阅读说明：本技术 一种高分子量烟炱无灰分散剂的制备方法 (Preparation method of high molecular weight soot ashless dispersant ) 是由 郭海燕 王龙龙 赵东北 范金凤 于 2021-08-04 设计创作，主要内容包括：本申请提供了一种高分子量烟炱无灰分散剂的制备方法,包括：将线型端基烯酸与聚α烯烃、顺丁烯二酸酐混合,在自由引发剂的作用下发生三元共聚反应,生成一种双官能团大分子链,这种双官能团大分子链与胺类物质进行脱水反应,生成含有多酰亚胺、酰胺和/或胺基的高分子量烟炱无灰分散剂。本发明提供的高分子量烟炱无灰分散剂的制备方法,提高了烟炱分散性能和低温流动性,产品具有优异的烟炱分散能力、高温稳定性、低温性能和氧化安定性。(The application provides a method for preparing a high molecular weight soot ashless dispersant, comprising: linear terminal olefine acid, poly-alpha olefin and maleic anhydride are mixed and subjected to ternary polymerization reaction under the action of a free initiator to generate a bifunctional macromolecular chain, and the bifunctional macromolecular chain and an amine substance are subjected to dehydration reaction to generate a high-molecular-weight soot ashless dispersant containing polyimide, amide and/or amino. The preparation method of the high molecular weight soot ashless dispersant provided by the invention improves the soot dispersing performance and low-temperature fluidity, and the product has excellent soot dispersing ability, high-temperature stability, low-temperature performance and oxidation stability.)

1. A preparation method of a high molecular weight ashless dispersant is characterized by comprising the following steps:

s1, mixing linear terminal olefine acid and poly-alpha-olefin, adding maleic anhydride, and reacting under the action of a free radical initiator to generate a macromolecular chain compound containing carboxyl and succinic anhydride;

and S2, reacting the macromolecular chain compound with an amine compound to generate the high-molecular-weight ashless dispersant.

2. The method of claim 1, wherein the linear terminal olefinic acid has a structure containing a carboxyl group and a double bond at each end of the molecule, and the formula of the linear terminal olefinic acid compound is as follows:

wherein n is an integer of 1, 2, 3 ….

3. The method of claim 2, wherein the linear terminal olefinic acid compound comprises at least one of 10-undecylenic acid, dodecenoic acid, 13-tetradecenoic acid, and 15-hexadecenoic acid.

4. The method of making a high molecular weight ashless dispersant according to claim 1, wherein said polyalphaolefin comprises at least one of polydecene, polydodecene, deca-and dodeca-mixed-ene polymers.

5. The method of claim 1, wherein the free radical initiator comprises at least one of di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxybenzoate.

6. The method of claim 1, wherein the amine-based material comprises at least one of aromatic amines, alkyl amines;

the aromatic amine comprises at least one of p-phenylenediamine, p-aminodiphenylamine, 4 '-diaminodiphenylmethane and 4, 4' -diaminodiphenyl ether;

the alkylamine comprises at least one of ethylenediamine, diethylenetriamine and polyethylene polyamine.

7. The method of claim 1, wherein the molar ratio of the linear terminal olefinic acid compound to the polyalphaolefin in S1 is (1:4) - (2: 1); the molar ratio of the mole of the maleic anhydride to the total mole of the linear terminal olefine acid and the poly-alpha olefin is (1:1) - (2: 1).

8. The method for preparing the high molecular weight ashless dispersant according to claim 1, characterized in that, in S1, the reaction temperature is 130-210 ℃, after adding the free radical initiator, the reaction is continued for 15-60 min; in S2, the reaction temperature is 120-240 ℃.

9. The method of claim 1, wherein the molar ratio of the total moles of the acid anhydride and the carboxylic acid of the macromolecular chain compound to the moles of the primary amine of the amine compound in S2 is (1:1) to (1.5: 1).

10. The method of claim 1, wherein in S2, the high molecular weight soot ashless dispersant as a final reaction product contains polyimide, amide and/or amine groups, and has a number average molecular weight of 7000-20000.

Technical Field

The application relates to the technical field of dispersants, in particular to a preparation method of a high molecular weight soot ashless dispersant.

