A composition and its preparation method and application

Abstract

The present invention relates to the field of ashless dispersants, and in particular to a composition and a preparation method and application thereof, wherein the composition is prepared by reacting a polyisobutylene succinimide compound with vinyl pyridine, wherein the polyisobutylene succinimide compound is prepared by reacting polyisobutylene maleic anhydride with polyethylene polyamine. The composition of one embodiment of the present invention is used as an ashless dispersant and can have excellent soot dispersibility, thereby solving the problem of insufficient soot dispersibility of existing ashless dispersants.

Description

Technical Field

[0001] The invention relates to a lubricating oil additive, in particular to a composition and a preparation method and application thereof. Background Art

[0002] Environmental regulations have increasingly tightened restrictions on diesel engine nitrogen oxide emissions. The use of a series of new technologies such as EGR (exhaust gas recirculation technology) has reduced nitrogen oxide emissions, but has increased the degree of incomplete combustion of diesel, leading to an increase in the soot content in heavy-duty diesel engine oil. The combination of soot and polar oxidation products in the lubrication system will increase the viscosity of the lubricating oil and adsorb acidic substances, causing corrosion and wear. At the same time, soot will gather and adsorb on the friction and corrosion surface, causing wear of engine parts, and will also cause problems such as blockage of the oil filter and increased oxidation of oil products.

[0003] The main way to reduce soot pollution is to improve the oil's ability to disperse soot. The usual method is to increase the amount of dispersant, but increasing the amount of dispersant will affect the low-temperature fluidity of the oil and the wear resistance of diesel engine parts. Therefore, there is an urgent need for a dispersant with excellent soot dispersibility, so that the oil's dispersibility to soot can be guaranteed at a low addition amount. Summary of the invention

[0004] To overcome at least one defect of the above-mentioned prior art, in a first aspect, an embodiment of the present invention provides a composition, which is prepared by reacting a polyisobutylene succinimide compound with vinyl pyridine, wherein the polyisobutylene succinimide compound is prepared by reacting polyisobutylene maleic anhydride with polyethylene polyamine.

[0005] In a second aspect, an embodiment of the present invention provides an ashless dispersant, including the above-mentioned composition.

[0006] In a third aspect, an embodiment of the present invention provides a method for preparing an ashless dispersant, comprising the following steps:

[0007] S1: providing polyisobutylene succinimide compounds;

[0008] S2: reacting the polyisobutylene succinimide compound with vinyl pyridine to obtain the ashless dispersant;

[0009] The polyisobutylene succinimide compound is prepared by reacting polyisobutylene maleic anhydride with polyethylene polyamine.

[0010] In a fourth aspect, an embodiment of the present invention provides a lubricating oil, comprising the above-mentioned ashless dispersant or the ashless dispersant prepared by the above-mentioned preparation method.

[0011] The composition of one embodiment of the present invention is used as an ashless dispersant and can have excellent soot dispersibility, thereby solving the problem of insufficient soot dispersibility of existing ashless dispersants. DETAILED DESCRIPTION

[0012] Typical embodiments that embody the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various changes in different embodiments without departing from the scope of the present invention, and the descriptions therein are essentially used as illustrations rather than to limit the present invention.

[0013] One embodiment of the present invention provides a composition, which is prepared by reacting a polyisobutylene succinimide compound with vinyl pyridine, and the polyisobutylene succinimide compound is prepared by reacting polyisobutylene maleic anhydride with polyethylene polyamine.

[0014] In one embodiment, the polyisobutylene succinimide compound comprises the following structure:

[0015] and

[0016] Wherein, PIB is a polyisobutylene segment, n is selected from an integer of 1 to 5, such as 1, 2, 3, 4 or 5; the above structures are monopolyisobutylene succinimide and bispolyisobutylene succinimide, respectively.

[0017] In one embodiment, the number average molecular weight of the PIB or polyisobutylene segment is 900 to 2500, for example, 1000, 1300, 1500, 1800, 2000, 2300, 2400.

[0018] In one embodiment, the polyethylene polyamine includes one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine.

[0019] In one embodiment, the vinyl pyridine includes one or more of 2-vinyl pyridine, 3-vinyl pyridine, and 4-vinyl pyridine.

