Ashless dispersing agent as well as preparation method and application thereof

Abstract

The invention discloses an ashless dispersant as well as a preparation method and application thereof. The ashless dispersant is a compound prepared by carrying out Mannich reaction on a multifunctional polar cross-linking agent A containing multiple reaction sites, the single-hanging aliphatic amine type polyisobutylene succinimide B and / or the single-hanging polyether amine type polyisobutylene succinimide C and a paraformaldehyde compound D. The preparation method comprises the following steps: carrying out Mannich reaction on the multifunctional polar cross-linking agent A, the single-hanging aliphatic amine type polyisobutylene succinimide B and / or the single-hanging polyether amine type polyisobutylene succinimide C and the paraformaldehyde compound D to obtain the ashless dispersant. The ashless dispersant prepared by the preparation method disclosed by the invention is integrally of a star-shaped structure, and the dispersant has stronger suspension capacity in an oil product due to a multi-point-position grafted polyisobutene olefin chain; in addition, the ashless dispersant prepared by the invention has excellent dispersing performance, oxidation resistance and high-temperature detergency, and has excellent storage stability after being blended into an oil product.

Description

Technical Field

[0001] The invention relates to an ashless dispersant and a preparation method and application thereof. Background Art

[0002] At present, the ashless dispersants used in lubricating oils are mainly divided into three categories: succinimide type, succinate type and Mannich type. Ashless dispersants are the main additives of lubricating oils and are widely used in various engine oils, transmission oils and industrial gear oils. Their main function is to disperse the sediment precursors, sediments and soot particles generated by lubricating oil products due to long-term high-load work, prevent sediments and soot particles from being adsorbed on the metal surface to cause wear on the friction pair, and thus prevent the viscosity of the lubricating oil from increasing.

[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 properties of dispersants. For example, in U.S. Patents US4863623, US13698082, US13130638, US13202647, US8969266B2, EP2222825A2 and CN106459812A, 4-aminodiphenylamine is used as the polar end to introduce ashless dispersants to enhance their dispersing properties. Unfortunately, after the ashless dispersant prepared with 4-aminodiphenylamine as the polar end is blended into lubricating oil, the color of the oil gradually deepens as the storage time of the oil increases, resulting in discoloration of the appearance, which seriously affects the storage stability of the oil. Summary of the invention

[0004] In order to increase the selection space of ashless dispersants and at least partially solve the storage stability problem of lubricating oil, an embodiment of the present invention provides an ashless dispersant and a preparation method and application thereof.

[0005] As one aspect of the present invention, an ashless dispersant is provided, wherein the ashless dispersant is as shown in 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 mono-hanging fatty amine type polyisobutylene succinimide B and / or mono-hanging polyether amine type polyisobutylene succinimide C.

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

[0009]

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

[0011] In one or some possible embodiments, the mono-hedral polyetheramine type polyisobutylene succinimide C is as shown in formula (III):

[0012]

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

[0014] As another aspect of the present invention, it relates to a method for preparing the above-mentioned ashless dispersant, wherein the friction-modifying dispersant is a compound prepared by a Mannich reaction of a multifunctional polar crosslinking agent A containing multiple reaction sites, the mono-hanging fatty amine type polyisobutylene succinimide B and / or the mono-hanging 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 a Mannich reaction of a multifunctional polar crosslinking agent A containing multiple reaction sites, the mono-hanging fatty amine type polyisobutylene succinimide B, the mono-hanging 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 mono-hanging fatty amine type polyisobutylene succinimide B, the mono-hanging 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] Under stirring conditions, the multifunctional polar crosslinking agent A containing multiple reaction sites, the monohedral fatty amine type polyisobutylene succinimide B, the monohedral polyether amine type polyisobutylene succinimide C and the polyformaldehyde compound D are heated and mixed according to the molar ratio, and then water is removed, the temperature is reduced and filtered to obtain a dispersant.

[0019] In one or some possible embodiments, the multifunctional polar crosslinking agent A containing multiple reaction sites is as 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 multifunctional polar crosslinking agent A containing multiple reaction sites comprises the following steps:

[0023] The aromatic amine compound, the carboxyl-containing phenolic compound and the organic solvent are heated and mixed under stirring, refluxed under the protection of an inert gas, filtered, and distilled under reduced pressure to obtain the multifunctional polar crosslinking agent A containing multiple reaction sites.

