Polymer soot dispersant

Abstract

A high molecular weight polymer dispersant composition is described. The dispersant has a generalized structure. [Formula 1] TIFF2026522379000026.tif1031 It is represented by the formula, where A is an olefin copolymer, B is an alkylimide or alkylamide, C is a polyamine, alkylamine, alkyl etheramine or alkylhydroxylamine, D is 1-(arene-2-yloxy)propan-2-ol, and n is 1 to 15.

Description

[Technical Field]

[0001] This disclosure relates to lubricating additives and lubricating oil compositions containing such additives. More specifically, this disclosure relates to polymer dispersants that, when used as lubricating additives, can improve wear and / or soot dispersibility. [Background technology]

[0002] Internal combustion engines can produce soot as a result of incomplete combustion. Soot formation is generally more widespread in diesel engines compared to gasoline engines due to differences in fuel injection and ignition methods. Soot accumulation can lead to many problems, such as increased engine failure due to engine wear. Therefore, improving the dispersibility of suspended soot or suspended sludge that forms during the action or use of lubricating oil in the engine is crucial for maintaining engine operation. [Overview of the Initiative]

[0003] In one embodiment, the present disclosure relates to a high molecular weight polymer dispersant composition, wherein the polymer dispersant is represented by the following generalized structure: [ka] In the formula, A is an olefin copolymer, B is an alkylimide or alkylamide, C is a polyamine, alkylamine, alkyl etheramine or alkylhydroxylamine, D is 1-(arene-2-yloxy)propan-2-ol, and n is 1 to 15.

[0004] In another aspect, the present disclosure relates to a lubricating oil composition comprising a base oil of lubricating viscosity as the main component and a high molecular weight polymer dispersant represented by the following generalized structure: [ka] In the formula, A is an olefin copolymer, B is an alkylimide or alkylamide, C is a polyamine, alkylamine, etheramine or hydroxylamine, D is 1-(arene-2-yloxy)propan-2-ol, and n is 1 to 15.

[0005] In yet another aspect, the present disclosure relates to a method for improving wear or soot dispersibility of an internal combustion engine, the method comprising lubricating the engine with a lubricating oil composition comprising a base oil of lubricating viscosity as the main component and a high molecular weight polymer dispersant represented by the following generalized structure, [ka] In the formula, A is an olefin copolymer, B is an alkylimide or alkylamide, C is a polyamine, alkylamine, etheramine or hydroxylamine, D is 1-(arene-2-yloxy)propan-2-ol, and n is 1 to 15. [Modes for carrying out the invention]

[0006] definition The following terms are used throughout this specification and, unless otherwise indicated, have the following meanings:

[0007] The term “major amount” of base oil refers to an amount of base oil that is at least 40% by weight of the lubricating oil composition. In some embodiments, “major amount” of base oil refers to an amount of base oil that is more than 50% by weight, more than 60% by weight, more than 70% by weight, more than 80% by weight, or more than 90% by weight of the lubricating oil composition.

[0008] The term "Total Base Number" or "TBN" refers to the level of alkalinity in an oil sample, which indicates the ability of the composition to continue neutralizing corrosive acids according to ASTM standard No. D2896 or an equivalent procedure. This test measures the change in conductivity and expresses the result as mgKOH / g (the equivalent number of milligrams of KOH required to neutralize 1 gram of the product). Therefore, a high TBN reflects a strongly over-basidified product and, as a result, a greater surplus of base to neutralize the acid.

[0009] "HOB" refers to high overbasicity with a TBN of over 250 based on the active substance, while "LOB" refers to low overbasicity with a TBN of less than 100 based on the active substance.

[0010] In this disclosure, the term "hydrocarbon polymer" generally refers to a hydrocarbon polymer that is solid at ambient temperature and pressure. Furthermore, the solid hydrocarbon polymers used in the present invention are generally pelletizable. In some embodiments, the solid polymers of this disclosure have a KV100 greater than 3000 cSt and are chemically graftable. However, the KV100 of solid polymers can be difficult to measure.

[0011] explanation This disclosure relates to polymer dispersants and lubricating oil compositions containing such dispersants. The high molecular weight polymer dispersants of this disclosure can be used as lubricating additives to provide one or more performance benefits to lubricating oil compositions.

[0012] Polymer dispersant This polymer dispersant can be used as a lubricating additive to protect against wear and / or improve soot dispersibility in internal combustion engines.

[0013] In some embodiments, the high molecular weight polymer dispersant can be represented by the following generalized structure: [ka] Wherein, A is an olefin copolymer, B is independently an alkyl imide or an alkyl amide, C is independently a polyamine, an alkyl amine, an alkyl ether amine, or an alkyl hydroxyl amine, D is 1-(arene-2-yloxy)propan-2-ol, and n is from 1 to 15. In some preferred embodiments, n is from 3 to 12. The olefin copolymer has an average molecular weight (Mn) of about 5,000 to about 150,000.

[0014] The polymer dispersant of the present disclosure can be synthesized or obtained by any suitable means. One synthetic approach involves grafting a hydrocarbon polymer with an acylating grafting agent, functionalizing the grafted polymer with a nucleophilic compound (such as a polyamine), and post-treating with an epoxide (such as an aryl glycidyl ether). Another synthetic approach involves grafting a hydrocarbon polymer with a grafting agent of allylamine or vinylamine and post-treating with an epoxide (such as an aryl glycidyl ether).

[0015] According to the present disclosure, the polymer dispersant can be obtained by a series of reaction steps determined by the type of grafting agent used.

[0016] In one series of reactions, the polymer dispersant can be obtained by: i) grafting a hydrocarbon polymer with an acylating grafting agent, ii) functionalizing with a polyamine, and iii) post-treating with an aryl glycidyl ether.

[0017] In another series of reactions, the polymer dispersant can be obtained by: i) grafting a hydrocarbon polymer with a grafting agent of allylamine or vinylamine, and ii) post-treating with an aryl glycidyl ether.

