CN1104680A - Method of and apparatus for dehydrating biological products and dehydrated biological poructs - Google Patents

Abstract

The present invention discloses the gasoline composite and additive containing the compound whose chemical formula is described in prescription of this patent. The compound can decrease the deposit on air inlet valve. The application of additive and its preparing process are also disclosed.

Description

Method of and apparatus for dehydrating biological products and dehydrated biological poructs

The present invention relates to gasoline composition and gasoline dope enriched material, this enriched material contains some dinitrile compound and derivative thereof, and they are as reducing the additive that the air inlet valve settling generates.

People are the various gasoline compositions of allotment usually, to improve the performance of carburettor and throttle body injection engine.Approximately since 1984, the electric ignition fuel injected engine was generally adopted by the automaker.Shortly after that (greatly about 1985), begin to report the sedimental problem of air inlet valve in the relevant electric ignition fuel injected engine, the feature of these problems is to force to start, overload in accelerator and stop working and instability and engine idling under undesired operating mode.

Conventional commercial gasoline additive contains nitrogen.These nitrogen are connected on the polymkeric substance, and by two or three carbon atoms separately.This structure provides sequestering power.But because polymkeric substance connects by one of nitrogen-atoms, steric restriction makes the chelating decline in the conventional additive.

The present invention is not subjected to the restriction of any theory of operation, and people have now found that chelating helps settling to be reduced.Therefore, wishing has a kind of new gasoline dope, and it can improve chelating, thereby can reduce or eliminate undesirable air inlet valve settling in the electric ignition fuel injected engine.Equally, because some carburettor and throttle body injection engine in a foreseeable future still can use, wish that therefore the gasoline that contains such additive also can be suitable for these engines.

So,, provide a kind of contain a large amount of (by total composition greater than 50%(weight) according to the present invention) and the gasoline composition of the compound of gasoline and a small amount of following general formula,

By the total amount of composition, the consumption of above-claimed cpd for example is 5～1000ppmW, preferred 50～500ppmW, most preferably 75～350ppmW, most preferably 75～250ppmW.R in the formula I ¹Represent hydrogen atom or alkyl, aryl or alkaryl; R ²O is formula R ²The residue polyethers list alcohol of OH or alkyl list alcohol; R ³And R ⁴All represent hydrogen atom or represent a carbon-carbon single bond together, wherein work as R ³And R ⁴When all representing hydrogen atom, R so ⁵And R ⁶In each represent independently-CH ₂N(R ⁷) ₂Base, wherein each R ⁷Represent hydrogen atom or an optional alkyl that replaces independently, and work as R ³And R ⁴When representing a carbon-carbon single bond together, R so ⁵And R ⁶All represent cyano group.

In this manual, unless add explanation in addition, that the moieties in alkyl or the alkaryl can be straight chain or side chain, preferably contain 20 carbon atoms at the most, more preferably contain 12 carbon atoms at the most, more preferably contain 10 carbon atoms at the most, most preferably contain 6 carbon atoms at the most.Cycloalkyl can contain 3～8 carbon atoms, preferred 3～6 carbon atoms.Aryl can be any aromatic group, particularly phenyl or naphthyl.The aryl that alkaryl is replaced by one or more (preferred 1～2) alkyl.Heterocyclic radical can be any saturated or unsaturated ring system, for example C ₅～C ₇Ring system, it contains at least a heteroatoms that is selected from oxygen, nitrogen and sulphur, and 5 yuan of rings and 6 yuan of rings are particularly preferred, for example tetrahydrofuran base, furyl, piperidyl, pyridyl, tetrahydrochysene thio-phenyl or thio-phenyl (thienyl).

Preferably, R in the formula I ¹Represent hydrogen atom, C ₁～C ₂₀Alkyl or can be by one or more C ₁～C ₆The phenyl or naphthyl that alkyl replaces.

More preferably, R ¹Represent hydrogen atom, C ₁～C ₁₀Alkyl, or can be by one or more (for example at the most 3) C ₁～C ₄The optional phenyl or naphthyl that replaces of alkyl.

