阅读说明：本技术 一种多功能高硼含量硼化分散剂及其制备方法 (Multifunctional high-boron-content boration dispersing agent and preparation method thereof ) 是由 郭海燕 王龙龙 赵东北 范金凤 于 2021-07-26 设计创作，主要内容包括：本申请提供了一种多功能高硼含量硼化分散剂及其制备方法,包括：将聚异丁烯丁二酸酐、胺类化合物混合,反应得到聚异丁烯丁二酰亚胺无灰分散剂,将聚异丁烯丁二酰亚胺无灰分散剂、硼酸混合反应,再加入脂肪酸二乙醇酰胺反应,收集反应产物。本发明提供的多功能高硼含量硼化分散剂的制备方法,提高了硼化分散剂中的硼含量、分散性能、防锈性能和抗磨性能,产品可用于内燃机油、汽车自动变速箱油及工业用润滑油中。(The application provides a multifunctional high-boron-content boration dispersing agent and a preparation method thereof, wherein the preparation method comprises the following steps: mixing polyisobutylene succinic anhydride and an amine compound, reacting to obtain a polyisobutylene succinimide ashless dispersant, mixing the polyisobutylene succinimide ashless dispersant and boric acid for reaction, adding fatty acid diethanolamide for reaction, and collecting a reaction product. The preparation method of the multifunctional high-boron-content borated dispersant provided by the invention improves the boron content, the dispersing property, the antirust property and the wear resistance in the borated dispersant, and the product can be used in internal combustion engine oil, automobile automatic transmission oil and industrial lubricating oil.)

1. A multifunctional high boron content boration dispersant, characterized in that, the general formula of the high boron content boration dispersant is as follows:

the PIB is polyisobutylene, the number average molecular weight of the polyisobutylene is 500-5000, n is a natural number, and R is saturated or unsaturated straight chain or branched chain alkyl.

2. The multifunctional high boron content boration dispersant according to claim 1 characterized in that said polyisobutylene in said high boron content boration dispersant has a number average molecular weight of 1000 to 3000 and n is 2 to 7.

3. A process for preparing a multifunctional high boron content borated dispersant according to any of claims 1-2, characterized by the steps of:

s1, mixing polyisobutylene succinic anhydride and an amine compound, adding base oil, and reacting to obtain a polyisobutylene succinimide ashless dispersant;

and S2, mixing the polyisobutylene succinimide ashless dispersant with boric acid for reaction, and adding fatty acid diethanolamide for reaction to prepare the high boron content borated dispersant.

4. The method for preparing the multifunctional high boron content borated dispersant according to claim 3, characterized in that said polyisobutylene succinic anhydride substitution degree is 1.1-2.0, said amine compound is a polyene polyamine; the polyisobutylene succinic anhydride and the amine compound are prepared from the following components in percentage by weight: the molar ratio of the polyene polyamine is 1.2-2.8: 1.

5. The method for preparing the multifunctional high boron content boration dispersant according to claim 3, wherein said polyisobutylene succinic anhydride and said amine compound are reacted at 130-200 ℃ for 1-6 hours, and water produced by the reaction is separated by nitrogen blowing or vacuum pumping at the same time of the reaction.

6. The method for preparing the multifunctional high boron content boration dispersant according to claim 3, characterized in that in S2, it further comprises a reaction promoter, wherein the reaction promoter is water or fatty alcohol, and the fatty alcohol includes but is not limited to isopropanol, n-butanol, isobutanol.

7. The method of preparing a multifunctional high boron content boration dispersant according to claim 3 characterized in that the alkyl group of the fatty acid of said fatty acid diethanolamide is saturated or unsaturated, linear or branched, comprising from 5 to 30 carbon atoms;

the fatty acid diethanolamides include, but are not limited to, caprylic acid diethanolamide, lauric acid diethanolamide, myristic acid diethanolamide, palmitic acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, linoleic acid diethanolamide.