Background

The polyisobutylene succinimide is used as one of main additives of the current gasoline engine oil and diesel engine oil, has the characteristics of good thermal stability, oxidation stability, high-temperature dispersibility and the like, mainly has the effect of inhibiting low-temperature oil sludge, high-temperature carbon deposition and paint film generation, and is an ashless dispersant which is most widely applied at present. However, ashless dispersants of this type have poor soot dispersing ability and have not been able to meet the ever-increasing environmental requirements. In order to improve the soot dispersion problem, more researchers improve the soot dispersing ability of the dispersant by introducing aromatic amine containing a conjugated structure, and although the conjugated structure enables the dispersant to obtain excellent dispersing ability and stability, the conjugated structure also causes the problems that the dispersant has high viscosity and is not beneficial to application. Meanwhile, the research on the soot dispersant tends to be multifunctional increasingly, and the research direction of the soot dispersant is also changed into the research direction of the soot dispersant by improving other application performances of the dispersant, thereby improving the application performance of the dispersant in a complexing agent and improving the overall performance of the complexing agent.

CN111635469 provides a preparation method of a novel high molecular weight ashless dispersant, which improves the soot adsorption and suspension capabilities of the novel high molecular weight ashless dispersant, but the improvement is not obvious in the aspects of low temperature performance, oxidation stability and the like.

Disclosure of Invention

The present application provides a method for preparing a high molecular weight soot ashless dispersant in order to solve or partially solve at least one of the above-mentioned problems associated with the background art or other disadvantages of the prior art.

The present application provides a method for preparing such a high molecular weight soot ashless dispersant, which may comprise:

s1, mixing linear terminal olefine acid and poly-alpha-olefin, adding maleic anhydride, and reacting under the action of a free radical initiator to generate a macromolecular chain compound containing carboxyl and succinic anhydride;

s2, reacting the macromolecular chain compound with an amine compound to generate the high-molecular-weight ashless dispersant.

In some embodiments, the linear terminal olefinic acid has a structure containing one carboxyl group and one double bond at each end of the molecule, and the linear terminal olefinic acid compound has the following formula:

wherein n is an integer of 1, 2 and 3 …, preferably 5-27, and the linear terminal olefinic acid compound comprises at least one of 10-undecylenic acid, dodecenoic acid, 13-tetradecatetraenoic acid and 15-hexadecenoic acid, but is not limited thereto. Preferably, the linear terminal olefine acid compounds are 10-undecylenic acid, dodecenoic acid, 13-tetradecenoic acid and 15-hexadecenoic acid.

In some embodiments, the Polyalphaolefin (PAO) includes at least one of polydecene, polydodecene, deca-and dodeca-mixed-olefin polymers, but is not limited thereto. Preferably, the polyalphaolefin is polydecene, polydodecene, deca-and dodeca-mixed olefin polymer.

In some embodiments, the free radical initiator includes at least one of di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxybenzoate, but is not limited thereto. Preferably, the free radical initiator is di-tert-butyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate.

In some embodiments, the amine species comprises at least one of aromatic amines, alkyl amines; the aromatic amine includes at least one of p-phenylenediamine, p-aminodiphenylamine, 4 '-diaminodiphenylmethane, 4' -diaminodiphenyl ether, but is not limited thereto; the alkylamine includes at least one of ethylenediamine, diethylenetriamine, and polyethylenepolyamine, but is not limited thereto.

Preferably, the aromatic amine is p-phenylenediamine, p-aminodiphenylamine, 4 '-diaminodiphenylmethane, 4' -diaminodiphenyl ether; the alkylamine is ethylenediamine, diethylenetriamine or polyethylene polyamine.

In some embodiments, the mole ratio of the linear terminal olefinic acid compound to the polyalphaolefin in S1 is (1:4) to (2:1), preferably (1:2) to (2: 1); the molar ratio of the moles of maleic anhydride to the total moles of linear terminal olefinic acid and polyalphaolefin is (1:1) to (2:1), preferably (1:1) to (1.5: 1).