Equally more preferably, R ¹Represent hydrogen atom, C ₁～C ₆Alkyl or phenyl.R ¹Preferred especially hydrogen atom.

R ²O is formula R ²The residue of the polyethers list alcohol of OH or alkyl list alcohol.

Work as R ²OH is alkyl list when alcohol, and is that hydrocarbyl portion can be aliphatic series or aromatics, straight chain or side chain, preferably contains 400 carbon atoms at the most, more preferably contains 200 carbon atoms at the most, for example 50～150 carbon atoms.

R ²OH is formula R preferably ₁-O-(R ₂O) the oil soluble polyethers list alcohol of n-H, wherein R ¹Representative contains the alkyl of aliphatic series, cyclic aliphatic or the aromatics of 40 carbon atoms at the most, every kind of R ₂Segment can be identical or different, and its representative contains at the most 16 carbon atoms, the preferred alkylidene group of 12 carbon atoms at the most, and n is at least 7 integer.

R ²OH is formula R more preferably ₁O-(EO) c-(XO b-(BO a-(PO))) d-H, wherein R ¹Representative contains the alkyl of aliphatic series, cyclic aliphatic or the aromatics of 40 carbon atoms at the most, and E is the ethylidene segment, and P is the propylene segment, and B is the butylidene segment, and X is the alkylidene group segment that 5～16 carbon atoms are arranged, and is preferred 1,2-alkylidene group segment; A, b, c and d respectively do for oneself 0～100, and a, b, c and d's and be at least 7.This-R ²In the OH form, a, b and d are preferably 0 separately, and c is 10～40.More preferably, R ₁O is 1, the segment that the open loop of 2-butylene oxide ring obtains.

At another preferred R ²In the O form, it is the residue of polyethers list alcohol, wherein R ¹Preferably butyl or C ₁₂～C ₁₈Alkyl, n are 10～40, just C ₁₂H ₂₃O-C ₁₈H ₃₇O(-CH ₂-CH(C ₂H ₅) O-) nH or C ₄H ₉O(-CH ₂-CH(C ₂H ₅) O-) and nH(wherein n be 10～40) and composition thereof.In this group group, R ²O is more preferably by C ₄H ₉O(-CH ₂-CH(C ₂H ₅) O-) nH obtains, wherein n is 10～40.

Preferably, the number-average molecular weight of polyethers list alcohol (Mn) is not more than 5000.More preferably, the number-average molecular weight of polyethers list alcohol is in 500～3000, especially more preferably 500～2500, most preferably 1000～2000 scopes.At R ²O is by C ₄H ₉O(-CH ₂-CH(C ₂H ₅) O-) under the occasion that obtains of nH, R ²The number-average molecular weight of O is preferably in 1900～2100 scopes.

Preferably, in the formula I, R ³And R ⁴All represent hydrogen atom, R ⁵And R ⁶In each represent independently as above regulation-CH ₂N(R ⁷) ₂Base.

Preferably, every-R ⁷Represent hydrogen atom independently or can be chosen wantonly the C that replaces by one or more (preferred 1～2) substituting group ₁～C ₂₀Alkyl, substituting group are selected from halogen atom (as the chlorine atom), nitro, hydroxyl, cycloalkyl, alkoxyl group, halogenated alkoxy, amino, dialkylamino, formyl radical, carbalkoxy, carboxyl, alkanoyl, alkylthio, alkyl sulphinyl, alkyl sulphonyl, formamyl, alkylamino, aryl, alkaryl and heterocyclic radical.When any above-mentioned replacement wherein contains alkyl, that this alkyl can be straight chain or side chain, and can contain 12 carbon atoms at the most, preferred 6 carbon atoms at the most, especially preferably 4 carbon atoms at the most.

More preferably, every-R ⁷Represent hydrogen atom or C independently ₁～C ₁₀Alkyl particularly preferably is hydrogen atom.

