test 4-7.

[00120] low loss of flow means good performance and low thus formation of deposits.

[00121] test 4 and 6 additive are in same concentration and identical carrier.Additive use among the embodiment 5 as the carrier fluid in the test 2 form.The ratio that additive forms is that the ratio of Mannich reaction products and carrier is 1 to 0.8.Same vehicle fluid in the additive use test 3 among the embodiment 6 forms.

[00122] typical Mannich reaction products of the present invention is compared with commercial Mannich product in IVD and PFI rig test with basic fuel and is had the superior spatter property of becoming reconciled.When the Mannich product that uses the present invention to obtain, show low relatively formation of deposits amount.

[00123] effect of the Mannich reaction products of the present invention's statement also can be by " Mercedes " test, the evaluation test of M102E (CEC-05-A-93) oil engine cleaning.Untreated basic fuel uses identical standard engine testing (test 10) to test separately.Contain the following table 3 that the results are shown in by a test rate of the additive of the typical Mannich reaction products of the present invention and M102E (CEC-05-A-93) test.

[00124] table 3

M102E?2.3L?IVDT

60 hours results

Europe IVD test procedure

Deposition, mg.

Test Additive IVD CCD

8 embodiment 5 20.6 864.9

9 embodiment 6 27.1 662.4

10 do not have 160.6 315.8

[00125] additive in the test 8 and 9 is identical concentration.The solids content that the additive of test in 8 has be 76.9 and use test 2 in carrier fluid form.The solids content that additive among the embodiment 6 has be 76.9 and use test 3 in carrier fluid form.What solids content was represented is that sanitising agent (Mannich reaction products) and carrier mix.

[00126] when lack of fuel is a kind of when containing the additive of Mannich reaction products of the present invention of significant quantity of example, the IVD data show that IVD is tangible opposite height in the test 10.

[00127] identical hydrocarbon fuel is used in test 8-10.

[00128] fuel consumption measure and the test 8 and 9 in about 229 liters.

[00129] test can be used

Lubricating oil (15W-40).

[00130] You consumption can measuredly guarantee that internal combustion engine operation is normal, in addition, is not that this test needs.

[00131] the top port rated value is lower than 10 needs.Usually, combine with test described herein and can adopt the rated value of air inlet port.The top port rated value is 10 or lowlyer is considered to clean that when the Mannich reaction products of the present invention of significant quantity joined in the fuel, this ratio can obtain.Reactor product is present in the carrier fluid usually, for example, and as a kind of additive.When in theory, using the additive contain the Mannich reaction products of the present invention that cleans significant quantity about 5 or lower rated value can obtain.

[00132] Mannich reaction products of the present invention can provide superior improved engine testing performance, can demonstrate the sedimentary amount of PFI of reduction by using this product.Compare with the Mannich product or the untreated basic fuel of commercialization, the result is significant improvement.

[00133] fuel that contains the Mannich reaction products of the present invention that cleans significant quantity can demonstrate improved IVD performance.

[00134] compares the pollution speed that Mannich reaction products of the present invention can provide with the Mannich additive product of conventional commercial.

[00135] is appreciated that, the reactant and the component of the chemical name indication at arbitrary place in this specification sheets and the claim, it no matter is single or plural number, be defined as itself and another with chemical name or chemical type (basic fuel for example, solvent, etc.) existing state before the contact of the material of indication.Which kind of chemical transformation is its importance do not lie in, conversion and/or reaction, if possible, occur in final mixture or solvent or the reaction intermediate, because this variation, transform and/or reaction is the result of the nature of putting together in reaction conditions decline specific reactants of the present invention and/or component.Therefore, reactant and component are defined as putting together the chemical reaction (for example a kind of mannich condensation reaction) that can expect or the composition that forms compositions desired (for example fuel mixture of multifunctional additive for lubricating oils or interpolation).Can recognize that also additive component itself adds in the basic fuel separately or mixes with basic fuel and/or as the component that forms described additive binding substances and/or inferior binding substances.Other aforementioned additive enriched material, wherein a high proportion of binder component usually and one or more diluents or solvent mix jointly, mix with basic fuel and obtain the final fuel composition thereby can form next enriched material.Therefore, although following claim may be pointed out material with present tense, component and/or composition (" comprising " "Yes", Deng), be meant this material, the time of component or its existence of composition is at the first time and one or more other materials of the present invention, before component or composition doping or the mixing.Material, component and composition in this doping or mixing process by chemical reaction or transform the fact may lose its original characteristic for correct understanding and estimate this specification sheets and what is claimed is fully unnecessary.

[00136] term used herein " fuel fusile " meaning is that the material discussed is dissolved in the basic fuel of selecting for use fully at 20 ℃ and is able to make material to demonstrate the minimum concentration of its function.Preferred this material has in basic fuel than this high solvability.But material need can not be dissolved in the basic fuel with any ratio.

[00137] related each or all patent of this specification sheets any part or its open text be used for various with reference to introduce the present invention=, as in this sets forth in detail.