8. The preparation method of the multifunctional high boron content boration dispersant according to claims 3 to 7, characterized in that in S2, the ashless polyisobutylene succinimide dispersant is mixed with the boric acid, the reaction accelerator is added, the mixture is reacted at 80 to 120 ℃ for 1 to 7 hours, nitrogen is introduced, the temperature is raised to 140 to 190 ℃, the reaction is carried out for 0.5 to 2 hours, fatty acid diethanolamide is added, and the reaction is continued for 2 to 5 hours under the condition of heat preservation, so as to obtain the multifunctional high boron content boration dispersant.

9. The method for preparing the multifunctional high boron content boration dispersant according to claim 8, characterized in that in S2, the ashless polyisobutylene succinimide dispersant is mixed with the boric acid, the reaction accelerator is added, the mixture is reacted at 80-120 ℃ for 2-5 hours, nitrogen is introduced, the temperature is raised to 150-180 ℃ for 1-1.5 hours, fatty acid diethanolamide is added, and the mixture is kept warm and continuously reacted for 3-4 hours to obtain the multifunctional high boron content boration dispersant.

10. Use of the multifunctional high boron-content borated dispersant according to any one of claims 1-2 in internal combustion engine oils, automotive automatic transmission oils, industrial lubricating oils.

Technical Field

The application relates to the technical field of dispersing agents, in particular to a multifunctional high-boron-content boration dispersing agent and a preparation method thereof.

Background

With the development of economy, the progress of science and technology and the continuous improvement of the requirements of environmental protection and energy conservation, the oil products of lubricating oil are continuously upgraded and updated, the development of the high-efficiency multifunctional lubricating oil additive is in a necessary trend, and the development of the high-efficiency multifunctional additive can reduce the addition amount of a single agent of the required additive, realize more excellent effect by less addition amount, even reduce the types of the required additive and avoid the problem of incompatibility possibly existing among the additives. The boronized ashless dispersant with both dispersibility and anti-wear performance also becomes the research focus of scholars at home and abroad.

The boronized ashless dispersant has good dispersing performance, wear resistance and oxidation resistance, and can improve the compatibility of the ashless dispersant and a rubber sealing ring, so that the boronized ashless dispersant is favored by numerous scholars. The boronized ashless dispersant is widely applied to high-grade internal combustion engine oil, secondary stroke oil and automobile automatic transmission fluid, can also be applied to energy-saving and environment-friendly industrial oil products, particularly to the automatic transmission fluid, can improve the dynamic and static friction coefficient of the automatic transmission fluid, meets the requirements of people on stable gear shifting, and becomes an ideal substitute of a phosphorus-containing anti-wear additive.

The boronized ashless dispersants are more in variety, and the boronized polyisobutylene succinimide type is the mainstream product at present. The traditional synthesis process of the boronized ashless dispersant comprises the steps of reacting polyisobutylene succinic anhydride with polyene polyamine to obtain polyisobutylene succinimide, then reacting with boric acid under the action of an accelerator (water or fatty alcohols and the like), and removing water, a solvent and the accelerator generated by the reaction in vacuum to obtain the boronized polyisobutylene succinimide ashless dispersant. Although the synthesis process of the boronized ashless dispersant is mature, the boronized ashless dispersant obtained by the method has low boron content which is difficult to be higher than 1.0wt percent, and has the defects of poor stability, easy precipitation of boron and the like.

Disclosure of Invention

The present application provides a multifunctional high boron content boration dispersant and a method for preparing the same, in order to solve or partially solve the above-mentioned problems involved in the background art or at least one other disadvantage of the prior art.

The application provides a multifunctional high-boron-content boration dispersing agent, which has the following general formula:

wherein, PIB is polyisobutylene, the number average molecular weight of polyisobutylene is 500-5000, preferably 1000-3000, n is a natural number, preferably n is 2-7, and R is saturated or unsaturated straight chain or branched chain alkyl.