Particularly preferred one group of formula I compound is some such compounds, wherein R ¹Represent hydrogen atom; R ²O is formula R ₁-O-(R ₂O) residue of the polyethers list alcohol of n-H, wherein R ₁Represent butyl, R ₂Represent C ₄Alkylidene group, preferred 1,2-butylidene, n are an integer in 10～30; R ³And R ⁴All represent hydrogen atom, R ⁵And R ⁶All represent-CH ₂NH ₂Base, or R ³And R ⁴Represent a carbon-carbon single bond and R together ⁵With R ⁶All represent cyano group.

When being used for gasoline composition, the quantity of the compound of formula I in gasoline is preferably 75ppmW or more (by the total amounts of gasoline composition).The compound of formula I can be chosen wantonly and at least a carrier ingredients.These carriers comprise (ⅰ) C ₂～C ₆The multipolymer of monoolefine; (ⅱ) oil soluble polyoxygenated enol, dibasic alcohol or polyvalent alcohol or its monoether or diether; (ⅲ) 100 ℃ of polyalphaolefins that following viscosity is 2～20 centistokes(cst)s.

These polymer supports that use with formula I compound of the present invention all are what to be familiar with in the art, about their preparation and the patent of application comprise United States Patent (USP) 2692257,2692258,2692259,2918508 and 2970179.

Being characterized as of monoolefine multipolymer that can be used as the carrier of gasoline composition of the present invention, the number-average molecular weight that obtains with osmometry is in 500～1900 scopes, more preferably in 550～1500 scopes.Particularly preferably being number-average molecular weight is the interior monoolefine multipolymers of 600～950 scopes.

The number-average molecular weight of its major portion greater than 1500 polymeric blends may weak effect some.Polyolefine can for example comprise ethene, propylene, butylene, iso-butylene, divinyl, amylene, isoprene and hexene by the unsaturated olefin preparation that 2～6 carbon atoms are arranged.

With regard to its validity and industrial availability, the multipolymer of propylene and butylene preferably; Particularly preferably be the polymkeric substance of iso-butylene.Being equally applicable to of the present invention is the derivative that is obtained by above-mentioned hydrogenation of polymer.

Polyoxyalkylene is to be applicable to preferred vector of the present invention.It can be formula R ₃-O-(R ₄O) m-R ₅Polyoxy for ene compound, R wherein ₃And R ₅In each represents hydrogen atom independently, or aliphatic series, cyclic aliphatic or aromatic hydrocarbyl, wherein each alkyl maybe can contain 40 carbon atoms at the most, R ₄Represent alkylidene group, preferred 1, the 2-alkylidene group, it contains 12 carbon atoms at the most, and the m representative is at least 7 integer, works as R ₄M preferably was at least 20 integer when O was propylene.At polyoxyalkylene chain-(R ₄O) among the m-, R ₄Base is an alkylidene group.Polyoxyalkylene chain is optional to contain two or more dissimilar alkylidene groups, and it is preferably the alkylidene group of 2～8 carbon atoms, particularly preferably is ethylidene or propylene.These groups can be chosen stochastic distribution in whole chain wantonly, or arrange by predetermined unit or block pattern, and each unit or block all contain one or more oxyalkylenes.

In one embodiment of the invention, R ₃And R ₅In at least one is to contain the alkyl or the alkyl phenyl of 20 carbon atoms at the most, for example propyl group, butyl, amyl group, hexyl, octyl group, nonyl, decyl, dodecyl, octyl phenyl or nonyl phenyl.Preferably, R ₃Be hydrogen, R ₅Be alkyl; More preferably, R ₅Be dodecyl or C ₁₂～C ₁₅The mixed group of alkyl.

The carrier that is suitable for comprises polyoxyalkylene diols and contains the glycol of ethylidene and propylene and the monoalky lether and the dialkyl ether of these glycol in polyoxyalkylene chain.

The commercial polyoxyalkylene compounds of buying is the mixture of compound normally, and in these compounds, the molecular weight of m value and mixture is a mean value.The m value of representative compounds is generally 7～100, and preferred 8～80.Number-average molecular weight is 400～6000, and is preferred 500～4000, more preferably 1000～2000.

