CN113913227B

CN113913227B - Boronizing ashless dispersant and preparation method thereof

Info

Publication number: CN113913227B
Application number: CN202111329318.0A
Authority: CN
Inventors: 李思; 郭松; 芮大庆; 缐伟; 温莹; 陈冲; 刘翠丹
Original assignee: Rianlon Corp; Jinzhou Kangtai Lubricant Additives Co ltd
Current assignee: Jinzhou Kangtai Lubricant Additives Co ltd; Rianlon Corp
Priority date: 2021-11-10
Filing date: 2021-11-10
Publication date: 2022-08-19
Anticipated expiration: 2041-11-10
Also published as: CN113913227A

Abstract

The invention provides a boronized ashless dispersant and a preparation method thereof. The preparation method comprises the following steps: mixing polyisobutylene succinic anhydride with base oil, adding a boration agent, adding a polyamine compound in an interval feeding mode, carrying out boronization and amination reaction simultaneously in the feeding process, continuing the reaction after the feeding of the polyamine compound is finished, and dehydrating after the neutralization reaction is finished in the reaction process to obtain the boronized ashless dispersant. Compared with the existing two-step method, the method provided by the invention has the advantages of simple operation, short reaction time, no need of using solvent and accelerator, capability of preparing various boronized ashless dispersant products with the boron content of less than or equal to 2.0 wt%, good compatibility of the obtained boronized ashless dispersant with rubber, lower turbidity, good stability and good abrasion resistance.

Description

Boronizing ashless dispersant and preparation method thereof

Technical Field

The invention belongs to the technical field of lubricating oil additives, and particularly relates to a boronized ashless dispersant and a preparation method thereof.

Background

Ashless dispersants have evolved as major additives for lubricating oils and fuel oils independently of the development of the modern automotive industry. When the oil temperature of the crankcase is low under the low-speed running state of an automobile, paint-like substances and sludge deposits in lubricating oil can be generated, and simultaneously a large amount of water vapor is generated and condensed to generate a large amount of emulsified oil sludge, so that a pipeline and a filter screen are blocked, and the normal use of the crankcase is seriously influenced. Based on the background, an ashless dispersant (polyisobutylene succinimide is commonly used) without metal is produced, and the problem of low-temperature oil sludge dispersibility is effectively solved.

With the improvement of the performance of the engine, the engine continuously develops towards high speed, heavy load and high temperature resistance, the requirements on the internal combustion engine oil and the industrial lubricating oil are increasingly strict, and the oil product is required to have excellent high-temperature detergency, oxidation resistance, wear resistance and friction reduction performance and oil sludge dispersion performance, which puts higher requirements on the performance of the dispersant.

The boronized ashless dispersant is endowed with high-temperature oxidation resistance, wear resistance and good thermal stability on the basis of the dispersing performance of the ashless dispersant. The boronized ashless dispersant has the advantages of excellent environmental protection, energy conservation and the like, and is increasingly applied to oil products such as internal combustion engine oil, gear oil, transmission fluid and the like.

The existing preparation methods of boronized ashless dispersants are two-step methods, namely, polyisobutylene succinic anhydride (PIBSA) and a polyamine compound are reacted to form a polyisobutylene succinimide ashless dispersant, and then the polyisobutylene succinimide ashless dispersant is reacted with a boronizing agent to form the boronized ashless dispersant. The method has the advantages of complex operation and long reaction time, a large amount of organic solvents and accelerators are needed for the boronization reaction, environmental pollution is easily caused, the boron content of the prepared product is low, the development of the boronization ashless dispersant industry is not facilitated, and the boronization ashless dispersant industry is to be improved.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a boronized ashless dispersant and a preparation method thereof. Compared with the existing two-step method, the method provided by the invention has the advantages that the reaction time is shorter, no solvent or accelerator is used, and the prepared boronized ashless dispersant has good compatibility with rubber and good stability and abrasion resistance.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a method for preparing a boronized ashless dispersant, comprising the steps of:

mixing polyisobutylene succinic anhydride with base oil, adding a boration agent, adding a polyamine compound in an interval feeding mode, carrying out boronization and amination reaction simultaneously in the feeding process, continuing the reaction after the feeding of the polyamine compound is finished, and dehydrating after the neutralization reaction is finished in the reaction process to obtain the boronized ashless dispersant.