[00138] the present invention allows considerable difference in actual applications.Therefore, in front being described in is not to mean restriction here, can not be interpreted as being restricted to the present invention's special disclosed example described herein.Should be that usefulness claim and its allowed by law equivalents of wanting to protect are set forth.

Claims

1, a kind of fuel additive composition comprises

(a) Mannich reaction products (i) that obtains of the reaction by following substances has the polyamines of primary amine group, be selected from by quadrol, 1,3-two amido propane and 1, the group that 2-diamines basic ring shape aliphatics constitutes is the hydroxy-aromatic compound of alkyl replacement (ii), (iii) aldehyde, wherein reaction is at (i): (ii): mol ratio (iii) is selected under the situation by the group of forming that is approximately 1: 2: 3 and 1: 1: 2 carries out; With

(b) liquid carrier.

2, the described fuel additive composition of claim 1, wherein polyamines comprises 1,2-diamines basic ring hexane.

3, the described fuel additive composition of claim 1, wherein polyamines comprises quadrol.

4, the described fuel additive composition of claim 1, wherein polyamines comprises 1,3-two amido propane.

5, the described fuel additive composition of claim 1, wherein the hydroxy-aromatic compound of alkyl replacement comprises ortho-cresol, or phenol, or the mixture of neighbour-cresols and phenol, the aliphatic hydrocarbon substituting group that has is from about 300 to about 2000 polyolefine derived from average molecular weight range.

6, the described fuel additive composition of claim 5, aliphatic hydrocarbon substituting group wherein comprises polyisobutene.

7, claim 1 or 5 described fuel additive compositions, wherein aldehyde comprises fatty aldehyde, heterocyclic aldehydes, aromatic aldehyde, or its mixture.

8, the described fuel additive composition of claim 7, wherein said aldehyde comprises C ₁To C ₆Fatty aldehyde.

9, the described fuel additive composition of claim 7, wherein said aldehyde comprises heterocyclic aldehydes.

10, the described fuel additive composition of claim 7, wherein said aldehyde comprises aromatic aldehyde.

11, the described fuel additive composition of claim 1, wherein said aldehyde are at least a aldehyde that is selected from the group of being made up of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral and hexanal, phenyl aldehyde and salicylic aldehyde.

12, the described fuel additive composition of claim 1, wherein said aldehyde comprises the reactant that generates formaldehyde.

13, the described fuel additive composition of claim 1, wherein said aldehyde is selected from the group that is made of furfural, thiophene aldehyde, Paraformaldehyde 96 and formalin.

14, the described fuel additive composition of claim 1, wherein carrier be selected from by liquid state poly--group that α-ethylene oligomerization body, liquid polyolefine, liquid hydrogen treatment polyolefine, mineral oil, liquid poly-(oxyalkylene) compound and its any mixture constitute.

15, a kind of fuel additive composition, comprise that Mannich reaction products (i) that (a) reaction by following substances obtains has the polyamines of primary amine group, it can form pure basically intermediate in mannich condensation reaction, described intermediate has 5 yuan or 6 member heterocyclic ring containing nitrogen segments, the (ii) hydroxy-aromatic compound that replaces of alkyl, (iii) aldehyde, wherein react (i) that carries out: (ii): (iii) mol ratio makes described polyamines (i) (ii) to react with the hydroxy-aromatic compound that described alkyl replaces and obtains described pure basically intermediate, and it is pure basically product that described intermediate can (iii) react the described Mannich reaction products that obtains with described aldehyde;

(b) liquid carrier.

16, a kind of mannich detergents comprises (i) at least a 1, the 2-diamino-cyclohexane, quadrol or 1,3-two amido propane, the (ii) cresols and/or the phenol that replace of polyisobutene, wherein the molecular-weight average of polyisobutene is from about 300 to about 2,000, the (iii) reactor product of formaldehyde, wherein reaction is at (i): (ii): mol ratio (iii) is approximately 1: 2: 3 and carries out under the situation.

17, a kind of pure basically Mannich reaction products obtains the polyamines that (i) has primary amine group by the reaction of following substances, it can form pure basically intermediate in mannich condensation reaction, described intermediate has 5 yuan or 6 member heterocyclic ring containing nitrogen segments, the (ii) hydroxy-aromatic compound that replaces of alkyl, (iii) aldehyde, wherein react (i) that carries out: (ii): (iii) mol ratio makes described polyamines (i) (ii) to react with the hydroxy-aromatic compound that described alkyl replaces and obtains described pure basically intermediate, and described intermediate can (iii) react with described aldehyde and obtain described pure basically Mannich reaction products.

18, pure basically Mannich reaction products as claimed in claim 17, wherein the hydroxy-aromatic compound of alkyl replacement comprises ortho-cresol, or phenol, or the mixture of neighbour-cresols and phenol, have derived from average molecular weight range and be from about 300 to about 2000 polyolefinic aliphatic hydrocarbon substituting group.