When carrier was polyalphaolefin, the viscosity under its 100 ℃ was 2～20 centistokes(cst)s.Such polyalphaolefin is the suitable hydrogenant oligopolymer of warp that the alpha olefin monomers by at least 6 carbon atoms obtains.Oligopolymer after the hydrogenation itself preferably contains 18～80 carbon atoms.Preferably, monomer contains 6～24 carbon atoms, particularly preferably be and contain 8～12 carbon atoms, and oligopolymer preferably contains 30～80 carbon atoms.Hydrocarbon Processing February nineteen eighty-two number since 75 pages of preparations of describing these oligopolymer.

Can use the mixture of more than one carriers, the mixture of equivalent normally.Carrier is the polyoxygenated enol preferably, and dibasic alcohol or polyvalent alcohol, particularly their ether help to prevent the air inlet valve low temperature bonding.The consumption of such component is preferably 75～175ppmW, is preferably the total amount of 125ppmW(by gasoline composition especially).

Suitable liquid hydrocarbon fuel in gasoline boiling range scope is that boiling range is the hydrocarbon mixture of 25 ℃ (77)～232 ℃ (450), and it is the mixture of stable hydrocarbon, alkene and aromatic hydrocarbons.Preferably saturated hydrocarbon content is 40～80%(volume), olefin(e) centent is 0～30%(volume) and aromaticity content be 10～60%(volume) the gasoline concoction thing.The synthetic aromatic hydrocarbons mixture that basic fuel for example can be obtained by straight-run spirit, polymer gasoline, natural gasoline, olefin dimers or trimer, hydro carbons thermal reforming or catalytic reforming, or make by catalytic cracking or thermally splitting petroleum oil, or their mixture.The hydrocarbon composition and the octane value of basic fuel are unimportant.Octane value ((R+M)/2) is usually greater than 85.The automotive fuel base oil of any routine all can be used for the present invention.For example, in gasoline, hydro carbons can replace with alcohols that becomes known for fuel usually or ethers, and its quantity may be up to the major part that accounts for gasoline, wishes that basic fuel is in fact not moisture, because water hinders steady fuel.

Preferably, it is unleaded being used for gasoline of the present invention, but can contain a small amount of blending agents such as methyl alcohol, ethanol, methyl tertiary butyl ether, and its amount for example is 0.1～15%(volume of basic fuel).Gasoline also can contain 1～40ppmW(by the gasoline composition total amount) phenolic antioxidant (as 2, the 6-di-tert-butylphenol) and phenylenediamine oxidation inhibitor (as N, N '-di-sec-butyl-p-phenyl enediamine); Dyestuff; Metal passivator; Remove the alkylphenol-formaldehyde resin of smoke substance such as polyester type ethoxylation; Corrosion inhibitor is (as a kind of polyol ester of succinic acid derivative, the aliphatic hydrocarbyl that on its at least one alpha-carbon atom, contains the unsubstituted of 20～500 carbon atoms or replace, the pentaerythritol diester of the succsinic acid that replaces as polyisobutene, the number-average molecular weight of its polyisobutenyl is 950), its consumption is 1～1000ppmW; And antiknock shake compound such as methyl cyclopentadienyl tricarbonyl manganese or adjacent nitrine phenol.Additive of the present invention can in all sorts of ways and be incorporated into the burning zone of engine, to prevent accumulation of deposits or settling to be reduced or change.For example, additive is injected in the intake manifold unceasingly or basically continuously, preferably additive is dissolved in the hydro carbons carrier of final boiling point less than 232 ℃ of (450) (ASTMD86 methods).Preferable methods is that additive is added in the gasoline.For example, this additive can be added in the gasoline separately, or concoct with other gasoline dopes.

Therefore, the present invention further provides a kind of gasoline dope enriched material, it comprises that the compatible thinner of gasoline and 20～80w%(are by thinner) the formula I compound stipulated above.