The application also provides a preparation method of the multifunctional high-boron-content boration dispersing agent, which comprises the following steps:

s1, mixing polyisobutylene succinic anhydride and an amine compound, adding base oil, and reacting to obtain a polyisobutylene succinimide ashless dispersant;

and S2, mixing the polyisobutylene succinimide ashless dispersant with boric acid for reaction, and adding fatty acid diethanolamide for reaction to prepare the high boron content borated dispersant.

In some embodiments, the polyisobutylene succinic anhydride substitution degree is 1.1-2.0, and the amine compound is a polyene polyamine; the polyisobutylene succinic anhydride and the amine compound are mixed according to the following ratio of succinic anhydride: the molar ratio of the polyene polyamine is 1.2-2.8: 1.

Wherein the degree of substitution of the polyisobutylene succinic anhydride represents the number of succinic anhydrides per polyisobutylene molecule.

Further, the amine compound is one or more of polyene polyamine, including but not limited to diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

In some embodiments, polyisobutylene succinic anhydride is mixed with an amine compound, added with base oil, and reacted at 130-200 ℃ for 1-6 hours, preferably at 140-170 ℃ for 2-4 hours; while the reaction is carried out, the water produced by the reaction is separated by means of nitrogen blowing or vacuum pumping.

Further, the base oil accounts for 30-50 wt% of the total product quality.

In some embodiments, S2 further comprises a reaction promoter, wherein the reaction promoter is water or a fatty alcohol with a lower boiling point, and the fatty alcohol includes, but is not limited to, isopropanol, n-butanol, and isobutanol.

Further, the mass ratio of the reaction accelerator to the boric acid is 0.5-2.5: 1, preferably 1-2: 1.

In some embodiments, the alkyl group of the fatty acid diethanolamide is saturated or unsaturated, linear or branched, the alkyl group comprising from 5 to 30 carbon atoms; fatty acid diethanolamides include, but are not limited to, caprylic acid diethanolamide, lauric acid diethanolamide, myristic acid diethanolamide, palmitic acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, linoleic acid diethanolamide.

In some embodiments, in S2, mixing the ashless polyisobutylene succinimide dispersant with boric acid, adding a reaction accelerator, reacting at 80-120 ℃ for 1-7 hours, introducing nitrogen, heating to 140-190 ℃, reacting for 0.5-2 hours, adding fatty acid diethanolamide, keeping the temperature at 140-190 ℃ under the purging of nitrogen, continuing to react for 2-5 hours, and finishing the reaction to obtain the multifunctional high-boron-content boration dispersant.

Further, in S2, mixing the ashless polyisobutylene succinimide dispersant with boric acid, adding a reaction accelerator, reacting for 2-5 hours at 80-120 ℃, introducing nitrogen, heating to 150-180 ℃, reacting for 1-1.5 hours, adding fatty acid diethanolamide, keeping the temperature at 150-180 ℃ under the purging of the nitrogen, continuing to react for 3-4 hours, and finishing the reaction to obtain the multifunctional high-boron-content boration dispersant.

Furthermore, the mass of the fatty acid diethanolamide accounts for 2-8 wt%, preferably 2-5 wt% of the product mass, and the boron content of the multifunctional high-boron-content boration dispersant of the reaction product is 0.8-2.5 wt%.

The application also provides the application of the multifunctional high-boron-content boration dispersing agent in internal combustion engine oil, automobile automatic transmission oil and industrial lubricating oil.

The invention can be briefly described as follows:

a multifunctional high-boron-content boration dispersant and a preparation method thereof are disclosed, polyisobutylene succinic anhydride is mixed with amine compounds to react to obtain polyisobutylene succinimide ashless dispersant; mixing polyisobutylene succinimide ashless dispersant with boric acid for reaction, and adding fatty acid diethanolamide for reaction to dehydrate hydroxyl in fatty acid diethanolamide and B-OH in boronized dispersant to obtain multifunctional high-boron-content boronized ashless dispersant containing fatty acid diethanolamide borate structure.