[0018] Without being limited by theory, it is considered that the post-treatment step greatly improves the dispersant properties of the polymer dispersant.

[0019] Reaction products In some embodiments, the polymer dispersant has a number-average molecular weight (M n It is a reaction product of a hydrocarbon polymer with a iontophoresis ratio of approximately 5,000 to 150,000, an acylation grafting agent, a polyamine, and an aryl glycidyl ether.

[0020] In some embodiments, the polymer dispersant has a number-average molecular weight (M n It is a reaction product of a hydrocarbon polymer with a ratio of approximately 5,000 to 150,000, an allylamine or vinylamine grafting agent, and an arylglycidyl ether.

[0021] The manganese (Mn) in the hydrocarbon polymer can be measured by any suitable method, such as gel permeation chromatography.

[0022] Arylglycidyl ether is added as a work-up step. During the series of reaction steps that yield the reaction product (i.e., the low molecular weight polymer dispersant), the arylglycidyl ether is added during the final reaction step.

[0023] number average molecular weight The number-average molecular weight (Mn) of hydrocarbon polymers is approximately 5,000 to 150,000, 5,000 to 140,000, 5,000 to 130,000, 5,000 to 120,000, 5,000 to 110,000, 5,000 to 100,000, 5,000 to 90,000, 5,000 to 80,000, 5,000 to 70,000, 5,000 to 60,000, 5,000 to 50,000, 5,000 to 40,000, 5,000 to 30,000, 5,000 to 20,000, and 5,000 to 10,000. 0, approximately 5,000 to approximately 8,000, approximately 8,000 to approximately 150,000, approximately 8,000 to approximately 140,000, approximately 8,000 to approximately 130,000, approximately 8,000 to approximately 120,000, for example, approximately 8,000 to approximately 110,000, approximately 8,000 to approximately 100,000, approximately 8,000 to approximately 9 0,000, approximately 8,000-70,000, approximately 8,000-60,000, approximately 8,000-50,000, approximately 8,000-40,000, approximately 8,000-30,000, approximately 8,000-20,000, approximately 8,000-10,000, approximately 8,000-9,000 Approximately 9,000 to 150,000, approximately 9,000 to 140,000, approximately 9,000 to 130,000, approximately 9,000 to 120,000, approximately 9,000 to 110,000, approximately 9,000 to 100,000, approximately 9,000 to 90,000, approximately 9,000 to 80,000 00, approximately 9,000-70,000, approximately 9,000-60,000, approximately 9,000-50,000, approximately 9,000-40,000, approximately 9,000-30,000, approximately 9,000-20,000, approximately 9,000-10,000, approximately 10,000-150,000, Approximately 10,000 to 140,000, approximately 10,000 to 130,000, approximately 10,000 to 120,000, approximately 10,000 to 110,000, approximately 10,000 to 100,000, approximately 10,000 to 90,000, approximately 10,000 to 80,000, approximately 10,000 to Approximately 70,000, approximately 10,000-60,000, approximately 10,000-50,000, approximately 10,000-40,000, approximately 10,000-30,000, approximately 10,000-20,000, approximately 12,000-150,000, approximately 12,000-140,000, approximately 12,000~approx. 130,000, approx. 12,000~approx. 120,000, approx. 12,000~approx. 110,000, approx. 12,000~approx. 100,000, approx. 12,000~approx. 90,000, approx. 12,000~approx. 80,000, approx. 12,000~approx. 70,000, approx. 12,000~approx. 60, 000, approximately 12,000-50,000, approximately 12,000-40,000, approximately 12,000-30,000, 12,000-20,000, approximately 15,000-150,000, approximately 15,000-140,000, approximately 15,000-130,000, approximately 15,000 0 to approximately 120,000, approximately 15,000 to approximately 110,000, approximately 15,000 to approximately 100,000, approximately 15,000 to approximately 90,000, approximately 15,000 to approximately 80,000, approximately 15,000 to approximately 70,000, approximately 15,000 to approximately 60,000, approximately 15,000 to approximately 50,000 Approximately 15,000 to 40,000, approximately 15,000 to 30,000, approximately 15,000 to 20,000, approximately 16,001 to 150,000, approximately 16,001 to 140,000, approximately 16,001 to 130,000, approximately 16,001 to 120,000, approximately 16,001 to Approximately 110,000, approximately 16,001 to approximately 100,000, approximately 16,001 to approximately 90,000, approximately 16,001 to approximately 80,000, approximately 16,001 to approximately 70,000, approximately 16,001 to approximately 60,000, approximately 16,001 to approximately 50,000, approximately 16,001 to approximately 40,000, approximately 1 6,001 to approximately 30,000, approximately 16,001 to approximately 20,000, approximately 20,000 to approximately 150,000, approximately 20,000 to approximately 140,000, approximately 20,000 to approximately 130,000, approximately 20,000 to approximately 120,000, approximately 20,000 to approximately 110,000, approximately 20,000 to approximately 100,000, approximately 20,000-90,000, approximately 20,000-80,000, approximately 20,000-70,000, 20,000-60,000, approximately 20,000-50,000, approximately 20,000-40,000, approximately 20,000-30,000, approximately 30,000 00~approx. 150,000, approx. 30,000~approx. 140,000, approx. 30,000~approx. 130,000, approx. 30,000~approx. 120,000, approx. 30,000~approx. 110,000, approx. 30,000~approx. 100,000, approx. 30,000~approx. 90,000, approx. 30,000~approx. 80,000, approximately 30,000~approximately 70,000, approximately 30,000~approximately 60,000, approximately 30,000~approximately 50,000, approximately 30,000~approximately 40,000, approximately 40,000~approximately 150,000, approximately 40,000~approximately 140,000, approximately 40,000~approximately 130,000, approximately 40,0 00~approx. 120,000, approx. 40,000~approx. 110,000, approx. 40,000~approx. 100,000, approx. 40,000~approx. 90,000, approx. 40,000~approx. 80,000, approx. 40,000~approx. 70,000, approx. 40,000~approx. 60,000, approx. 40,000~approx. 50,000 Approximately 50,000 to 150,000, approximately 50,000 to 140,000, approximately 50,000 to 130,000, approximately 50,000 to 120,000, approximately 50,000 to 110,000, approximately 50,000 to 100,000, approximately 50,000 to 90,000, approximately 50,0 00~approx. 80,000, approx. 50,000~approx. 70,000, approx. 50,000~approx. 60,000, approx. 60,000~approx. 150,000, approx. 60,000~approx. 140,000, approx. 60,000~approx. 130,000, approx. 60,000~approx. 120,000, approx. 60,000~approx. 110,000 00, approximately 60,000 to approximately 100,000, approximately 60,000 to approximately 90,000, approximately 60,000 to approximately 80,000, approximately 60,000 to approximately 70,000, approximately 70,000 to approximately 150,000, approximately 70,000 to approximately 140,000, approximately 70,000 to approximately 130,000, approximately 70,0 00~approx. 120,000, approx. 70,000~approx. 110,000, approx. 70,000~approx. 100,000, approx. 70,000~approx. 90,000, approx. 70,000~approx. 80,000, approx. 80,000~approx. 150,000, approx. 80,000~approx. 140,000, approx. 80,000~approx. 130, 000, approximately 80,000-120,000, approximately 80,000-110,000, approximately 80,000-100,000, approximately 80,000-90,000, approximately 90,000-150,000, approximately 90,000-140,000, approximately 90,000-130,000, approximately 9 0,000~approx. 120,000, approx. 90,000~approx. 110,000, approx. 90,000~approx. 100,000, approx. 100,000~approx. 150,000, approx. 100,000~approx. 140,000, approx. 100,000~approx. 130,000, approx. 100,000~approx. 120,000, approx. 100,The ranges are approximately 000 to 110,000, approximately 110,000 to 150,000, approximately 110,000 to 140,000, approximately 110,000 to 130,000, approximately 110,000 to 120,000, approximately 120,000 to 150,000, approximately 120,000 to 140,000, approximately 120,000 to 130,000, approximately 130,000 to 150,000, approximately 130,000 to 140,000, or approximately 140,000 to 150,000.

