CN1552829A - Diesel multi-effect additive composition - Google Patents

Abstract

A diesel multi-effect additive composition, comprising the following components: a) hydroxyaromatic acid and alkenyl succinimide are reacted at 60-200°C for 0.5-200°C in the presence of an organic solvent in a molar ratio of 0.5-5:1 The reaction product or product mixture of 20 hours; b) the reaction product or product mixture of one or more of C ₆ ~C ₄₀ organic acids and alcohols, amines, alcohol amines or epoxides; wherein component a and component The weight ratio of b is 1:0.1-10. The addition amount of the multi-effect additive provided by the invention in diesel oil is generally 50-2000ppm. The additive composition can not only improve the lubricity of low-sulfur diesel oil, but also has good oxidation resistance and cleansing and dispersing properties, and can be used not only as a diesel antiwear agent, but also as a diesel stabilizer and dispersant.

Description

Diesel multi-effect additive composition

technical field

The invention belongs to the multi-effect additive for diesel oil, specifically, it can be used not only as an antiwear agent for diesel oil, but also as a multi-effect additive for diesel oil stabilizer and ashless dispersant for diesel oil.

technical background

As countries around the world pay more and more attention to environmental protection issues, in order to reduce diesel exhaust pollution and produce high-quality clean diesel oil, it has become the development direction of the modern oil refining industry. This kind of diesel oil generally has the characteristics of low sulfur content, low aromatics content, high cetane number, and light distillate. Studies have shown that sulfur is the most harmful element that increases CH and CO in diesel engine emissions, especially inhalable particulate matter (PM), so reducing the sulfur content in diesel is particularly important for improving air pollution. Now the diesel specifications of the United States, Canada, and Western European countries all stipulate that the S content of diesel is less than 0.05%, and some countries require that the S content is less than 0.0015%, and the aromatic content is also low. Because they generally adopt a harsh hydrogenation process, the content of polar oxygen-containing and nitrogen-containing compounds in diesel oil is very low, and the content of polycyclic and bicyclic aromatic hydrocarbons is also small, thus reducing the natural lubrication performance of diesel oil and causing Some fuel injection pumps that rely on diesel oil for lubrication, such as rotary pumps and distributor pumps, have worn out, reducing their service life.

It is well known that non-hydrocarbon compounds such as olefins, diolefins, sulfides, and nitrogen compounds in diesel oil generate a series of oxidized intermediate products under the action of oxygen, and produce insoluble precipitates through condensation. These insoluble particles generated during the storage of diesel oil will affect the performance of the fuel, cause blockage of the filter system, cause failure of fuel system components, affect fuel injection atomization, cause incomplete combustion, and even form excessive carbon deposits in the engine. clog the nozzle.

The above problems can be alleviated by adding additives to diesel. It is generally believed that the diesel antiwear agent can make up for the loss of lubricating components in the oil caused by the hydrotreating of diesel oil and improve the lubricity of diesel oil; the diesel stabilizer can terminate, weaken, or interfere with the above-mentioned reactions to inhibit the deterioration of diesel oil. Improve its stability; Diesel cleaning and dispersing agent can clean the carbon deposit formed on the nozzle, and form a protective film on the surface of the nozzle to prevent new carbon deposit, and at the same time, it can also disperse the sediment formed in the diesel oil to improve the filtration prevents clogging of injectors and nozzles, and improves exhaust emissions.

Diesel antiwear agents are mostly derivatives of fatty acid esters, amides or salts. EP773279 discloses carboxylic acid esters prepared by reacting dimer acids with alcohol amines as diesel antiwear agents. EP798364 discloses salts or amides prepared by the reaction of fatty acids and fatty amines as diesel antiwear agents. EP1209217 discloses the reaction products of C ₆ -C ₅₀ saturated fatty acids and dicarboxylic acids with short-chain oil-soluble primary, secondary and tertiary amines as diesel antiwear agents. WO9915607 discloses reaction products of dimerized fatty acids and epoxides as diesel antiwear agents. However, these additives have no effect on the stability and detergency and dispersibility of diesel oil, and in many cases may also deteriorate the oxidation stability of diesel oil.

