CN1766064A - A kind of copolymer type diesel oil multi-effect additive - Google Patents

Abstract

The invention relates to a copolymer type multi-effect additive of diesel oil, which is prepared from: (1) acrylic acid with a number average molecular weight of 500-10000 and C6-C22 alkyl ester-maleic anhydride copolymer, (2) one or more selected from polyhydric alcohol, epoxide, polyamine and alkamine, (3) C6-C50 organic acid through reaction at 50-200 deg. C. The molar ratio of reaction (1), (2) and (3) is 1:0.1-10:0.1-10. The addition agent can substantially improve the lubricity of diesel, and lower the cold filter plugging point and condensation point for diesel.

Description

A kind of copolymer type diesel oil multi-effect additive

technical field

The invention belongs to the diesel oil additive, specifically, it can be used not only as a diesel anti-wear agent, but also as a multi-effect additive of a diesel flow improver.

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 oil is less than 0.05%, and some countries have even reached less than 0.0015%; the content of aromatics 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.

Diesel oil contains various amounts of alkanes, especially the amount of long-chain n-alkanes that determines the low-temperature fluidity of the oil. When the temperature is lowered, n-paraffins are separated as flaky crystals, and they interact to form a three-dimensional network structure in which the liquid oil is still sealed, so that the viscosity of the oil increases and the fluidity decreases. The clogging of the filter screen affects the normal use of the vehicle, and also affects the storage, transportation, loading and unloading of diesel oil.

It is known that these problems can be alleviated by adding additives to diesel fuel. Diesel anti-wear agent (also called lubricity additive) can improve the lubricity of low-sulfur diesel; diesel flow improver can improve the low-temperature fluidity of diesel, reduce the cold filter point and freezing point of diesel, so that diesel can work normally in low-temperature environment use. The method of using additives has the advantages of low cost, flexible production, and less pollution, and has been widely valued in industry.

The fatty acid antiwear agents used in jet fuel, such as acidic additives of dimer acids, cannot be applied to diesel oil due to their poor compounding properties with lubricating oils, so diesel antiwear agents are mostly derivatives of fatty acid esters, amides or salts . EP773279 discloses carboxylic acid ester prepared by reacting dimer acid with alcohol amine as diesel antiwear agent. 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, none of the above additives can improve the low temperature fluidity of diesel.

CN 1102416A discloses acrylate-maleic anhydride copolymer as a flow improver for crude oil and gas oil, wherein the degree of alternation of acrylate and maleic anhydride is at least 85%.

The article "Studies on Reducing the Cold Filter Point of Diesel Oil by Maleic Anhydride Copolymers" published in "Journal of Petroleum Science (Petroleum Processing)" 1996, Volume 12, No. 4, reported the C ₈ of alkyl acrylate-maleic anhydride copolymers. Synthesis of -C ₁₈ amide derivatives and their effects on pour point and filter depressants. It is stated in the article that the agent has good sensitivity to diesel with a wide fraction, but does not mention the effect on diesel with a narrow fraction. Moreover, none of the above diesel flow improvers mentions their impact on diesel lubricity.

US 6,364,918, USP6,391,071 disclose binary or ternary copolymers as anti-wear agents and low-temperature flow improvers for low-sulfur diesel oil, such as diethanolamine derivatives of stearyl acrylate-maleic anhydride copolymer, but it reduces diesel oil The effect of improving the lubricity of diesel oil is not obvious.

Contents of the invention

Based on the prior art, the invention provides a copolymer type diesel oil multi-effect additive which can improve both the lubricity of diesel oil and the low-temperature fluidity of diesel oil.

The copolymer-type diesel oil multi-effect additive provided by the present invention is composed of: (a) _C6 - _C22 alkyl acrylate-maleic anhydride copolymer with a number average molecular weight of 500-10000; (b) polyol, epoxy, One or more of polyamines, amino alcohols, etc.; and (c) C ₆ ~ C ₅₀ organic acids reacted at 50 ~ 200 ° C; the reaction molar ratio of a, b, c is 1: 0.1 ~ 10: 0.1～10, wherein the mole number of a is calculated by maleic anhydride.

