Ashless dispersant, process for its preparation and use thereof

Abstract

The application discloses ashless dispersants and a preparation method and application thereof. The ashless dispersant is a compound prepared through a Mannich reaction of a multifunctional polar crosslinking agent A containing multiple reaction sites, a single-hanging fatty amine type polyisobutylene succinimide B and / or a single-hanging polyether amine type polyisobutylene succinimide C, and a polyformaldehyde compound D. The ashless dispersant prepared by the application has a star-shaped structure as a whole, and the polyisobutylene olefin chain grafted at multiple sites makes the dispersant have stronger suspension capacity in oil products. In addition, the ashless dispersant prepared by the application has excellent dispersing performance, oxidation resistance and high-temperature detergency, and has excellent storage stability after being adjusted into oil products.

Description

TECHNICAL FIELD

[0001] The present application relates to an ashless dispersant and its preparation method and application. BACKGROUND

[0002] At present, the ashless dispersants applied in lubricating oil mainly include three categories of succinimide type, succinate type and Mannich type. As the main additive of lubricating oil, the ashless dispersant is widely applied in various engine oils, transmission oils and industrial gear oils, etc. Its main function is to disperse the sediment precursors, sediments and soot particles generated by the long-period high-load work of the lubricating oil product, prevent the sediments and soot particles from being adsorbed to the metal surface to cause wear of the friction pair, and further prevent the viscosity increase of the lubricating oil.

[0003] In recent years, researchers have found that the introduction of aromatic amines into ashless dispersants can enhance the polarity of ashless dispersants and effectively improve the dispersing performance of the dispersants. For example, US4863623, US13698082, US13130638, US13202647, US8969266B2, EP2222825A2 and CN106459812A all use 4-aminodiphenylamine as the polar end to introduce into ashless dispersants to enhance their dispersing performance. However, it is regrettable that the ashless dispersants prepared by using 4-aminodiphenylamine as the polar end will cause the color of the oil to gradually deepen after being blended into lubricating oil, thereby causing the appearance to discolor and seriously affecting the storage stability of the oil. SUMMARY

[0004] In order to increase the selection space of ashless dispersants and at least partially solve the storage stability problem of lubricating oil, the embodiments of the present application provide an ashless dispersant and its preparation method and application.

[0005] As an aspect of the present application, an ashless dispersant is provided, which is shown as formula (I):

[0006]

[0007] In formula (I), R is -CH2-, -O- or -SO2-; R1 is -CH2-, -CH2CH2-, -CH(CH3)- or -CH(OH)-; R2, R3, R4 and R5 are each independently selected from a single hanging fatty amine type polyisobutylene succinimide B and / or a single hanging polyether amine type polyisobutylene succinimide C.

[0008] In one or some possible embodiments, the single hanging fatty amine type polyisobutylene succinimide B is shown as formula (II):

[0009] In formula (II), R1 is -CH2-, -CH2CH2-, -CH(CH3)- or -CH(OH)-; R2, R3, R4 and R5 are each independently selected from a single hanging fatty amine type polyisobutylene succinimide B and / or a single hanging polyether amine type polyisobutylene succinimide C.

[0010] In formula (II), n is an integer in the range of 1≤n≤8.

[0011] In one or some possible embodiments, the single-hung polyether amine type polyisobutylene succinimide C is shown in formula (III):

[0012]

[0013] In formula (III), x and z are integers in the range of 1≤(x+z)≤4, and y is an integer in the range of 1≤y≤9.

[0014] As another aspect of the present application, a method for preparing the ashless dispersant described above is provided. The friction-modifying dispersant is a compound prepared by Mannich reaction of a multifunctional polar crosslinking agent A containing multiple reaction sites, a single-hung fatty amine type polyisobutylene succinimide B, and / or a single-hung polyether amine type polyisobutylene succinimide C, and a polyformaldehyde compound D.

[0015] In one or some possible embodiments, the friction-modifying dispersant is a compound prepared by Mannich reaction of a multifunctional polar crosslinking agent A containing multiple reaction sites, a single-hung fatty amine type polyisobutylene succinimide B, a single-hung polyether amine type polyisobutylene succinimide C, and a polyformaldehyde compound D.

[0016] The molar ratio of the multifunctional polar crosslinking agent A containing multiple reaction sites, the single-hung fatty amine type polyisobutylene succinimide B, the single-hung polyether amine type polyisobutylene succinimide C, and the polyformaldehyde compound D is 1:(1-4):(1-4):(3.5-4.2).

[0017] In one or some possible embodiments, the method specifically comprises the following steps:

[0018] After the multifunctional polar crosslinking agent A containing multiple reaction sites, the single-hung fatty amine type polyisobutylene succinimide B, the single-hung polyether amine type polyisobutylene succinimide C, and the polyformaldehyde compound D are mixed in the molar ratio and heated under stirring, water is removed, and the mixture is filtered after cooling to prepare the dispersant.

[0019] In one or some possible embodiments, the multifunctional polar crosslinking agent A containing multiple reaction sites is shown in formula (IV):

[0020]

[0021] In formula (IV), R is -CH2-, -O- or -SO2-; R1 is -CH2-, -CH2CH2-, -CH(CH3)- or -CH(OH)-.