GB 2,245,588 reports that substituted triazines and substituted methane compounds generated by the reaction of primary amines, secondary amines and formaldehyde are used as diesel stabilizers. This type of additive has a certain stabilizing effect on the color, but under the accelerated oxidation conditions (SH/T0175-94, 95 ° C, 16 hours of oxygen), the ability to inhibit diesel oxidation sediment is not strong, and its oil solubility is not very good. good. Moreover, the above-mentioned diesel stabilizers have no anti-wear and detergent-dispersing effects.

The alkenyl succinimide disclosed in US 3,024,237, 3,172,892, 3,202678, 3,257554 etc. is currently the most widely used ashless dispersant for lubricating oil and fuel. Its typical structure is monosuccinimide, bisuccinimide and polysuccinimide obtained by reacting polyisobutylene succinic anhydride and tetraethylenepentamine in different proportions (commonly known as single-hung, double-hung, hang more) and so on. However, such additives have weak anti-oxidation effects, and are generally used in combination with antioxidants or stabilizers, which not only increases the amount of additives used, but also causes compatibility problems between additives.

Chemical modification of succinimide can enhance its dispersibility, or make it have multiple functions such as dispersion and anti-oxidation. For example, US 4,780,111 discloses the reaction product of alkenyl succinimide and phthalic acid (anhydride) to reduce the amount of fuel oil sediment and improve nozzle deposition. US 5,435,812 discloses the reaction product of mono-, bis-succinimide and aromatic triacid dimer ether ester as an anti-oxidant and detergent dispersant for fuel or lubricating oil; Chinese patent application number 00124808.1 discloses alkenyl succinimide and hydroxyl The reaction product of aromatic acid is used as diesel stabilizer and dispersant. However, the above products are not ideal for improving the lubricity of diesel oil.

Contents of the invention

The object of the present invention is to provide a multi-effect additive with anti-wear, stabilizing, dispersing and other functions, which can not only improve the lubricity of low-sulfur diesel oil, but also prevent the oxidation of olefins and diolefins in diesel oil and the formation of non-hydrocarbon compounds. Condensation between them, preventing the aggregation of tiny oxidation products that have been produced, so that they can be evenly dispersed in the diesel oil, thereby improving the stability of diesel oil and delaying the clogging of engine filters and nozzles.

The low-sulfur diesel oil multi-effect additive composition provided by the invention comprises the following components:

a) reaction product or product mixture of hydroxyaromatic acid and alkenyl succinimide;

b) reaction products or product mixtures of C ₆ -C ₄₀ fatty acids and one or more of alcohols, amines, alcoholamines or epoxides;

Wherein the weight ratio of component a to component b is 1:0.1-10, preferably 1:0.2-6, more preferably 1:0.3-3.

About component a

Said component a is prepared by the following method:

The hydroxyaromatic acid and alkenyl succinimide are reacted at 60-200° C., preferably 80-160° C., for 0.5 to 20 minutes in the presence of an organic solvent at a molar ratio of 0.5 to 5:1, preferably 1 to 4:1. hours, preferably 1 to 10 hours.

Wherein the organic solvent can be benzene, toluene, xylene, C ₉ heavy aromatics (distillation range is 159～185 ℃), solvent gasoline or mineral oil (boiling point is more than 120 ℃), or their mixture. The amount of solvent used is generally 30-150% of the total weight of monomer materials. The reaction system can be protected with nitrogen, or the system can be carried out under the condition of solvent reflux. The reaction can be done without a catalyst, or a small amount (0.01-1%) of acidic compounds such as sulfuric acid, p-toluenesulfonic acid or acid clay can be added as a catalyst to speed up the reaction. In order to facilitate subsequent operation and storage, the final product can be made into about 50% dilution with _C9 heavy aromatics.

Said hydroxyaromatic acid has the structure shown in formula (I):

HOOC-[Ar] _a -(OH) _b (I)

In the formula, [Ar] represents an aromatic ring including a benzene ring and a naphthalene ring, a is 1 or 2, and b is an integer of 1-4. Said hydroxyaromatic acid is preferably salicylic acid (o-hydroxybenzoic acid), m-hydroxybenzoic acid, p-hydroxybenzoic acid, 3-hydroxyl 2-naphthoic acid, 3,4,5-trihydroxybenzoic acid (gallic acid) and the like .