[0024] Hydrocarbon polymers Suitable examples of hydrocarbon polymers include, but are not limited to, ethylene-olefin copolymers such as ethylene-propylene copolymers. Copolymers as used herein may include blends or reaction products of ethylene with one or more C3-C28α-olefins, and in addition, any other dienes or polyenes, and therefore may also include terpolymers and other higher forms thereof.

[0025] In some embodiments, the ethylene content of the copolymer is 10-80 percent by weight, for example, 10-75 percent, 10-70 percent, 10-65 percent, 10-60 percent, 10-50 percent, 10-45 percent, 10-40 percent, 10-35 percent, 10-30 percent, 10-25 percent, 10-20 percent, 10-15 percent, 15-80 percent, 15-75 percent, 15-70 percent, 15-65 percent, 15-60 percent, 15-55 percent, 15-5 percent. 0 percent, 15-45 percent, 15-40 percent, 15-35 percent, 15-30 percent, 15-25 percent, 15-20 percent, 20-80 percent, 20-75 percent, 20-70 percent, 20-65 percent, 20-60 percent, 20-55 percent, 20-50 percent, 20-45 percent, 20-40 percent, 20-35 percent, 20-30 percent, 20-25 percent, 25-80 percent, 25-75 percent, 25-70 percent, 25-65 percent 25-60 percent, 25-55 percent, 25-50 percent, 25-45 percent, 25-40 percent, 25-35 percent, 25-30 percent, 30-80 percent, 30-75 percent, 30-70 percent, 30-65 percent, 30-60 percent, 30-55 percent, 30-50 percent, 30-45 percent, 30-40 percent, 30-35 percent, 35-80 percent, 35-75 percent, 35-70 percent, 35-65 percent, 35-60 percent, 35-55 percent Percentage, 35-50 percent, 35-45 percent, 35-40 percent, 40-80 percent, 40-75 percent, 40-70 percent, 40-65 percent, 40-60 percent, 40-55 percent, 40-50 percent, 40-45 percent, 45-80 percent, 45-75 percent, 45-70 percent, 45-65 percent, 45-60 percent, 45-55 percent, 45-50 percent, 50-80 percent, 50-75 percent, 50-70 percent, 50-65 percent,The range is 50-60 percent, 50-55 percent, 55-80 percent, 55-75 percent, 55-70 percent, 55-65 percent, 55-60 percent, 60-80 percent, 60-75 percent, 60-70 percent, 60-65 percent, 65-80 percent, 65-75 percent, 65-70 percent, 70-80 percent, 70-75 percent, or 75-80 percent.