In the prior art, a two-step method is usually adopted to prepare the boronized ashless dispersant, namely polyisobutylene succinic anhydride and a polyamine compound are subjected to amination reaction and then subjected to boronization reaction with a boronizing agent, wherein the boronization reaction needs to be carried out in a solvent, and the boronized ashless dispersant with the boron content of more than 1 wt% is generally very unstable, so that the stable boronized ashless dispersant with the boron content of more than 1 wt% is not easy to prepare even though an accelerator is added. The method provided by the invention can carry out amination and boronization reactions at the same time, obtain boronized ashless dispersants in one step, has shorter reaction time, does not need solvents and accelerators, can prepare various boronized ashless dispersant products with the boron content of less than or equal to 2.0 wt%, and particularly can prepare boronized ashless dispersant products with stable boron content and the boron content of 1.0-2.0 wt%; compared with a continuous dropwise adding method, the polyamine compound is added in an interval feeding mode, the turbidity of the product is reduced, the stability of the product is improved, and the obtained boronized ashless dispersant has good compatibility with rubber, lower turbidity, good stability and good abrasion resistance.

The intermittent feeding of the invention refers to that polyamine compound is discontinuously added, the feeding time interval is more than 5 minutes, and the batch feeding is uniform according to the total amount and time.

In some embodiments of the present invention, the number average molecular weight of the polyisobutylene succinic anhydride is 600 to 5000, for example, 600, 1000, 1300, 1600, 2300, 3000, 4000, 5000, or the like; preferably 1000 to 2300.

In some embodiments of the invention, the base oil is a petroleum fractionated type one, and/or a petroleum fractionated type two, such as 100N, 100SN, 150N, 150SN, 250N, 250SN, mixtures of two or more thereof, and the like.

In the invention, the base oil is mainly used as a diluent to reduce the viscosity of a reaction system, is beneficial to the reaction and does not participate in the reaction.

In some embodiments of the invention, the borating agent is selected from one or a combination of at least two of boric acid, a borate ester, metaboric acid, and a boron halide, preferably boric acid.

In some embodiments of the present invention, the polyamine compound is one or a combination of at least two of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and heavy amines.

In some embodiments of the invention, the feeding temperature of the borating agent is 20-105 ℃; for example, the temperature may be 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or 105 ℃.

In some embodiments of the present invention, the reaction temperature during the feeding process of the polyamine compound and after the feeding process is 105-160 ℃ independently; for example, the temperature may be 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃ or 160 ℃.

In some embodiments of the present invention, the reaction temperature after the feeding of the polyamine compound is completed is higher than the reaction temperature during the feeding of the polyamine compound; thus being beneficial to accelerating the reaction speed after feeding and shortening the reaction time.

In some embodiments of the present invention, the feeding time of the polyamine compound is 1-6 h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, or 6 h; preferably 2-4 h.

In some embodiments of the invention, the reaction time after the feeding of the polyamine compound is finished is 2-7 h; for example, it may be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, or the like.

In some embodiments of the invention, the mass ratio of the base oil to the polyisobutylene succinic anhydride is 1: 0.4-2.1; for example, it may be 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0 or 1: 2.1.

In some embodiments of the invention, the molar ratio of the polyamine compound to the polyisobutylene succinic anhydride is 1: 0.9-2.5; for example, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:22, 1:2.3, 1:2.4, or 1:2.5, etc. may be mentioned.

In some embodiments of the invention, the molar ratio of the polyamine compound to the borating agent is from 1:2 to 10; for example, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:8, 1:9, or 1:10, etc.