The compatible thinner of gasoline that is suitable for comprises hydro carbons such as heptane, alcohols or ethers such as methyl alcohol, ethanol, propyl alcohol, butoxy ethanol or methyl tertiary butyl ether.Preferably, thinner is an aromatic solvent, as toluene, dimethylbenzene, their mixture or the mixture of toluene or dimethylbenzene and alcohol.Thinner is toluene preferably.This enriched material also can be chosen wantonly and contain smoke substance, particularly the alkyl resinox of polyether-type ethoxyquin.If you are using, go the suitable number of smoke substance in enriched material to count 0.01～2%(weight) by thinner.

On the other hand, the invention provides a kind of working method of spark ignition IC engine, this method comprises the combustion chamber of the gasoline composition of stipulating above of the present invention being introduced described engine.

On the other hand, the invention provides the application that the formula I compound of stipulating above is used as the gasoline dope that reduces the generation of air inlet valve settling.

Some formula I compounds are compound known, and other are new compounds.Therefore, the present invention also provides general formula following compound:

R wherein ¹Represent hydrogen atom or alkyl, aryl or alkaryl; R ²O is formula R ²The residue of the polyethers list alcohol of OH or alkyl list alcohol; R ³And R ⁴All represent hydrogen atom or represent a carbon-carbon single bond together, wherein work as R ³And R ⁴When all representing hydrogen atom, R so ⁵And R ⁶In each represent independently-CH ₂N(R ⁷) ₂Base, wherein each R ⁷Represent hydrogen atom or the optional alkyl that replaces independently, and work as R ³And R ⁴When representing a carbon-carbon single bond together, R so ⁵And R ⁶All represent cyano group, its condition is to work as R ¹Be hydrogen atom or C ₁～C ₄Alkyl, R ³And R ⁴Represent a carbon-carbon single bond and R together ⁵And R ⁶When all representing cyano group, R so ²O is formula R ²The residue of the polyethers list alcohol of OH.

The present invention further provides a kind of method for preparing the formula I new compound of stipulating above, this method comprises compound and the formula R that makes following general formula ²The polyethers list alcohol of OH or the reaction of alkyl list alcohol, production I compound,

Wherein R represents alkyl, for example C ₁～C ₆Alkyl, R ¹Stipulate as top, in the formula I, R ³And R ⁴Represent a carbon-carbon single bond together; Subsequently, work as R ¹Be hydrogen atom or C ₁～C ₄Alkyl and R ²When O was the residue of polyethers list alcohol, the formula I compound of generation carried out hydrogenation, works as R ²O is the residue of polyethers list alcohol or works as R ¹Be alkyl or aryl or alkaryl and the R that has 5 carbon atoms at least ²When O was the residue of alkyl list alcohol, the formula I compound of generation was chosen wantonly and is carried out hydrogenation; The formula I compound that generates (wherein whenever-R ⁷All represent hydrogen atom) can react with the compound of following general formula

Wherein L represents leavings group, as halogen atom, and R ⁷Be the group of stipulating above except that hydrogen atom.

The compound of formula II and R ²The reaction of OH is preferably under the normal pressure and being enough to make ROH(such as ethanol, represents ethyl at R under this occasion) carry out under the temperature that keeps emitting.Preferably, temperature is in 100～140 ℃ of scopes.Reaction is preferably carried out with interrupter method, and this reaction times will be enough to reach desirable transformation efficiency, for example 4～5 hours.The dinitrile compound of formula II preferably at catalyzer (as ZnCl ₂) exist down and R ²The OH reaction.

Hydrogenation for example can realize by reacting down at normal pressure and temperature (20 ℃) with metal hydride (as lithium hydride).In reaction is under the occasion of heat release, and it is preferred being lower than room temperature.

On the other hand, hydrogenation can be under high pressure, in the presence of hydrogenation catalyst (as Raney cobalt or Raney nickel catalyst), realize by contacting with hydrogen.For using such Raney catalyst, hydrogen pressure for example is 2000～3000 a pounds/inch ²(13790～20684KPa).Temperature is preferably 80～150 ℃.