[0024] In one or some possible embodiments, the molar ratio of the aromatic amine compound to the carboxyl-containing phenol 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-hydroxyphenylethanic acid, 2-(p-hydroxyphenylazo)benzoic acid or 2-amino-5-hydroxybenzoic acid.

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

[0030] Under stirring conditions, the polyethylene polyamine compound and the base oil are heated and mixed, and then polyisobutylene succinic anhydride is added, the temperature is raised for reaction, water is removed, and the mono-hanging fatty amine type polyisobutylene succinimide B is obtained by 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 polyamines.

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

[0035] In one or some possible embodiments, the preparation of the mono-hedral polyetheramine type polyisobutylene succinimide C comprises the following steps:

[0036] Under stirring conditions, the polyetheramine compound and the base oil are heated and mixed, and then polyisobutylene succinic anhydride is added, the temperature is raised for reaction, water is removed, and the mono-hanging polyetheramine type polyisobutylene succinimide C is obtained by cooling.

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

[0038] In one or some possible embodiments, the mass fraction of the base oil in the mono-peptide polyetheramine polyisobutylene succinimide C is 45-55%.

[0039] As another aspect of the present invention, it relates to the use of the above-mentioned ashless dispersant in the preparation of lubricating oil.

[0040] As another aspect of the present invention, it relates to a lubricating oil, wherein the lubricating oil contains the ashless dispersant prepared by the above method.

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

[0042] In the preparation method of the present invention, firstly, an aromatic amine with a specific structure is selected as the core polar point, and a phenolic compound containing a carboxyl group is grafted onto the aromatic amine through an amide reaction, thereby providing multiple reaction sites for the next step of the Mannich reaction; then, a single-hanging polyisobutylene succinimide containing aliphatic amine and polyether amine is grafted onto the above reaction sites through the Mannich reaction to obtain a dispersant. The dispersant obtained by the preparation method has a higher molecular weight, thereby increasing its dispersibility in oil products.

[0043] The ashless dispersant prepared by the present invention has excellent dispersibility, oxidation resistance and high temperature detergency, and has excellent storage stability after being added to oil products. The ashless dispersant of the present invention has a star-shaped structure as a whole, and the polyisobutylene olefin chain that can be grafted at multiple points makes the dispersant have stronger suspension ability in oil products.

[0044] Other features and advantages of the present invention will be described in the following description, and partly become apparent from the description, or understood by practicing the present invention. The purpose and other advantages of the present invention are realized and obtained by the structures particularly pointed out in the description and claims. DETAILED DESCRIPTION

[0045] The following is a detailed description of the embodiments of the present invention: The embodiments of the present invention are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and processes are given, but the protection scope of the present invention is not limited to the following embodiments. The process parameters for which specific conditions are not specified in the following embodiments are generally based on conventional conditions.

[0046] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

[0047] The inventors implemented relevant technical solutions with reference to U.S. Patents US4863623, US13698082, US13130638, US13202647, US8969266B2, US2008082944 and US2008082944, and found that: the lubricating oil products in the above patent documents all use 4-aminodiphenylamine as the polar end ashless dispersant, but as the storage time increases, the color of the oil deepens, resulting in discoloration of the appearance, which seriously affects the storage stability of the oil.

[0048] As the prior art is not as good as the inventor's expectations, the inventor made the present invention through further research and development.

[0049] After in-depth research and analysis of the above phenomenon, the inventors found and reached the following conclusions: When ashless dispersant is prepared using 4-aminodiphenylamine, the primary amine -NH2 at position 4 is more active and first participates in the reaction to generate amide or imide, but the secondary amine -NH-, a connecting group between the two benzene rings, is affected by the steric hindrance of the two benzene rings and can hardly participate in the amination reaction. In the process of oil blending, some additives (such as metal cleaners, viscosity modifiers, antioxidants, extreme pressure anti-wear agents, rust inhibitors, corrosion inhibitors, etc.) contain acidic substances, which ionize H in the oil. +The ions react with the -NH- on 4-aminodiphenylamine to generate aromatic amine cation coupling products, which changes the charge of the aromatic ring and causes discoloration, which eventually causes the entire oil product to change color, seriously affecting the storage stability of the oil product. This technical problem has not been reported in the prior art.

