CN101962586B - Gasoline detergent prepared from aromatic amine polyoxypropylene ether - Google Patents
Gasoline detergent prepared from aromatic amine polyoxypropylene ether Download PDFInfo
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- CN101962586B CN101962586B CN2010105176647A CN201010517664A CN101962586B CN 101962586 B CN101962586 B CN 101962586B CN 2010105176647 A CN2010105176647 A CN 2010105176647A CN 201010517664 A CN201010517664 A CN 201010517664A CN 101962586 B CN101962586 B CN 101962586B
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Abstract
The invention relates to a gasoline detergent prepared from aromatic amine polyoxypropylene ether. The aromatic amine polyoxypropylene ether is represented by a structural formula (I), wherein R is hydrogen or an alkyl group of C1 to C10, and can be positioned at an ortho-position, a meta-position or a para-position on a benzene ring relative to nitrogen atoms; and the summation of a and b is a natural number in the range of 9 to 33. When used in gasoline, the gasoline detergent prepared from the aromatic amine polyoxypropylene ether serving as a main component can remarkably reduce the generation of sediments in fuel-intake system of a gasoline engine.
Description
Technical field
The present invention relates to a kind of gasoline cleaning agent with the preparation of aromatic amine polyethenoxy ether, also relate to the synthetic method of aromatic amine polyethenoxy ether.
Background technology
The aromatic amine polyethenoxy ether is a kind of of polyetheramine, belongs to the tertiary amine-type polyetheramine.Can be applicable to that epoxy resin accelerate to solidify, bonding, weaving help dye, printing ink and colo(u)rant dispersion etc.Because this aromatic amine polyethenoxy ether has good surfactivity and oil soluble, and at high temperature be difficult for generating settling and colloid, therefore can be used as the Main Components of motor spirit purification agent.
The purification agent that is used for motor spirit can suppress and remove the sedimental formation of petrol engine fuel oil inlet system, motor car engine fuel oil inlet system can be kept as much as possible and returns to the new car state, thereby reach the minimizing of relative oil consumption and discharging, this is the propelling vehicle fuels cleaning, puts into practice one of important means of automotive energy-saving emission-reducing.
Main active princlple in present disclosed gasoline cleaning agent CN1133873A, CN1167136A, CN1187474C, CN1227866A, CN1718696A is PIBA, polyisobutene succinimide, mineral oil and polyethers.Such gasoline cleaning agent has good keeping a public place clean and cleanup action to petrolic fuel injection nozzle, intake valve, can effectively suppress and clean the settling on these parts of petrol engine.But the settling that such gasoline cleaning agent can wash down the fuel oil inlet system is brought combustion chamber into, and the settling of combustion chamber is obviously increased.
The total settling of gasoline engine combustion chamber obviously increases, the compression ratio of engine is increased, and be difficult for heat radiation, to cause compression end of a period gas temperature in combustion chamber to raise, OR Octane Requirements increases, and increases the mechanical disturbance between top land and cylinder cap when serious, produces " carbon engine knock ", cause that finally engine consumption increases, deterioration of emission.
The main active princlple that on November 25th, 2009, State Intellectual Property Office's Granted publication number used for CN100562560C " a kind of gasoline cleaning agent that can remarkably reducing deposit of gasoline engine combustion chamber " is polyetheramine, and its structural formula is:
This is a kind of primary amine type polyetheramine tensio-active agent of buying from U.S. Huntsman company.Its preparation process is tediously long, and need to high temperature (200～250 ℃), high pressure (5～20MPa) and the nickel-containing catalyst condition under face the hydrogen aminating reaction, production difficulty is large, product cost is high.And the present invention's aromatic amine polyethenoxy ether used is different from the polyetheramine structure of above-mentioned U.S. Huntsman company, belongs to the tertiary amine-type polyetheramine.Its simple synthetic method, working condition is gentle, and temperature of reaction is at 100～180 ℃, and reaction pressure is 0.1～0.5MPa, and the catalyzer that reacts used is KOH, product cost is low, excellent property.Therefore, make the gasoline cleaning agent of main component preparation of this aromatic amine polyethenoxy ether and compare for the CN100562560C patented product with Granted publication number, all have obvious characteristics and progress on the molecular structure of Main Components, on synthetic method and on the purification agent product cost.