Said alkenyl succinimide is prepared by reacting alkenyl succinic anhydride with polyene polyamine. The alkenyl group is derived from a C ₃ -C ₄ monoolefin copolymer or homopolymer, which can be polyisobutylene, random polypropylene or ethylene-propylene copolymer. Its number average molecular weight is 300-5000, preferably 800-2500, more preferably 500-2000. The degree of substitution of alkenyl succinic anhydride is generally 0.5-1.0. The structural formula of the polyene polyamine is H ₂ N[(CH ₂ ) _n NH] _m H, n is an integer of 2-4, preferably 2-3, and m is an integer of 1-5, preferably 3-4. Such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, etc. Preference is given to triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

The molar ratio of polyene polyamine and alkenyl succinic anhydride during reaction can be 1:1-2, and the reaction temperature is between 100-200°C, preferably within the range of 110-160°C. The reaction medium can be an organic solvent such as benzene, toluene, xylene, C ₉ heavy aromatics (distillation range 159-185°C), solvent gasoline or mineral oil (boiling point above 120°C), or a mixture thereof. The amount of solvent used is generally 30-150% of the total weight of monomer materials.

Regarding component b

The component b is the reaction product or product mixture of C ₆ -C ₄₀ organic acid and one or more of alcohol, amine, alcohol amine or epoxide.

The C ₆ -C ₄₀ organic acid, preferably C ₈ -C ₃₆ organic acid, can be fatty acid or naphthenic acid; can be monocarboxylic acid or polycarboxylic acid; can be saturated acid or unsaturated acid. e.g. caproic acid, adipic acid, caprylic acid, isooctanoic acid (2-ethylhexanoic acid), capric acid, dodecanoic acid, myristic acid, palmitic acid, octadecanoic acid, oleic acid, linoleic acid, stearic acid , palmitic acid, ricinoleic acid, eicosic acid, dimer acid, etc.; it can also be a mixed acid, such as naphthenic acid of various specifications, vegetable oil fatty acid such as palmitic acid, etc., preferably Acids that are liquid at room temperature, such as naphthenic acid, oleic acid, linoleic acid, dimer acid, ricinoleic acid, etc.

The alcohol refers to a C ₁ -C ₁₈ fatty alcohol, which may be a monohydric alcohol or a polyhydric alcohol. Monohydric alcohols can be ethanol, propanol, butanol, pentanol, hexanol, octanol, etc., and both normal and isomeric ones are available. Polyols can be ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerin, butanediol of various structures, pentanediol, hexanediol, heptanediol, octane Diol, nonanediol, decanediol, pentaerythritol, sorbitol, sorbitan, etc. C ₂ -C ₈ fatty alcohols are preferred, and polyhydric alcohols are more preferred.

The amine is an aliphatic amine, a cycloalkylamine or a heterocyclic amine with a carbon number of C ₁ -C ₁₈ , preferably C ₂ -C ₁₀ . Wherein the fatty amine can be a primary amine or a secondary amine, and can be a monoamine or a polyamine. Monoamines such as ethylamine, propylamine, butylamine, pentylamine, hexylamine, etc., can be both normal and isomeric. The polyamine may be ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like. Cycloalkylamines can be cyclopentylamine, cyclohexylamine, etc.; heterocyclic amines can be morpholine, piperazine, etc.

Epoxides can be C ₂ -C ₁₈ epoxides, such as ethylene oxide, 1,2-propylene oxide, 1,2-epoxybutylene, 1,2-epoxyoctadecane, etc. or their Mixtures, preferably C ₂ -C ₈ epoxides.

Alcoholamines may be ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, and the like.

The above-mentioned alcohols, amines, alcohol amines or epoxides are collectively referred to as "acylates" in the present invention, and said component b can be a reaction in which one or more of organic acids and acylates are fed in any proportion The product can also be a mixture of any proportion of the above reaction products. The organic acid reacts with the acylate according to the stoichiometric amount, that is, the number of moles of the organic acid is basically the same as the total number of moles of the acylate, but when the acylate contains polyhydric alcohol, polyamine or alcohol amine, due to the active group If the amount is more than the number of moles of the acylate, the proportion of the organic acid should be appropriately increased; when the acylate contains epoxide, the proportion of the organic acid should be appropriately reduced in consideration of the self-polymerization characteristics of the epoxide.