[0022] In one or some possible embodiments, the preparation of the multi-functionalized polar crosslinking agent A with multiple reaction sites comprises the following steps:

[0023] The multi-functionalized polar crosslinking agent A with multiple reaction sites is obtained by heating and mixing the aromatic amine compound, the carboxyl-containing phenolic compound and the organic solvent under stirring, refluxing under inert gas protection, filtering and distilling under reduced pressure.

[0024] In one or some possible embodiments, the molar ratio of the aromatic amine compound to the carboxyl-containing phenolic compound is 1:(1.8-2.3).

[0025] In one or some possible embodiments, the aromatic amine compound is as shown in formula (V):

[0026]

[0027] In formula (V), R is -CH2-, -O- or -SO2-.

[0028] In one or some possible embodiments, the carboxyl-containing phenolic compound is selected from one or more of p-hydroxybenzoic acid, p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, 2-(4-hydroxyphenyl)propionic acid, 3-hydroxyphenylglycolic acid, 2-(p-hydroxyphenylazo)benzoic acid or 2-amino-5-hydroxybenzoic acid.

[0029] In one or some possible embodiments, the preparation of the single-hanging fatty amine type polyisobutylene succinimide B comprises the following steps:

[0030] The single-hanging fatty amine type polyisobutylene succinimide B is obtained by heating and mixing the polyethylene polyamine compound and the base oil under stirring, adding polyisobutylene succinic anhydride, warming and reacting, removing water and cooling.

[0031] In one or some possible embodiments, the molar ratio of the polyisobutylene succinic anhydride to the polyethylene polyamine compound is 1:(0.8-1).

[0032] In one or some possible embodiments, the number average molecular weight of the polyisobutylene succinic anhydride is 900-5000.

[0033] In one or some possible embodiments, the polyethylene polyamine compound is selected from one or more of diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine or heavy polyamine.

[0034] In one or some possible embodiments, the mass fraction of the base oil in the single-hung fatty amine type polyisobutylene succinimide B is 50-65%.

[0035] In one or some possible embodiments, the preparation of the single-hung polyether amine type polyisobutylene succinimide C comprises the following steps:

[0036] After the polyether amine compound and the base oil are heated under stirring, the polyisobutylene succinic anhydride is added, the temperature is raised for reaction, water is removed, and the single-hung polyether amine type polyisobutylene succinimide C is obtained after cooling.

[0037] In one or some possible embodiments, the molar ratio of the polyisobutylene succinic anhydride to the polyether amine compound is 1:(0.75-1).

[0038] In one or some possible embodiments, the mass fraction of the base oil in the single-hung polyether amine type polyisobutylene succinimide C is 45-55%.

[0039] As a further aspect of the present application, the use of the ashless dispersant described above in the preparation of lubricating oil is involved.

[0040] As a further aspect of the present application, a lubricating oil containing the ashless dispersant prepared by the method described above is involved.

[0041] The aromatic amine compound provided by the embodiments of the present application has at least two primary amine groups (-NH2) in the molecular formula and does not contain a secondary amine group (-NH-), which can solve the problem that the ashless dispersant prepared by using 4-aminodiphenylamine causes the color change of lubricating oil and thus affects the storage stability thereof.

[0042] In the preparation method, first, a specific structure of aromatic amine is selected as a core polar point, a phenolic compound containing a carboxyl group is grafted onto the aromatic amine through an amide reaction to provide multiple reaction sites for the next Mannich reaction; then, a single-hung polyisobutylene succinimide containing a fatty amine and a polyether amine is grafted onto the reaction sites through the Mannich reaction to obtain a dispersant. The dispersant obtained by the preparation method has a higher molecular weight, thereby increasing the dispersion performance thereof in oil.

[0043] The ashless dispersant prepared by the present application has excellent dispersion performance, oxidation resistance, and high-temperature detergency, and has excellent storage stability after being added into oil. The ashless dispersant of the present application has a star-shaped structure as a whole, and the polyisobutylene olefin chain grafted at multiple sites makes the dispersant have stronger suspension capacity in oil.

[0044] Other features and advantages of the present application will be set forth in the following specification, and in part will be apparent from the description, or can be learned by practice of the application. The objects and other advantages of the application will be realized and attained by the structure particularly pointed out in the written description and claims hereof. DETAILED DESCRIPTION

[0045] The following detailed description of the embodiments of the present application is made with the technical solutions of the present application as the premise, and detailed implementation manners and processes are given, but the protection scope of the present application is not limited to the following embodiments. The process parameters not specified in the following embodiments are usually according to the conventional conditions.

[0046] The endpoints of the ranges and any values described herein are not limited to the precise values stated. The ranges and values should be construed to be approximations that allow for significant variation. Various ranges of values are stated in terms of being "between" and "between about and." When such values are read as "between," it is meant that the range is from the lower value, and to the upper value, only that is not including the endpoints values. When the values are read as "between about and," it is meant that the range is from the lower value, and to the upper value, including the endpoints values. Ranges of values for the same material or property are not necessarily mutually exclusive, as some embodiments can be formulated to fall within the value range of more than one category.