R wherein ⁷Represent the reaction of the formula I compound of hydrogen atom and formula III compound to be easy under normal pressure and temperature (20 ℃)～100 ℃, carry out.

The compound of formula III is a compound known, maybe can be by preparing with the similar method of currently known methods.

Equally, the compound of formula II is a compound known, maybe can be by preparing with the similar method of currently known methods, the method for describing among GB-A-542403, GB-A-1018455, GB-A-1275882, GB-A-1314801, GB-A-1579438 and the GB-A-2175900 for example.

R wherein ¹Represent hydrogen atom and R to represent the formula II compound of ethyl can be easy to by equivalent propane dinitrile (CH ₂(CN) ₂) and triethyl orthoformate ((C ₂H ₅O) ₃CH) reaction prepares, reaction conditions basically with the aforesaid method reaction the first step, just (R wherein in formula I compound ³And R ⁴Represent a carbon-carbon single bond together) used reaction conditions is identical.

Can further understand the present invention from following examples.

Embodiment 1

2-polybutylene oxide-1,1-dintrile ethene (a kind of formula I compound, wherein R ¹Be H, R ²O is polybutylene oxide (C ₄H ₉OC-CH ₂-CH(C ₂H ₅) O-) nH) residue, R ³And R ⁴Represent a carbon-carbon single bond and R together ⁵And R ⁶All represent cyano group)

(ⅰ) by α butylene oxide ring (1, the 2-butylene oxide ring) polybutylene oxide (Mn 1500) and the ethoxy methylene malononitrile (being provided by Aldrich company) that (is provided) polymerization to obtain by Dow company pressed 1: 1.02 mixed in molar ratio, obtain the solution of 50% dimethylbenzene, it also contains 0.08～0.2%(weight) zinc chloride.Temperature of reaction remains on is enough to level that ethanol is emitted, is generally 100～140 ℃.React after 4～5 hours, reaction is just complete when further not emitting ethanol.With reactant cool to room temperature (20 ℃), filter out zinc chloride, tell dimethylbenzene simultaneously, obtain solvent-free material and be used for analyzing.With the analysis revealed that nuclear magnetic resonance spectrum (NMR) carries out, about 100% polybutylene oxide is promptly generated required formula I compound by dintrile functional group end-blocking.

(ⅱ) repeat (ⅰ) step, different is to replace ethoxy methylene malononitrile with equimolar amount propane dinitrile and triethyl orthoformate.The amount of ethanol of emitting be increased to 3 equivalents/whenever the amount polybutylene oxide.Obtain required product: 2-polybutylene oxide-1,1-dinitrile ethene.

Embodiment 2

2-polybutylene oxide-1, preparation (a kind of formula I compound, the wherein R of 1-two (methylene amino) ethane ¹Be H, R ²O is polybutylene oxide (C ₄H ₉O(-CH ₂-CH(C ₂H ₅O-) residue nH), R ³And R ⁴All represent hydrogen atom and R ⁵And R ⁶All represent-CH ₂NH ₂Base)

As described in embodiment 1 preparation 2-polybutylene oxide-1,1-dinitrile ethene in dry toluene 1: the 1(volume ratio) the industrial Na of solution ₂AlH ₂-(OCH ₂CH ₂OCH ₃) ₂(70% solution in toluene) reduction.Because exothermic heat of reaction adopts exterior cooling.The 15%NaOH neutralization of molar equivalents such as reaction product usefulness, water quenching subsequently.Obtain required product after conventional separation and the drying.

Embodiment 3

With 2-polybutylene oxide-1,1-dinitrile ethene repeats the step of embodiment 2, and wherein the pulsating Mn of polybutylene oxide is 1000.

Embodiment 4

With 2-polybutylene oxide-1,1-dinitrile ethene repeats the step of embodiment 2, and wherein the pulsating Mn of polybutylene oxide is 2000.