In some embodiments of the invention, the dehydration is performed by applying a vacuum. Specifically, the reaction system can be maintained in a vacuum state during the reaction and after the reaction is completed, thereby achieving the effect of dehydration. The vacuum degree in the vacuum state can be 0.05-0.1 Mpa.

In some embodiments of the invention, the preparation method comprises the following steps:

mixing polyisobutylene succinic anhydride with base oil, adding a boration agent at the temperature of 20-105 ℃, heating to the temperature of 105-140 ℃, adding a polyamine compound in an interval feeding mode, simultaneously carrying out a boration and amination reaction in the feeding process, continuing to react for 2-7 hours at the temperature of 105-140 ℃ after the feeding of the polyamine compound is finished, and carrying out vacuum dehydration after the neutralization reaction in the reaction process to obtain the boronized ashless dispersant.

In a second aspect, the invention provides a boronized ashless dispersant having a nitrogen content of 0.8 to 2.5 wt% and a boron content of 1.0 to 2.0 wt%, prepared by the method of the first aspect.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, polyisobutylene succinic anhydride, a polyamine compound and boric acid are taken as raw materials, base oil is taken as a diluent, a catalyst is not needed, amination and boronization are simultaneously carried out under a certain temperature condition, and a boronized ashless dispersant product is obtained by a one-step method.

Compared with the existing two-step method, the method provided by the invention has the advantages of simple operation, short reaction time and no need of using solvents and accelerators, and can be used for preparing various boronized ashless dispersant products with the nitrogen content of 0.8-2.5 wt% and the boron content of less than or equal to 2.0 wt%, and particularly obtaining the boronized ashless dispersant with the boron content of 1-2 wt%. The obtained boronized ashless dispersant has good compatibility with rubber, lower turbidity, good stability and good abrasion resistance.

Drawings

FIG. 1 is an infrared spectrum of a boronated ashless dispersant provided in example 1 of the present invention.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the specific embodiments are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Example 1

This example provides a boronized ashless dispersant, which is prepared as follows:

151.3g of 150SN base oil and 200g of PIBSA (number average molecular weight 1300, total acid value: 96mg KOH/g) are put into a 1000mL four-necked bottle at normal temperature and stirred uniformly; heating to 50 ℃, and adding 21.6g of boric acid; continuously heating to 105 ℃, adding 13.84g of tetraethylenepentamine in an interval feeding manner, simultaneously carrying out boronization and amination reaction, and finishing the addition within 2 hours; then heating to 115 ℃, and reacting for 3 hours at constant temperature; and after the neutralization reaction is finished in the reaction process, performing vacuum dehydration under the condition that the vacuum degree is 0.1Mpa, and filtering to obtain a transparent brownish red boronized ashless dispersant product.

The infrared spectrum of the product was measured and the results are shown in FIG. 1.

Example 2

This example provides a boronated ashless dispersant prepared according to a method different from that of example 1: the reaction temperature in the feeding process of tetraethylenepentamine is 125 ℃, and the reaction temperature after the feeding of the tetraethylenepentamine is 135 ℃.

Example 3

This example provides a boronated ashless dispersant prepared according to a method different from that of example 1: the reaction temperature in the charging process of tetraethylenepentamine is 125 ℃, and the reaction temperature after the charging of the tetraethylenepentamine is 140 ℃.

Example 4

150SN base oil 175g and PIBSA (number average molecular weight 1300, total acid number 96mg KOH/g)180g are put into a 1000mL four-mouth bottle at normal temperature and stirred uniformly; heating to 50 ℃, and adding 22.5g of boric acid; continuously heating to 125 ℃, adding 27.68g of tetraethylenepentamine in an interval feeding mode, simultaneously carrying out boronization and amination reaction, and finishing the addition for 4 hours; then heating to 140 ℃, and reacting for 3 hours at constant temperature; and after the neutralization reaction is finished in the reaction process, dehydrating in vacuum under the condition that the vacuum degree is 0.1Mpa, and filtering to obtain a transparent brownish red boronized ashless dispersant product.