[0047] The inventor refers to US4863623, US13698082, US13130638, US13202647, US8969266B2, US2008082944 and US2008082944, and implements the related technical solutions, and finds that the 4-amino diphenylamine is used as a polar end ashless dispersant in the lubricating oil products in the above patent documents, but as the storage time is prolonged, the color of the oil product is deepened, thereby causing the appearance to be discolored, and seriously affecting the storage stability of the oil product.

[0048] In view of the fact that the prior art does not meet the inventor's expectations, the inventor makes the present application through further research and development.

[0049] The inventor makes a deep exploration and analysis on the above phenomenon, finds and draws the following conclusion: when the 4-amino diphenylamine is used to prepare the ashless dispersant, the primary amine-NH2 at the 4th position has a relatively large activity, first participates in the reaction and generates amide or imide, but the secondary amine-NH- between the two benzene rings cannot participate in the amination reaction almost due to the influence of the space steric hindrance of the two benzene rings. In the oil product blending process, some of the additives (such as metal cleaning agent, tackifier, antioxidant, extreme pressure anti-wear agent, rust inhibitor, preservative, etc.) contain acidic substances, and H +The ion couples with -NH- on 4-amino diphenylamine to generate aromatic amine positive ion coupling, which changes the charge of the aromatic ring and causes discoloration, and finally leads to discoloration of the whole oil product, which seriously affects the storage stability of the oil product. The technical problem has not been reported in the prior art.

[0050] To solve the above technical problem, the inventors first select an aromatic amine having at least two primary amine groups (-NH2) and no secondary amine group (-NH-) as the core polar point, graft a phenolic compound containing a carboxyl group to the aromatic amine through an amide reaction to provide multiple reaction sites for the next Mannich reaction; then use the Mannich reaction to graft a single-hung polyisobutylene succinimide containing a fatty amine and a polyether amine at the reaction sites to obtain a dispersant with excellent dispersibility, oxidation resistance and high-temperature detergency, and further to give the oil product excellent storage stability.

[0051] The application will be further described below in combination with specific examples, and the protection scope of the application is not limited by the following examples. The main materials involved in the examples are all conventional commercially available products.

[0052] The following are the preparation examples of the application, which respectively provide the preparation processes of the multifunctional polar crosslinking agent A containing multiple reaction sites, the single-hung fatty amine type polyisobutylene succinimide B and the single-hung polyether amine type polyisobutylene succinimide C, and the products.

[0053] (1) Preparation of multifunctional polar crosslinking agent A containing multiple reaction sites

[0054] Preparation Example 1

[0055] Under stirring, 59.4 g of 4,4'-diaminodiphenylmethane, 91.2 g of p-hydroxyphenylacetic acid and 100 g of dimethylbenzene were mixed at 130°C, nitrogen was introduced, refluxed for 4 h, filtered and distilled under reduced pressure to obtain multifunctional polar crosslinking agent A1 containing multiple reaction sites.

[0056] The multifunctional polar crosslinking agent A1 containing multiple reaction sites is as follows:

[0057]

[0058] Preparation Example 2

[0059] Under stirring, 60 g of 3,4'-diaminodiphenyl ether, 82.8 g of p-hydroxybenzoic acid and 100 g of dimethylbenzene were mixed at 133°C, nitrogen was introduced, refluxed for 3 h, filtered and distilled under reduced pressure to obtain multifunctional polar crosslinking agent A2 containing multiple reaction sites.

[0060] The multi-functionalized polar crosslinking agent A2 with multiple reaction sites is as follows:

[0061]

[0062] Preparation Example 3

[0063] Under stirring, 74.4 g of 4, 4'-diaminodiphenyl sulfone, 99.6 g of p-hydroxyphenyl propionic acid and 100 g of xylene were mixed at 138 ℃, nitrogen was introduced, refluxed for 3 h, filtered, and distilled under reduced pressure to obtain the multi-functionalized polar crosslinking agent A3 with multiple reaction sites.

[0064] The multi-functionalized polar crosslinking agent A3 with multiple reaction sites is as follows:

[0065]

[0066] (2) Preparation of a single hanging fatty amine type polyisobutylene succinimide B

[0067] Preparation Example 4

[0068] Under stirring, 23.2 g of heavy polyamine (Huntsman E100) and 123.2 g of base oil Y4 were mixed at 102 ℃, then 115 g of polyisobutylene succinic anhydride PIBSA-1000 was added, the feeding time was controlled for 1 h, after the feeding was completed, the system was kept at 102 ℃ for 3 h, then the temperature was increased to 160 ℃ at a rate of 10 ℃ / h, nitrogen was introduced into the system, and water was stripped for 6 h, and then the system was cooled to obtain the single hanging fatty amine type polyisobutylene succinimide B1.

