CN1249209C - Diesel oil antifriction dispersion additive composition - Google Patents
Diesel oil antifriction dispersion additive composition Download PDFInfo
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Abstract
The present invention relates to an antifriction dispersion additive composition for diesel oil, and comprises the following components: (A) a reaction product or a reaction product mixture of mannich base which is generated by a reaction of polyolefin phenol, aldehyde of C1 to C6 and polyene polyamine, and hydroxy aromatic acid, and (B) a reaction product or a reaction product mixture of organic acid of C6 to C40 and one of alcohol, amine, alkylol amine or epoxide, or a mixture of at least one of the alcohol, the amine, the alkylol amine or the epoxide, wherein a weight ratio of the component (A) to the component (B) is 1:0.1 to 10. The general addition level of the multi-effect additive of the present invention in diesel oil is from 50 to 2000 ppm; the additive composition can be used as an antifriction agent for diesel oil, and can be used as a stabilizer and a dispersing agent for diesel oil.
Description
Technical field
The invention belongs to diesel oil multi-efficient additive, definite saying so both can be used as diesel antiwear additive, also can be used as the multipurpose additive of diesel oil stabilizing agent, diesel oil ashless dispersant.
Technical background
Along with the pay attention to day by day of countries in the world to environmental issue, pollute in order to reduce diesel exhaust gas, produce high-quality clean diesel, become the developing direction of modern petroleum refining industry.This diesel oil has generally that sulphur content is low, and it is low to contain aromatic hydrocarbons, cetane value height, characteristics such as cut is light.Studies show that sulphur is the harmful element that increases CH, CO, particularly pellet (PM) in the diesel engine emissions, so it is particularly important to improving topsoil to reduce in the diesel oil sulphur content.The diesel oil specification of the present U.S., Canada, every Western Europe country, all regulation diesel oil contains the S amount less than 0.05%, and aromaticity content is also lower.Because they have generally adopted harsh hydrogenation technique, the content that polarity in the diesel oil contains oxygen, nitrogenous compound is all very low, the content of many rings, double ring arene is also less, thereby reduced the natural lubricity of diesel oil, some oil injection pumps that rely on diesel oil itself to be lubricated have been caused, wearing and tearing occur as rotor pump (rotary pumps), proportioning pump (distributor pumps), reduced their work-ing life.
As everyone knows, non-hydrocarbon compounds such as the alkene in the diesel oil, diolefin and sulfide, nitride generate a series of intermediate oxidation product, and produce insoluble precipitation through condensation under the effect of oxygen.These insoluble particles that generate in the diesel oil storage process can have influence on the use properties of fuel, cause filtering system to stop up, and cause the prime the fuel system unit failure; influence oil atomizing; cause incomplete combustion, even in engine, form too much carbon deposit, make spray nozzle clogging.
The problems referred to above can be alleviated by add additive in diesel oil.It is generally acknowledged that diesel antiwear additive can remedy because of diesel oil causes the loss that plays lubricated composition in the oil through hydrotreatment, improves diesel fuel lubricity; Diesel oil stabilizing agent can stop, weakens or disturb above-mentioned various reaction, and is rotten to suppress diesel oil, improves its stability; Diesel cleaning and dispersing agent can wash down established carbon deposit on the nozzle, and forms protective membrane at nozzle surface, prevents that new carbon deposit from producing, and also can disperse established sediment in the diesel oil simultaneously, improves purifier and spray nozzle clogging, and improves exhaust emissions.
Diesel antiwear additive mostly is the derivative of fatty acid ester, acid amides or salt.EP773279 discloses and has used the carboxylicesters of dimeracid and hydramine prepared in reaction as diesel antiwear additive.EP798364 discloses with the salt of lipid acid and aliphatic amide prepared in reaction or acid amides as diesel antiwear additive.EP1209217 discloses C
6～C
50The reaction product of saturated fatty acid and dicarboxylic acid and short chain oils dissolubility primary, the second month in a season, tertiary amine is as diesel antiwear additive.WO9915607 discloses the reaction product of dimer (fatty acid) yl and epoxide as diesel antiwear additive.But these additives to the stability of diesel oil and detergent-dispersant performance to no effect, and may also can make the oxidation stability and the dispersed variation of diesel oil in many cases.