[0020] In one embodiment, the reaction for generating the composition is described by a chemical reaction formula, wherein the reaction listed is only an example and does not mean that the reactants and products are limited to those described in the following formula:

[0021]

[0022] (Ⅰ)

[0023]

[0024] (Ⅱ)

[0025] In the chemical formulas (I) and (II), the value of a is selected from 0 to 3 (e.g., 1, 2), and R1 represents a polyisobutylene segment (PBI); wherein, formula (I) represents that the amino groups at both ends of the polyethylene polyamine molecule react with polyisobutylene maleic anhydride to obtain di-polyisobutylene succinimide; and formula (II) represents that only the amino group at one end of the polyethylene polyamine molecule reacts with polyisobutylene maleic anhydride to obtain mono-polyisobutylene succinimide.

[0026] In one embodiment, the molar ratio of the anhydride groups (-C(=O)OC(=O)-) contained in the polyisobutylene maleic anhydride to the polyethylene polyamine can be 1.1 to 1.7:1, and can further be 1.3 to 1.5:1, such as 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1. By limiting the molar ratio of the anhydride groups contained in the polyisobutylene maleic anhydride to the polyethylene polyamine within the above range, the content of monopolyisobutylene succinimide and dipolyisobutylene succinimide in the product can be regulated to obtain a polyisobutylene succinimide compound mixed with monopolyisobutylene succinimide and dipolyisobutylene succinimide.

[0027] In one embodiment, the molar ratio of polyethylene polyamine to vinyl pyridine is 1:(0.8-1.3), for example, 1:0.9, 1:1, 1:1.1, 1:1.2.

[0028] In one embodiment, polyisobutylene maleic anhydride is prepared by reacting polyisobutylene and maleic anhydride, wherein the number average molecular weight of the polyisobutylene is 900-2500, such as 1000, 1300, 1500, 1800, 2000, 2300, 2400.

[0029] In one embodiment, the total acid value of polyisobutylene maleic anhydride is 65 to 110 mgKOH / g, for example 65 mgKOH / g, 68.9 mgKOH / g, 70 mgKOH / g, 90 mgKOH / g, 92.5 mgKOH / g, 95 mgKOH / g, 100 mgKOH / g, 105 mgKOH / g, 106.8 mgKOH / g, 110 mgKOH / g.

[0030] In one embodiment, polyisobutylene maleic anhydride is an existing product, which can be obtained from the market or prepared by an existing method, for example, by the method disclosed in CN112851864B or CN112851838A.

[0031] One embodiment of the present invention provides use of the above composition as an ashless dispersant.

[0032] One embodiment of the present invention provides an ashless dispersant, including the above composition.

[0033] One embodiment of the present invention provides a method for preparing the above-mentioned composition or ashless dispersant, comprising the following steps:

[0034] S1: providing polyisobutylene succinimide compounds;

[0035] S2: reacting a polyisobutylene succinimide compound with vinyl pyridine to prepare an ashless dispersant;

[0036] Among them, the polyisobutylene succinimide compound is prepared by reacting polyisobutylene maleic anhydride with polyethylene polyamine.

[0037] In one embodiment, the types and amounts of vinyl pyridine, polyisobutylene maleic anhydride and polyethylene polyamine in the preparation method of the ashless dispersant are subject to the aforementioned limitations.

[0038] In one embodiment, step S1 comprises: reacting polyisobutylene maleic anhydride and polyethylene polyamine at a temperature of 90 to 140° C. (e.g., 100° C., 110° C., 115° C., 120° C., 125° C., 130° C.), and then heating to 150 to 180° C. (e.g., 160° C., 165° C., 170° C., 175° C.) for reaction.

[0039] In one embodiment, the reaction time of the reaction system in step S1 at 90-140° C. is 0.5-4 hours (e.g., 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours), and the reaction is carried out at 150-180° C. until the total acid value of the reaction system is less than 2 mgKOH / g.

[0040] In one embodiment, in step S1, polyethylene polyamine is added dropwise to a reaction system containing polyisobutylene maleic anhydride for 0.5 to 2 hours, such as 1 hour or 1.5 hours. Further, polyethylene polyamine is added dropwise to the reaction system at a temperature of 90 to 140°C (e.g., 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, or 135°C).

[0041] In one embodiment, the reaction system of step S1 includes a solvent, which may be a base oil, such as 100SN, 150SN, or 250SN. Further, polyethylene polyamine may be added dropwise to the reaction system including polyisobutylene maleic anhydride and the solvent for reaction.

[0042] In one embodiment, the reaction temperature of step S2 can be 90-130°C, for example, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C; the reaction time can be 0.5-3 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours.

[0043] In one embodiment, vinyl pyridine may be added dropwise to the system after the reaction in step S1, and the adding time may be 1 to 3 hours, such as 1.5 hours, 2 hours, or 2.5 hours.