Example 5

This example provides a boronated ashless dispersant prepared according to a method different from that of example 4: the reaction temperature in the charging process of tetraethylenepentamine is 130 ℃, and the reaction temperature after the charging of the tetraethylenepentamine is 140 ℃.

Example 6

150SN base oil 107.82g and 200g of PIBSA (number average molecular weight 2300, total acid number 55mg KOH/g) were put into a 1000mL four-necked bottle at room temperature and stirred uniformly; heating to 80 ℃, and adding 34.9g of methyl borate; continuously heating to 110 ℃, adding 22.78g of pentaethylenehexamine at intervals, carrying out boronization and amination reaction simultaneously, and finishing adding for 1 h; continuously reacting for 7 hours at the constant temperature of 110 ℃; and after the neutralization reaction is finished in the reaction process, performing vacuum dehydration under the condition that the vacuum degree is 0.1Mpa, and filtering to obtain a transparent brownish red boronized ashless dispersant product.

Example 7

150SN base oil 132.5g and 200g of PIBSA (number average molecular weight 1300, total acid value 96mg KOH/g) are put into a 1000mL four-mouth bottle at normal temperature and stirred uniformly; heating to 50 ℃, and adding 22.4g of metaboric acid; continuously heating to 105 ℃, adding 12.51g of triethylene tetramine in an interval feeding mode, simultaneously carrying out boronization and amination reaction, and finishing the adding within 3 hours; then heating to 140 ℃, and reacting for 3 hours at constant temperature; and after the neutralization reaction is finished in the reaction process, performing vacuum dehydration under the condition that the vacuum degree is 0.1Mpa, and filtering to obtain a transparent brownish red boronized ashless dispersant product.

Example 8

97.5g of 200N base oil and 200g of PIBSA (number average molecular weight 1600, total acid value: 69mg KOH/g) were put into a 1000mL four-necked flask at room temperature, and stirred uniformly; heating to 50 ℃, and adding 27.3g of metaboric acid; continuously heating to 125 ℃, adding 11.83g of tetraethylenepentamine in an interval feeding mode, simultaneously carrying out boronization and amination reaction, and finishing the addition for 2 hours; then heating to 160 ℃, and reacting for 3 hours at constant temperature; and after the neutralization reaction is finished in the reaction process, dehydrating in vacuum under the condition that the vacuum degree is 0.1Mpa, and filtering to obtain a transparent brownish red boronized ashless dispersant product.

Comparative example 1

97.5g of 200N base oil and 200g of PIBSA (number average molecular weight 1600, total acid value: 69mg KOH/g) were put into a 1000mL four-necked flask at room temperature, and stirred uniformly; heating to 140 ℃, dropwise adding 11.83g of tetraethylenepentamine at constant speed for 2h, after dropwise adding, carrying out constant temperature reaction for 3h while dehydrating with nitrogen, and obtaining an acid value of the product which is 1.2mg KOH/g, thus obtaining an ashless dispersant product for later use.

Adjusting the temperature of the product to 90 +/-2 ℃, adding 27.3g of metaboric acid, heating to 145 +/-2 ℃, reacting at constant temperature for 3 hours, introducing nitrogen for dehydration while reacting, and filtering to obtain a transparent brownish red boronized ashless dispersant product, wherein the water content of the product is less than 0.08 percent, and the product is qualified.

After the product is placed for 2 days, white crystals are separated out, the content of nitrogen is detected to be unchanged, the content of boron is 1.5 wt%, and after the product is placed for 7 days, the content of boron is 1.2 wt%; along with the prolonging of the standing time of the product, more and more crystals are separated out, and the boron content is lower.