Mannich base (Mannich base) class lubricating oil and oil fuel ashless dispersant are the big classes in the dispersion agent that uses at present, US 3,649,229 reports are with high molecular (600～3000) alkylphenol, aldehyde, the mannich base product that contains the amine of the H-N＜group detergent-dispersant additive that acts as a fuel.
Mannich base is carried out chemical modification can make effects such as its dispersion, antioxygen all strengthen to some extent.As US 5,399,273 reports with the derivative of the mannich base product of high molecular (900～4000) alkylphenol, aldehyde, polyamines and two-ketone/sulfo-ketone compound as lubricating oil and fuel dispersants etc.
Summary of the invention
The purpose of this invention is to provide a kind of multipurpose additive with functions such as wear-resistant, stable, dispersions, it can not only improve the oilness of low-sulfur diesel-oil and can also stop condensation between alkene, diolefin oxidation and the non-hydrocarbon compound in the diesel oil, gathering between the small oxidation products that prevents to have produced, make it to be dispersed among the diesel oil, thereby improve the stability of diesel oil, delay engine filter and spray nozzle clogging.
Diesel oil multi-efficient additive provided by the invention comprises following component:
(A) reaction product of mannich base and phenol acids or product mixtures, wherein mannich base by
Polyolefin-based phenol, C
1～C
6Aldehyde and polyamines polyene reaction generate;
(B) C
6～C
40The reaction of one or more in organic acid and alcohol, amine, hydramine or the epoxide
Product or product mixtures;
Wherein component (A) is 1: 0.1～10 with the weight ratio of component (B), preferred 1: 0.2～6, more preferably 1: 0.3～3.
About component (A)
Said component (A) prepares by following method:
With mannich base and phenol acids according to 1: 0.5～5, preferred 1: 1～4 mixed in molar ratio (mole number of mannich base in wherein the mole number of polyamines polyene), in 50～200 ℃, preferred 80～160 ℃ were reacted preferred 1～10 hour 0.5～20 hour in the presence of solvent.Available nitrogen protection in the reaction system perhaps allows and carries out under the condition that is reflected at solvent refluxing.This reaction can not add catalyzer, also can add a small amount of (0.01～1%) acidic cpd such as sulfuric acid, tosic acid or acidic white earth as catalyzer, so that fast reaction speed.Said reaction solvent is hydrocarbon polymer such as benzene,toluene,xylene, aromatic hydrocarbons thinning oil, industrial naptha or mineral oil (boiling point is more than 120 ℃), or their mixture.Solvent load generally is 30～150% of a monomer material gross weight.For the ease of postorder operation and storage, last product can be made into about 50% diluent with the aromatic hydrocarbons thinning oil.
Said phenol acids is selected from Whitfield's ointment (salicylic acid), m-Salicylic acid, P-hydroxybenzoic acid, 3-hydroxyl 2-naphthoic acid, 3,4,5-trihydroxybenzoic acid (gallic acid), 4, two (4-hydroxyphenyl) valeric acids (diphenolic acid) of 4-etc. or their mixture.
Said mannich base is made by polyolefin-based phenol, aldehyde and polyamines polyene reaction, and three's mol ratio is generally 1: 0.1～10: 0.1～10, be preferably 1: 1～4: 0.5～and 2.The mannich reaction temperature is generally 50～200 ℃, is preferably within 70～150 ℃ of scopes.Reaction medium can be hydrocarbon polymer such as benzene,toluene,xylene, aromatic hydrocarbons thinning oil (boiling range is 159～185 ℃), industrial naptha or mineral oil (boiling point is more than 120 ℃), or their mixture.Solvent load generally is 30～150% of a monomer material gross weight.Available nitrogen protection in the reaction system perhaps allows system carry out under the condition of solvent refluxing.The preparation method is at US 3,413, and 347, US3,649,229, description is all arranged in US 3,798,165, US 4,116,644, US 4,553,979 patent documentations such as grade.