[0069] Preparation Example 5

[0070] Under stirring, 11.6 g of polyethylene polyamine (E100) and 190 g of base oil 100SN were mixed at 110 ℃, then 115 g of polyisobutylene succinic anhydride PIBSA-2300 was added, the feeding time was controlled for 1 h, after the feeding was completed, the system was kept at 110 ℃ for 2 h, then the temperature was increased to 150 ℃ at a rate of 8 ℃ / h, nitrogen was introduced into the system, and water was stripped for 4 h, and then the system was cooled to obtain the single hanging fatty amine type polyisobutylene succinimide B2.

[0071] (3) Single hanging polyether amine type polyisobutylene succinimide C

[0072] Preparation Example 6

[0073] Under stirring, 60 g of polyether diamine (Jeffamine D-230) and 190 g of base oil 100SN were mixed at 110 ℃, then 115 g of polyisobutylene succinic anhydride PIBSA-2300 was added, the feeding time was controlled for 1 h, after the feeding was completed, the system was kept at 110 ℃ for 2 h, then the temperature was increased to 150 ℃ at a rate of 8 ℃ / h, nitrogen was introduced into the system, and water was stripped for 4 h, and then the system was cooled to obtain the single hanging polyether amine type polyisobutylene succinimide C1. ED-600 and 160g of base oil Y4 were mixed at 110℃, and then 100g of polyisobutylene succinic anhydride PIBSA-1300 was added. The feeding time was controlled at 30min. After the feeding was completed, the mixture was reacted at 120℃ for 3h, and then the temperature was raised to 160℃. Nitrogen gas was introduced into the system, and water was removed by gas stripping for 6h. After cooling, mono-linked polyetheramine type polyisobutylene succinimide C1 was obtained.

[0074] Preparation Example 7

[0075] Under stirring conditions, 36g of polyether diamine ( ED-900 and 159g of base oil MVI150 were mixed at 120℃, and then 92g of polyisobutylene succinic anhydride PIBSA-2300 were added. The feeding time was controlled at 30min. After the feeding was completed, the mixture was reacted at 130℃ for 2h, and then the temperature was raised to 170℃. Nitrogen gas was introduced into the system, and water was removed by gas stripping for 5h. After cooling, mono-linked polyetheramine type polyisobutylene succinimide C2 was obtained.

[0076] The following are embodiments of the present invention, each of which provides an ashless dispersant.

[0077] Example 1

[0078] Under stirring conditions, 46.6 g of the multifunctional polar crosslinking agent A1 containing multiple reaction sites from Preparation Example 1, 492.8 g of the mono-linked aliphatic amine polyisobutylene succinimide B1 from Preparation Example 4, 581.8 g of the mono-linked polyether amine polyisobutylene succinimide C1 from Preparation Example 6, and 36 g of paraformaldehyde were mixed. After 1 h, the temperature was increased to 110 °C at a rate of 7 °C / h. After 3 h, the temperature was increased to 150 °C. Nitrogen gas was introduced into the system, and water was removed by gas stripping for 4 h. After cooling to 130 °C, the mixture was filtered using diatomaceous earth filter aid to obtain ashless dispersant SSL1.

[0079] Example 2

[0080] Under stirring conditions, 46.6 g of the multifunctional polar crosslinking agent A1 containing multiple reaction sites from Preparation Example 1, 492.8 g of the mono-linked aliphatic amine polyisobutylene succinimide B1 from Preparation Example 4, 1300 g of the mono-linked polyether amine polyisobutylene succinimide C2 from Preparation Example 7, and 36 g of paraformaldehyde were mixed. After 2 h, the temperature was increased to 110 °C at a rate of 10 °C / h. After 4 h, the temperature was increased to 160 °C. Nitrogen gas was introduced into the system, and water was removed by gas stripping for 6 h. After cooling to 145 °C, the mixture was filtered using diatomaceous earth filter aid to obtain ashless dispersant SSL2.

[0081] Example 3

[0082] Under stirring, 46.6 g of the multi-reactive site multifunctional polar crosslinker A1 of Preparation 1, 1266 g of the mono-attached fatty amine type polyisobutylene succinimide B2 of Preparation 5, 581.8 g of the mono-attached polyether amine type polyisobutylene succinimide C1 of Preparation 6 and 36 g of paraformaldehyde were mixed. After 1 h, the temperature was increased to 110°C at a rate of 10°C / h, and after 3 h, the temperature was increased to 150°C. Nitrogen was bubbled through the system to strip off water for 5 h. After cooling to 130°C, filtration was performed using diatomite filter aid to obtain ashless dispersant SSL3.

[0083] Example 4

[0084] Under stirring, 46.6 g of the multi-reactive site multifunctional polar crosslinker A1 of Preparation 1, 1266 g of the mono-attached fatty amine type polyisobutylene succinimide B2 of Preparation 5, 581.8 g of the mono-attached polyether amine type polyisobutylene succinimide C1 of Preparation 6 and 36 g of paraformaldehyde were mixed. After 1 h, the temperature was increased to 110°C at a rate of 10°C / h, and after 3 h, the temperature was increased to 150°C. Nitrogen was bubbled through the system to strip off water for 5 h. After cooling to 130°C, filtration was performed using diatomite filter aid to obtain ashless dispersant SSL3.