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

According to the invention, the borated ashless dispersant containing the fatty acid diethanolamine borate ester structure is prepared by reacting the borated polyisobutylene succinimide ashless dispersant with the fatty acid diethanolamide, the boron content is higher than 1.0 wt%, the long-term stability of a boron element in a product can be maintained, and the borated polyisobutylene succinimide ashless dispersant has excellent dispersibility and has antirust property and wear resistance. The multifunctional boronized ashless dispersant can be used in internal combustion engine oil, and can also be used in automobile automatic transmission oil and industrial lubricating oil.

The invention adopts a unique synthetic route to prepare the multifunctional boronized ashless dispersant with a novel structure. After the reaction of the boron ester, the boronized dispersant contains boron-nitrogen internal coordination and boron-oxygen internal coordination at the same time, and the introduced boric acid ester contains long-chain alkyl, so that the steric hindrance of molecules is increased, and the stability of the boronized dispersant is obviously improved due to two reasons. Meanwhile, the fatty acid diethanolamide borate has excellent antirust performance, so that the boronized ashless dispersant has certain antirust performance.

Compared with the traditional boronized polyisobutylene succinimide ashless dispersant, the boronized polyisobutylene succinimide ashless dispersant not only has higher boron content, but also is stable and difficult to separate out boron, and simultaneously integrates good dispersing performance, wear resistance and antirust performance into a whole, can be used as a novel boronized ashless additive to replace the traditional boronized polyisobutylene succinimide ashless dispersant in internal combustion engine oil for use, can also be used in automatic transmission fluid and industrial oil products, and is a multifunctional boronized dispersant with high boron content.

Detailed Description

For a better understanding of the present application, the present invention is further illustrated by the following examples, and it is to be understood that the detailed description is merely a description of exemplary embodiments of the present application and is not intended to limit the scope of the present application in any way. The expression "and/or" includes any and all combinations of one or more of the associated listed items.

The invention is described in further detail below:

the invention provides a multifunctional high-boron-content boration dispersing agent and a preparation method thereof, wherein the preparation method comprises the following steps:

step 1, mixing polyisobutylene succinic anhydride and an amine compound, adding base oil, and reacting to obtain the polyisobutylene succinimide ashless dispersant.

And further, metering polyisobutylene succinic anhydride with the substitution degree of 1.1-2.0 and an amine compound according to the molar ratio of succinic anhydride to polyene polyamine of 1.2-2.8: 1, adding base oil, reacting for 1-6 hours at 130-200 ℃, and separating water generated in the reaction by using a nitrogen blowing or vacuum pumping mode while the reaction is carried out to obtain the product polyisobutylene succinimide ashless dispersant. Wherein the content of the first and second substances,

the amine compound is one or more of polyene polyamine, including but not limited to diethylenetriamine, triethylene tetramine, tetraethylene pentamine.

And 2, mixing the polyisobutylene succinimide ashless dispersant with boric acid for reaction, adding fatty acid diethanolamide, and reacting for a certain time at a certain temperature to obtain the boronized ashless dispersant containing the fatty acid diethanolamide borate structure.

Further, mixing polyisobutylene succinimide with boric acid, adding water or fatty alcohol with a low boiling point as an accelerator, reacting at 80-120 ℃ for 1-7 hours, preferably 2-5 hours, introducing nitrogen, heating to 140-190 ℃, preferably 150-180 ℃, reacting for 0.5-2 hours, preferably 1-1.5 hours, adding fatty acid diethanolamide, keeping the temperature and reacting for 2-5 hours, preferably 3-4 hours, and finishing the reaction to obtain the multifunctional high-boron-content boration dispersant. Wherein the content of the first and second substances,

the mass ratio of the accelerator to the boric acid is 0.5-2.5: 1, preferably 1-2: 1; the mass of the fatty acid diethanolamide accounts for 2-8 wt%, preferably 2-5 wt% of the mass of the product; the boron content of the multifunctional high-boron-content boration dispersing agent of the reaction product is 0.8-2.5 wt%.