The said (a) is a C ₆ ~C ₂₂ alkyl acrylate-maleic anhydride copolymer, in the copolymer, the alkyl group can be C ₆ ~C ₂₂ , preferably C ₁₀ ~C ₂₀ , most preferably C ₁₂ ~C ₁₈ Alkyl, and preferably straight chain linear alkyl. For example lauryl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate or mixtures thereof. The number average molecular weight of the copolymer may be 500-10000, preferably 1000-8000. The molar ratio of alkyl acrylate to maleic anhydride is 1:0.1-10, preferably 1:0.2-5, most preferably 1:0.25-4.

The preparation of alkyl acrylate-maleic anhydride copolymer is generally to carry out free radical solution polymerization reaction between alkyl acrylate and maleic anhydride under the action of an initiator that can generate free radicals. The initiator used may be a peroxide or an azo compound, such as di-tert-butyl peroxide, benzoyl peroxide, azobisisobutyronitrile and the like. The dosage of the initiator is generally 0.5-2% of the total weight of alkyl acrylate and maleic anhydride. The solvent may be toluene, xylene, ethylbenzene, n-hexane, cyclohexane, etc., or aromatic diluent oil, with a distillation range of 159-185° C., the latter being preferred. The amount of solvent used is generally 30-150% of the total weight of the monomer material. The feeding method of the reactants can be added all at once, or the highly reactive alkyl acrylate can be added in batches. Add 40-100% of the total amount per hour, preferably 50-80% of the feed rate into the reaction system containing maleic anhydride and 30-80% solvent, and then reflux for 2-7 hours.

Said (b) can be a polyhydric alcohol with C ₂ to C ₁₈ hydroxyl numbers of 2 to 6, such as ethylene glycol, diethylene glycol (diethylene glycol), triethylene glycol (triethylene glycol) , polyethylene glycol, glycerol, propylene glycol of various structures (such as 1,2-propanediol, 1,3-propanediol), butanediol, pentanediol, hexanediol, heptanediol, octanediol, Nonanediol, decanediol, pentaerythritol, sorbitol, sorbitan, etc. Preferred are C ₂ -C ₁₂ polyols, more preferably C ₂ -C ₆ polyols, such as ethylene glycol, diethylene glycol, triethylene glycol, glycerol, propylene glycol of various structures, butanediol Alcohol, pentylene glycol, hexanediol, pentaerythritol, etc.

Said (b) can be C ₂ ~C ₁₈ epoxides, such as ethylene oxide, 1,2-propylene oxide, 1,2-epoxybutane, 1,2-epoxyoctadecane, etc. or their mixture. C ₂ -C ₈ epoxides are preferred.

Said (b) may also be a polyene polyamine having a structural formula of H ₂ N[(CH ₂ ) _n NH] _m H, wherein n is an integer of 2 to 4, preferably 2 to 3, and m is 1 to 5, preferably An integer of 3 to 4. Such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, etc. Preference is given to diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

Said (b) can also be an aminoalcohol. The aminoalcohol is selected from 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 3-amino-1-propanol, ethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine or its mixture.

Said (b) may also be an alkoxypolyamine. The alkoxy polyamine is a reaction product of polyene polyamine and epoxide in a molar ratio of 1:0.5-10, preferably 1:1-5, and the structural formula of the polyene polyamine is H ₂ N[(CH ₂ ) _n NH] _m H, wherein n is an integer of 2 to 4, preferably 2 to 3, and m is an integer of 1 to 5, preferably 3 to 4. Such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, etc. Preference is given to diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine. The epoxide is preferably ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide.

Said (c) is a C ₆ -C ₅₀ organic acid, which may be a fatty acid, a naphthenic acid, or a mixture thereof, preferably a C ₈ -C ₄₀ fatty acid. The fatty acid may be a monobasic acid, a dibasic acid or a polybasic acid; it may be a saturated acid or an unsaturated acid, or a mixture thereof. For example caproic acid, adipic acid, octanoic acid, isooctanoic acid (2-ethylhexanoic acid), capric acid, dodecanoic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, stearic acid, One or more of palmitic acid, ricinoleic acid, eicosenoic acid, eicosanic acid, erucic acid, docosenoic acid, dimerized oleic acid, dimerized linoleic acid, etc. Said fatty acid is preferably _C8 ～ _C40 vegetable oil fatty acid, such as oleic acid, linoleic acid, linolenic acid, dimerized oleic acid, dimerized linoleic acid, ricinoleic acid, palmitic acid, soybean oleic acid, arachidic acid, vegetable oil Seed oleic acid, tall oil (tall oil) acid, etc.