[0050] In order to solve the above technical problems, the inventors first selected aromatic amines with at least two primary amine groups (-NH2) and no secondary amine groups (-NH-) as the core polar points, and grafted phenolic compounds containing carboxyl groups onto the aromatic amines through amide reaction, providing multiple reaction sites for the next Mannich reaction; then, using the Mannich reaction, mono-hanging polyisobutylene succinimide containing fatty amines and polyether amines was grafted onto the above reaction sites to obtain a dispersant with excellent dispersibility, antioxidant properties and high-temperature detergency, thereby giving the oil product excellent storage stability.

[0051] The present invention is further described below in conjunction with specific examples, and the protection scope of the present invention is not limited by the following examples. The sources of materials mainly involved in the examples are all conventional commercial products.

[0052] The following are preparation examples of the present invention, and the preparation examples respectively provide the preparation processes and products of the multifunctional polar crosslinker A containing multiple reaction sites, the mono-hanging fatty amine type polyisobutylene succinimide B, and the mono-hanging polyether amine type polyisobutylene succinimide C.

[0053] (1) Preparation of multifunctional polar crosslinker A containing multiple reactive sites

[0054] Preparation Example 1

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

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

[0057]

[0058] Preparation Example 2

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

[0060] The multifunctional polar crosslinking agent A2 containing multiple reaction sites is as follows:

[0061]

[0062] Preparation Example 3

[0063] Under stirring conditions, 74.4 g of 4,4'-diaminodiphenyl sulfone, 99.6 g of p-hydroxyphenylpropionic acid and 100 g of xylene were mixed at 138°C, nitrogen was introduced, refluxed for 3 h, filtered, and distilled under reduced pressure to obtain a multifunctional polar crosslinking agent A3 containing multiple reaction sites.

[0064] The multifunctional polar cross-linking agent A3 containing multiple reaction sites is as follows:

[0065]

[0066] (2) Preparation of mono-heptyl fatty amine type polyisobutylene succinimide B

[0067] Preparation Example 4

[0068] Under stirring conditions, 23.2 g of heavy polyamine (Huntsman E100) and 123.2 g of base oil Y4 were mixed at 102 ° C, and then 115 g of polyisobutylene succinic anhydride PIBSA-1000 was added. The feeding time was controlled to be 1 h. After the feeding was completed, the mixture was kept warm for 3 h, and then the temperature was raised to 160 ° C at a rate of 10 ° C / h. Nitrogen was introduced into the system, and water was removed by gas stripping for 6 h. The mono-hanging fatty amine type polyisobutylene succinimide B1 was obtained after cooling.

[0069] Preparation Example 5

[0070] Under stirring conditions, 11.6 g of polyethylene polyamine (E100) and 190 g of base oil 100SN were mixed at 110°C, and then 115 g of polyisobutylene succinic anhydride PIBSA-2300 was added. The addition time was controlled to be 1 h. After the addition was completed, the mixture was kept warm for 2 h, and then the temperature was raised to 150°C at a rate of 8°C / h. Nitrogen was introduced into the system, and water was removed by gas stripping for 4 h. The mono-hanging fatty amine type polyisobutylene succinimide B2 was obtained after cooling.

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

[0072] Preparation Example 6

[0073] Under stirring conditions, 60g of polyether diamine ( ED-600) and 160g base oil Y4 were mixed at 110°C, and then 100g polyisobutylene succinic anhydride PIBSA-1300 was added, and the feeding time was controlled to be 30min. After the feeding was completed, the reaction was carried out at 120°C for 3h, and then the temperature was raised to 160°C. Nitrogen was introduced into the system, and water was removed by gas stripping for 6h. The mono-hedral polyetheramine type polyisobutylene succinimide C1 was obtained by cooling.

[0074] Preparation Example 7

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

[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 cross-linking agent A1 containing multiple reaction sites of Preparation Example 1, 492.8 g of the single-hanging fatty amine type polyisobutylene succinimide B1 of Preparation Example 4, 581.8 g of the single-hanging polyether amine type polyisobutylene succinimide C1 of Preparation Example 6 and 36 g of polyformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 7°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 4 hours. After cooling to 130°C, filtration was performed using a diatomaceous earth filter aid to obtain an ash-free dispersant SSL1.