Summary of the invention
The objective of the invention is the polyetheramine tensio-active agent of synthetic a kind of new texture-aromatic amine polyethenoxy ether, it is easy to prepare, excellent property, and cost is lower.Use in motor spirit and can reduce significantly the sedimental generation of petrol engine fuel oil inlet system with the gasoline cleaning agent that this aromatic amine polyethenoxy ether is done the preparation of main component.Thereby make motor car engine be in for a long time good operation condition state, can reduce the motor car engine oil consumption, reduce the tail gas hazardous emission, extend the work-ing life of engine.
Gasoline cleaning agent of the present invention is comprised of aromatic amine polyethenoxy ether, oxidation inhibitor, rust-preventive agent, corrosion inhibitor and the solubility promoter of high surface, and the quality proportioning of above each component is:
Aromatic amine polyethenoxy ether 60.0～80.0%
Oxidation inhibitor 2.0～5.0%
Rust-preventive agent 1.0～3.0%
Corrosion inhibitor 0.5～1.5%
Solubility promoter 14.0～34.0%
The structural formula of described aromatic amine polyethenoxy ether is:
Wherein, R is the alkyl of hydrogen or C1～C10; A+b is 9～33 natural number; With respect to nitrogen-atoms, R can be positioned at ortho position, a position or the contraposition on phenyl ring; The weight-average molecular weight of aromatic amine polyethenoxy ether is 700～2000, and total amine value is 28～79mgKOH/g.
Described oxidation inhibitor is selected from the mixture of one or more compositions in commercially available T501, T502, T531, T534.
Described rust-preventive agent is selected from the mixture of one or more compositions in commercially available T703, T706, T747, SP-80, SP-85.
Described corrosion inhibitor is selected from commercially available T551, the mixture of one or both compositions in T561.
Described solubility promoter is selected from the mixture of one or more compositions in commercially available toluene, dimethylbenzene, alkylbenzene, aromatic hydrocarbon oil, solvent oil, methyl alcohol, ethanol, butanols, isooctyl alcohol.
The dosage of gasoline cleaning agent of the present invention by 500～1000ppm is added in commercially available gasoline, rate of descent according to the settling on the experimental technique simulated automotive intake valve of GB/T19230.4 regulation generates, change by thermogravimetric analyzer simulated automotive deposition of combustion chamber of engine increment.Under high pure nitrogen protection,, respectively the sample of gasoline cleaning agent of the present invention and marketable gasolines purification agent, be under the condition of 10 ℃/minute, to be heated to more than 500 ℃ and to carry out the residual rate contrast in temperature rise.Compare with commercially available gasoline cleaning agent, the settling rate of descent that gasoline cleaning agent of the present invention can produce intake valve is brought up to more than 80% from 50～60%, and the total settling increment of automotive engine combustion chamber can reduce more than 60%.
Embodiment
Aromatic amine polyethenoxy ether synthesis example one:
The preparation of synthesis reaction vessel: with distilled water the autoclave of 2L brush several times first, until clean, the oven dry reactor, be cooled to 50～70 ℃ standby.
The first step, add 535g to monomethylaniline in reactor, after twice of nitrogen replacement, intensification limit, limit vacuumizes, and when temperature is raised to 120 ℃, closes vacuum valve.Slowly add the 380g propylene oxide, after 130～175 ℃ of reactions extremely fully, be cooled to 80 ℃ of dischargings.
second step: the product and the 4.0g solid KOH that add 366g the first step gained in reactor, be warmed up to 90～110 ℃, vacuum hydro-extraction 0.5～1.0h, then the 1240g propylene oxide is pressed into reactor, control feed rate, keep reactor pressure at 0.1～0.5MPa, keep temperature of reaction at 135～165 ℃, till reacting and no longer descending to reactor pressure, be cooled to normal temperature, to entering in beaker, adding the acid atlapulgite of 28g to neutralize decolours and the k adsorption ion, then carry out suction filtration with Bush's funnel, solution after suction filtration is 90～110 ℃ in temperature, vacuum tightness is to deviate from moisture and volatile small molecular weight impurity under the condition of 0.085～0.095MPa, namely obtain light yellow transparent thick to the monomethylaniline polyethenoxy ether.Through chemical analysis, total amine value of this product is 69.8mgKOH/g, and potassium content is 1.7mg/L, and moisture content is 0.22%, and weight-average molecular weight is about 803.