Example 1

150 g of polyisobutylene succinic anhydride with the PIB number average molecular weight of 1300 and the substitution degree of 1.1-1.2 and 106 g of 150N hydrogenated base oil are added into a 500ml four-mouth glass bottle, the mixture is stirred and heated to 70-80 ℃, 11.3 g of tetraethylenepentamine is added, the mixture is slowly heated to 150-160 ℃, nitrogen is introduced for purging for 2 hours, and water generated in the reaction is purged to obtain the polyisobutylene succinimide ashless dispersant.

Example 2

100 g of the product of example 1, 8 g of boric acid and 12 g of isopropanol are added into a 500ml four-mouth glass bottle, the mixture is stirred and slowly heated to 95-105 ℃, the temperature is kept for reaction for 4 hours, then nitrogen is introduced, the temperature is slowly heated to 150 ℃, and the temperature is kept for reaction for 1 hour. Then adding 3.7 g of oleic acid diethanolamide, and carrying out heat preservation reaction for 3 hours under the blowing of nitrogen to obtain a reaction product. The detection proves that the nitrogen content of the reaction product is 1.45 wt%, and the boron content is 1.18 wt%.

Example 3

100 g of the product of example 1, 8 g of boric acid and 12 g of isopropanol are added into a 500ml four-mouth glass bottle, the mixture is stirred and slowly heated to 95-105 ℃, the temperature is kept for reaction for 4 hours, then nitrogen is introduced, the temperature is slowly heated to 150 ℃, and the temperature is kept for reaction for 1 hour. Then 3.7 g of lauric diethanolamide is added, and the reaction is carried out for 3 hours under the blowing of nitrogen, thus obtaining the reaction product. The detection proves that the nitrogen content of the reaction product is 1.50 wt%, and the boron content is 1.20 wt%.

Example 4

Adding 120 g of polyisobutylene succinic anhydride with PIB number average molecular weight of 1000 and substitution degree of 1.1-1.2 and 110 g of 150N hydrogenated base oil into a 500ml four-mouth glass bottle, stirring and heating to 70-80 ℃, adding 13.5 g of tetraethylenepentamine, slowly heating to 150-160 ℃, introducing nitrogen to purge for 2 hours, and blowing off water generated in the reaction to obtain the polyisobutylene succinimide ashless dispersant.

Example 5

100 g of the product of example 4, 9.5 g of boric acid and 14 g of isobutanol are added into a 500ml four-mouth glass bottle, the mixture is stirred and slowly heated to 95-105 ℃, the temperature is kept for reaction for 4 hours, then nitrogen is introduced, the temperature is slowly heated to 150 ℃, and the temperature is kept for reaction for 1 hour. Then 4.3 g of oleic acid diethanolamide is added, and the mixture is subjected to heat preservation reaction for 3 hours under the blowing of nitrogen, so as to obtain a reaction product. The detection proves that the nitrogen content of the reaction product is 1.65 wt%, and the boron content is 1.40 wt%.

Comparative example 1

Adding 100 g of the product of example 1, 4.3 g of boric acid and 6 g of isopropanol into a 500ml four-mouth glass bottle, stirring, slowly heating to 95-105 ℃, carrying out heat preservation reaction for 4 hours, introducing nitrogen, slowly heating to 150 ℃, and carrying out heat preservation reaction for 2 hours to obtain a reaction product. The detection proves that the nitrogen content of the reaction product is 1.38 wt%, and the boron content is 0.68 wt%.

Comparative example 2

And adding 100 g of the product of the example 4, 5 g of boric acid and 8 g of isobutanol into a 500ml four-mouth glass bottle, stirring, slowly heating to 95-105 ℃, carrying out heat preservation reaction for 4 hours, introducing nitrogen, slowly heating to 150 ℃, and carrying out heat preservation reaction for 2 hours to obtain a reaction product. Through detection, the nitrogen content is 1.57wt percent, and the boron content is 0.75wt percent

The final products obtained in example 2, example 3, example 5 and two comparative examples were evaluated for their dispersibility according to the industry standard (SH/T0623 annex A ashless dispersant low-temperature dispersibility evaluation method), and the evaluation results are shown in Table 1.