[0079] Example 2

[0080] Under stirring conditions, 46.6 g of the multifunctional polar cross-linking agent A1 containing multiple reaction sites of Preparation Example 1, 492.8 g of the single-hanging fatty amine type polyisobutylene succinimide B1 of Preparation Example 4, 1300 g of the single-hanging polyether amine type polyisobutylene succinimide C2 of Preparation Example 7 and 36 g of polyformaldehyde were mixed. After 2 hours, the temperature was raised to 110°C at a rate of 10°C / h. After 4 hours, the temperature was raised to 160°C, nitrogen was introduced into the system, and water was removed by air stripping for 6 hours. After cooling to 145°C, filtration was performed using diatomaceous earth filter aid to obtain ash-free dispersant SSL2.

[0081] Example 3

[0082] Under stirring conditions, 46.6 g of the multifunctional polar cross-linking agent A1 containing multiple reaction sites of Preparation Example 1, 1266 g of the single-hanging fatty amine type polyisobutylene succinimide B2 of Preparation Example 5, 581.8 g of the single-hanging polyether amine type polyisobutylene succinimide C1 of Preparation Example 6 and 36 g of polyformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 10°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 5 hours. After cooling to 130°C, filtration was performed using a diatomaceous earth filter aid to obtain an ash-free dispersant SSL3.

[0083] Example 4

[0084] Under stirring conditions, 46.6 g of the multifunctional polar cross-linking agent A1 containing multiple reaction sites of Preparation Example 1, 1266 g of the single-hanging fatty amine type polyisobutylene succinimide B2 of Preparation Example 5, 1300 g of the single-hanging polyether amine type polyisobutylene succinimide C2 of Preparation Example 7 and 36 g of polyformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 10°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 5 hours. After cooling to 130°C, filtration was performed using diatomaceous earth filter aid to obtain ash-free dispersant SSL4.

[0085] Example 5

[0086] Under stirring conditions, 46.8 g of the multifunctional polar cross-linking agent A2 containing multiple reaction sites of Preparation Example 2, 492.8 g of the single-hanging fatty amine type polyisobutylene succinimide B1 of Preparation Example 4, 581.8 g of the single-hanging polyether amine type polyisobutylene succinimide C1 of Preparation Example 6 and 36 g of polyformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 10°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 5 hours. After cooling to 130°C, filtration was performed using a diatomaceous earth filter aid to obtain an ash-free dispersant SSL5.

[0087] Example 6

[0088] Under stirring conditions, 46.8 g of the multifunctional polar cross-linking agent A2 containing multiple reaction sites of Preparation Example 2, 492.8 g of the single-hanging fatty amine type polyisobutylene succinimide B1 of Preparation Example 4, 1300 g of the single-hanging polyether amine type polyisobutylene succinimide C2 of Preparation Example 7 and 36 g of polyformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 10°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 5 hours. After cooling to 130°C, filtration was performed using diatomaceous earth filter aid to obtain ash-free dispersant SSL6.

[0089] Example 7

[0090] Under stirring conditions, 46.8 g of the multifunctional polar cross-linking agent A2 containing multiple reaction sites of Preparation Example 2, 1266 g of the single-hanging fatty amine type polyisobutylene succinimide B2 of Preparation Example 5, 581.8 g of the single-hanging polyether amine type polyisobutylene succinimide C1 of Preparation Example 6 and 36 g of polyformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 10°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 5 hours. After cooling to 130°C, filtration was performed using diatomaceous earth filter aid to obtain ash-free dispersant SSL7.

[0091] Example 8

[0092] Under stirring conditions, 46.8 g of the multifunctional polar cross-linking agent A2 containing multiple reaction sites of Preparation Example 2, 1266 g of the single-hanging fatty amine type polyisobutylene succinimide B2 of Preparation Example 5, 1300 g of the single-hanging polyether amine type polyisobutylene succinimide C2 of Preparation Example 7 and 36 g of polyformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 10°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 5 hours. After cooling to 130°C, filtration was performed using diatomaceous earth filter aid to obtain ash-free dispersant SSL8.