[0026] In some embodiments, the ethylene copolymer is an ethylene-propylene copolymer. The propylene content of the ethylene-propylene copolymer is 20-90 percent by weight, for example, 20-85 percent, 20-80 percent, 20-75 percent, 20-70 percent, 20-65 percent, 20-60 percent, 20-50 percent, 20-45 percent, 20-40 percent, 20-35 percent, 20-30 percent, 20-25 percent, 25-90 percent, 25-85 percent, 25-80 percent, 25-75 percent, 25-70 percent, 25-6 percent. 5 percent, 25-60 percent, 25-55 percent, 25-50 percent, 25-45 percent, 25-40 percent, 25-35 percent, 25-30 percent, 30-90 percent, 30-85 percent, 30-80 percent, 30-75 percent, 30-70 percent, 30-65 percent, 30-60 percent, 30-55 percent, 30-50 percent, 30-45 percent, 30-40 percent, 30-35 percent, 35-90 percent, 35-85 percent 35-80 percent, 35-75 percent, 35-70 percent, 35-65 percent, 35-60 percent, 35-55 percent, 35-50 percent, 35-45 percent, 35-40 percent, 40-90 percent, 40-85 percent, 40-80 percent, 40-75 percent, 40-70 percent, 40-65 percent, 40-60 percent, 40-55 percent, 40-50 percent, 40-45 percent, 45-90 percent, 45-85 percent, 45-80 percent Percentage, 45-75 percent, 45-70 percent, 45-65 percent, 45-60 percent, 45-55 percent, 45-50 percent, 50-90 percent, 50-85 percent, 50-80 percent, 50-75 percent, 50-70 percent, 50-65 percent, 50-60 percent, 50-55 percent, 55-90 percent, 55-85 percent, 55-80 percent, 55-75 percent, 55-70 percent, 55-65 percent, 55-60 percent,The range is 60-90 percent, 60-85 percent, 60-80 percent, 60-75 percent, 60-70 percent, 60-65 percent, 65-90 percent, 65-85 percent, 65-80 percent, 65-75 percent, 65-70 percent, 70-90 percent, 70-85 percent, 70-80 percent, 70-75 percent, 75-90 percent, 75-85 percent, 75-80 percent, 80-90 percent, 80-85 percent, or 85-90 percent.

[0027] In some embodiments, the hydrocarbon polymer can be obtained as a solid hydrocarbon polymer in the form of a bale, powder, or pelletized polymer.

[0028] In some embodiments, the crushed polymer bale or other form of polymer is fed into an extruder, such as a single-screw or twin-screw extruder, or into a Banbury mixer or other mixer capable of heating the polymer substrate for a dewatering process and applying a desired level of mechanical action (agitation). A nitrogen blanket can be maintained in the feed section of the extruder to minimize the introduction of air.

[0029] The polymer is typically heated in a vented extruder or other mixer to remove moisture from the feed material before being mixed with other reactants. The dried polymer is then fed continuously into another extruder section or a separate extruder to carry out the graft reaction. A more detailed discussion of grafting techniques can be found in US9487731, which is incorporated herein by reference.

[0030] Free radical initiator The graft reaction of the present invention can be catalyzed by a free radical initiator. Examples of free radical initiators include peroxides, hydroperoxides, peresters, and azo compounds, preferably those with a boiling point higher than 100°C and that thermally decompose within the graft temperature range to produce free radicals. Typical examples of these free radical initiators include peroxides (dialkylperoxides), such as benzoyl peroxide, dialkylperoxides, such as 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,2-bis(tert-butylperoxy)butane, dicumyl peroxide, tert-butylcumyl peroxide, bis(tert-butylperoxyisopropyl)benzene, and di-tert-butylperoxide (DT Examples of initiators include BP, di-tert-amyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexine, hydroperoxides, peroxyesters, such as tert-butylperoxybenzoate, tert-butylperoxyacetate, O,O-tert-butyl-O-(2-ethylhexyl)monoperoxycarbonate, and peroxyketals, such as n-butyl4,4-di-(tert-butylperoxy)valerate. The initiator is typically used in an amount of about 0.005% to about 1% by weight relative to the weight of the reaction mixture solution.

[0031] The grafting is preferably carried out in an inert atmosphere, for example, under a nitrogen blanket. A more detailed discussion of free radical initiators can be found in the reprint of the original 1997 first edition of Reactive Modifiers for Polymers Softcover by S. Al-Malaika (ed.), the relevant parts of which are incorporated herein by reference.

[0032] Grafting agent Suitable grafting agents of this disclosure include i) acylation grafting agents (e.g., ethylenically unsaturated acylation agents), or ii) allylamine or vinylamine grafting agents (e.g., allylamine or vinylamine). The grafting agents of this disclosure generally feature two reaction sites. One reaction site allows the grafting agent to form a chemical bond with a high molecular weight hydrocarbon polymer. A second reaction site allows the grafting agent to form a chemical bond with a polyamine, in the case of an acylation grafting agent. When using allylamine or vinylamine grafting agents, the second reaction site can be used for post-treatment with arylglycidyl ethers.

[0033] Acylated graft In some embodiments, the acylation grafting agent is an ethylenically unsaturated acylation agent. In some embodiments, the ethylenically unsaturated acylation agent can be used to graft polymers. In some embodiments, the ethylenically unsaturated acylation agent is a carboxylic acid or a functional group derivative thereof (including esters and anhydrides). Examples of the carboxylic acid include acrylic acid, crotonic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, chloromaleic acid, aconitic acid, methylcrotonic acid, or sorbic acid. In some embodiments, the acylation agent is an ester of a carboxylic acid. In some embodiments, the acylation agent is an anhydride of a carboxylic acid.

[0034] The ethylenically unsaturated carboxylic acid or its functional group derivative is typically grafted onto the main chain of a hydrocarbon polymer at approximately 100°C to 250°C in the presence of a free radical initiator. In this regard, it is appropriate to functionalize the main chain of the hydrocarbon polymer with an acylation grafting agent in an amount ranging from 0.5 to 10.0% by weight relative to the total mass of the polymer.

[0035] Allylamine or vinylamine grafting agent In some embodiments, the grafting agent is an allylamine or vinylamine grafting agent. As described above, the allylamine or vinylamine grafting agent generally comprises a first reaction site, i.e., an allyl or vinyl group that can react with the polymer, and a second reaction site, i.e., an amine that can be post-treated with a post-treatment agent, such as a glycidyl ether.