19, pure basically Mannich reaction products as claimed in claim 17, wherein aldehyde comprises fatty aldehyde, heterocyclic aldehydes, aromatic aldehyde or its mixture.

20, pure basically Mannich reaction products as claimed in claim 19, wherein said aldehyde comprises C ₁To C ₆Fatty aldehyde.

21, pure basically Mannich reaction products as claimed in claim 19, wherein said aldehyde comprises heterocyclic aldehydes.

22, pure basically Mannich reaction products as claimed in claim 19, wherein said aldehyde comprises aromatic aldehyde.

23, pure basically Mannich reaction products as claimed in claim 17, wherein said aldehyde are at least a aldehyde that is selected from the group of being made up of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral and hexanal, phenyl aldehyde and salicylic aldehyde.

24, pure basically Mannich reaction products as claimed in claim 17, wherein said aldehyde comprise formaldehyde or generate the reactant of formaldehyde.

25, pure basically Mannich reaction products as claimed in claim 17, wherein said aldehyde is selected from the group that is made of furfural, thiophene aldehyde, Paraformaldehyde 96 and formalin.

26, a kind of fuel composition that is used for oil engine comprises (a) main content, the hydrocarbon fuel that spark ignition is inflammable; With a spot of fuel dope that contains Mannich reaction products as claimed in claim 17 in the carrier fluid.

27, a kind of fuel composition that is used for oil engine comprises

(a) main content, the hydrocarbon fuel that spark ignition is inflammable; With

(b) a spot of, the fuel additive composition (i) that comprises the Mannich reaction products that obtains by the following substances reaction is selected from by quadrol, 1,3-diaminopropanes and 1, the polyamines of the group that the 2-diamino-cyclohexane constitutes, the (ii) hydroxy-aromatic compound that replaces of alkyl, (iii) aldehyde, wherein reaction (i) that adopt: (ii): mol ratio (iii) is selected from the group of forming in 1: 2: 3 and 1: 1: 2 by being approximately, and wherein the amount that exists of Mannich reaction products can reduce the oil engine deposition in the oil engine of use fuel composition fully.

28, fuel composition as claimed in claim 27 comprises content range from about 100 to about 1, the fuel additive composition of 000ppm.

29, fuel composition as claimed in claim 27, wherein Mannich reaction products obtains (1) 1 by the reaction of following substances, the 2-diamino-cyclohexane, (2) cresols and/or polyisobutene fortified phenol or its mixture of polyisobutene replacement, wherein the molecular-weight average of polyisobutene from about 300 to about 2,000 and (3) formaldehyde.

30, fuel composition as claimed in claim 27, wherein Mannich reaction products obtains (1) quadrol by the reaction of following substances, (2) cresols and/or polyisobutene fortified phenol or its mixture of polyisobutene replacement, wherein the molecular-weight average of polyisobutene from about 300 to about 2,000 and (3) formaldehyde.

31, fuel composition as claimed in claim 27, wherein Mannich reaction products obtains (1) 1 by the reaction of following substances, the 3-diaminopropanes, (2) cresols and/or polyisobutene fortified phenol or its mixture of polyisobutene replacement, wherein the molecular-weight average of polyisobutene from about 300 to about 2,000 and (3) formaldehyde.

32, fuel composition as claimed in claim 27 further comprises at least a additive that is selected from by oxidation inhibitor, carrier fluid, demulsifying compound, the antirust or group that sanitas, metal passivator, combustionregulator, pure cosolvent, octane improving agent, purification agent for treating waste gas, friction modifiers, slip additive, auxiliary sanitising agent/dispersant additives, biocide, anti static additive, flow improver, gasoline de-misting agent, crashworthiness agent, anti-icer, the damaged agent of anti-valve (door) seat, combustion improving agent, sign (markers) and staining agent constitute.

33, the sedimentary method of oil engine is included in and adopts fuel composition as claimed in claim 26 in the described oil engine in a kind of controlling combustion engine.

34, method as claimed in claim 33, the oil engine of wherein being controlled deposition comprises the intake valve deposition.

35, method as claimed in claim 33, the oil engine of wherein being controlled deposition comprises the port fuel-injectors deposition.

36, method as claimed in claim 33, the oil engine of wherein being controlled deposition comprises the combustion chamber deposition.

37, method as claimed in claim 33, the oil engine of wherein being controlled deposition comprises that the air inlet port pollutes.

38, method as claimed in claim 33, the oil engine of wherein being controlled deposition comprises the leak stopping of direct injection device.

39, according to claim 1 or 15 described fuel additive compositions, wherein reaction is at (i): (ii): mol ratio (iii) is approximately under 1: 2: 3 the situation carries out.

40, according to claim 1 or 15 described fuel additive compositions, wherein reaction is at (i): (ii): mol ratio (iii) is approximately under 1: 1: 2 the situation carries out.

41, fuel additive composition according to claim 15, wherein polyamines comprises quadrol.