Polyolefin-based phenol wherein is the macromolecular compound with following structure:
Wherein R is Atactic Polypropelene, polybutene, polyisobutene or ethylene-propylene copolymer, and the number-average molecular weight of R is 300～3000, preferred 500～2000.The preparation of polyolefin-based phenol can be adopted existing alkylation of phenol technology.For example, under a small amount of acid catalyst action, 0.1～10 moles of phenol (being preferably 1～2.5 mole) and 1 mole of polyolefine are carried out alkylated reaction under 50～150 ℃.An acidic catalyst can be sulfuric acid, phosphoric acid or Lewis acid, as BF
3-diethyl ether solution, BF
3-ethanolic soln, BF
3-phenol solution etc., preferred Lewis acids.Reaction finishes back distilled water flush away catalyzer, and underpressure distillation or wet distillation are removed unreacted phenol again.
Aldehyde wherein is meant C
1～C
6Aldehyde, as formaldehyde, acetaldehyde, propionic aldehyde, hexamethylene aldehyde etc., formaldehyde preferably, 36% formaldehyde solution or Paraformaldehyde 96 all can.
The structural formula of polyamines polyene wherein is H
2N[(CH
2)
nNH]
mH, n are 2～4, and preferred 2～3 integer, m are 1～5, preferred 3～4 integer.As quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, propylene diamine, two propylene triamines, three propylene tetramines, tetrapropylene five amine, five propylene hexamines etc.Preferred triethylene tetramine, tetraethylene pentamine and five ethene hexamines.
About component (B)
Said component (B) is C
6～C
40The reaction product or the product mixtures of one or more in organic acid and alcohol, amine, hydramine or the epoxide.
Described C
6～C
40Organic acid, preferred C
8～C
36Organic acid can be a lipid acid, also can be naphthenic acid; Can be monocarboxylic acid or polycarboxylic acid; Can be saturated acid or unsaturated acid.A kind of and multiple in caproic acid, hexanodioic acid, sad, isocaprylic acid (2 ethyl hexanoic acid), capric acid, laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid, oleic acid, linolic acid, stearic acid, Palmiticacid, ricinolic acid, 20 acid, dimeracid etc. for example; Can also be mixing acid, as the naphthenic acid of all size, vegetable fatty acids such as palmitinic acid etc., preferably normal temperature is down liquid acid such as oleic acid, linolic acid, dimeracid, ricinolic acid, naphthenic acid etc.
Described alcohol refers to C
1～C
18Fatty Alcohol(C12-C14 and C12-C18) can be a monohydroxy-alcohol, also can be polyvalent alcohol.Monohydroxy-alcohol can be ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol etc., and just structure and isomery all can.Polyvalent alcohol can be ethylene glycol, polyoxyethylene glycol, 1, and 2-propylene glycol, 1, ammediol, glycerol, the butyleneglycol of various structures, pentanediol, hexylene glycol, heptanediol, ethohexadiol, nonanediol, decanediol, tetramethylolmethane, sorbyl alcohol, anhydrous sorbitol etc.Wherein, preferred C
2～C
8Fatty Alcohol(C12-C14 and C12-C18), more preferably polyvalent alcohol.
Described amine is that carbon number is C
1～C
10, preferred C
2～C
6Aliphatic amide, Cycloalkyl amine or heterocyclic amine.Wherein aliphatic amide can be primary amine or secondary amine, can be monoamine, also can be polyamine.Monoamine such as ethamine, propylamine, butylamine, amylamine, hexylamine etc., just structure and isomery all can.Polyamine can be quadrol, propylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines etc.Cycloalkyl amine can be cyclopentamine, hexahydroaniline etc.; Heterocyclic amine can be morpholine, piperazine etc.
Epoxide can be C
2～C
18Epoxide, as oxyethane, 1,2 epoxy prapane, 1,2-butylene oxide ring, 1,2-epoxy octadecane etc. or their mixture, preferred C
2～C
8Epoxide.
Hydramine can be thanomin, diethanolamine, trolamine, methyldiethanolamine etc.