In some embodiments, in S1, the reaction temperature is 130-210 ℃, preferably 130-180 ℃, and after adding the free radical initiator, the reaction is continued for 15-60 min, preferably 20-40 min; s2, the reaction temperature is 120-240 ℃, and the preferable temperature is 140-220 ℃.

In some embodiments, in S2, the molar ratio of the total mole of the acid anhydride and the carboxylic acid of the macromolecular chain compound to the primary amine of the amine compound is (1:1) to (1.5:1), preferably (1:1) to (1.3: 1).

In some embodiments, the reaction product, high molecular weight soot ashless dispersant, S2, comprises a polyimide, amide and/or amine group and has a number average molecular weight of 7000 to 20000, preferably 12000 to 18000.

The invention can be briefly described as follows:

mixing linear end group olefine acid compound with PAO and maleic anhydride, under the action of free radical initiator making ternary polymerization reaction to obtain a prefabricated ternary copolymer containing carboxyl group and succinic anhydride bifunctional group, mixing said ternary copolymer with amine material and making dehydration reaction so as to obtain the high-molecular weight ashless soot dispersant containing polyimide, amide and/or amino group.

According to the technical scheme of the embodiment, at least one of the following advantages can be obtained.

Compared with the traditional polyisobutylene succinimide ashless dispersant, the high molecular weight compound has better soot dispersing performance and excellent low-temperature fluidity under the same dosage, and can be used as a novel multifunctional dispersant to replace the polyisobutylene succinimide ashless dispersant in the internal combustion engine oil.

The invention selects PAO (poly-alpha-olefin), terminal olefine acid compound containing bifunctional groups (alpha-olefin and carboxylic acid) and aromatic amine compound with good low-temperature fluidity, high viscosity index, good oxidation stability and other excellent performances as raw materials to prepare a novel high molecular weight soot ashless dispersant containing polyimide, amide and/or amido and having a novel structure. The aromatic amine contains a conjugated structure, so that the novel ashless dispersant has excellent soot dispersing capacity and high-temperature stability; meanwhile, due to the excellent performance of PAO, the defects of low-temperature performance, oxidation stability, compatibility with rubber rings and other application performances of the high-molecular-weight ashless dispersant are improved.

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to be limiting.

The invention is described in further detail below:

the invention provides a preparation method of a high molecular weight soot ashless dispersant, which comprises the following steps:

step 1, mixing linear end-group olefine acid and poly-alpha-olefin (PAO), adding maleic anhydride, and reacting under the action of a free radical initiator to generate a macromolecular chain compound containing carboxyl and succinic anhydride;

specifically, a linear end group olefinic acid compound and PAO are uniformly mixed, a molten liquid of Maleic Anhydride (MA) is slowly dripped at 130-210 ℃, preferably 130-180 ℃, a free radical initiator is dripped into a reaction system at the same time, the three components can perform ternary polymerization reaction under the action of the initiator, after the dripping is finished, the reaction is continued for 15-60 min, preferably 20-40 min, and unreacted MA and initiator decomposition products are separated out to obtain a preformed terpolymer, namely a macromolecular chain compound.

More specifically, the molar ratio of the alkenoic acid to the PAO is (1:4) to (2:1), preferably (1:2) to (2: 1); the molar ratio of the moles of MA to the total moles of olefinic acid and PAO is (1:1) to (2:1), preferably (1:1) to (1.5: 1).

Step 2, reacting the macromolecular chain compound with an amine compound to generate a high-molecular-weight ashless dispersant;

specifically, the preformed terpolymer, i.e. the macromolecular chain compound and the amine substance are subjected to dehydration reaction at 120-240 ℃, preferably 140-220 ℃, so as to generate a product containing polyimide, amide and/or amino, i.e. the high molecular weight soot ashless dispersant.

More specifically, the total mole ratio of anhydride/carboxylic acid to primary amine is (1:1) to (1.5:1), preferably (1:1) to (1.3: 1); the number average molecular weight of the high molecular weight soot ashless dispersant is 7000 to 20000, preferably 12000 to 18000.