The reaction of organic acid and above-mentioned various acylates can be carried out as follows:

When carrying out esterification reaction between organic acid and alcohol, an acidic catalyst such as sulfuric acid, p-toluenesulfonic acid, etc. with about 1% of the reactant can be added to the normal pressure container to speed up the reaction speed, and the solvent can be refluxed at 80-160°C to separate water or Nitrogen is purged to remove water for 2-10 hours, and then an appropriate amount of alkali is added to neutralize the acidic catalyst.

When carrying out esterification reaction between organic acid and alcohol amine, a basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide/methanol, organic base such as dimethylcyclohexylamine can be added in a normal pressure vessel Wait to speed up the reaction, and reflux the solvent at 80-160°C to separate water or purging with nitrogen to remove water for 2-10 hours, and then add an appropriate amount of acidic substance to neutralize the basic catalyst.

When the organic acid reacts with the epoxide, a basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide/methanol, organic base such as dimethylcyclohexylamine, etc. can be added to the normal pressure vessel. To speed up the reaction, it can also be carried out in a high-pressure reactor without adding a catalyst at a certain pressure and at 80-160 °C.

When the amination reaction of organic acid and amine is carried out, no catalyst can be added in the normal pressure container or an acidic catalyst such as sulfuric acid, p-toluenesulfonic acid, etc. with about 1% of the reactant can be added to speed up the reaction speed, and the solvent can be heated at 80-160 ° C. Reflux for water separation or nitrogen purging to remove water for 2 to 10 hours. If a catalyst is added, an appropriate amount of alkali must be added to neutralize the acidic catalyst.

The addition amount of the multi-effect additive provided by the invention in diesel oil is generally 50-2000ppm, preferably 100-1000ppm.

According to the needs of use, the additives provided by the present invention can also be used together with other additives, such as flow improvers, cetane number improvers, metal deactivators, anti-corrosion agents and the like.

The diesel multi-effect additive provided by the invention not only has better anti-wear performance, but also has anti-oxidation ability and clean and dispersive performance, and has strong adsorption and capture ability for colloid and other polar compounds and fine particles, which can prevent them Oxidation and aggregation, thereby reducing the generation of oxidation deposits in diesel.

In addition, the additive of the present invention also has other functions, such as improving the copper sheet corrosion of diesel oil and reducing the emission of exhaust gas from diesel engines.

Detailed ways

Example 1

This example is the preparation of alkenyl succinimide.

In the three-necked flask, add 200 grams (0.14mol) polyisobutylene succinic anhydride (polyisobutylene number-average relative molecular mass Mn=1200, saponification value 80 mg KOH/gram, degree of substitution is 1.0) and 200 grams distillation range is 159 ~185°C _C9 heavy aromatics (platinum reforming bottom material), heated to 80°C and stirred evenly, slowly added 20.2 grams (0.138mol) of triethylenetetramine, heated to 150°C under nitrogen protection for 6 hours of dehydration reaction, Intermediate product 1 was obtained with a nitrogen content of 1.9% by weight. Add 25 grams of C ₉ heavy aromatics to make about 50% dilution.

Example 2

This example is the preparation of alkenyl succinimide.

In the three-necked flask, add 18.2 grams (0.096mol) of tetraethylenepentamine, 20 grams of toluene and 200 grams of _C9 heavy aromatics (platinum reforming bottom material) with a distillation range of 159 to 185 ° C, heat and stir to 50 ° C , in the presence of nitrogen, slowly add 200 g (0.107 mol) of polyisobutylene succinic anhydride (polyisobutylene number-average molecular mass Mn=900, saponification value 60 mg KOH/g, degree of substitution 0.65), heat up to 110°C for reaction After 3 hours, the toluene was distilled off by heating, and the reaction was carried out at 145° C. for another 2 hours to obtain an intermediate product 2 with a nitrogen content of 2.0% by weight. Then add 20 grams of C ₉ heavy aromatics to make about 50% dilution.