[0036] Specific examples of suitable allylamine or vinylamine grafting agents include, for example, 1-ethenylpiperazine, 1-(propa-1-en-2-yl)piperazine, 1-allylpiperazine, N-allylmethylamine, allylcyclohexylamine, N-allylaniline, N,2-dimethyl-2-propen-1-amine, N-ethyl-2-methylallylamine, 1-(2-methylpropa-2-en-1-yl)piperazine, and N-vinylformamide. Specific examples of suitable allylamine or vinylamine grafting agents requiring a deprotection reaction before post-treatment with arylglycidyl ether include, for example, N-vinylacetamide, N-vinylbenzamide, and methylvinylcarbamate.

[0037] Radical initiation using acylated grafts A non-limiting example of a radical-initiated graft reaction using an acylation grafting agent (maleic anhydride) is shown below. [ka]

[0038] Functionalization with polyamines As previously suggested, polyamines can be used to functionalize acylated grafting agents during the synthesis of polymer dispersants. Functionalization allows for work-up with aryl glycidyl ethers. The following describes the functionalization of graft products with polyamines to form functionalized graft products. [ka]

[0039] Polyamines used in the synthesis of polymer dispersants can be represented by the following structure: [ka] In the formula, X is a C2-C10 hydrocarbyl group, an aminoalkyl group, an ether group, a thioether group, or an aromatic group, and Y is an amino C1-C 10 It is a hydrocarbyl group, an aminoalkylhydroxyl group, an aminoalkyl ether group, an aminoalkylthioether group, an aminoaromatic group, or a piperazine.

[0040] Non-specific examples of polyamines include the following: [ka]

[0041] Glycidyl ether The graft product (in the case of allylamine or vinylamine grafts) or the functionalized graft product (in the case of polyamine-functionalized acylated grafts) contains a second reaction site (amine nitrogen) that allows for work-treatment with glycidyl ether. Due to its reactivity, secondary nitrogen is generally preferred over primary or tertiary nitrogen.

[0042] Appropriate examples of arylglycidyl ethers include, but are not limited to, phenylglycidyl ether and naphthylglycidyl ether. [ka]

[0043] While not limited by theory, it is thought that post-treatment of the graft product or functionalized graft product can significantly enhance its soot-dispersing ability. For post-treatment(s), the presence of secondary nitrogen on the graft product or functionalized graft product is considered highly desirable compared to primary or tertiary nitrogen, due to the reactivity of secondary nitrogen.

[0044] Other additives Optionally, the lubricating oil compositions of the present invention may further contain additives that can impart or improve any of the desirable properties of the lubricating oil composition. Any additive known to those skilled in the art can be used in the lubricating oil compositions disclosed herein. Several suitable additives are described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition. London, Springer, (1996); and Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” New York, Marcel Dekker (2003), both of which are incorporated herein by reference. In some embodiments, the additives can be selected from the group consisting of antioxidants, anti-wear agents, detergents, rust inhibitors, anti-emulsifiers, friction modifiers, multi-functional additives, viscosity index improvers, pour point depressants, anti-foaming agents, metal deactivators, dispersants, corrosion inhibitors, lubricity improvers, thermal stability improvers, anti-fogging additives, anti-icing agents, dyes, markers, antistatic agents, biocides, and combinations thereof.

[0045] Generally, the concentration of each additive in the lubricating oil composition may be in the range of about 0.001% to about 10% by weight, about 0.01% to about 5% by weight, or about 0.1% to about 2.5% by weight relative to the total weight of the lubricating oil composition when used. Furthermore, the total amount of additives in the lubricating oil composition may be in the range of about 0.001% to about 20% by weight, about 0.01% to about 10% by weight, or about 0.1% to about 5% by weight, based on the total weight of the lubricating oil composition.

[0046] Cleansing agent The lubricating oil composition of the present invention may contain a metallic detergent, such as a metal salicylate, metal phenate, or metal sulfonate. The metal can be any metal suitable for the manufacture of the detergent. Non-limiting examples of suitable metals include alkali metals, alkaline earth metals, and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li, etc.

[0047] Generally, the amount of the cleaning agent is approximately 0.001% to 10% by weight, approximately 0.05% to 3% by weight, or approximately 0.1% to 1% by weight relative to the total weight of the lubricating oil composition.

[0048] Optionally, the lubricating oil composition may contain additional detergents commonly known in the art. Several suitable detergents are described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 3, pages 75-85 (1996) and Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” New York, Marcel Dekker, Chapter 4, pages 113-136 (2003), both of which are incorporated herein by reference. Examples of these detergents include phenates, salicylates, and phosphonates.

[0049] In some embodiments, the cleaning agent comprises at least one highly overbasic substance (TBN greater than 250 based on the active substance).

[0050] Overbasic metal detergents are generally produced by carbonating a mixture of hydrocarbons, a cleansing acid (e.g., sulfonic acid, alkyl hydroxybenzoate, etc.), a metal oxide or metal hydroxide (e.g., calcium oxide or calcium hydroxide), and an accelerator (e.g., xylene, methanol, and water). For example, when preparing overbasic calcium sulfonate, during carbonation, calcium oxide or calcium hydroxide reacts with gaseous carbon dioxide to form calcium carbonate. The sulfonic acid is neutralized with excess CaO or Ca(OH)2 to form a sulfonate.

[0051] Generally speaking, an overbasic detergent may be a low-overbasic (LOB) overbasic salt, for example, an overbasic salt with a TBN of less than 100 based on the active substance. In one embodiment, the TBN of a low-overbasic salt may be about 10 to about 100. In another embodiment, the TBN of a low-overbasic salt may be about 10 to about 80. An overbasic detergent may be a moderately overbasic (MOB) overbasic salt, for example, an overbasic salt with a TBN of about 100 to about 250 based on the active substance. In one embodiment, the TBN of a moderately overbasic salt may be about 100 to about 200. In another embodiment, the TBN of a moderately overbasic salt may be about 125 to about 175. An overbasic detergent may be a high-overbasic (HOB) overbasic salt, for example, an overbasic salt with a TBN greater than 250 based on the active substance. In one embodiment, the TBN of a high-overbasic salt may be about 250 to about 800 based on the active substance.