The molar ratio of a, b and c reaction is 1: 0.1～10: 0.1～10, preferably 1: 0.2～5: 0.2～5, wherein the molar number of a is calculated by maleic anhydride.

The reaction can be carried out in a normal pressure vessel or in an autoclave. The reaction can be carried out without a catalyst or with an appropriate catalyst to accelerate the reaction. Depending on the nature of the reaction, an acidic or basic catalyst can be added. In the reaction, the solvent can be refluxed to separate water, or the water can be purged with nitrogen flow. The solvent can be toluene, xylene, ethylbenzene, n-hexane, cyclohexane, petroleum ether, solvent gasoline, etc., or it can be an aromatic hydrocarbon diluent oil with a distillation range of 159-185°C. The reaction temperature is 50-200°C, preferably 80-160°C, and the reaction time is 0.5-20 hours, preferably 1-10 hours.

Specifically, it can be synthesized in the following three ways:

1. A and b undergo esterification or amination reaction first, and then add c to react.

2.b and c are esterified or aminated first, and then a is added to react.

3. A, b, c are added at the same time for reaction.

In order to make the additive compatible with lubricating oil, the acid value of the final reaction product should be less than 40mgKOH/g, preferably less than 20mgKOH/g, most preferably less than 10mgKOH/g. When the amount of maleic anhydride is excessive, other amines/or alcohols may be added to react with it in order to reduce the acid value. The "other amines" here are preferably C ₂ -C ₂₂ fatty amines, which can be primary or secondary amines, more preferably C ₈ -C ₂₀ fatty amines, preferably C ₁₀ -C ₁₈ normal amines, such as decylamine, n-deca Diamine (laurylamine), n-tetradecylamine, n-hexadecylamine, n-octadecylamine or mixtures thereof. "Other alcohols" are preferably C ₂ -C ₂₂ alkanols, more preferably C ₆ -C ₂₀ , most preferably C ₁₀ -C ₁₈ normal alkanols, such as decyl alcohol, n-dodecyl alcohol (lauryl alcohol), n- Myristyl alcohol, n-hexadecanol, n-stearyl alcohol or mixtures thereof.

In order to facilitate subsequent operation and storage, the final products are all diluted with aromatic hydrocarbon diluent oil to make about 50%.

The amount of the additive provided by the invention in diesel oil is generally 50-2000 mg/kg, preferably 70-1000 mg/kg, more preferably 100-800 mg/kg.

According to the needs of use, the additive provided by the present invention can also be used together with other additives, such as cetane number improver, detergent and dispersant, metal deactivator, anti-corrosion agent and so on.

Detailed ways

Below by embodiment the present invention will be further described.

In these examples, the average molecular weight is all according to gel permeation chromatography (GPC) with polystyrene as standard determination; Lubricity of diesel oil is according to the method described in CEC-F-06-A-96 or ISO/FDIS12156-1 (The American method is ASTM D-6079-97) on the high-frequency reciprocating testing machine (High-Frequency Reciprocating Rig, HFRR) (produced by British PCS Instrument Company) to measure the wear scar diameter (Wear Scar Diameter, WSD) at 60 ° C, Results are reported as WS _1.4 corrected for the effects of temperature and humidity. ; In the low-temperature fluidity evaluation of diesel oil, the cold filter point (CFPP) is determined according to the method of SH/T 0248-92, and the freezing point (SP) is determined according to the method of GB 510-83.

Example 1

This example is the preparation of alkyl acrylate-maleic anhydride copolymer.

Put 49.0g (0.5mol) of maleic anhydride and 100g of aromatic hydrocarbon diluent oil solvent into a reactor equipped with electric stirrer, thermometer, reflux condenser, dropping funnel and nitrogen gas inlet tube, and pass nitrogen gas for 5 to 10 minutes , and maintain a weak nitrogen flow during the reaction, heat and stir to raise the temperature to 140-150 ° C, drop 162.0 g of stearyl acrylate, 4.0 g of di-tert-butyl peroxide and 110 g of aromatic diluent oil mixture from the dropping funnel Put it into the reactor (the molar ratio of stearyl acrylate to maleic anhydride is 1:1), drop it off within 1.5 hours, keep the temperature at 140-150°C, reflux for 3 hours, cool down, and leave it for the next step of preparation. A small amount of sample was taken to measure the number average molecular weight Mn=1650 by gel permeation chromatography.