[0093] Example 9

[0094] Under stirring conditions, 51.6 g of the multifunctional polar cross-linking agent A3 containing multiple reaction sites of Preparation Example 3, 492.8 g of the single-hanging fatty amine type polyisobutylene succinimide B1 of Preparation Example 4, 581.8 g of the single-hanging polyether amine type polyisobutylene succinimide C1 of Preparation Example 6 and 36 g of polyformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 10°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 5 hours. After cooling to 130°C, filtration was performed using diatomaceous earth filter aid to obtain ash-free dispersant SSL9.

[0095] Example 10

[0096] Under stirring conditions, 51.6 g of the multifunctional polar cross-linking agent A3 containing multiple reaction sites of Preparation Example 3, 492.8 g of the single-hanging fatty amine type polyisobutylene succinimide B1 of Preparation Example 4, 1300 g of the single-hanging polyether amine type polyisobutylene succinimide C2 of Preparation Example 7 and 36 g of polyformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 10°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 5 hours. After cooling to 130°C, filtration was performed using diatomaceous earth filter aid to obtain ash-free dispersant SSL10.

[0097] Embodiment 11

[0098] Under stirring conditions, 51.6 g of the multifunctional polar cross-linking agent A3 containing multiple reaction sites of Preparation Example 3, 1266 g of the single-hanging fatty amine type polyisobutylene succinimide B2 of Preparation Example 5, 581.8 g of the single-hanging polyether amine type polyisobutylene succinimide C1 of Preparation Example 6 and 36 g of polyformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 10°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 5 hours. After cooling to 130°C, filtration was performed using diatomaceous earth filter aid to obtain ash-free dispersant SSL11.

[0099] Example 12

[0100] Under stirring conditions, 51.6 g of the multifunctional polar cross-linking agent A3 containing multiple reaction sites of Preparation Example 3, 1266 g of the single-hanging fatty amine type polyisobutylene succinimide B2 of Preparation Example 5, 1300 g of the single-hanging polyether amine type polyisobutylene succinimide C2 of Preparation Example 7 and 36 g of polyformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 10°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 5 hours. After cooling to 130°C, filtration was performed using diatomaceous earth filter aid to obtain ash-free dispersant SSL12.

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

[0102] Comparative Example 1

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

[0104] Comparative Example 2

[0105] The ashless dispersant DBL2 prepared in this comparative example is different from that in Example 12 in that it does not contain the mono-heptyl polyetheramine type polyisobutylene succinimide C2 of Preparation Example 7.

[0106] Comparative Example 3

[0107] The difference from Example 1 is that in the multifunctional polar cross-linking agent A1 containing multiple reaction sites, the aromatic amine compound is not treated with a phenolic group. The specific steps are as follows:

[0108] Under stirring conditions, 19.8 g of 4,4'-diaminodiphenylmethane, 246.4 g of the single-hanging fatty amine type polyisobutylene succinimide B1 of Preparation Example 4, 290.9 g of the single-hanging polyether amine type polyisobutylene succinimide C1 of Preparation Example 6 and 18 g of polyformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 7°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 4 hours. After cooling to 130°C, diatomaceous earth filter aid was used for filtration to obtain ashless dispersant DBL3.

[0109] Comparative Example 4

[0110] The difference from Example 1 is that in the multifunctional polar cross-linking agent A1 containing multiple reaction sites, 4-aminodiphenylamine is used instead of 4,4'-diaminodiphenylmethane. The specific steps are as follows:

[0111] Under stirring conditions, 36.8 g of 4-aminodiphenylamine, 246.4 g of the single-hanging fatty amine type polyisobutylene succinimide B1 of Preparation Example 4, 290.9 g of the single-hanging polyether amine type polyisobutylene succinimide C1 of Preparation Example 6 and 18 g of paraformaldehyde were mixed. After 1 hour, the temperature was raised to 110°C at a rate of 7°C / h. After 3 hours, the temperature was raised to 150°C, nitrogen was introduced into the system, and water was removed by air stripping for 4 hours. After cooling to 130°C, filtration was performed using diatomaceous earth filter aid to obtain ashless dispersant DBL4.