[0085] Example 5

[0086] Under stirring, 46.6 g of the multi-reactive site multifunctional polar crosslinker A1 of Preparation 1, 1266 g of the mono-attached fatty amine type polyisobutylene succinimide B2 of Preparation 5, 581.8 g of the mono-attached polyether amine type polyisobutylene succinimide C1 of Preparation 6 and 36 g of paraformaldehyde were mixed. After 1 h, the temperature was increased to 110°C at a rate of 10°C / h, and after 3 h, the temperature was increased to 150°C. Nitrogen was bubbled through the system to strip off water for 5 h. After cooling to 130°C, filtration was performed using diatomite filter aid to obtain ashless dispersant SSL3.

[0087] Example 6

[0088] Under stirring, 46.6 g of the multi-reactive site multifunctional polar crosslinker A1 of Preparation 1, 1266 g of the mono-attached fatty amine type polyisobutylene succinimide B2 of Preparation 5, 581.8 g of the mono-attached polyether amine type polyisobutylene succinimide C1 of Preparation 6 and 36 g of paraformaldehyde were mixed. After 1 h, the temperature was increased to 110°C at a rate of 10°C / h, and after 3 h, the temperature was increased to 150°C. Nitrogen was bubbled through the system to strip off water for 5 h. After cooling to 130°C, filtration was performed using diatomite filter aid to obtain ashless dispersant SSL3.

[0089] Example 7

[0090] Under stirring, 46.8 g of the multi-reactive site multifunctional polar crosslinker A2 of Preparation 2, 1266 g of the mono-attached fatty amine type polyisobutylene succinimide B2 of Preparation 5, 581.8 g of the mono-attached polyether amine type polyisobutylene succinimide C1 of Preparation 6 and 36 g of paraformaldehyde were mixed, after 1 h, the temperature was increased to 110 °C at a rate of 10 °C / h, after 3 h, the temperature was increased to 150 °C, nitrogen was bubbled through the system to strip off water for 5 h, after cooling to 130 °C, filtration was performed using diatomite filter aid to obtain ashless dispersant SSL7.

[0091] Example 8

[0092] Under stirring, 46.8 g of the multi-reactive site multifunctional polar crosslinker A2 of Preparation 2, 1266 g of the mono-attached fatty amine type polyisobutylene succinimide B2 of Preparation 5, 581.8 g of the mono-attached polyether amine type polyisobutylene succinimide C1 of Preparation 6 and 36 g of paraformaldehyde were mixed, after 1 h, the temperature was increased to 110 °C at a rate of 10 °C / h, after 3 h, the temperature was increased to 150 °C, nitrogen was bubbled through the system to strip off water for 5 h, after cooling to 130 °C, filtration was performed using diatomite filter aid to obtain ashless dispersant SSL7.

[0093] Example 9

[0094] Under stirring, 46.8 g of the multi-reactive site multifunctional polar crosslinker A2 of Preparation 2, 1266 g of the mono-attached fatty amine type polyisobutylene succinimide B2 of Preparation 5, 581.8 g of the mono-attached polyether amine type polyisobutylene succinimide C1 of Preparation 6 and 36 g of paraformaldehyde were mixed, after 1 h, the temperature was increased to 110 °C at a rate of 10 °C / h, after 3 h, the temperature was increased to 150 °C, nitrogen was bubbled through the system to strip off water for 5 h, after cooling to 130 °C, filtration was performed using diatomite filter aid to obtain ashless dispersant SSL7.

[0095] Example 10

[0096] Under stirring, 46.8 g of the multi-reactive site multifunctional polar crosslinker A2 of Preparation 2, 1266 g of the mono-attached fatty amine type polyisobutylene succinimide B2 of Preparation 5, 581.8 g of the mono-attached polyether amine type polyisobutylene succinimide C1 of Preparation 6 and 36 g of paraformaldehyde were mixed, after 1 h, the temperature was increased to 110 °C at a rate of 10 °C / h, after 3 h, the temperature was increased to 150 °C, nitrogen was bubbled through the system to strip off water for 5 h, after cooling to 130 °C, filtration was performed using diatomite filter aid to obtain ashless dispersant SSL7.

[0097] Example 11

[0098] Under stirring, 51.6 g of the multi-reactive multifunctional polar crosslinking agent A3 of Preparation 3, 1266 g of the mono-attached fatty amine type polyisobutylene succinimide B2 of Preparation 5, 581.8 g of the mono-attached polyether amine type polyisobutylene succinimide C1 of Preparation 6 and 36 g of paraformaldehyde were mixed, after 1 h, the temperature was raised to 110°C at a rate of 10°C / h, after 3 h, the temperature was raised to 150°C, nitrogen was bubbled into the system, water was stripped off for 5 h, after cooling to 130°C, filtration was performed using diatomite filter aid, to obtain ashless dispersant SSL11.

[0099] Example 12

[0100] Under stirring, 51.6 g of the multi-reactive multifunctional polar crosslinking agent A3 of Preparation 3, 1266 g of the mono-attached fatty amine type polyisobutylene succinimide B2 of Preparation 5, 1300 g of the mono-attached polyether amine type polyisobutylene succinimide C2 of Preparation 7 and 36 g of paraformaldehyde were mixed, after 1 h, the temperature was raised to 110°C at a rate of 10°C / h, after 3 h, the temperature was raised to 150°C, nitrogen was bubbled into the system, water was stripped off for 5 h, after cooling to 130°C, filtration was performed using diatomite filter aid, to obtain ashless dispersant SSL12.