Above-mentioned alcohol, amine, hydramine or epoxide are referred to as " acylable thing " in the present invention; said B component can be one or more reaction product that feed intake by arbitrary proportion in organic acid and the acylable thing, also can be the mixture of the arbitrary proportion of above-mentioned reaction product.Organic acid and acylable thing are pressed the chemical dose reaction, the total mole number that is organic acid mole number and acylable thing is basic identical, but when containing polyvalent alcohol, polyamine or hydramine in the acylable thing, because the quantity of reactive group should suitably increase the organic acid ratio more than the mole number of acylable thing; When containing epoxide in the acylable thing, consider the autohemagglutination characteristic of epoxide, should suitably reduce the organic acid ratio.
The reaction of organic acid and above-mentioned various acylable things can be carried out by the following method:
When organic acid and alcohol carry out esterification, can in non-pressure vessel, add an acidic catalyst of reactant about 1% such as sulfuric acid, tosic acid etc. with fast reaction speed, and divide water or nitrogen purging to dewater 2～10 hours at 80～160 ℃ of following solvent refluxings, add in an amount of alkali then and an acidic catalyst.
When organic acid and hydramine carry out esterification, can in non-pressure vessel, add the basic catalyst of reactant about 1% such as sodium hydroxide, potassium hydroxide, sodium methylate/methyl alcohol, organic bases such as dimethyl cyclohexyl amine etc. with fast reaction speed, and divide water or nitrogen purging to dewater 2～10 hours at 80～160 ℃ of following solvent refluxings, add in an amount of acidic substance then and basic catalyst.
When organic acid and epoxide react, can in non-pressure vessel, add the basic catalyst of reactant about 1% such as sodium hydroxide, potassium hydroxide, sodium methylate/methyl alcohol, organic bases such as dimethylcyclohexylamine etc. with fast reaction speed, also can in high-pressure reactor, not add catalyzer and under certain pressure and 80～160 ℃, carry out.
When organic acid and amine carry out amination reaction, can in non-pressure vessel, not add catalyzer or add an acidic catalyst of reactant about 1% such as sulfuric acid, tosic acid etc. with fast reaction speed, and divide water or nitrogen purging to dewater 2～10 hours, as be added with catalyzer and then need add in an amount of alkali and an acidic catalyst at 80～160 ℃ of following solvent refluxings.
The addition of multipurpose additive provided by the invention in diesel oil generally is 50～2000ppm, preferred 100～1000ppm.
According to using needs, additive provided by the invention can also with other additive, use simultaneously as FLOW IMPROVERS, cetane number improver, metal passivator, sanitas etc.
Diesel oil multi-efficient additive provided by the invention not only has preferably resistance to abrasion, also has resistance of oxidation and a detergent-dispersant performance energy, colloid isopolarity compound and fine particles had very strong absorption and capturing ability, can stop its further oxidation, gathering, thereby reduce the generation of oxidation sediment in the diesel oil.
In addition, additive of the present invention also has other function, as improves the copper corrosion of diesel oil, reduces the discharging of diesel motor exhaust.
Embodiment
Example 1
This example is the preparation of polyolefin-based phenol:
In a 1000ml three-necked bottle, add 363.3 gram polyisobutene (polyisobutene number average relative molecular mass Mn=1100, source are Jinzhou petro-chemical corporation) and 62.1 gram phenol, be heated with stirring to 50 ℃, with 14.1 gram BF
3-diethyl ether solution divides and is added drop-wise in the reaction system about two hours for three times.Be warming up to 60 ℃, clock reaction 4.5 hours.Stopped reaction, it is inferior to give a baby a bath on the third day after its birth with the distilled water of heat, and unreacted phenol is removed in underpressure distillation again.Adopt the column chromatography analysis method to calculate transformation efficiency, unreacted polyisobutene is 32% in the sherwood oil, and then alkylating transformation efficiency is 68%.
Example 2
This example is the preparation of polyolefin-based phenol:
In a 500ml three-necked bottle, add 100 gram polyisobutene (polyisobutene number average relative molecular mass Mn=1000, source are German BASF AG) and 18.8 gram phenol, be heated with stirring to 60 ℃, with 4.3 gram BF
3-diethyl ether solution divides and is added drop-wise in the reaction system about two hours for three times.Be warming up to 70 ℃, clock reaction 4 hours.Stopped reaction, it is inferior to give a baby a bath on the third day after its birth with the distilled water of heat, and unreacted phenol is removed in underpressure distillation again.Adopt the column chromatography analysis method to calculate transformation efficiency, unreacted polyisobutene is 30% in the sherwood oil, and then alkylating transformation efficiency is 70%.