Embodiment 5 testing of engine

The fuel of compound that contains or do not contain embodiment 1～4 test 100 hours in one or two 3.3 liter Dodge engines (V-6) that port fuel injection (PFI) arranged and Quad-4 Oldsmobile engine is so that determine the efficient of these compounds in reducing the air inlet valve settling.

Basic fuel contains the high-quality white gasoline.Except the unreacted reactant that reaction not exclusively produces in the additive preparation process, do not use carrier.The compound of embodiment 1 is added in the gasoline, and its concentration is 198ppmW active substance and 2ppmW unreacted matters, mainly is polybutylene oxide R ²OH, and the compound of embodiment 2～4 is added in the gasoline separately, its concentration is 125ppmW active substance (being the 125ppmW diamines) and residual unreacted matters.

Each engine all is in when on-test under the clean condition, i.e. more oil change and strainer, and And removes all settlings from intake manifold, inlet mouth and the combustion zone of engine.In order to detect sedimental accumulation in each process of the test, these engines carry out cyclical operation, the cyclical operation that promptly has acceleration and the idling mode of slowing down or normal fast mode to constitute, normal fast mode is per hour 30,35,45,55 and 65 miles (corresponding to per hour 48.3,56.3,72.4,88.5 and 104.6 kilometers).Test was carried out 100 hours, measured the sedimental weight of air inlet valve then.The result of these tests lists the following table I in.

These test-results show, compare with the effect of basic fuel, and gasoline composition of the present invention is preventing that significantly settling from being effectively in the accumulation, wants much lower indicated as the valve settling in the engine of test.The gasoline composition that contains the compound of embodiment 4 has good especially performance.

Embodiment 6 BMW testing of engine

Usually the detergent action of measuring air inlet valve with the BMWNA standard of the air inlet valve degree of cleaning of unrestricted mileage, this standard are rideability and 100 milligrams or less than fixed mutual relationship between 100 milligrams of air inlet valve settlings.The air inlet valve deposit test is carried out in Southwest Research Institute is equipped with 1985 type BMW318i cars of 1.8 liter four cylinder engines, with test fuel travel 10000 miles (16093 kilometers).Before on-test, remove settling, weigh and new air inlet valve is installed from cylinder head, intake manifold and top land.More oil change and strainer are installed new sparking plug, and check fuel injection stream.With housebroken officer accumulated distance number on highway.Test course by about 10% city travel, 20% Class II highway travels and 70% motorway travels, and (top speed 65 miles per hours (104.6 kilometers/hour)) are formed.

Main testing data is the weight of air inlet valve settling (IVD) when 10000 miles (16093 kilometers) off-tests.Also when 5000 miles (8047 kilometers), measure IVD weight, if the result is undesirable, but termination test then.The criterion of acceptability of BMW is as follows: when off-test, the average deposition thing weight of each valve is just to reach the requirement that BMW checks and accepts unrestricted mileage below 100 milligrams or 100 milligrams; When off-test, the average deposition thing weight of each valve is just to reach the requirement of BMW to 50000 miles (80467 kilometers) operation below 250 milligrams or 250 milligrams.

In the BMW testing of engine, tested the unleaded base gasoline of high-quality of the compound (concentration is the 172ppmW active substance) that contains embodiment 4.When test (10000 miles/16093 kilometers) finished, average air inlet valve settling weight was 46 milligrams.Therefore, the result of this test shows that the unrestricted tyre mileage test of the BMW of gasoline composition of the present invention is qualified, and low sediment yield is arranged.

Claims (10)

1, a kind of gasoline composition, it contains the gasoline of main quantity and the compound of a small amount of following general formula:

R wherein ¹Represent hydrogen atom or alkyl, aryl or alkaryl; R ²O is formula R ²The residue polyethers list alcohol of OH or alkyl list alcohol; R ³And R ⁴All represent hydrogen atom or represent a carbon-carbon single bond together, wherein work as R ³And R ⁴When all representing hydrogen atom, R so ⁵And R ⁶In each is represented-CH independently ₂N (R ⁷) ₂Base, wherein each R ⁷Represent hydrogen atom or an optional alkyl that replaces independently, work as R ³And R ⁴When representing a carbon-carbon single bond together, R so ⁵And R ⁶All represent cyano group.