[0052] In some embodiments, the lubricating oil composition contains low levels of sulfur-containing calcium phenate (for example, about 40 mmol or less of Ca derived from sulfur phenate, e.g., 35 mmol or less, 30 mmol or less, 25 mmol or less, 20 mmol or less, 10 mmol or less, 5 mmol or less, and 0 mmol).

[0053] wear-resistant agent Optionally, the lubricating oil compositions disclosed herein may contain one or more anti-wear agents. In some embodiments, the lubricating oil compositions do not contain or substantially contain sulfur-containing anti-wear compositions.

[0054] The wear of metal parts is reduced by an anti-wear agent. Suitable anti-wear agents include metal salts of dihydrocarbyl dithiophosphoric acid such as zinc dihydrocarbyl dithiophosphate (ZDDP) having the following structure, Zn[S-P(=S)(OR 1 )(OR 2 )]2 wherein R 1 and R 2 are the same or different hydrocarbyl groups having 1 to 18 (e.g., 2 to 12) carbon atoms and including groups such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and alicyclic groups. Particularly preferred as the R 1 and R 2 groups are alkyl groups having 2 to 8 carbon atoms (e.g., the alkyl radical can be ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl). In order to obtain oil solubility, the average number of carbon atoms in the mixture of R 1 and R 2 is at least 4.5 on a molar basis. Thus, the zinc dihydrocarbyl dithiophosphate can contain zinc dialkyl dithiophosphate. The zinc dialkyl dithiophosphate is primary zinc dialkyl dithiophosphate, secondary zinc dialkyl dithiophosphate, or a combination thereof. ZDDP can be present at 3 wt% or less (e.g., 0.1 to 1.5 wt%, or 0.5 to 1.0 wt%) of the lubricating oil composition.

[0055] Dispersant The lubricating oil compositions disclosed herein may further include dispersants. Dispersants hold in a suspended state substances that are insoluble in oil and are produced by oxidation during engine operation, thereby preventing the aggregation and deposition or accumulation of soot or sludge on metal parts. Useful dispersants herein include nitrogen-containing ashless (metal-free) dispersants known to be effective in reducing deposit formation when used in gasoline and diesel engines. Suitable dispersants include hydrocarbyl succinimide, hydrocarbyl succinamide, mixed esters / amides of hydrocarbyl-substituted succinic acid, hydroxy esters of hydrocarbyl-substituted succinic acid, and Mannich condensation products of hydrocarbyl-substituted phenol, formaldehyde, and polyamines. Condensation products of polyamines and hydrocarbyl-substituted phenyl acids are also suitable. Mixtures of these dispersants can also be used. More specifically, succinimide-based dispersants include boric succinimide, non-boric succinimide, and post-treated succinimide.

[0056] Basic nitrogen-containing ashless dispersants are well-known lubricant additives, and their preparation methods are extensively described in this patent document. Preferred dispersants are alkenyl succinimides and succinamides, where the alkenyl substituent is preferably a long chain with more than 40 carbon atoms. These materials are readily produced by reacting hydrocarbyl-substituted dicarboxylic acid materials with molecules containing amine functional groups. Suitable amines include polyamines, e.g., polyalkylene polyamines, hydroxy-substituted polyamines, and polyoxyalkylene polyamines. As is known in the art, the dispersants may be post-treated (e.g., with boronating agents, epoxides, ethylene carbonates, or cyclic carbonates). Nitrogen-containing ashless (metal-free) dispersants are basic and contribute to the TBN of the lubricant composition to which they are added without introducing additional sulfate ash. The dispersant may be present in the lubricating oil composition at a concentration of 0.1 to 10% by weight (e.g., 0.5 to 8, 0.7 to 7, 0.7 to 6, 0.7 to 6, 0.7 to 5, 0.7 to 4% by weight) based on the active substance level. Nitrogen from the dispersant is present at a concentration of more than 0.0050 to 0.30% by weight (e.g., more than 0.0050 to 0.10%, 0.0050 to 0.080%, 0.0050 to 0.060%, 0.0050 to 0.050%, 0.0050 to 0.040%, and more than 0.0050 to 0.030% by weight) based on the weight of the dispersant in the finished oil.

[0057] Antioxidant Optionally, the lubricating oil compositions disclosed herein may further include additional antioxidants that can reduce or prevent the oxidation of the base oil. Any antioxidant known to those skilled in the art may be used in the lubricating oil compositions. Non-limiting examples of suitable antioxidants include amine antioxidants (e.g., alkyldiphenylamine, phenyl-α-naphthylamine, alkyl-substituted or aralkyl-substituted phenyl-α-naphthylamine, alkylated p-phenylenediamine, tetramethyl-diaminodiphenylamine, etc.), phenolic antioxidants (e.g., 2-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2, Examples of antioxidants include 6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 4,4'-methylenebis-(2,6-di-tert-butylphenol), 4,4'-thiobis(6-di-tert-butyl-o-cresol), sulfur-based antioxidants (e.g., dilauryl-3,3'-thiodipropionate, sulfur-phenol-based antioxidants, etc.), phosphorus-based antioxidants (e.g., phosphates, etc.), zinc dithiophosphate, oil-soluble copper compounds, and combinations thereof. The amount of antioxidant can vary from about 0.01% to about 10% by weight, from about 0.05% to about 5% by weight, or from about 0.1% to about 3% by weight, based on the total weight of the lubricating oil composition. Several suitable antioxidants are described in Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” New York. Marcel Dekker, Chapter 1, pages 1-28 (2003), which are incorporated herein by reference.