Aromatic amine polyethenoxy ether synthesis example two:
The preparation of synthesis reaction vessel: with distilled water the autoclave of 2L brush several times first, until clean, the oven dry reactor, be cooled to 50～70 ℃ standby.
The first step, add 596g 3-tertiary butyl aniline in reactor, after twice of nitrogen replacement, intensification limit, limit vacuumizes, and when temperature is raised to 120 ℃, closes vacuum valve.Slowly add the 348g propylene oxide, after 140～160 ℃ of reactions extremely fully, be cooled to 80 ℃ of dischargings.
second step: the product and the 4.3g solid KOH that add 280g the first step gained in reactor, be warmed up to 90～110 ℃, vacuum hydro-extraction 0.5～1.0h, then the 1500g propylene oxide is pressed into reactor, control feed rate, keep reactor pressure at 0.1～0.5MPa, keep temperature of reaction at 130～150 ℃, till reacting and no longer descending to reactor pressure, be cooled to normal temperature, to entering in beaker, adding the acid atlapulgite of 30g to neutralize decolours and the k adsorption ion, then carry out suction filtration with Bush's funnel, solution after suction filtration is 100～110 ℃ in temperature, vacuum tightness is to deviate from moisture and volatile small molecular weight impurity under the condition of 0.085～0.095MPa, namely obtain light yellow transparent thick 3-tertiary butyl aniline polyethenoxy ether.Through chemical analysis, total amine value of this product is 37.5mgKOH/g, and potassium content is 4.3mg/L, and moisture content is 0.15%, and weight-average molecular weight is about 1496.
Embodiment 1:
Composite with obtain in synthesis example one monomethylaniline polyethenoxy ether and oxidation inhibitor, rust-preventive agent, corrosion inhibitor and solubility promoter are carried out, the quality proportioning of its each component is: 65.0% pair of monomethylaniline polyethenoxy ether, 2.5% T502,1.5% T747,1.0%T551 and 34.0% aromatic hydrocarbon oil.
According to adding ratio metering, mixing and stirring at room temperature, until transparent, namely obtain gasoline cleaning agent of the present invention after filtration with above-mentioned component.Gasoline cleaning agent of the present invention is pressed the dosage of 600ppm, added in commercially available 93# gasoline, through specialized department's evaluation, the physical and chemical index of oil product all meets the requirement of GB17930-2006.Generate the settling rate of descent according to GB/T19230.4 test method simulated automotive intake valve, by the variation of thermogravimetric analyzer simulated automotive deposition of combustion chamber of engine increment.After tested, simulation intake valve settling rate of descent reaches 85.3%, and with high temperature thermogravimetric analysis more than 500 ℃, simulated combustion chamber settling increment changes, and than at present commercially available purification agent, descends 94%, and measured data is listed in table 1.
Embodiment 2:
The 3-tertiary butyl aniline polyethenoxy ether that obtains with synthesis example two and oxidation inhibitor, rust-preventive agent, corrosion inhibitor and solubility promoter carry out composite, and the quality proportioning of each component is: 70.0%3-tertiary butyl aniline polyethenoxy ether, 2.5% T502,1.5% T747,1.5%T551 and 24.5% aromatic hydrocarbon oil.Repeat the preparation method of embodiment 1, obtain gasoline cleaning agent of the present invention.
Gasoline cleaning agent of the present invention is pressed the dosage of 700ppm, added in commercially available 93# gasoline, through specialized department's evaluation, the physical and chemical index of oil product all meets the requirement of GB17930-2006.Generate the settling rate of descent according to GB/T19230.4 test method simulated automotive intake valve, by the variation of thermogravimetric analyzer simulated automotive deposition of combustion chamber of engine increment.After tested, simulation intake valve settling rate of descent reaches 86.5%, and with high temperature thermogravimetric analysis more than 500 ℃, simulated combustion chamber settling increment changes, and than at present commercially available purification agent, descends 91%, and measured data is listed in table 1.
Embodiment 3:
The 3-tertiary butyl aniline polyethenoxy ether that obtains with synthesis example two and oxidation inhibitor, rust-preventive agent, corrosion inhibitor and solubility promoter carry out composite, and the quality proportioning of each component is: 80.0%3-tertiary butyl aniline polyethenoxy ether, 2.5% T502,1.5% T706,1.0%T551 and 15.0% aromatic hydrocarbon oil.Repeat the preparation method of embodiment 1, obtain gasoline cleaning agent of the present invention.