2, according to the gasoline composition of claim 1, R wherein ³And R ⁴All represent hydrogen atom, R ⁵And R ⁶In each is represented-CH independently ₂N(R ⁷) ₂Base, its meaning is as claim 1 regulation.

3, according to the gasoline composition of claim 2, every-R wherein ⁷Represent hydrogen atom or C independently ₁～C ₂₀Alkyl.

4, according to any one gasoline composition in the claim 1～3, wherein R ¹Represent hydrogen atom, C ₁～C ₂₀Alkyl or by one or more C ₁～C ₆The optional phenyl or naphthyl that replaces of alkyl.

5, according to any one gasoline composition in the claim 1～4, wherein R ²OH is formula R ₁-O-(R ₂O) the oil soluble polyethers list alcohol of n-H, wherein R ₁Representative contains the alkyl of aliphatic series, cyclic aliphatic or the aromatics of 40 carbon atoms at the most, and is every-R ₂Segment can be identical or different, and their representatives contain the alkylidene group of 16 carbon atoms at the most, and n is an integer of at least 7.

6, according to any one gasoline composition in the claim 1～5, wherein R ²OH is formula R ₁O(EO) c-(XO b-(BO a-(PO))) d-H, wherein R ₁Representative contains the alkyl of aliphatic series, cyclic aliphatic or the aromatics of 40 carbon atoms at the most, and E is the ethylidene segment, and P is the propylene segment, and B is the butylidene segment, and X is the alkylidene group segment that 5～16 carbon atoms are arranged; Respectively do for oneself 0～100 number of a, b, c and d, and a, b, c and d's and be at least 7.

7, a kind of gasoline dope enriched material, it contain can with thinner and 20～80%(weight of gasoline compatibility) the formula I compound of any one defined in the requirement of (by thinner) aforesaid right.

8, in the claim 1～6 the formula I compound of any one regulation as the application that reduces the sedimental gasoline dope of air inlet valve.

9, a kind of compound of following general formula:

R wherein ¹Represent hydrogen atom or alkyl, aryl or alkaryl; R ²O is formula R ²The residue of the polyethers list alcohol of OH or alkyl list alcohol; R ³And R ⁴All represent hydrogen atom or represent a carbon-carbon single bond together, wherein work as R ³And R ⁴When all representing hydrogen atom, R so ⁵And R ⁶In each represent independently-CH ₂N(R ⁷) ₂Base, wherein each R ⁷Represent hydrogen atom or the optional alkyl that replaces independently, work as R ³And R ⁴When representing a carbon-carbon single bond together, R so ⁵And R ⁶All represent cyano group, its condition is to work as R ¹Be hydrogen atom or C ₁～C ₄Alkyl, R ³And R ⁴Represent a carbon-carbon single bond together, R ⁵And R ⁶When all representing cyano group, R so ²O is formula R ²The residue of the polyethers list alcohol of OH.

10, a kind of method for preparing the formula I compound of claim 9 regulation, this method comprises compound and the formula R that makes following general formula ²The polyethers list alcohol of OH or the reaction of alkyl list alcohol, production I compound,

Wherein R represents alkyl, R ¹Group for claim 9 regulation; In the formula I, R ³And R ⁴Represent a carbon-carbon single bond together; Work as R ¹Be hydrogen atom or C ₁～C ₄Alkyl, and R ²When O was the residue of alkyl list alcohol, the formula I compound of generation carried out hydrogenation, works as R ²O is the residue of polyethers list alcohol or works as R ¹Be alkyl or aryl or alkaryl and the R that has 5 carbon atoms at least ²When O is the residue of alkyl list alcohol, also can choose the hydrogenation of carrying out formula I compound wantonly; The formula I compound that generates (wherein whenever-R ⁷All represent hydrogen atom) compound that also can choose wantonly with following general formula reacts,

Wherein L represents leavings group, R ⁷The group except that hydrogen atom for claim 9 regulation.