Table 1 low temperature sludge dispersancy performance comparison of dispersants

In the analytical evaluation process, the same dosage is used, and according to the dispersibility evaluation data, the novel boronized ashless dispersants (example 2, example 3 and example 5) prepared in the examples of the invention have comparable dispersibility to the traditional boronized ashless dispersants (comparative example 1 and comparative example 2), and the introduced fatty acid diethanolamine molecules do not affect the dispersibility of the product.

The final products obtained in example 2, example 3, example 5 and two comparative examples were prepared into 50 wt% n-hexane solutions in 100ml centrifuge tubes, respectively, and the solutions were hermetically left standing at room temperature for 30 days, and then centrifuged at 2000r/min for 1h, and the stability was evaluated by the volume of the precipitation amount in the centrifuge tubes. The evaluation results are shown in Table 2.

Table 2 stability comparison of dispersants

Examples of the invention	Volume of precipitate/ml
		Example 2	<0.01
Example 3	<0.01
		Example 5	<0.01
Comparative example 1	0.03
		Comparative example2	0.04

As can be seen from evaluation result data, compared with a comparative example, the multifunctional high-boron-content boronized dispersing agent prepared in the embodiment of the invention has the advantages that the stability is far superior to that of the traditional boronized polyisobutylene succinimide dispersing agent, and boron is not easy to separate out.

The final products obtained in example 2, example 3, example 5 and two comparative examples were evaluated for anti-wear properties according to the industry standard (NB/SH/T0189-2017 lubricating oil antiwear performance four-ball method). The evaluation results are shown in Table 3.

TABLE 3 results comparing antiwear Properties of dispersants

The dosages used were the same during the analytical evaluation. As can be seen from the evaluation result data, compared with the comparative example, the multifunctional high-boron-content boronized ashless dispersant prepared in the embodiment of the invention has obviously better anti-wear and anti-friction performance than the traditional boronized ashless dispersant and certain anti-wear and anti-friction performance.

The final products obtained in example 2, example 3, example 5 and two comparative examples were evaluated for rust inhibition according to the industry standard (GB/T11143-2008 test method for rust inhibition performance of mineral oil with inhibitor in the presence of water, method B). The evaluation results are shown in Table 4.

TABLE 4 comparative results of rust inhibitive performance of dispersants

The dosages used were the same during the analytical evaluation. As can be seen from the evaluation data, compared with the comparative example, the novel boronized ashless dispersant prepared in the embodiment of the invention has obviously better antirust performance than the traditional boronized ashless dispersant and has certain antirust performance.

In conclusion, the multifunctional high-boron-content boronized ashless dispersant has higher and more stable boron content than the traditional boronized ashless dispersant, maintains equivalent dispersing capacity, has better stability, wear resistance and certain rust resistance, and has the service performance far exceeding that of the traditional boronized polyisobutylene succinimide ashless dispersant.

The multifunctional high-boron-content boronized ashless dispersant has better wear resistance and wear reduction performance because the molecule of the multifunctional high-boron-content boronized ashless dispersant contains more boron elements and a small amount of boric acid ester structures. The boron element is grafted with the fatty acid diethanolamide, the boron element can simultaneously form an internal coordination bond with nitrogen and oxygen, and the steric hindrance of molecules is increased by the longer fatty acid chain, so that the boronized dispersing agent has better stability, and boron is not easy to separate out. Meanwhile, the molecule contains the structure of fatty acid diethanolamide borate, so that the borated dispersant has certain antirust performance. The boronized dispersant in the invention is a multifunctional lubricating oil additive integrating good dispersibility, wear resistance and rust resistance. The objects, technical solutions and advantageous effects of the present invention are further described in detail with reference to the above-described embodiments. It should be understood that the above description is only a specific embodiment of the present invention, and is not intended to limit the present invention. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.