Examples 3-6 are the preparation of component a.

Example 3

In the three-necked flask, add 50 grams of intermediate product prepared by example 1 and 3.9 grams of p-hydroxybenzoic acid (the molar ratio of p-hydroxybenzoic acid and triethylenetetramine is about 1.8: 1), and 4 grams _{of C9} heavy aromatics, Nitrogen was blown, reacted at 100°C for 5 hours, and then cooled to room temperature.

Example 4

In the three-necked flask, add 50 grams of the intermediate product prepared by Example 2 and 3.0 grams of o-hydroxybenzoic acid (salicylic acid) and 3 grams of _C9 heavy aromatics (the molar ratio of o-hydroxybenzoic acid to tetraethylenepentamine is about 2.0 : 1), reacted at 150° C. for 2 hours in the presence of nitrogen, and then cooled to room temperature.

Example 5

In the three-necked flask, add 50 grams of intermediate product prepared by example 2 and 2.4 gram p-hydroxybenzoic acid and 3 gram _C9 heavy aromatics (p-hydroxybenzoic acid and tetraethylenepentamine mol ratio is about 1.6: 1), in The reaction was carried out at 90° C. for 6 hours in the presence of nitrogen, and then cooled to room temperature.

Example 6

2.4 g of p-hydroxybenzoic acid in Example 5 was replaced with 3.0 g of 3,4,5-trihydroxybenzoic acid (gallic acid), reacted at 120° C. for 1 hour, and then cooled to room temperature.

Examples 7-11 are the preparation of component b.

Example 7

Put 100g of ricinoleic acid and 25.5g of 1,2-propanediol (the molar ratio of ricinoleic acid to 1,2-propanediol is about 1:1) and 1.3g of p-toluenesulfonic acid catalyst in a tank equipped with electric stirrer and thermometer , water separator, reflux condensing pipe and nitrogen inlet pipe, feed nitrogen into the reactor for 5-10 minutes, and maintain the nitrogen flow during the reaction process, heat and stir to raise the temperature to 140 ° C, react with water separation for 5 hours, and then cool to At 80°C, add 0.6g Ca(OH) ₂ , neutralize for half an hour and then filter, the filtrate is the product with an acid value of 3.8mgKOH/g.

Example 8

Put 100g of dimer acid and 12.9g of n-butylamine (the molar ratio of dimer acid to n-butylamine is about 1:1) in a reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube , feed nitrogen for 5 to 10 minutes, and maintain a weak nitrogen flow during the reaction, first react at 60°C for half an hour, then raise the temperature to 130°C and react with water for 5 hours, and cool to obtain the product.

Example 9

Put 100g of oleic acid, 52.8g of triethanolamine (the molar ratio of oleic acid to triethanolamine is about 1:1) and 2.8g of sodium methoxide/methanol catalyst in an electric stirrer, thermometer, reflux condenser and nitrogen inlet tube Into the reactor, feed nitrogen for 5-10 minutes, and maintain a weak nitrogen flow during the reaction, heat and stir to raise the temperature to 160°C, react for 5 hours, then cool to 90°C, add 3.2g of acid clay to neutralize and filter , collect filtrate, record its acid value 8.3mgKOH/g.

Example 10

Put 100g of linoleic acid, 15.5g of morpholine, and 26.1g of triethylenetetramine (the molar ratio of linoleic acid, morpholine, and triethylenetetramine is about 1:0.5:0.5) in a tank equipped with an electric stirrer and a thermometer. , reflux condensing tube and the reactor of the nitrogen gas inlet tube, feed nitrogen gas for 5 to 10 minutes, and maintain a weak nitrogen flow during the reaction process, heat and stir to raise the temperature to 140 ° C, react with water separation for 8 hours, and cool to obtain the product.

Example 11

Mix 100g naphthenic acid (acid value 216mgKOH/g) and 44.8g 1,2-propylene oxide (the molar ratio of naphthenic acid to 1,2-propylene oxide is about 1:2) and 1.0g dimethylcyclo The hexane catalyst is placed in a reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, and nitrogen gas is passed through for 5 to 10 minutes to maintain a nitrogen atmosphere. Heating, stirring and reflux reaction, when the temperature rises to 140°C, the reaction is stopped, and the product is obtained after cooling, the acid value of which is 28.9 mgKOH/g.