And (3) performance testing:

the boronated ashless dispersants obtained in the above examples and comparative examples were tested for their performance according to the following table 1:

TABLE 1

The results of the above property tests are shown in table 2 below:

TABLE 2

Wherein PB is the maximum load at which seizure does not occur under test conditions;

PD is the minimum load under which the rotating ball sinters with three stationary balls under test conditions;

the wear scar diameter is the size of the wear scar diameter on the surface of the bearing steel ball caused by friction under the test condition.

As can be seen from Table 2, the boronized ashless dispersants provided by the examples of the present invention have a nitrogen content of 1.1-2.5 wt%, a boron content of 1.0-2.0 wt%, no change in boron content after 30 days of standing, a turbidity of 15NTU or less, a low temperature dispersibility of 65 or more, and good abrasion resistance.

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims

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

mixing polyisobutylene succinic anhydride with base oil, adding a boration agent, adding a polyamine compound in an interval feeding mode, carrying out boronization and amination reaction simultaneously in the feeding process, continuing the reaction after the feeding of the polyamine compound is finished, and dehydrating after the neutralization reaction is finished in the reaction process to obtain a boronized ashless dispersant;

the intermittent feeding refers to that the polyamine compound is added discontinuously, the feeding time interval is more than 5 minutes, and the batch feeding is uniform according to the total amount and time.

2. The method of claim 1, wherein the polyisobutylene succinic anhydride has a number average molecular weight of 600 to 5000;

and/or the base oil is petroleum fraction first oil and/or petroleum fraction second oil.

3. The method according to claim 2, wherein the number average molecular weight of the polyisobutylene succinic anhydride is 1000 to 2300.

4. The method according to claim 2, wherein the base oil is one or a mixture of two or more of 100N, 100SN, 150N, 150SN, 250N, and 250 SN.

5. The production method according to claim 1, wherein the borating agent is selected from one or a combination of at least two of boric acid, a boric acid ester, metaboric acid and a boron halide.

6. The production method according to claim 5, wherein the borating agent is boric acid.

7. The method according to claim 1, wherein the polyamine compound is one or a combination of at least two of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and heavy amines.

8. The production method according to claim 1, wherein the feeding temperature of the borating agent is 20 to 105 ℃;

and/or the reaction temperature during the feeding process of the polyamine compound and after the feeding process is respectively and independently 105-160 ℃.

9. The method according to claim 8, wherein the reaction temperature after the completion of the feeding of the polyamine compound is higher than the reaction temperature during the feeding of the polyamine compound.

10. The method according to claim 1, wherein the feeding time of the polyamine compound is 1 to 6 hours.

11. The method according to claim 10, wherein the feeding time of the polyamine compound is 2 to 4 hours.

12. The method according to claim 1, wherein the reaction time after the completion of the feeding of the polyamine compound is 2 to 7 hours.

13. The preparation method according to claim 1, wherein the mass ratio of the base oil to the polyisobutylene succinic anhydride is 1: 0.4-2.1.

14. The method according to claim 1, wherein the molar ratio of the polyamine compound to the polyisobutylene succinic anhydride is 1:0.9 to 2.5.

15. The method according to claim 1, wherein the molar ratio of the polyamine compound to the borating agent is 1:2 to 10.

16. The production method according to claim 1, wherein the reaction system is kept in a vacuum state during the reaction and after the reaction is completed to remove moisture.

17. The method according to claim 16, wherein the degree of vacuum in the vacuum state is 0.05 to 0.1 Mpa.

18. The method of claim 1, comprising the steps of:

mixing polyisobutylene succinic anhydride with base oil, adding a boration agent at the temperature of 20-105 ℃, heating to the temperature of 105-140 ℃, adding a polyamine compound in an interval feeding manner, simultaneously performing a boration and amination reaction in the feeding process, after 2-4 h feeding is finished, continuing to react at the temperature of 105-140 ℃ for 2-7 h after the feeding of the polyamine compound is finished, and keeping a vacuum state during the reaction and after the reaction is finished to remove water, thereby obtaining the boration ashless dispersant.