Example 1:

20.0 g of 10-undecylenic acid and 260.5 g of PAO-40 are added into a 500ml four-mouth glass bottle, stirred and heated to 150 ℃, and 39.8 g of molten maleic anhydride and 24 ml of di-tert-butyl peroxide initiator are respectively and simultaneously dripped into the reaction system within 60 min. After the maleic anhydride and the initiator are added dropwise, the reaction is continued for 1h at the temperature of 150 ℃ to ensure that the reaction is completely carried out. After the reaction is finished, separating the decomposition product of the di-tert-butyl peroxide and unreacted maleic anhydride in the four-mouth bottle in a reduced pressure distillation mode at the temperature of 70-110 ℃ to obtain a reaction product.

Example 2:

160.0 g of the reaction product of example 1 and 120.2 g of 150N hydrogenated base oil are added into a 500ml four-neck flask, stirred and heated to 70-80 ℃, 4.0 g of p-aminodiphenylamine is added, and then 20.5 g of tetraethylenepentamine is slowly added dropwise. After the dropwise addition, slowly heating the materials to 165 ℃, introducing nitrogen to purge and react for 4 hours, and completely blowing off water produced by the reaction to obtain a reaction product. The number average molecular weight of the reaction product was found to be 16454, and the nitrogen content was found to be 2.58 wt%.

Example 3:

150.0 g of the reaction product obtained in example 1 and 107.1 g of 150N hydrogenated base oil are added into a 500ml four-neck flask, stirred and heated to 70-80 ℃, and 3.7 g of p-aminodiphenylamine and 11.0 g of p-phenylenediamine are added. And then slowly heating the materials to 200 ℃, introducing nitrogen to purge and react for 4 hours, and completely purging water produced by the reaction to obtain a reaction product. The number average molecular weight of the reaction product was 15642 and the nitrogen content was 1.28 wt%.

Example 4:

10.0 g of dodecenoic acid and 204.9 g of PAO-40 were added into a 500ml four-necked glass bottle, stirred and heated to 130 ℃, and 15.1 g of molten maleic anhydride and 9 ml of di-tert-butyl peroxide initiator were added dropwise to the reaction system simultaneously within 60 min. After the maleic anhydride and the initiator are added dropwise, the reaction is continued for 60min at the temperature of 130 ℃ to ensure that the reaction is completely carried out. After the reaction is finished, separating the decomposition product of the di-tert-butyl peroxide and unreacted maleic anhydride in the four-mouth bottle in a reduced pressure distillation mode at the temperature of 70-110 ℃ to obtain a reaction product.

Example 5:

120.0 g of the reaction product of example 1 and 83.2 g of 150N hydrogenated base oil were added to a 500ml four-necked flask, stirred and heated to 70-80 ℃ and then 6.7 g of tetraethylenepentamine was slowly added dropwise. After the dropwise addition is finished, slowly heating the materials to 120 ℃, introducing nitrogen to purge and react for 4 hours, and completely blowing off water produced by the reaction to obtain a reaction product. The number average molecular weight of the reaction product was 8623 and the nitrogen content was 1.10 wt%.

Example 6:

5.0 g of 10-undecylenic acid and 217.1 g of PAO-40 are added into a 500ml four-mouth glass bottle, stirred and heated to 150 ℃, and 26.6 g of molten maleic anhydride and 16 ml of di-tert-butyl peroxide initiator are respectively and simultaneously dripped into the reaction system within 60 min. After the maleic anhydride and the initiator are added dropwise, the reaction is continued for 15min at the temperature of 210 ℃ to ensure that the reaction is completely carried out. After the reaction is finished, separating the decomposition product of the di-tert-butyl peroxide and unreacted maleic anhydride in the four-mouth bottle in a reduced pressure distillation mode at the temperature of 70-110 ℃ to obtain a reaction product.

Example 7:

120.0 g of the reaction product obtained in example 1 and 88.2 g of 150N hydrogenated base oil are added into a 500ml four-neck flask, stirred and heated to 70-80 ℃, 2.7 g of p-aminodiphenylamine is added, and then 12.3 g of tetraethylenepentamine is slowly added dropwise. After the dropwise addition is finished, slowly heating the materials to 180 ℃, introducing nitrogen to purge and react for 4 hours, and completely blowing off water produced by the reaction to obtain a reaction product. The number average molecular weight of the reaction product was determined to be 19845, and the nitrogen content was determined to be 2.12 wt%.