Gasoline cleaning agent of the present invention is pressed the dosage of 800ppm, added in commercially available 93# gasoline, through specialized department's evaluation, the physical and chemical index of oil product all meets the requirement of GB17930-2006.Generate the settling rate of descent according to GB/T19230.4 test method simulated automotive intake valve, by the variation of thermogravimetric analyzer simulated automotive deposition of combustion chamber of engine increment.After tested, simulation intake valve settling rate of descent reaches 88.0%, and with high temperature thermogravimetric analysis more than 500 ℃, simulated combustion chamber settling increment changes, and than at present commercially available purification agent, descends 90%, and measured data is listed in table 1.
Table 1
Claims (4)
1. the gasoline cleaning agent with the preparation of aromatic amine polyethenoxy ether, is characterized in that this gasoline cleaning agent is comprised of aromatic amine polyethenoxy ether, oxidation inhibitor, rust-preventive agent, corrosion inhibitor and solubility promoter, and the quality proportioning of above each component is:
The structural formula of described aromatic amine polyethenoxy ether can be represented by general formula (I):
Wherein, R is hydrogen or C
1～C
10Alkyl, with respect to nitrogen-atoms, R can be positioned at ortho position, a position or the contraposition on phenyl ring; A+b is 9～33 natural number; The weight-average molecular weight of aromatic amine polyethenoxy ether is 700～2000, and total amine value is 28～79mgKOH/g;
Described oxidation inhibitor is selected from the mixture of one or more compositions in commercially available T501, T502, T531, T534;
Described rust-preventive agent is selected from the mixture of one or more compositions in commercially available T703, T706, T747, SP-80, SP-85;
Described corrosion inhibitor is selected from commercially available T551, the mixture of one or both compositions in T561;
Described solubility promoter is selected from the mixture of one or more compositions in commercially available toluene, dimethylbenzene, aromatic hydrocarbon oil, solvent oil, methyl alcohol, ethanol, butanols, isooctyl alcohol.
2. gasoline cleaning agent as claimed in claim 1 is characterized in that the quality proportioning of each component is:
3. gasoline cleaning agent as claimed in claim 1 is characterized in that the quality proportioning of each component is:
4. gasoline cleaning agent as claimed in claim 1 is characterized in that the quality proportioning of each component is:
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010105176647A CN101962586B (en) | 2010-10-25 | 2010-10-25 | Gasoline detergent prepared from aromatic amine polyoxypropylene ether |
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| CN2010105176647A CN101962586B (en) | 2010-10-25 | 2010-10-25 | Gasoline detergent prepared from aromatic amine polyoxypropylene ether |
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| CN101962586A CN101962586A (en) | 2011-02-02 |
| CN101962586B true CN101962586B (en) | 2013-11-13 |
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| CN110240959B (en) * | 2019-07-01 | 2021-07-16 | 山东益丰生化环保股份有限公司 | Gasoline detergent and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW341580B (en) * | 1996-02-15 | 1998-10-01 | Dow Chemical Co | Preparation of polyetheramines and polyetheramine derivatives |
| US6267791B1 (en) * | 1993-03-20 | 2001-07-31 | Basf Aktiengesellschaft | Mixtures suitable as fuel additives |
| WO2002079353A1 (en) * | 2001-03-29 | 2002-10-10 | The Lubrizol Corporation | Gasoline additive concentrate composition and fuel composition and method thereof |
| CN101230298A (en) * | 2007-09-29 | 2008-07-30 | 天津悦泰石化科技有限公司 | Petrol detergent capable of remarkably reducing deposit of gasoline engine combustion chamber |
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2010
- 2010-10-25 CN CN2010105176647A patent/CN101962586B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6267791B1 (en) * | 1993-03-20 | 2001-07-31 | Basf Aktiengesellschaft | Mixtures suitable as fuel additives |
| TW341580B (en) * | 1996-02-15 | 1998-10-01 | Dow Chemical Co | Preparation of polyetheramines and polyetheramine derivatives |
| WO2002079353A1 (en) * | 2001-03-29 | 2002-10-10 | The Lubrizol Corporation | Gasoline additive concentrate composition and fuel composition and method thereof |
| CN101230298A (en) * | 2007-09-29 | 2008-07-30 | 天津悦泰石化科技有限公司 | Petrol detergent capable of remarkably reducing deposit of gasoline engine combustion chamber |
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