[0101] To verify the main factors affecting the performance of ashless dispersants, the inventors made the following comparative examples.

[0102] Comparative Example 1

[0103] The ashless dispersant DBL1 prepared in this comparative example differs from that of Example 10 in that it does not contain the mono-attached fatty amine type polyisobutylene succinimide B1 of Preparation 4.

[0104] Comparative Example 2

[0105] The ashless dispersant DBL2 prepared in this comparative example differs from that of Example 12 in that it does not contain the mono-attached polyether amine type polyisobutylene succinimide C2 of Preparation 7.

[0106] Comparative Example 3

[0107] The difference from Example 1 is that the aromatic amine compound in the multi-reactive multifunctional polar crosslinking agent A1 is not treated with a phenolic group. The specific steps are as follows:

[0108] Under stirring, mix 19.8 g 4,4'-diaminodiphenyl methane, 246.4 g of the mono-attached fatty amine type polyisobutylene succinimide B1 prepared in Preparation Example 4, 290.9 g of the mono-attached polyether amine type polyisobutylene succinimide C1 prepared in Preparation Example 6, and 18 g of paraformaldehyde, after 1 h, heat the system to 110°C at a rate of 7°C / h, after 3 h, heat to 150°C, introduce nitrogen into the system, strip water for 4 h, after cooling to 130°C, filter using diatomite filter aid, to obtain ashless dispersant DBL3.

[0109] Comparative Example 4

[0110] The difference from Example 1 is that 4-aminodiphenylamine is used instead of 4,4'-diaminodiphenyl methane in the multi-reactive site multifunctional polar crosslinking agent A1. The specific steps are as follows:

[0111] Under stirring, mix 36.8 g 4-aminodiphenylamine, 246.4 g of the mono-attached fatty amine type polyisobutylene succinimide B1 prepared in Preparation Example 4, 290.9 g of the mono-attached polyether amine type polyisobutylene succinimide C1 prepared in Preparation Example 6, and 18 g of paraformaldehyde, after 1 h, heat the system to 110°C at a rate of 7°C / h, after 3 h, heat to 150°C, introduce nitrogen into the system, strip water for 4 h, after cooling to 130°C, filter using diatomite filter aid, to obtain ashless dispersant DBL4.

[0112] Alternatively, commercially available ashless dispersant T161, aromatic amine type ashless dispersant prepared in Examples 1 and 2 disclosed in US8557753, are respectively taken as Comparative Example 5 and Comparative Example 6 of the present application.

[0113] The various performances of the ashless dispersants prepared in the above Examples 1-12 and Comparative Examples 1-6 are tested as follows.

[0114] Test one physicochemical performance analysis, and the data results are shown in Table 1 below.

[0115] Table 1 physicochemical performance data results

[0116]

[0117]

[0118] From the results of the physico-chemical property data in Table 1, in combination with Examples 1-12 and Comparative Examples 1-6, the inventors believe that: because the aromatic amine compound with at least two primary amine groups (-NH2) and no secondary amine groups (-NH-) is used as the core polar point, the phenolic compound containing a carboxyl group is grafted onto the aromatic amine through an amide reaction to provide multiple reaction sites for the next Mannich reaction, so that the ashless dispersant prepared has a relatively high molecular weight. The aromatic amine that is not treated with a phenolic group has fewer reaction sites, resulting in fewer grafted single-pendant polyisobutylene succinimides containing fatty amines and polyether amines, and a smaller molecular weight.

[0119] Test 2: Evaluation of low-temperature oil sludge dispersibility

[0120] According to SH / T 0623-1995 "Double Succinimide Dispersant" Appendix A: Low-temperature dispersibility evaluation method of ashless dispersant, the specific steps are as follows:

[0121] 0.5 g of ashless dispersant, 5 g of base oil Y4, and 4.5 g of oil sludge were added into a 50 ml beaker, and stirred at 150°C for 1.5 hours. A drop of the above test oil was taken while hot and dropped onto filter paper, which was then placed in an oven at a constant temperature of 80°C for 2 hours. The ratio of the oil sludge diffusion ring to the oil ring was measured to obtain the spot test data.

[0122] Wherein: the higher the spot dispersant value, the better the low-temperature oil sludge dispersibility.

[0123] Test 3: Evaluation of antioxidant performance

[0124] A mass fraction of 6.3% ashless dispersant was added to base oil Y4, and the antioxidant performance was evaluated according to SH / T0193-1992 Rotating Pressure Vessel Oxidation Test (RPVOT) method; the high-temperature antioxidant performance was evaluated according to SH / T 0719 High Pressure Differential Scanning Calorimetry (PDSC) method.

[0125] Wherein: the longer the RPVOT time, the higher the PDSC initial oxidation temperature, the better the high-temperature oxidation resistance of the dispersant.