Examples 12-16 are the preparation of the diesel multi-effect additive composition of the present invention.

Component a selected from Examples 3-6 and Component b selected from Examples 7-11 were mixed according to the weight ratio shown in Table 1 to obtain different compositions.

The preparation of table 1 multi-effect additive composition

Example Component a Component b Component a, b weight ratio

Example 12 Example 3 Example 7 1:0.8

Example 13 Example 3 Example 8 1:0.4

Example 14 Example 4 Example 9 1:2

Example 15 Example 5 Example 10 1.5:1

Example 16 Example 6 Example 11 1:1

              Table 2 Physical and chemical properties of diesel oil

diesel fuel

(A) (B)

Density (20℃)/g·cm ^-3 0.8576 0.8360

Viscosity (40℃)/mm ² ·s ^-1 2.548 2.510

S content/ppm 238 197

N content/ppm 120 163

Basic nitrogen/ppm 10 36

Paraffins/m% 38.5 47.2

Total naphthenes/m% 18.4 22.3

Total monocyclic aromatic hydrocarbons/m% 29.6 21.6

Total bicyclic aromatic hydrocarbons/m% 11.9 7.9

Tricyclic aromatic hydrocarbons/m% 1.6 1.0

CFPP/°C 4 4 -3

SP/°C 1 1 -8

Initial boiling point/°C 188 190

20% boiling point/°C 230 214

50% boiling point/°C 252 260

90% boiling point/°C 343 324

Dry point/℃ 353 350

Normal hydrocarbon content/% 21.71 29.20

Normal hydrocarbon carbon number C ₈ -C ₂₈ C ₈ -C ₂₈

C _{≥ 17} Normal hydrocarbon content/% 8.96 10.92

Example 17

This example is the effect of using the multi-effect additive composition prepared in Examples 12-16 in diesel. Use Dagang 0 ^# blended oil (A) and Yanshan 0 ^# refined oil (B). Its physical and chemical properties are shown in Table 2. The HFRR method (ISO12156-1) wear scar diameter WSD _1.4 of the diesel oil before and after dosing, and the oxidation stability of the oil evaluated by the accelerated oxidation method (SH/T0175-94) are shown in Table 3. When the wear scar diameter is less than 460um (60°C), the lubricity of the diesel is qualified; the total insoluble matter is less than or equal to 2.5mg/100ml, the oxidation stability of the diesel is qualified.

Table 3 The improvement effect of multi-effect additive composition on diesel oil lubricity and oxidation stability

Addition Lubricity Oxidation Stability

Diesel additives/mg·kg ^-1 total insolubles

WSD _1.4 /um

/mg·100ml ^-1

/ / / 535 2.3

Example 5 300 480 1.5

Instance 10 200 298 2.7

Instance 12 500 236 1.0

A Example 13 500 287 1.1

Instance 14 600 218 1.5

Instance 15 500 223 1.2

Instance 16 600 227 1.6

/ / / 462 3.5

Example 3 300 390 1.9

Example 7 300 255 4.4

Example 12 500 197 1.6

B Example 13 600 205 1.5

Instance 14 500 243 1.8

Instance 15 600 219 2.0

Instance 16 400 231 2.3

As can be seen from Table 3, although the component a used alone has a certain improvement to the oxidation stability of diesel oil, the antiwear property is relatively poor (instance 3, 5); the component b used alone has certain antiwear property, But on the contrary, the oxidation stability of diesel oil is deteriorated (Example 7, 10). The diesel oil multi-effect additive composition provided by the present invention can not only improve the lubricity of low-sulfur diesel oil, but also improve the stability of diesel oil.

Example 18

In this example, the metal sheet deposition method is used to simulate and evaluate the dispersion performance of additives.

According to the properties of diesel oil, this method comprehensively improves the rotary oxygen bomb method used to measure the oxidation stability of lubricating oil and the metal flake deposition method used in SAE 872112 (Society of Automotive Engineers report) to evaluate the clean dispersibility of gasoline. The experimental equipment And test method refer to Chinese patent CN1382777. The test results are shown in Table 4, wherein the deposition improvement rate=(blank value-experimental value)/blank value×100%.