[0058] Foam inhibitor The lubricating oil compositions disclosed herein may optionally contain antifoaming agents or defoaming agents capable of breaking bubbles in the oil. Any antifoaming agents or defoaming agents known to those skilled in the art may be used in the lubricating oil compositions. Not limited examples of suitable defoaming agents include silicone oils or polydimethylsiloxanes, fluorosilicones, alkoxylated fatty acids, polyethers (e.g., polyethylene glycol), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines, and combinations thereof. In some embodiments, the defoaming agent includes glycerol monostearate, polyglycol palmitate, trialkyl monothiophosphate, esters of sulfonated ricinoleic acid, benzoylacetone, methyl salicylate, glycerol monooleate, or glycerol dioleate. The amount of the defoaming agent may vary from about 0.0005% to about 5% by weight, about 0.05% to about 3% by weight, or about 0.1% to about 1% by weight relative to the total weight of the lubricating oil composition. Several suitable antifoaming agents are described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 6, pages 190–193 (1996), which is incorporated herein by reference.

[0059] Molybdenum additive In some embodiments, the lubricating oil composition includes a molybdenum additive. Some non-limiting examples of suitable molybdenum additives include molybdenum succinimide, oxymolybdenum dithiocarbamate sulfide, oxymolybdenum organophosphodithioate sulfide, oxymolybdenum monoglyceride, oxymolybdenum diethylate amide, amine-molybdenum complex compounds, and sulfur-containing molybdenum complex compounds.

[0060] lubricating viscosity oil The lubricating oil compositions disclosed herein generally contain at least one lubricating viscosity oil. Any base oil known to those skilled in the art can be used as the lubricating viscosity oil disclosed herein. Several base oils suitable for preparing lubricating oil compositions are described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapters 1 and 2 (1996), A. Sequeria, Jr., “Lubricant Base Oil and Wax Processing,” New York, Marcel Decker, Chapter 6, (1994), and DVBrock, Lubrication Engineering, Vol. 43, pages 184-5, (1987), all of which are incorporated herein by reference. Generally, the amount of base oil in the lubricating oil composition may be about 70 to about 99.5% by weight of the total weight of the lubricating oil composition. In some embodiments, the amount of base oil in the lubricating oil composition is about 75 to about 99% by weight, about 80 to about 98.5% by weight, or about 80 to about 98% by weight, based on the total weight of the lubricating oil composition.

[0061] In certain embodiments, the base oil is either a natural or synthetic lubricating base oil fraction, or contains one. Some non-limiting examples of synthetic oils include oils such as polyalphaolefins or PAOs prepared from the polymerization of at least one alpha-olefin, such as ethylene, or from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gas, such as the Fischer-Tropsch process. In certain embodiments, the base oil contains one or more heavy fractions in less than about 10% by weight, based on the total weight of the base oil. A heavy fraction refers to a lubricating oil fraction having a viscosity of at least about 20 cSt at 100°C. In certain embodiments, the heavy fraction has a viscosity of at least about 25 cSt or at least about 30 cSt at 100°C. In further embodiments, the amount of one or more heavy fractions in the base oil is less than about 10% by weight, less than about 5% by weight, less than about 2.5% by weight, less than about 1% by weight, or less than about 0.1% by weight, based on the total weight of the base oil. In further embodiments, the base oil does not contain any heavy fractions.

[0062] In certain embodiments, the lubricating oil composition comprises a base oil with a primary lubricating viscosity. In some embodiments, the base oil has a kinematic viscosity of about 2.5 centistokes (cSt) to about 20 cSt, about 4 centistokes (cSt) to about 20 cSt, or about 5 cSt to about 16 cSt at 100°C. The kinematic viscosity of the base oils or lubricating oil compositions disclosed herein can be measured according to ASTM D 445, which is incorporated herein by reference.

[0063] In other embodiments, the base oil is or comprises a base stock or a blend of base stocks. In further embodiments, the base stock is produced using a variety of different processes, including but not limited to extraction, solvent purification, hydrogenation, oligomerization, esterification, and repurification. In some embodiments, the base stock comprises a repurified stock. In further embodiments, the repurified stock is substantially free of substances introduced by manufacture, contamination, or prior use.

[0064] In some embodiments, the base oil comprises one or more base stocks from groups I to V as specified in American Petroleum Institute (API) Publication 1509, Fourteen Edition, December 1996 (i.e., API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils) (incorporated herein by reference). The API guidelines define base stock as a lubricant component that can be produced using a variety of different processes. Group I, II, and III base stocks are mineral oils, each having a specific range of saturated mass, sulfur content, and viscosity index. Group IV base stocks are poly-alpha-olefins (PAOs). Group V base stocks comprise all other base stocks not included in groups I, II, III, or IV.

[0065] In some embodiments, the base oil comprises one or more base stocks from groups I, II, III, IV, V, or combinations thereof. In other embodiments, the base oil comprises one or more base stocks from groups II, III, IV, or combinations thereof. In further embodiments, the base oil comprises one or more base stocks from groups II, III, IV, or combinations thereof, wherein the base oil has a kinematic viscosity of about 2.5 centistokes (cSt) to about 20 cSt, about 4 cSt to about 20 cSt, or about 5 cSt to about 16 cSt at 100°C.

[0066] The base oil may be selected from the group consisting of natural oils of lubricating viscosity, synthetic oils of lubricating viscosity, and mixtures thereof. In some embodiments, the base oil includes base stocks obtained by isomerization of synthetic waxes and slack waxes, as well as hydrocracking base stocks produced by hydrocracking (rather than solvent extraction) the aromatic and polar components of crude oil. In other embodiments, the base oil of lubricating viscosity includes natural oils, e.g., animal oils, vegetable oils, mineral oils (e.g., liquid petroleum and paraffinic, naphthenic, or mixed paraffin-naphthenic solvent-treated or acid-treated mineral oils), coal or shale-derived oils, and combinations thereof. Some non-limiting examples of animal oils include bone oil, lanolin, fish oil, lard, dolphin oil, seal oil, shark oil, tallow oil, and whale oil. Some non-exclusive examples of vegetable oils include castor oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, soybean oil, sunflower oil, safflower oil, hemp oil, linseed oil, tung oil, oyster oil, jojoba oil, and meadowfoam oil. Such oils may be partially or completely hydrogenated.