Example 2

This example is the preparation of alkyl acrylate-maleic anhydride copolymer.

Put 49.0g (0.5mol) of maleic anhydride and 100g of aromatic hydrocarbon diluent oil solvent into a reactor equipped with electric stirrer, thermometer, reflux condenser, dropping funnel and nitrogen gas inlet tube, and pass nitrogen gas for 5 to 10 minutes , and maintain a weak nitrogen flow during the reaction, heat and stir to raise the temperature to 140-150 ° C, drop 324.0 g of stearyl acrylate, 3.5 g of di-tert-butyl peroxide and 273 g of aromatic diluent oil mixture from the dropping funnel Put it into the reactor (the molar ratio of octadecyl acrylate to maleic anhydride is 2:1), drop it off within 2 hours, keep the temperature at 140-150°C, reflux for 4 hours, and cool. Leave it for the next step of preparation. Take a small amount of sample and measure the number average molecular weight Mn=2930 by gel permeation chromatography.

Example 3

This example is the preparation of alkyl acrylate-maleic anhydride copolymer.

Put 49.0g (0.5mol) of maleic anhydride and 50g of aromatic hydrocarbon diluent oil solvent into a reactor equipped with electric stirrer, thermometer, reflux condenser, dropping funnel and nitrogen gas inlet tube, and pass nitrogen gas for 5 to 10 minutes , and maintain a weak nitrogen flow during the reaction, heat and stir to raise the temperature to 140-150 ° C, drop 134.0 g of tetradecyl acrylate, 2.0 g of di-tert-butyl peroxide and 134 g of aromatic diluent oil mixture from the dropping funnel Put it into the reactor (the molar ratio of tetradecyl acrylate to maleic anhydride is 1:1), drop it off within 1.5 hours, keep the temperature at 140-150°C, reflux for 5 hours, and cool. Leave it for the next step of preparation. Take a small amount of sample and measure the number average molecular weight Mn=6236 by gel permeation chromatography.

Example 4 (comparative example)

This example is the preparation of fatty acid and alcohol amine esterification.

Put 56.4g (0.2mol) oleic acid, 29.8g (0.2mol) triethanolamine, 3.0g sodium methoxide/methanol catalyst and 86g aromatic hydrocarbon dilution oil solvent into a tank equipped with electric stirrer, thermometer, reflux water separator and nitrogen gas introduction In the reactor with nitrogen gas, heat and stir to raise the temperature to 130-140°C, purge the reaction with nitrogen for 4 hours, then add 3.5g of acid clay to neutralize the catalyst and filter, the filtrate is the product, the acid value is 4.2mgKOH/g .

Example 5 (comparative example)

This example is the preparation of fatty acid and epoxide esterification.

Put 59.6g (0.2mol) ricinoleic acid in a reactor equipped with an electric stirrer, thermometer, reflux condenser, and dropping funnel, heat and stir to raise the temperature to 80°C, mix 23.2g (0.4mol) 1,2 -Propylene oxide and 1.0g NaOH catalyst are slowly added dropwise into the reactor, and the reaction is carried out under reflux for 5 hours. When the temperature rises to 135°C and the reflux flow is very small, add 4.0g of acid clay to neutralize the catalyst and filter, and the filtrate is diluted with aromatic hydrocarbons The oil dilution is 50%, and the acid value is 2.3 mgKOH/g.

Example 6

This example is the preparation of multi-effect additive of the present invention.

Add 85.6g Tetradecyl Alcohol, 45.6g1,3-Propanediol in the copolymer that example 1 makes 8.0 g of acidic ion exchange resin Amberlyst.RTM.15 (Rohm & Haas Co.). Under nitrogen protection, react at 140-150°C for 4 hours, then add 168.0g of linoleic acid (the molar ratio of linoleic acid to 1,3-propanediol is 1:1) into the reactor, reflux for 3 hours, and then add 270g of aromatic hydrocarbon diluent oil is made into about 50% diluent, and finally the ion exchange resin is removed by filtration. The acid value of the product is 8.6mgKOH/g.