[0044] In one embodiment, polyethylene polyamine is added dropwise to a reaction system containing polyisobutylene maleic anhydride, and reacted at a temperature of 90 to 140° C. for 0.5 to 2 hours; then the temperature is raised to 150 to 180° C. and reacted for 2 to 5 hours; thereafter, vinyl pyridine is added to the reaction system and reacted at a temperature of 90 to 130° C. for 0.5 to 3 hours.

[0045] In one embodiment, the nitrogen content in the prepared ashless dispersant or composition may be 2.5-3.5 wt %, such as 2.8 wt %, 3 wt %, 3.2 wt %, wherein the nitrogen content is measured by ASTM D5762 method.

[0046] One embodiment of the present invention provides a lubricating oil, comprising the above-mentioned ashless dispersant. Further, the lubricating oil can be an engine oil (such as gasoline engine oil, diesel engine oil), a transmission oil or a hydraulic oil.

[0047] One embodiment of the present invention provides the use of the above ashless dispersant as a lubricating oil additive.

[0048] In a method for preparing a composition or an ashless dispersant according to an embodiment of the present invention, a pyridine structure is introduced into a polyisobutylene succinimide compound through a Michael addition reaction, thereby improving the soot dispersing performance of the obtained dispersant.

[0049] In the method for preparing the composition or ashless dispersant according to one embodiment of the present invention, the reactions of steps S1 and S2 can be completed by a one-pot process.

[0050] The composition or ashless dispersant according to one embodiment of the present invention can effectively suppress the viscosity growth of an engine oil containing, for example, 8% soot (simulated by carbon black), and has good soot dispersibility.

[0051] Hereinafter, the preparation method of the ashless dispersant of one embodiment of the present invention is further described in conjunction with the examples. Among them, since vinyl pyridine is highly active and prone to self-polymerization, the commercially available vinyl pyridine used in each example contains 0.1 to 0.2 wt% of hydroquinone polymerization inhibitor. The polyethylene polyamine is Delamine S200, and the molecular weight of the polyethylene polyamine measured by GPC is 275. The number average molecular weight of polyisobutylene maleic anhydride is based on the molecular weight of the polyisobutylene segment therein. The nitrogen content of the products obtained in each example is measured by the NB / SH / T-0704 method.

[0052] Example 1

[0053] S1: 600 g of polyisobutylene maleic anhydride (total acid value 106.8 mgKOH / g) with a number average molecular weight of 1000 and 300 g of base oil 150SN were added to a 2L glass flask equipped with a mechanical stirrer, a thermometer, a heating jacket and a nitrogen pipeline, nitrogen was introduced, and the mechanical stirrer was turned on for stirring; the temperature in the flask was raised to 115°C, and 112.18 g of polyethylene polyamine was added dropwise thereto for 2 hours; after the addition was completed, the reaction system was reacted at 120°C for 2 hours; thereafter, the temperature in the flask was raised to 170°C, and nitrogen was purged for dehydration until the total acid value of the reaction solution was lower than 2 mgKOH / g.

[0054] S2: The temperature of the reaction liquid in step S1 was lowered to 120°C, and 42.9 g of 4-vinylpyridine was added dropwise to the reaction liquid for 2 hours. After the addition was completed, the reaction liquid was kept at a constant temperature of 120°C for 1 hour. After the constant temperature was completed, 10.5 g of diatomaceous earth (ZBS300) was added to the reaction liquid, and the final product was obtained by filter pressing after stirring for 10 minutes. The nitrogen content of the product was measured to be 3.5wt%.

[0055] Example 2

[0056] S1: In a 2L glass flask equipped with a mechanical stirrer, a thermometer, a heating jacket and a nitrogen pipeline, 600g of polyisobutylene maleic anhydride (total acid value 92.5mgKOH / g) with a number average molecular weight of 1300 and 300g of base oil were added, nitrogen was introduced, and the mechanical stirrer was turned on for stirring; the temperature in the flask was raised to 115°C, and 97.16g of polyethylene polyamine was added dropwise thereto for 1.5 hours; after the addition was completed, the reaction system was reacted at 120°C for 2 hours; thereafter, the temperature in the flask was raised to 170°C, and nitrogen was purged for dehydration until the total acid value of the reaction solution was lower than 2mgKOH / g.