[0112] In addition, a commercially available ashless dispersant T161 and an aromatic amine type ashless dispersant prepared in Examples 1 and 2 disclosed in US Pat. No. 8,557,753 were selected as Comparative Examples 5 and 6 of the present invention, respectively.

[0113] The following performance tests were performed on the various properties of the ashless dispersants prepared in Examples 1 to 12 and Comparative Examples 1 to 6.

[0114] Test 1: Physical and chemical performance analysis, the data results are shown in Table 1 below.

[0115] Table 1 Physical and chemical properties data results

[0116]

[0117]

[0118] Through the physicochemical property data results in Table 1, combined with Examples 1 to 12 and Comparative Examples 1 to 6, the inventors believe that: because the present invention uses an aromatic amine compound having at least two primary amine groups (-NH2) and no secondary amine group (-NH-) as the core polar point, the phenolic compound containing a carboxyl group is grafted onto the aromatic amine through an amide reaction, providing multiple reaction sites for the next Mannich reaction, so the prepared ashless dispersant has a higher molecular weight. However, the use of aromatic amines that have not been treated with phenolic groups lacks reaction sites, resulting in less grafted single-hanging polyisobutylene succinimide containing fatty amines and polyether amines, and the corresponding molecular weight is also smaller.

[0119] Test 2 Evaluation of low temperature sludge dispersibility

[0120] According to Appendix A of SH / T 0623-1995 "Bis-succinimide Dispersants": Low-temperature dispersibility evaluation method for ashless dispersants, the specific steps are as follows:

[0121] 0.5g ashless dispersant, 5g base oil Y4 and 4.5g oil sludge were added to a 50ml beaker, stirred at 150℃ for 1.5 hours, a drop of the test oil was dropped on filter paper while hot, and placed in an oven at 80℃ for 2 hours, and the ratio of the oil sludge diffusion circle to the oil circle was measured to obtain the spot test data;

[0122] Among them: the higher the spot dispersion value, the better the dispersion of the low-temperature sludge.

[0123] Test 3 Antioxidant Evaluation

[0124] 6.3% ashless dispersant was added to base oil Y4, and the antioxidant performance was evaluated according to the rotating oxygen bomb test (RPVOT) method of SH / T0193-1992; the high temperature antioxidant performance was evaluated according to the high pressure differential scanning calorimetry (PDSC) method of SH / T 0719;

[0125] Among them: the longer the RPVOT time, the higher the PDSC initial oxidation temperature, which means that the dispersant has better resistance to high-temperature oxidation.

[0126] Test 4 High temperature cleanliness

[0127] According to the relevant standards in SH / T 0300-1992 "Crankcase Simulation Test Method", the coking plate test is carried out. The specific steps are as follows:

[0128] Add 3% ash-free dispersant by mass to base oil Y4 to prepare 300ml test oil. Set the parameters of the coke plate tester to: plate temperature of 310℃, oil temperature of 100℃, and observe the formation of paint film after continuous oil splashing for 2h. This method is to make the internal combustion engine oil containing additives splash onto the high-temperature metal surface to form a paint film, so as to simulate the amount of paint formed when the crankcase is working with the piston, and to examine the high-temperature cleaning performance of the oil by measuring the weight of coke on the metal plate.

[0129] The results of Tests 2 to 4 are recorded in Table 2 below.

[0130] Table 2 Performance evaluation results

[0131]

[0132]

[0133] Through the physical and chemical performance data results in Table 2, combined with Examples 1 to 12 and Comparative Examples 1 to 6, we can find that: in Examples 10 and 12, the mono-hanging fatty amine type polyisobutylene succinimide and the mono-hanging polyether amine type polyisobutylene succinimide are simultaneously introduced into the prepared ashless dispersant, and its dispersibility, oxidation resistance and high-temperature detergency are all higher than the ashless dispersant prepared by introducing the mono-hanging fatty amine type polyisobutylene succinimide (Comparative Example 1) and the mono-hanging polyether amine type polyisobutylene succinimide (Comparative Example 2) respectively. In addition, the aromatic amine having at least two primary amine groups (-NH2) and no secondary amine group (-NH-) in the molecular formula, after being treated with phenolic groups, such as the dispersant prepared in Example 1, its dispersibility, oxidation resistance and high-temperature detergency are all better than the dispersant not treated with phenolic groups (such as: Comparative Example 3) and the dispersant with monoamine aromatic amine and not treated with phenolic groups (such as: Comparative Example 4).