Example 7

This example is the preparation of multi-effect additive of the present invention.

Put 56.4g (0.2mol) oleic acid, 29.8g (0.2mol) triethanolamine, 3.0g sodium methoxide/methanol catalyst and 86g aromatic hydrocarbon dilution oil solvent into a tank equipped with electric stirrer, thermometer, reflux water separator and nitrogen gas introduction In the reactor of the tube, nitrogen gas was introduced to heat and stir to raise the temperature to 130-140° C., and the reaction was carried out by nitrogen purging for 4 hours. Then add the copolymer (containing 0.1mol maleic anhydride) that 149.2g example 2 makes, keep 140～150 ℃ of reactions for 3 hours, add 3.5g acid clay to neutralize the catalyst and filter at last, the filtrate is the product, and the product acid value is 6.7 mgKOH/g.

Example 8

This example is the preparation of multi-effect additive of the present invention.

Put 59.6g (0.2mol) ricinoleic acid in a reactor equipped with an electric stirrer, thermometer, reflux condenser, and dropping funnel, heat and stir to raise the temperature to 80°C, mix 23.2g (0.4mol) 1,2 -Propylene oxide, 1.0gNaOH catalyst is slowly added dropwise in the reactor, reflux reaction 5 hours, when temperature rises to 135 ℃ when reflux flow is very little, then add the multipolymer that 149.2g example 2 makes (containing 0.1mol horsepower anhydride) and 80g of aromatic diluent oil, kept at 140°C and purged with nitrogen for 2 hours, and finally added 4.0g of acid clay to neutralize the catalyst and filtered, and the filtrate was the product. The acid value of the product is 7.8mgKOH/g.

Example 9

This example is the preparation of multi-effect additive of the present invention.

In the copolymer that example 3 makes, add 73.0g triethylenetetramine, 141.0g dimerized oleic acid (the mol ratio of maleic anhydride, triethylenetetramine and dimerized oleic acid in the copolymer is 1: 1: 0.5) , nitrogen purging reaction at 150° C. for 5 hours, and then add 210 g of aromatic hydrocarbon diluent oil to prepare about 50% dilution. The acid value of the product is 4.3mgKOH/g.

Example 10

This example is the use effect of the additives prepared in Examples 1-9 in diesel. Two kinds of diesel oil were selected as the test oil, namely (A) Dagang 0 ^# blend oil and (B) Yanshan-20 ^# blend oil. The physical and chemical properties of the two diesels are shown in Table 1. The HFRR method (ISO12156-1) wear scar diameter WS _1.4 , cold filter point and freezing point of the diesel oil before and after dosing are shown in Table 2. When the wear scar diameter is less than 460um (60°C), Then the lubricity of diesel oil is qualified.

Table 1 The physical and chemical properties of diesel oil diesel fuel (A) (B) Density (20°C)/g·cm ^-3 Viscosity/mm ² .s ^-1 S content/mg·kg-1 Paraffins/m% total naphthenes/m% total single-ring aromatics/m% total bicyclic aromatics/m %Tricyclic aromatic hydrocarbons/m%CFPP/°CSP/°C initial boiling point/°C20% boiling point/°C50% boiling point/°C90% boiling point/°C dry point/°C 0.85762.548 (40°C) 23838.518.429.611.91.641188230252343353 0.82983.229(20℃)0.544.831.621.91.70-23-29193226249276286

Table 2 Improvement of diesel lubricity and low temperature fluidity by multi-effect additives oil sample Dosage/mg.kg ^-1 WS1.4/μm CFPP/℃ SP/℃ Blank Diesel Oil AA+ Example 1 Product A+ Example 2 Product A+ Example 4 Product A+ Example 5 Product A+ Example 6 Product A+ Example 7 Product A+ Example 8 Product A+ Example 9 Product /400300300300700600600500 525506497432418352299319342 42144-2-1-10 10022-10-12-9-9 Blank Diesel Oil BB + Example 1 Product B + Example 2 Product B + Example 4 Product B + Example 5 Product B + Example 6 Product B + Example 7 Product B + Example 8 Product B + Example 9 Product /400300300300700600600500 619594602507494398412384427 -23-25-25-22-21-29-27-27-27 -29-33-34-25-27<-35<-35<-35<-35