[0057] S2: The temperature of the reaction liquid in step S1 was lowered to 120°C, and 37.1 g of 4-vinylpyridine was added dropwise to the reaction liquid for 2 hours. After the addition was completed, the reaction liquid was kept at a constant temperature of 120°C for 1 hour. After the constant temperature was completed, 10.3 g of diatomaceous earth (ZBS300) was added to the reaction liquid, and the final product was obtained by filter pressing after stirring for 10 minutes. The nitrogen content of the product was measured to be 3.0 wt%.

[0058] Example 3

[0059] S1: 600 g of polyisobutylene maleic anhydride (total acid value 68.9 mgKOH / g) with a number average molecular weight of 2300 and 300 g of base oil 150SN were added to a 2L glass flask equipped with a mechanical stirrer, a thermometer, a heating jacket and a nitrogen pipeline, nitrogen was introduced, and the mechanical stirrer was turned on for stirring; the temperature in the flask was raised to 115°C, and 92.11 g of polyethylene polyamine was added dropwise thereto for 1 hour; after the addition was completed, the reaction system was reacted at 120°C for 2 hours; thereafter, the temperature in the flask was raised to 170°C, and nitrogen was purged for dehydration until the total acid value of the reaction solution was lower than 2 mgKOH / g.

[0060] S2: The temperature of the reaction liquid in step S1 was lowered to 120°C, and 35.2 g of 4-vinylpyridine was added dropwise to the reaction liquid for 2 hours. After the addition was completed, the reaction liquid was kept at a constant temperature of 120°C for 1 hour. After the constant temperature was completed, 10.5 g of diatomaceous earth (ZBS300) was added to the reaction liquid, and the final product was obtained by filter pressing after stirring for 10 minutes. The nitrogen content of the product was measured to be 2.7wt%.

[0061] Example 4

[0062] This example uses the same raw materials and process as Example 1 to prepare an ashless dispersant, except that the amount of 4-vinylpyridine used is 34.25 g. The nitrogen content of the obtained product is measured to be 3.4 wt%.

[0063] Example 5

[0064] This example uses the same raw materials and process as Example 1 to prepare an ashless dispersant, except that the amount of 4-vinylpyridine used is 51.37 g. The nitrogen content of the obtained product is measured to be 3.5 wt%.

[0065] Example 6

[0066] This embodiment uses the same raw materials and process as in embodiment 1 to prepare an ashless dispersant, except that the dropping temperature and reaction temperature of the polyethylene polyamine in step S1 are 90°C and the reaction time is 4 hours. The nitrogen content of the obtained product is measured to be 3.5wt%.

[0067] Example 7

[0068] This embodiment uses the same raw materials and process as in embodiment 1 to prepare an ashless dispersant, except that the dropping temperature and reaction temperature of the polyethylene polyamine in step S1 are 140°C and the reaction time is 0.5 hours. The nitrogen content of the obtained product is measured to be 3.5 wt%.

[0069] Example 8

[0070] This embodiment uses the same raw materials and process as in embodiment 1 to prepare an ashless dispersant, except that the dropping temperature and reaction temperature of 4-vinylpyridine in step S2 are 90°C, the dropping time is 3 hours, and the reaction time is 3 hours. The nitrogen content of the obtained product is measured to be 3.5wt%.

[0071] Example 9

[0072] This embodiment uses the same raw materials and process as in embodiment 1 to prepare an ashless dispersant, except that the dropping temperature and reaction temperature of 4-vinylpyridine in step S2 are 130°C, the dropping time is 1 hour, and the reaction time is 0.5 hour. The nitrogen content of the obtained product is measured to be 3.4wt%.

[0073] Comparative Example 1

[0074] The product of step S1 of Example 1 was used as the dispersant of Comparative Example 1.

[0075] Comparative Example 2

[0076] The ashless dispersant was synthesized according to the example of CN106281580A.

[0077] In a 250mL glass flask equipped with a stirrer, a thermometer, a heating jacket and a nitrogen pipeline, 50.0g of polyisobutylene maleic anhydride with a molecular weight of 1000, 30.0g of base oil and 15.0g of toluene were added, nitrogen was introduced, a mechanical stirrer was turned on for stirring, 3.9g of triethylenetetramine was added at 40°C, and the reaction was carried out at 110°C for 4 hours. 3.5g of heptaldehyde and 3.6g of N,N'-diphenyl-p-phenylenediamine were added, and the reaction was carried out at 80°C for 2 hours and 110°C for 4 hours. After the reaction was completed, the solvent was evaporated under reduced pressure to obtain the final product.