[0134] In summary, the inventors believe that the ashless dispersant prepared by the present invention has excellent dispersibility, antioxidant properties and high-temperature detergency because three functional groups are simultaneously introduced into the polar end of the present invention: aromatic amine group, phenolic group and polyether group. Therefore, the inventors believe that the compound use of the above three groups has a better synergistic effect.

[0135] Test 5 Storage stability test

[0136] The test method comprises the following steps:

[0137] 4.8% ashless dispersant by mass was blended into API CI-4 oil. After being stored for a period of time under sunlight, the chromaticity was regularly measured using the GB / T 6540 petroleum product color determination method. The results are shown in Table 3 below.

[0138] Table 3 Oil chromaticity changes

[0139]

[0140]

[0141] By comparing the embodiments of the present invention and the comparative examples, the inventors found that the ashless dispersant embodiments 1 to 12, which are prepared by using aromatic amine compounds having at least two primary amine groups (-NH2) in their molecular formula and no secondary amine group (-NH-), solve the problem in the prior art that the ashless dispersant prepared by using 4-aminodiphenylamine, such as comparative examples 4 and 6, causes discoloration of the lubricating oil and affects its storage stability. The ashless dispersant prepared by the present invention has excellent storage stability after being added to the oil product.

[0142] In summary, the present invention selects aromatic amine compounds containing at least two primary amine groups (-NH2) and no secondary amine groups (-NH-) in the molecular formula as the core polar point, and grafts the phenolic compounds containing carboxyl groups onto the aromatic amines through an amide reaction, thereby providing multiple reaction sites for the next Mannich reaction. The prepared ashless dispersant has a higher molecular weight and improves its dispersibility in oil products. On the other hand, aromatic amine groups, phenolic groups and polyether groups are introduced into the polar end of the dispersant, so that it has excellent dispersibility, antioxidant properties and high-temperature detergency.

[0143] The above are only preferred feasible embodiments of the present invention, and the protection scope of the present invention is not limited thereto. Various modifications or applications made according to the above embodiments are within the protection scope of this technical solution.

[0144] Although the specific embodiments of the present invention have been described in detail, it will be understood by those skilled in the art. According to all the teachings disclosed, various modifications and replacements can be made to those details, and these changes are all within the protection scope of the present invention. The full scope of the present invention is given by the attached claims and any equivalents thereof.

Claims

1. Ashless dispersant, characterized in that The ashless dispersant is shown in formula (I): 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 mono-hanging fatty amine type polyisobutylene succinimide B and / or mono-hanging polyether amine type polyisobutylene succinimide C.

2. The ashless dispersant according to claim 1, characterized in that The mono-hanging fatty amine type polyisobutylene succinimide B is as shown in formula (II): In formula (II), the value range of n is 1≤n≤8, and n is an integer.

3. The ashless dispersant according to claim 1, characterized in that The mono-hedral polyetheramine type polyisobutylene succinimide C is as shown in formula (III): In formula (III), the value range of x and z is 1≤(x+z)≤4, and x and z are both integers; the value range of y is 1≤y≤9, and y is an integer.

4. A method for preparing the ashless dispersant according to any one of claims 1 to 3, characterized in that: The friction-modifying dispersant is a compound prepared by a Mannich reaction of a multifunctional polar crosslinking agent A containing multiple reaction sites, the monohedral fatty amine type polyisobutylene succinimide B and / or the monohedral polyether amine type polyisobutylene succinimide C, and a polyformaldehyde compound D.

5. The method for preparing the ashless dispersant according to claim 4, characterized in that: The friction-modifying dispersant is a compound prepared by a Mannich reaction of a multifunctional polar crosslinking agent A containing multiple reaction sites, the mono-hanging fatty amine type polyisobutylene succinimide B, the mono-hanging polyether amine type polyisobutylene succinimide C and a polyformaldehyde compound D; The molar ratio of the multifunctional polar crosslinking agent A containing multiple reaction sites, the mono-hanging fatty amine type polyisobutylene succinimide B, the mono-hanging polyether amine type polyisobutylene succinimide C and the polyformaldehyde compound D is 1:(1-4):(1-4):(3.5-4.2).