Example 3
This example is the synthetic of mannich base:
In three-necked bottle, add polyolefin-based phenol, 9.4 gram triethylene tetramines and the 120 gram toluene of 100 grams by example 1 preparation, heated and stirred to 70 ℃ was added drop-wise to (mol ratio of polyolefin-based phenol, formaldehyde, triethylene tetramine is 1: 3: 1.2) in the reaction system with the formaldehyde solution of 13.4 grams 36% in 2 hours.Be warmed up to 100 ℃ after dripping off, and 100 ℃ of clock reactions 2 hours.Remove toluene solvant and water with underpressure distillation then, add 50 gram aromatic hydrocarbons thinning oils again, be made into about 50% diluent.
Example 4
This example is the synthetic of mannich base:
In three-necked bottle, add polyolefin-based phenol, 1.8 gram Paraformaldehyde 96s, 11.3 gram tetraethylene pentamine and the 50 gram aromatic hydrocarbons thinning oils (mol ratio of polyolefin-based phenol, formaldehyde, tetraethylene pentamine be 1: 1: 1) of 100 grams by example 2 preparations, heated and stirred to 90 ℃, reaction is 6 hours under nitrogen purging, divide water outlet, add 10 gram aromatic hydrocarbons thinning oils again, be made into about 50% diluent.
Example 5～8th, the preparation of component (A).
Example 5
In three-necked bottle, add mannich base and the 3.5 gram P-hydroxybenzoic acid (P-hydroxybenzoic acid and triethylene tetramine mol ratio be about 1.3: 1) of 50 grams by example 3 preparations, and 4 gram aromatic hydrocarbons thinning oil, logical nitrogen, reacted 5 hours down at 100 ℃, be cooled to room temperature then, make component A1 of the present invention.
Example 6
In three-necked bottle, add mannich base and 4.9 gram salicylic acids (Whitfield's ointment) and the 5 gram aromatic hydrocarbons thinning oils (salicylic acid and triethylene tetramine mol ratio be about 1.8: 1) of 50 grams by example 3 preparations, in the presence of nitrogen, reacted 3 hours in 130 ℃, be cooled to room temperature then, make component A2 of the present invention.
Example 7
In three-necked bottle, add mannich base and 4.3 gram P-hydroxybenzoic acid and the 5 gram aromatic hydrocarbons thinning oils (P-hydroxybenzoic acid and tetraethylene pentamine mol ratio be about 1.8: 1) of 50 grams by example 4 preparations, in the presence of nitrogen, reacted 6 hours in 80 ℃, be cooled to room temperature then, make component A3 of the present invention.
Example 8
With 4.8 grams 3,4, the 5-trihydroxybenzoic acid replaces 4.3 gram P-hydroxybenzoic acid of example 7, in 120 ℃ of reactions 5 hours, is cooled to room temperature in the presence of nitrogen, makes component A4 of the present invention.
Example 9～13rd, the preparation of component (B).
Example 9
With 100g ricinolic acid and 25.5g 1,2-propylene glycol (ricinolic acid and 1, the mol ratio of 2-propylene glycol is about 1: 1) and the agent of 1.3g Catalyzed by p-Toluenesulfonic Acid place a reactor that electric mixer, thermometer, water trap, reflux condensing tube and nitrogen ingress pipe be housed, fed nitrogen 5～10 minutes, and in reaction process, keep nitrogen gas stream, heated and stirred to be warming up to 140 ℃, divide water reaction 5 hours, be cooled to 80 ℃ then, add 0.6gCa (OH)
2, in and half an hour after-filtration, filtrate is B component 1, its acid number is 3.8mgKOH/g.
Example 10
100g dimeracid, 12.9g n-Butyl Amine 99 (mol ratio of dimeracid and n-Butyl Amine 99 is about 1: 1) are placed a reactor that electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe be housed, fed nitrogen 5～10 minutes, and in reaction process, keep faint nitrogen gas stream, react half an hour at 60 ℃ earlier, be warming up to 130 ℃ of branch water reactions 5 hours then, cooling promptly gets B component 2.