[0078] Application Examples

[0079] The dispersants of the embodiments and comparative examples were respectively prepared into CK-4 engine oil at a dosage of 2 wt%. 8 wt% of carbon black was added to the engine oil to simulate the working condition of high soot content, and the oil was homogenized by a high shear homogenizer for 30 minutes (60-70°C, 10000-20000 r / min). The viscosity of the homogenized oil sample at 100°C was measured by the countercurrent viscosity method according to the GB / T11137-1989 standard. The lower the viscosity, the better the soot dispersibility of the dispersant. The results are shown in Table 1.

[0080] Table 1 Viscosity of engine oil products containing dispersants of various examples and comparative examples

[0081]

[0082] It can be seen from the above table that the ashless dispersant obtained by the present invention has better soot dispersibility than existing products. Compared with the traditional succinimide ashless dispersant of Comparative Example 1 and the ashless dispersant of Comparative Example 2, the soot dispersibility is significantly improved under high soot (8%) conditions.

[0083] Unless otherwise defined, the terms used in the present invention have the meanings commonly understood by those skilled in the art.

[0084] The embodiments described in the present invention are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Those skilled in the art may make various other substitutions, changes and improvements within the scope of the present invention. Therefore, the present invention is not limited to the above embodiments, but is only limited by the claims.

Claims

1. A composition, characterized in that The invention is prepared by Michael addition reaction of polyisobutylene succinimide compounds and vinyl pyridine, wherein the polyisobutylene succinimide compounds are prepared by reaction of polyisobutylene maleic anhydride and polyethylene polyamine.

2. The composition according to claim 1, characterized in that The polyisobutylene succinimide compound comprises the following structure: and Wherein, PIB is a polyisobutylene segment, and n is an integer selected from 1 to 5; or The polyethylene polyamine includes one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine; and / or, The vinyl pyridine includes one or more of 2-vinyl pyridine, 3-vinyl pyridine, and 4-vinyl pyridine; and / or, The total acid value of the polyisobutylene maleic anhydride is 65 to 110 mgKOH / g.

3. The composition according to claim 2, characterized in that The number average molecular weight of PIB is 900 to 2500; and / or, The molar ratio of the anhydride groups contained in the polyisobutylene maleic anhydride to the polyethylene polyamine is 1.1 to 1.7:1; and / or, The molar ratio of the polyethylene polyamine to the vinyl pyridine is 1:(0.8-1.3); and / or, The nitrogen content of the composition is 2.5-3.5 wt %.

4. An ashless dispersant, characterized in that A composition comprising any one of claims 1 to 3.

5. A method for preparing an ashless dispersant, characterized in that: The steps include: S1: providing polyisobutylene succinimide compounds; S2: reacting the polyisobutylene succinimide compound with vinyl pyridine to obtain the ashless dispersant; The polyisobutylene succinimide compound is prepared by reacting polyisobutylene maleic anhydride with polyethylene polyamine.

6. The preparation method according to claim 5, characterized in that: The polyethylene polyamine includes one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine; and / or, The vinyl pyridine includes one or more of 2-vinyl pyridine, 3-vinyl pyridine, and 4-vinyl pyridine; and / or, The polyisobutylene maleic anhydride is prepared by reacting polyisobutylene and maleic anhydride, and the number average molecular weight of the polyisobutylene is 900 to 2500; and / or, The total acid value of the polyisobutylene maleic anhydride is 65 to 110 mgKOH / g.

7. The preparation method according to claim 5, characterized in that: Step S1 comprises: reacting the polyethylene polyamine with the polyisobutylene maleic anhydride at a temperature of 90 to 140° C., and then heating the temperature to 150 to 180° C. for reaction; and / or, The reaction temperature of step S2 is 90-130° C.; and / or, The molar ratio of the anhydride groups contained in the polyisobutylene maleic anhydride to the polyethylene polyamine is 1.1 to 1.7:

1.

8. The preparation method according to claim 7, characterized in that: The reaction time of the reaction system in step S1 is 0.5 to 4 hours at a temperature of 90 to 140° C., and the reaction is carried out at a temperature of 150 to 180° C. until the total acid value of the reaction system is less than 2 mgKOH / g; and / or, The molar ratio of the polyethylene polyamine to the vinyl pyridine is 1:(0.8-1.3); and / or, The nitrogen content of the ashless dispersant is 2.5-3.5 wt %.

9. A lubricating oil, characterized in that: The invention comprises the ashless dispersant according to claim 4 or the ashless dispersant prepared by the preparation method according to any one of claims 5 to 8.

10. Use of the ashless dispersant according to claim 4 or the ashless dispersant prepared by the preparation method according to any one of claims 5 to 8 as a lubricating oil additive.

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