Example 8:

30.0 g of 15-hexadecenoic acid and 117.9 g of PAO-40 were added to a 500ml four-necked glass bottle, stirred and heated to 150 ℃ and 26.0 g of molten maleic anhydride and 16 ml of di-t-butyl peroxide initiator were added dropwise to the reaction system simultaneously within 60 min. After the maleic anhydride and the initiator are added dropwise, the reaction is continued for 30min at the temperature of 150 ℃ to ensure the reaction to be complete. After the reaction is finished, separating the decomposition product of the di-tert-butyl peroxide and unreacted maleic anhydride in the four-mouth bottle in a reduced pressure distillation mode at the temperature of 70-110 ℃ to obtain a reaction product.

Example 9:

100.0 g of the reaction product of example 1 and 80.1 g of 150N hydrogenated base oil were added to a 500ml four-necked flask, stirred and heated to 70-80 ℃, 6.8 g of p-aminodiphenylamine was added, and 17.4 g of tetraethylenepentamine was slowly added dropwise. After the dropwise addition is finished, slowly heating the materials to 240 ℃, introducing nitrogen to purge and react for 4 hours, and completely blowing off water produced by the reaction to obtain a reaction product. The number average molecular weight of the reaction product was determined to be 7120 and the nitrogen content was determined to be 3.51 wt%.

Comparative example 1:

adding 2300 g (1.0mol) of high-activity polyisobutylene with the number average molecular weight of 2300 and the alpha olefin content of more than or equal to 85 wt% into a 5000ml stainless steel high-pressure reaction kettle, introducing nitrogen for protection, stirring and heating to 200 ℃; 176.5 g (1.8mol) of molten maleic anhydride are slowly added dropwise via a dropping device over a period of 30 min. After the dropwise addition, slowly raising the temperature in the reaction kettle to 230 ℃, continuously reacting for 4 hours at the temperature, blowing nitrogen into the reaction kettle after the reaction is finished, and blowing unreacted maleic anhydride out of the reaction kettle to obtain a reaction product. The saponification value of the reaction product was found to be 60 mgKOH/g.

Comparative example 2

150 g of the reaction product of comparative example 1 and 68.0 g of 150N hydrogenated base oil were added to a 500ml four-necked flask, slowly heated to 70-80 ℃ and stirred uniformly, and then 10.2 g of tetraethylenepentamine was slowly added dropwise. After the dropwise addition is finished, slowly heating the material to 150-170 ℃, introducing nitrogen to purge and react for 4 hours, and completely purging water produced by the reaction to obtain a reaction product. The detection shows that the number average molecular weight of the reaction product is 4216, and the nitrogen content is 1.60 wt%.

Comparative example 3

20.0 g of 10-undecylenic acid, 299.5 g of high-activity polyisobutene with the number average molecular weight 2300 and the alpha olefin content of more than or equal to 85 wt% are added into a 500ml four-mouth glass bottle, stirred and heated to 150 ℃, and 39.8 g of molten maleic anhydride and 24 ml of di-tert-butyl peroxide initiator are respectively and simultaneously dripped into the reaction system within 60 min. After the maleic anhydride and the initiator are added dropwise, the reaction is continued for 1h at the temperature of 150 ℃ to ensure that the reaction is completely carried out. After the reaction is finished, separating the decomposition product of the di-tert-butyl peroxide and unreacted maleic anhydride in the four-mouth bottle in a reduced pressure distillation mode at the temperature of 70-110 ℃ to obtain a reaction product.

Comparative example 4

150.0 g of the reaction product of comparative example 3 and 106.4 g of 150N hydrogenated base oil were placed in a 500ml four-necked flask, stirred and heated to 70-80 ℃ and then 3.3g of p-aminodiphenylamine and 9.8 g of p-phenylenediamine were added. And then slowly heating the materials to 200 ℃, introducing nitrogen to purge and react for 4 hours, and completely purging water produced by the reaction to obtain a reaction product. The reaction product was found to have a number average molecular weight of 16772 and a nitrogen content of 1.14 wt%.