        Table 4 Metal sheet deposition method to assess the deposition of diesel oil on metal sheets

Sample Adding Dose Deposition Amount Deposition Improvement Rate

/mg.kg ^-1 /mg/%

Blank Diesel B 0 22.4 0

B+ instance 12 product 300 13.3 40.6

B+ instance 13 product 300 14.1 37.1

B+ instance 14 product 300 15.2 32.1

B+ example 15 products 300 13.5 39.7

B+ instance 16 product 300 12.8 42.9

Example 19

This example uses the spot test method to evaluate the dispersibility of multi-effect additive compositions.

The spot method is to mix carbon black ointment (or engine oil sludge) with a dispersant, disperse through high-speed stirring and ultrasonic vibration, and then put it in an oven at 50°C for 18 hours, take it out and drop it on filter paper. The amount of oil droplets is controlled at 0.02～0.025g, and then put the latter in an oven at 50°C for 2 hours, then take it out and measure the diameter of the diffusion ring (d) and the diameter of the sludge ring (D), the ratio r=d/D×100 as a measure of the dispersion ability The larger the r value, the better the dispersion. The results are shown in Table 5.

Table 5 spot method to evaluate the dispersibility of multi-effect additives sample like r Blank 24.3 Example 12 65.8 Example 13 64.9 Instance 14 62.3 Instance 15 65.1 Instance 16 63.8

It can be seen from Table 4 and Table 5 that the diesel multi-effect additive composition prepared by the present invention has better detergency and dispersibility.

Claims (15)

1. diesel oil multi-efficient additive composition comprises following component:

A) reaction product of phenol acids and allyl butyrate imide;

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 the weight ratio of component a and components b is 1: 0.1～10.

2. according to the described composition of claim 1, it is characterized in that wherein the weight ratio of component a and components b is 1: 0.2～6.

3. according to the described composition of claim 2, it is characterized in that wherein the weight ratio of component a and components b is 1: 0.3～3.

4. according to the described composition of claim 1, it is characterized in that component a prepares by following method: with phenol acids and allyl butyrate imide according to 0.5～5: 1 mol ratio in the presence of organic solvent in 60～200 ℃ of reactions 0.5～20 hour down.

5. according to the described composition of claim 4, it is characterized in that component a prepares by following method: with phenol acids and allyl butyrate imide according to 1～4: 1 mol ratio in the presence of organic solvent in 80～160 ℃ of reactions 1～10 hour down.

6. according to the described composition of claim 1, it is characterized in that the structure of said phenol acids is: HOOC-[Ar] _a-(OH) _b, in the formula, [Ar] represents aromatic ring, comprises phenyl ring and naphthalene nucleus, and a is 1 or 2, and b is 1～4 integer.

7. according to the described composition of claim 6, 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.

8. according to the described composition of claim 1, it is characterized in that said allyl butyrate imide is to be made 100～200 ℃ of reactions by enetutanedioic acid anhydride and polyamines polyene, thiazolinyl wherein is that number-average molecular weight is 300～5000 C ₃～C ₄The multipolymer of monoolefine or homopolymer, polyamines polyene are selected from diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, two propylene triamines, three propylene tetramines, tetrapropylene five amine, five propylene hexamines.

9. according to the described composition of claim 8, it is characterized in that, said allyl butyrate imide is to be made 110～160 ℃ of reactions by enetutanedioic acid anhydride and polyamines polyene, thiazolinyl number-average molecular weight wherein is 800～2500, and polyamines polyene is selected from triethylene tetramine, tetraethylene pentamine and five ethene hexamines.

10. according to the described composition of claim 1, it is characterized in that said components 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, 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 according to the described composition of claim 10,1,2-propylene glycol, 1, ammediol, glycerol, butyleneglycol, pentanediol, hexylene glycol, heptanediol, ethohexadiol.

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, five ethene hexamines, said Cycloalkyl amine is cyclopentamine, hexahydroaniline, and said heterocyclic amine is morpholine, piperazine.

14., it is characterized in that said epoxide is oxyethane, propylene oxide, 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.