[0126] Test 4: High-temperature detergency

[0127] According to the relevant standards in SH / T 0300-1992 "Crankcase Simulation Test Method", the coke plate test was performed, and the specific steps are as follows:

[0128] The test oil was prepared by adding 3% by mass of ashless dispersant to base oil Y4 to make 300 ml. The test instrument parameters were set as follows: the plate temperature was 310°C, the oil temperature was 100°C, and the oil was splashed continuously for 2 h to observe the paint film formation. This method is to splash the additive-containing internal combustion engine oil onto a high-temperature metal surface to form a paint film, thereby simulating the paint formation of the crankcase during piston operation. The high-temperature detergency of the oil was observed by measuring the weight of the coke on the metal plate.

[0129] The results of tests two to four are recorded in Table 2 below.

[0130] Table 2 Performance evaluation results

[0131]

[0132]

[0133] From the physicochemical property data results in Table 2, combined with Examples 1-12 and Comparative Examples 1-6, we can find that in Examples 10 and 12, the dispersing performance, antioxidation, and high-temperature detergency of the ashless dispersant prepared by simultaneously introducing a single-pendant fatty amine type polyisobutylene succinimide and a single-pendant polyether amine type polyisobutylene succinimide are higher than those of the ashless dispersant prepared by introducing a single-pendant fatty amine type polyisobutylene succinimide (Comparative Example 1) and a single-pendant polyether amine type polyisobutylene succinimide (Comparative Example 2), respectively. In addition, the dispersing performance, antioxidation, and high-temperature detergency of the dispersant prepared in Example 1 using an aromatic amine having at least two primary amine groups (-NH2) and no secondary amine groups (-NH-) in the molecular formula and treated with a phenolic group are better than those of the dispersant (such as Comparative Example 3) not treated with a phenolic group and the single-amine aromatic amine dispersant (such as Comparative Example 4) not treated with a phenolic group.

[0134] In summary, the inventors believe that the ashless dispersant prepared in the examples of the present application has excellent dispersing performance, antioxidation, and high-temperature detergency due to the simultaneous introduction of three functional groups: an aromatic amine group, a phenolic group, and a polyether group at the polar end. Therefore, the inventors believe that the combination of the above three groups has a better synergistic effect.

[0135] Test five storage stability test

[0136] The test method comprises the following steps:

[0137] The ashless dispersant with a mass fraction of 4.8% was blended into API CI-4 oil, and after a period of storage under sunlight, its color was determined periodically by GB / T 6540 Petroleum Products Color Determination method, and the results are shown in Table 3 below.

[0138] Table 3 Color change of oil products

[0139]

[0140]

[0141] By comparing the examples and the comparative examples, the inventor found that the ashless dispersants of examples 1-12 prepared by using aromatic amine compounds with at least two primary amine groups (-NH2) and without secondary amine groups (-NH-) in the molecular formula solved the problem of the color change of lubricating oil and the influence on the storage stability caused by the ashless dispersants prepared by using 4-aminodiphenylamine, such as comparative example 4 and comparative example 6, and the ashless dispersants prepared by the application have excellent storage stability after being added into oil products.

[0142] In summary, the aromatic amine compounds with at least two primary amine groups (-NH2) and without secondary amine groups (-NH-) in the molecular formula are selected as the core polar point, the phenolic compounds containing carboxyl groups are grafted onto the aromatic amine through amide reaction to provide multiple reaction sites for the next Mannich reaction, and the ashless dispersants prepared by the application have higher molecular weight and improved dispersing performance in oil products; on the other hand, the polar end of the dispersant introduces aromatic amine groups, phenolic groups and polyether groups, so that the dispersant has excellent dispersing performance, antioxidant property and high-temperature detergency.

[0143] The above merely describes preferred and workable embodiments of the application, and is not intended to limit the protection scope of the application, and various modifications or applications according to the above embodiments are within the protection scope of the technical scheme.

[0144] Although the specific embodiments of the application have been described in detail, those skilled in the art will understand that various modifications and substitutions can be made to those details according to all the teachings disclosed herein, and these changes are within the protection scope of the application. The entire scope of the application is given by the appended claims and any equivalents thereof.

Claims

1. An ashless dispersant characterised in that, The ashless dispersant is a compound prepared by Mannich reaction of a multifunctional polar crosslinking agent A with multiple reaction sites, the single-hung fatty amine type polyisobutylene succinimide B, the single-hung polyether amine type polyisobutylene succinimide C and a polyformaldehyde compound D. ， In formula (I), R is -CH2-, -O- or -SO2-; R1 is -CH2-, -CH2CH2-, -CH(CH3)- or -CH(OH)-; R2, R3, R4 and R5 are each independently selected from groups formed by single-hung fatty amine type polyisobutylene succinimide B or single-hung polyether amine type polyisobutylene succinimide C, and simultaneously contain groups formed by single-hung fatty amine type polyisobutylene succinimide B and groups formed by single-hung polyether amine type polyisobutylene succinimide C. The single-hung fatty amine type polyisobutylene succinimide B is shown in formula (II): ； In formula (II), n is an integer in the range of 1≤n≤8. The single-hung polyether amine type polyisobutylene succinimide C is shown in formula (III): ； In formula (III), x and z are each an integer in the range of 1≤(x+z)≤4, and y is an integer in the range of 1≤y≤9.