Example 11
100g oleic acid, 52.8g trolamine (mol ratio of oleic acid and trolamine is about 1: 1) and 2.8g sodium methylate/catalyst for methanol are placed a reactor that electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe be housed, fed nitrogen 5～10 minutes, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 160 ℃, reacted 5 hours, be cooled to 90 ℃ then, add neutralization of 3.2g acidic white earth and filtration, promptly get B component 3, recording its acid number is 8.3mgKOH/g.
Example 12
100g linolic acid, 15.5g morpholine and 26.1g triethylene tetramine (mol ratio of Viscotrol C, morpholine, triethylene tetramine is about 1: 0.5: 0.5) are placed a reactor that electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe be housed, fed nitrogen 5～10 minutes, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 140 ℃, divide water reaction 8 hours, cooling promptly gets B component 4.
Example 13
With 100g naphthenic acid (acid number 216mgKOH/g) and 44.8g 1,2-propylene oxide (naphthenic acid and 1, the mol ratio of 2-propylene oxide is about 1: 2) and 1.0g dimethyl cyclohexane catalyzer place a reactor that electric mixer, thermometer, reflux condensing tube and nitrogen ingress pipe be housed, feed nitrogen 5～10 minutes, and kept nitrogen atmosphere.The heated and stirred back flow reaction, when temperature is raised to 140 ℃, stopped reaction, cooling promptly gets B component 5, and recording its acid number is 8.9mgKOH/g.
Example 14～20 is the preparation of diesel oil multi-efficient additive composition of the present invention.
To be selected from the component A of example 5～8, the B component of example 9～13, mix, obtain different compositions according to the weight ratio shown in the table 1.
The preparation of table 1 multi-effect composite additive
| Example | Component A | B component | A, B weight ratio |
| Example 14 examples 15 examples 16 examples 17 examples 18 examples 19 examples 20 | A1, (example 5) A2, (example 6) A1, (example 5) A3, (example 7) A2, (example 6) A3, (example 7) A4, (example 8) | B1, (example 9) B5, (example 13) B2, (example 10) B3, (example 11) B1, (example 9) B4, (example 12) B4, (example 12) | 1∶0.5 1∶0.25 1∶2 1∶1 1∶1 1∶0.8 1∶0.5 |
The physicochemical property of table 2 diesel oil
| Diesel oil | ||
| (a) | (b) | |
| Density (20 ℃)/gcm -3Viscosity (40 ℃)/mm 2·s -1S content/mgkg -1N content/mgkg -1Basic nitrogen/mgkg -1The total double ring arene of the total mononuclear aromatics/m% of the total cycloalkane/m% of alkane/m%/m% thrcylic aromatic hydrocarbon/m% initial boiling point/℃ 20% heats up in a steamer a little/℃ 50% heat up in a steamer a little/℃ 90% heat up in a steamer a little/℃ do/℃ positive structure hydrocarbon of positive structure hydrocarbon content/% carbon number C217Positive structure hydrocarbon content/% | 0.8576 2.548 238 120 10 38.5 18.4 29.6 11.9 1.6 188 230 252 343 353 21.71 C 8-C 28 8.96 | 0.8360 2.510 197 163 36 47.2 22.3 21.6 7.9 1.0 190 214 260 324 350 29.20 C 8-C 28 10.92 |
Example 21
This example is the result of use of multi-effect composite additive in diesel oil that example 14～20 makes.Select huge port 0 for use
#The mixed oil (a) and the Yanshan Mountain 0
#Processed oil (b).Its physicochemical property sees Table 2, adds HFRR method (ISO12156-1) the grinding defect diameter WSD of agent front and back diesel oil
1.4, the oxidation stability total insoluble substance of accelerating oxidation style (SH/T0175-94) evaluation oil product sees Table 3, when grinding defect diameter during less than 460um (60 ℃), then the oilness of diesel oil is qualified; Total insoluble substance is less than or equal to 2.5mg/100ml, and then the oxidation stability of diesel oil is qualified.