As can be seen from Table 2, although acrylate-maleic anhydride copolymers (example 1, 2, 3) can slightly reduce the cold filter point and freezing point of diesel oil, the improvement effect on the lubricity of diesel oil is very poor. Although the monoesters of fatty acids (Examples 4 and 5) can improve the lubricity of diesel oil to a certain extent, the cold filter point and freezing point of diesel oil will not change or rise. The multi-effect diesel oil additive composition provided by the invention can well improve the lubricity of low-sulfur diesel oil, and has good filtering and pour point depressing effects on diesel oil with high wax content.

Claims (17)

1. copolymer type multi-effect additive of diesel oil, by: (a) number-average molecular weight is 500～10000 vinylformic acid C ₆～C ₂₂Alkyl ester-copolymer-maleic anhydride; (b) one or more in polyvalent alcohol, epoxide, polyamine, the amino alcohol; (c) C ₆～C ₅₀Organic acid gets 50～200 ℃ of reactions; The reaction mol ratio of a, b, c is 1: 0.1～10: 0.1～10.

2. according to the described additive of claim 1, it is characterized in that the alkyl in the said multipolymer is C ₁₀～C ₂₀Straight chained alkyl.

3. according to the described additive of claim 1, it is characterized in that the number-average molecular weight of multipolymer is 1000～8000.

4. according to the described additive of claim 1, it is characterized in that in the said multipolymer, the mol ratio of alkyl acrylate and maleic anhydride is 1: 0.1～10.

5. according to the described additive of claim 1, it is characterized in that said polyvalent alcohol is C ₂～C ₁₈Hydroxyl quantity is 2～6 polyvalent alcohol.

6. according to the described additive of claim 5, it is characterized in that said polyvalent alcohol is C ₂～C ₁₂Polyvalent alcohol.

7. according to the described additive of claim 6, it is characterized in that said polyvalent alcohol is ethylene glycol, glycol ether, Triethylene glycol, propylene glycol, glycerol, butyleneglycol, pentanediol, hexylene glycol, tetramethylolmethane.

8. according to the described additive of claim 1, it is characterized in that said epoxide is C ₂～C ₁₈Epoxide.

9. according to the described additive of claim 8, it is characterized in that said epoxide is C ₂～C ₈Epoxide.

10. according to the described additive of claim 1, it is characterized in that said polyamines polyene structural formula is H ₂N[(CH ₂) _nNH] _mH's, wherein n is 2～4 integer, m is 1～5 integer.

11., it is characterized in that said polyamines polyene is diethylenetriamine, triethylene tetramine, tetraethylene pentamine or five ethene hexamines according to the described additive of claim 10.

12. according to the described additive of claim 1, it is characterized in that said amino alcohol is selected from 2-amino-1, ammediol, 3-amino-1,2-propylene glycol, 3-amino-1-propyl alcohol, thanomin, diethanolamine, N methyldiethanol amine, trolamine or its mixture.

13., it is characterized in that said alkoxy polyamine is that wherein the polyamines polyene structural formula is H by polyamines polyene and the epoxide product with 1: 0.5～10 molar ratio reaction according to the described additive of claim 1 ₂N[(CH ₂) _nNH] _mH, wherein n is 2～4 integer, m is 1～5 integer; Wherein epoxide is oxyethane, 1,2 epoxy prapane, 1, the 2-butylene oxide ring.

14., it is characterized in that said organic acid is C according to the described additive of claim 1 ₈～C ₄₀Lipid acid.

15., it is characterized in that said lipid acid is C according to the described additive of claim 14 ₈～C ₄₀Vegetable fatty acids.

16. according to the described additive of claim 15, it is characterized in that said vegetable fatty acids is selected from oleic acid, linolic acid, linolenic acid, dimerization oleic acid, linoleic acid dimer, ricinolic acid, palmitinic acid, soybean oleic acid, arachic acid, vegetable seed oleic acid, tall oil acid or its mixture.

17., it is characterized in that the mol ratio of a, b and c reaction is 1: 0.2～5: 0.2～5 according to the described additive of claim 1,80～160 ℃ of temperature of reaction, 0.5～20 hour reaction times.