6. The method for preparing the ashless dispersant according to claim 5, characterized in that: The preparation method comprises the following steps: Under stirring conditions, the multifunctional polar crosslinking agent A containing multiple reaction sites, the monohedral fatty amine type polyisobutylene succinimide B, the monohedral polyether amine type polyisobutylene succinimide C and the polyformaldehyde compound D are heated and mixed according to the molar ratio, and then water is removed, the temperature is reduced and filtered to obtain a dispersant.

7. The method for preparing the ashless dispersant according to claim 5, characterized in that: The multifunctional polar cross-linking agent A containing multiple reaction sites is as shown in formula (IV): In formula (IV), R is -CH2-, -O- or -SO2-; R1 is -CH2-, -CH2CH2-, -CH(CH3)- or -CH(OH)-.

8. The method for preparing the ashless dispersant according to claim 7, characterized in that: The preparation of the multifunctional polar cross-linking agent A containing multiple reaction sites comprises the following steps: The aromatic amine compound, the carboxyl-containing phenolic compound and the organic solvent are heated and mixed under stirring, refluxed under the protection of an inert gas, filtered, and distilled under reduced pressure to obtain the multifunctional polar crosslinking agent A containing multiple reaction sites.

9. The method for preparing the ashless dispersant according to claim 8, characterized in that: The molar ratio of the aromatic amine compound to the carboxyl-containing phenol compound is 1:(1.8-2.3).

10. The method for preparing an ashless dispersant according to claim 9, characterized in that: The aromatic amine compound is shown in formula (V): In formula (V), R is -CH2-, -O- or -SO2-.

11. The method for preparing an ashless dispersant according to claim 9, characterized in that: 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-hydroxyphenylethanic acid, 2-(p-hydroxyphenylazo)benzoic acid or 2-amino-5-hydroxybenzoic acid.

12. The method for preparing an ashless dispersant according to claim 6, characterized in that: The preparation of the monohedral fatty amine type polyisobutylene succinimide B comprises the following steps: Under stirring conditions, the polyethylene polyamine compound and the base oil are heated and mixed, and then polyisobutylene succinic anhydride is added, the temperature is raised for reaction, water is removed, and the mono-hanging fatty amine type polyisobutylene succinimide B is obtained by cooling.

13. The method for preparing an ashless dispersant according to claim 12, characterized in that: The molar ratio of the polyisobutylene succinic anhydride to the polyethylene polyamine compound is 1:(0.8-1).

14. The method for preparing an ashless dispersant according to claim 13, characterized in that: The number average molecular weight of the polyisobutylene succinic anhydride is 900-5000.

15. The method for preparing an ashless dispersant according to claim 12, characterized in that: The polyethylene polyamine compound is selected from one or more of diethylene triamine, triethylene tetraamine, tetraethylene pentamine, pentaethylene hexamine or heavy polyamine.

16. The method for preparing an ashless dispersant according to claim 12, characterized in that: The mass fraction of the base oil in the mono-hydroxylated fatty amine type polyisobutylene succinimide B is 50-65%.

17. The method for preparing an ashless dispersant according to claim 6, characterized in that: The preparation of the mono-hung polyetheramine type polyisobutylene succinimide C comprises the following steps: Under stirring conditions, the polyetheramine compound and the base oil are heated and mixed, and then polyisobutylene succinic anhydride is added, the temperature is raised for reaction, water is removed, and the mono-hanging polyetheramine type polyisobutylene succinimide C is obtained by cooling.

18. The method for preparing an ashless dispersant according to claim 17, characterized in that: The molar ratio of the polyisobutylene succinic anhydride to the polyetheramine compound is 1:(0.75-1).

19. The method for preparing an ashless dispersant according to claim 17, characterized in that: The mass fraction of the base oil in the mono-pendicular polyetheramine type polyisobutylene succinimide C is 45-55%.

20. Use of the ashless dispersant prepared by the method according to any one of claims 4 to 19 in the preparation of lubricating oil.

21. Lubricating oil, characterized in that The lubricating oil contains the ashless dispersant prepared by the method according to any one of claims 4 to 20.

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