Table 3 multi-effect composite additive is to the effect of improving of diesel fuel lubricity and oxidation stability
| Diesel oil | Additive | Addition/mgkg -1 | Oilness | Oxidation stability |
| WSD 1.4/um | Total insoluble substance/mg100ml -1 | |||
| a a a a a a a a a a | / example 5 examples 9 examples 14 examples 15 examples 16 examples 17 examples 18 examples 19 examples 20 | / 400 400 500 500 600 500 600 500 350 | 535 480 298 236 287 228 223 217 232 241 | 2.3 1.5 2.9 1.0 1.1 1.5 1.0 1.6 0.8 1.3 |
| b b b b b b b b b b | / example 5 examples 9 examples 14 examples 15 examples 16 examples 17 examples 18 examples 19 examples 20 | / 300 300 500 600 500 600 500 600 400 | 460 390 255 189 225 238 228 199 208 223 | 3.1 1.9 3.9 1.8 1.6 1.2 2.0 1.8 1.9 2.2 |
By table 3 as can be seen, though separately the component A that uses the oxidation stability of diesel oil is had certain improvement, resistance to abrasion relatively poor (example 5); The B component of using has certain resistance to abrasion separately, but makes the oxidation stability variation (example 9) of diesel oil on the contrary, and diesel oil multi-efficient additive composition provided by the invention can improve low-sulfur diesel-oil energy oilness, can improve the stability of diesel oil again.
Example 22
This example employing tinsel sedimentation is carried out simulation evaluation to the dispersing property of additive.
Present method is at the character of diesel oil, the tinsel sedimentation that the rotary oxygen bomb method that is used for measuring lubricating oil oxidation stability and SAE 872112 (Society of automotive engineers report) is used to evaluate the gasoline detergent dispersiveness has been carried out comprehensive improvement, and experimental installation and test method are referring to Chinese patent CN1382777.Test-results sees Table 4, wherein deposits improvement rate=(blank value one experimental value)/blank value * 100%.
Table 4 tinsel sedimentation evaluation diesel oil deposition conditions on tinsel
| Sample | Add dosage/mg.kg -1 | Deposition/mg | Deposition improvement rate/% |
| Blank diesel oil b b+ example 14 product b+ examples 15 product b+ examples 16 product b+ examples 17 product b+ examples 18 product b+ examples 19 product b+ examples 20 products | 0 300 300 300 300 300 300 300 | 22.4 13.6 14.4 12.8 14.3 13.0 12.9 14.4 | 0 39.3 35.7 42.9 36.2 41.9 42.4 35.7 |
Example 23
This example is estimated the dispersiveness of multi-effect composite additive with the spot test method.
Spotting method is with after carbon black ointment (or engine sludge) and the dispersant, disperse through high-speed stirring and sonic oscillation, in 50 ℃ of baking ovens, left standstill 18 hours then, drop in after the taking-up on the filter paper, the oil droplet amount is controlled at 0.02～0.025g, the latter is placed in 50 ℃ of baking ovens and leaves standstill 2 hours, take out then and measure diffusion circle diameter (d) and greasy filth loop diameter (D), its ratio r=d/D * 100 are as the index of weighing dispersive ability, and the r value is big more, and dispersiveness is good more.The results are shown in Table 5.
Table 5 spotting method is estimated the dispersiveness of multipurpose additive
| Sample | r | Sample | r |
| Blank sample example 14 examples 15 examples 16 | 24.3 66.8 66.3 64.8 | Example 17 examples 18 examples 19 examples 20 | 63.6 65.4 67.1 64.3 |
From table 4 and table 5 as can be seen, the diesel oil multi-efficient additive composition of the present invention's preparation has detergent-dispersant performance energy preferably.
Claims (15)
1. antiwear dispersing additive for diesel oil composition comprises following component:
(A) reaction product of mannich base and phenol acids or product mixtures, wherein mannich base is by polyolefin-based phenol, C
1～C
6Aldehyde and polyamines polyene reaction generate;
(B) C
6～C
40The reaction product or the product mixtures of one or more in organic acid and alcohol, amine, hydramine or the epoxide;
Wherein component (A) is 1: 0.1～10 with the weight ratio of component (B).
2. according to the described composition of claim 1, it is characterized in that component (A) is 1: 0.2～6 with the weight ratio of component (B).