2. A method of producing the ashless dispersant as claimed in claim 1, characterized in that, The ashless dispersant is a compound prepared by Mannich reaction of a multifunctional polar crosslinking agent A with multiple reaction sites, the single-hung fatty amine type polyisobutylene succinimide B, the single-hung polyether amine type polyisobutylene succinimide C and a polyformaldehyde compound D.

3. The preparation method of the ashless dispersant according to claim 2, characterized in that, The molar ratio of the multifunctional polar crosslinking agent A with multiple reaction sites, the single-hung fatty amine type polyisobutylene succinimide B, the single-hung polyether amine type polyisobutylene succinimide C and the polyformaldehyde compound D is 1:(1-4):(1-4):(3.5-4.2).

4. The method for producing the ashless dispersant according to claim 3, characterized by, The preparation method comprises the following steps: After heating and mixing the multifunctional polar crosslinking agent A with multiple reaction sites, the single-hung fatty amine type polyisobutylene succinimide B, the single-hung polyether amine type polyisobutylene succinimide C and the polyformaldehyde compound D in the molar ratio under stirring, water is removed, and the mixture is cooled and filtered to obtain the dispersant.

5. The method of preparing the ashless dispersant according to claim 3, characterized by, The multifunctional polar crosslinking agent A with multiple reaction sites is shown in formula (IV): ； In formula (IV), R is -CH2-, -O- or -SO2-; and R1 is -CH2-, -CH2CH2-, -CH(CH3)- or -CH(OH)-.

6. The method of preparing the ashless dispersant according to claim 5, characterized in that, The preparation of the multifunctional polar crosslinking agent A with multiple reaction sites comprises the following steps: After heating and mixing the multifunctional polar crosslinking agent A with multiple reaction sites, the single-hung fatty amine type polyisobutylene succinimide B, the single-hung polyether amine type polyisobutylene succinimide C and the polyformaldehyde compound D in the molar ratio under stirring, water is removed, and the mixture is cooled and filtered to obtain the dispersant.

7. The method of preparing the ashless dispersant according to claim 6, characterized in that, The molar ratio of the multifunctional polar crosslinking agent A with multiple reaction sites, the single-hung fatty amine type polyisobutylene succinimide B, the single-hung polyether amine type polyisobutylene succinimide C and the polyformaldehyde compound D is 1:(1-4):(1-4):(3.5-4.2).

8. The method of preparing the ashless dispersant according to claim 7, characterized by, The aromatic amine compound is shown in formula (V): ； In formula (V), R is -CH2-, -O- or -SO2-.

9. The method of preparing the ashless dispersant according to claim 7, characterized by, The carboxyl-containing phenolic compound is selected from one or more of p-hydroxybenzoic acid, p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, 2-(4-hydroxyphenyl)propionic acid, 3-hydroxyphenylglycolic acid, 2-(p-hydroxyphenylazo)benzoic acid, or 2-amino-5-hydroxybenzoic acid.

10. The method of preparing the ashless dispersant according to claim 4, characterized in that, The preparation of the single-hung fatty amine type polyisobutylene succinimide B comprises the following steps: After the polyisobutylene succinic anhydride is added to the mixed polyethylene polyamine compound and base oil under stirring, heating, reaction, water removal, and cooling, the single-hung fatty amine type polyisobutylene succinimide B is obtained.

11. The method of making the ashless dispersant of claim 10, wherein, The molar ratio of the polyisobutylene succinic anhydride to the polyethylene polyamine compound is 1: (0.8-1).

12. The method of making the ashless dispersant of claim 11, wherein, The number average molecular weight of the polyisobutylene succinic anhydride is 900-5000.

13. The method of making the ashless dispersant of claim 10, wherein, The polyethylene polyamine compound is selected from one or more of diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, or heavy polyamine.

14. The method of making the ashless dispersant of claim 10, wherein, The mass fraction of the base oil in the single-hung fatty amine type polyisobutylene succinimide B is 50-65%.

15. The method of making the ashless dispersant of claim 4, wherein, The preparation of the single-hung polyether amine type polyisobutylene succinimide C comprises the following steps: After the polyisobutylene succinic anhydride is added to the mixed polyethylene polyamine compound and base oil under stirring, heating, reaction, water removal, and cooling, the single-hung fatty amine type polyisobutylene succinimide B is obtained.

16. The method of making the ashless dispersant of claim 15, wherein, The molar ratio of the polyisobutylene succinic anhydride to the polyethylene polyamine compound is 1: (0.8-1).

17. The method of making the ashless dispersant of claim 15, wherein, The mass fraction of the base oil in the single-hung fatty amine type polyisobutylene succinimide B is 50-65%.

18. Use of the ashless dispersant prepared by the method of any one of claims 2-17 in the preparation of a lubricating oil.

19. Lubricating oil, characterized in that The lubricating oil contains the ashless dispersant prepared by the method of any one of claims 2-17.

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