The final products obtained in example 2, example 3, example 5, example 7 and example 9 and the final products obtained in comparative example 2 and example 4 were exogenously added to the old oil for engine bench test in a dosage of 0.5 wt% and 1.0 wt%, respectively, and the oil had a soot content of 5.5 wt% by TGA analysis and a kinematic viscosity at 100 ℃ of 48.32mm 2/s. And (3) stirring the old oil added with the dispersant for 2 hours at 100 ℃, detecting the kinematic viscosity at 100 ℃ and calculating the viscosity reduction rate, wherein the lower the kinematic viscosity and the higher the reduction rate, the stronger the capability of the added dispersant for preventing the oil product from thickening.

From the above dispersibility evaluation data, it can be seen that the high molecular weight soot-free dispersants prepared in the examples of this patent have better inhibitory effects on the thickening of the old oil than the comparative examples at the same addition levels than the conventional high molecular weight polyisobutylene succinimide (comparative example 2); meanwhile, by comparing example 3 with comparative example 4, it was confirmed that the dispersibility of the obtained dispersant was equivalent to that of the dispersant obtained when PAO-40 was used as the nonpolar chain and high molecular weight polyisobutylene (number average molecular weight 2300, alpha olefin content ≥ 85 wt%) was used as the nonpolar chain under the same polar terminal.

The dispersants from example 2, example 3, example 5, example 7, example 9 and comparative example 2, example 4 were blended in the same amount (5.0 wt%) into the same missing oil to make a 15W/40 viscosity grade diesel engine oil, and the low temperature dynamic viscosity (CCS) of the oil samples was determined at-20 ℃ according to the industry standard (GB/T6538-2010 appendix a, a procedure specific for the determination of high viscoelasticity samples using manual CCS).

According to the evaluation data of the low-temperature dynamic viscosity, the high-molecular-weight soot ashless dispersant prepared in the patent example can obviously improve the low-temperature performance of oil products compared with the comparative example.

Kinematic viscosities at 100 ℃ and 40 ℃ were measured according to the industry standards (GB/T265-1988 Petroleum products kinematic viscometry and kinetic viscometry calculations) and viscosity indices were calculated according to the industry standards (GB/T1995-1998 Petroleum products viscosity index calculations) using example 2, example 3, example 5, example 7, example 9 and comparative example 2, comparative example 4.

The higher the viscosity index, the better the viscosity-temperature properties of the product.

According to the evaluation data of the viscosity and the viscosity index, the high molecular weight soot ashless dispersant prepared in the embodiment of the invention has lower kinematic viscosity and better viscosity-temperature property at the same temperature, and is more convenient to use.

In the invention, PAO (poly-alpha-olefin), terminal olefine acid compound containing bifunctional groups (alpha-olefin and carboxylic acid) and aromatic amine compound with good performance such as good low-temperature fluidity, high viscosity index, good oxidation stability and the like are selected as raw materials, the terminal olefine acid compound, the PAO and maleic anhydride are subjected to ternary polymerization to obtain a bifunctional high molecular weight compound, and the bifunctional high molecular weight compound is reacted with aromatic amine and/or alkylamine to obtain the high molecular weight soot ashless dispersant containing polyimide, amide and/or amino, which has a novel structure and a molecular weight obviously higher than that of the traditional polyisobutylene succinimide. Compared with the traditional polyisobutylene succinimide, the dispersant not only has a nonpolar chain with larger molecular weight, but also contains aromatic amine conjugated groups and more polar groups in a molecular structure, so that the dispersant has excellent soot dispersing capacity and high-temperature stability. Due to the excellent performance of PAO, the defects of low-temperature performance, oxidation stability, compatibility with rubber rings and other application performances of the high-molecular-weight ashless dispersant are improved. The dispersant has good low-temperature performance due to the particularity of a nonpolar chain structure in a molecule, greatly enhances the application performance of the dispersant in a complexing agent, and can be used as a novel multifunctional dispersant to replace a polyisobutylene succinimide type ashless dispersant in internal combustion engine oil.