3. according to the described composition of claim 1, it is characterized in that wherein component (A) is 1: 0.3～3 with the weight ratio of component (B).
4. according to the described composition of claim 1, it is characterized in that, said component (A) prepares by following method: with mannich base and phenol acids according to 1: 0.5～5 mixed in molar ratio, in the presence of solvent, reacted 0.5～20 hour in 50～200 ℃, said solvent be benzene,toluene,xylene, aromatic hydrocarbons thinning oil, industrial naptha or boiling point at the mineral oil more than 120 ℃, or their mixture.
5. according to the described composition of claim 4, it is characterized in that said component (A) prepares by following method: with mannich base and phenol acids according to 1: 1～4 mixed in molar ratio, in the presence of solvent in 80～160 ℃ of reactions 1～10 hour.
6. according to the described composition of claim 1, it is characterized in that said phenol acids is selected from Whitfield's ointment, m-Salicylic acid, P-hydroxybenzoic acid, 3-hydroxyl 2-naphthoic acid, 3,4,5-trihydroxybenzoic acid, 4, two (4-hydroxyphenyl) valeric acids of 4-or their mixture.
7. according to the described composition of claim 1, it is characterized in that said mannich base is by polyolefin-based phenol, C
1～C
6Aldehyde and polyamines polyene make 50～200 ℃ of reactions, and three's mol ratio is 1: 0.1～10: 0.1～10.
8. according to the described composition of claim 7, it is characterized in that polyolefin-based phenol wherein is the macromolecular compound with following structure:
Wherein R is Atactic Polypropelene, polybutene, polyisobutene or ethylene-propylene copolymer, and the number-average molecular weight of R is 300～3000.
9. according to the described composition of claim 7, it is characterized in that polyamines polyene wherein is selected from diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, two propylene triamines, three propylene tetramines, tetrapropylene five amine or five propylene hexamines.
10. according to the described composition of claim 1, it is characterized in that said component (B) is C
8～C
36Organic acid and C
1～C
18Fatty Alcohol(C12-C14 and C12-C18), C
1～C
18Aliphatic amide, Cycloalkyl amine, heterocyclic amine amine, hydramine or C
2～C
18The reaction product of one or more in the epoxide or product mixtures.
11., it is characterized in that said organic acid is selected from naphthenic acid, oleic acid, linolic acid, dimeracid or ricinolic acid according to the described composition of claim 10.
12., it is characterized in that said Fatty Alcohol(C12-C14 and C12-C18) is selected from ethylene glycol, polyoxyethylene glycol, 1,2-propylene glycol, 1, ammediol, glycerol, butyleneglycol, pentanediol, hexylene glycol, heptanediol or ethohexadiol according to the described composition of claim 10.
13. according to the described composition of claim 10, it is characterized in that, said aliphatic amide is selected from ethamine, propylamine, butylamine, amylamine, hexylamine, quadrol, propylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine or five ethene hexamines, said Cycloalkyl amine is cyclopentamine or hexahydroaniline, and said heterocyclic amine is morpholine or piperazine.
14., it is characterized in that said epoxide is oxyethane, propylene oxide or butylene oxide ring according to the described composition of claim 10.
15., it is characterized in that said hydramine is thanomin, diethanolamine, trolamine or methyldiethanolamine according to the described composition of claim 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137920 CN1249209C (en) | 2003-05-30 | 2003-05-30 | Diesel oil antifriction dispersion additive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137920 CN1249209C (en) | 2003-05-30 | 2003-05-30 | Diesel oil antifriction dispersion additive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1552828A CN1552828A (en) | 2004-12-08 |
| CN1249209C true CN1249209C (en) | 2006-04-05 |
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ID=34323603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03137920 Expired - Lifetime CN1249209C (en) | 2003-05-30 | 2003-05-30 | Diesel oil antifriction dispersion additive composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1249209C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289763A (en) * | 2013-05-22 | 2013-09-11 | 吴江市德佐日用化学品有限公司 | Low sulfur diesel antiwear additive |
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2003
- 2003-05-30 CN CN 03137920 patent/CN1249209C/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| CN1552828A (en) | 2004-12-08 |
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