[0067] In some embodiments, synthetic oils of lubricating viscosity include hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and copolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, and their derivatives, analogs, and homologs. In other embodiments, synthetic oils include alkylene oxide polymers, interpolymers, copolymers, and their derivatives, where terminal hydroxyl groups can be modified by esterification, etherification, etc. In further embodiments, synthetic oils include esters of dicarboxylic acids and various alcohols. In specific embodiments, synthetic oils include C5-C 12 Examples include monocarboxylic acids, as well as esters produced from polyols and polyol ethers. In further embodiments, examples of synthetic oils include trialkyl phosphate oils such as tri-n-butyl phosphate and tri-iso-butyl phosphate.

[0068] In some embodiments, examples of synthetic oils with lubricating viscosity include silicone-based oils (such as polyalkylsiloxane oil, polyarylsiloxane oil, polyalkoxysiloxane oil, polyaryloxysiloxane oil, and polyalkyl silicate oil, polyaryl silicate oil, polyalkoxy silicate oil, and polyaryloxysilicate oil). In other embodiments, examples of synthetic oils include liquid esters of phosphorus-containing acids, high molecular weight tetrahydrofuran, and polyalphaolefins.

[0069] Base oils derived from the hydrogen isomerization of waxes may be used alone or in combination with the aforementioned natural and / or synthetic base oils. Such wax isomerized oils are produced by hydrogen isomerizing natural or synthetic waxes, or mixtures thereof, on a hydrogen isomerization catalyst.

[0070] In further embodiments, the base oil comprises poly-alpha-olefins (PAOs). Generally, poly-alpha-olefins can be derived from alpha-olefins having about 2 to about 30, about 4 to about 20, or about 6 to about 16 carbon atoms. Non-limiting examples of suitable poly-alpha-olefins include those derived from octene, decene, or mixtures thereof. These poly-alpha-olefins may have viscosities of about 2 to about 15 centistokes, about 3 to about 12 centistokes, or about 4 to about 8 centistokes at 100°C. In some examples, poly-alpha-olefins may be used with other base oils, such as mineral oil.

[0071] In further embodiments, the base oil includes polyalkylene glycol or polyalkylene glycol derivatives in which the terminal hydroxyl groups of the polyalkylene glycol can be modified by esterification, etherification, acetylation, etc. Non-limiting examples of suitable polyalkylene glycols include polyethylene glycol, polypropylene glycol, polyisopropylene glycol, and combinations thereof. Non-limiting examples of suitable polyalkylene glycol derivatives include ethers of polyalkylene glycol (e.g., methyl ether of polyisopropylene glycol, diphenyl ether of polyethylene glycol, diethyl ether of polypropylene glycol, etc.), monocarboxylic acid esters and polycarboxylic acid esters of polyalkylene glycol, and combinations thereof. In some cases, polyalkylene glycol or polyalkylene glycol derivatives can be used with other base oils such as poly-alpha-olefins and mineral oil.

[0072] In further embodiments, the base oil includes any ester of a dicarboxylic acid (e.g., phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Non-limiting examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelaate, diisodecyl azelaate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, and 2-ethylhexyl diester of linoleic acid dimer.

[0073] In further embodiments, the base oil comprises hydrocarbons prepared by the Fischer-Tropsch process. The Fischer-Tropsch process uses a Fischer-Tropsch catalyst to prepare hydrocarbons from a gas containing hydrogen and carbon monoxide. Further processing may be required to make these hydrocarbons useful as base oils. For example, the hydrocarbons can be dewaxed, hydrogen-isomerized, and / or hydrocrackened using methods known to those skilled in the art.

[0074] In further embodiments, the base oil may include unrefined oil, refined oil, re-refined oil, or mixtures thereof. Unrefined oil is oil obtained directly from a natural or synthetic source without further refining. Non-limiting examples of unrefined oil include shale oil obtained directly from a dry distillation operation, petroleum obtained directly from primary distillation, and ester oil obtained directly from an esterification process and used without further processing. Refined oil is similar to unrefined oil, except that the former is further processed by one or more refining processes to improve one or more properties. Many such refining processes are known to those skilled in the art, such as solvent extraction, secondary distillation, acid or base extraction, filtration, and leaching. Re-refined oil is obtained by applying a process similar to that used to obtain refined oil to refined oil. Such re-refined oil is also known as recycled oil or reprocessed oil and is often further processed by processes aimed at removing spent additives and oil decomposition products.

[0075] The following embodiments are provided to illustrate the embodiments, but are not intended to limit this application to any particular embodiment described. Unless otherwise indicated, all parts and percentages are by weight. All numerical values ​​are approximate. Where a numerical range is given, it should be understood that embodiments outside that range may still be included within the scope of this application. Specific details described in each embodiment should not be construed as essential features. [Examples]

[0076] The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

[0077] Comparative Example 1 A commercially available dispersant olefin copolymer (HiTEC® 1910B, manufactured by Afton Corporation) (N wt% = 0.130) is a high molecular weight ethylene propylene copolymer grafted with maleic anhydride and functionalized with N-phenyl-p-phenylenediamine (NPPDA).

[0078] Example 2 - Post-treatment of NPPDA-functionalized polymer [ka]

[0079] The dispersant olefin copolymer (DOCP) (N wt% = 0.130, 181.6 g) of Comparative Example 1 was added to a glass reactor equipped with an overhead stirrer, nitrogen sweep, thermocouple, and heating mantle. The contents of the reactor were heated to 165 ± 5 °C. 2-Naphthylglycidyl ether (NGE: 1.68 g) was added to the reactor, and the reaction mixture was held at 165 ± 5 °C for 3 hours.

[0080] Comparative Example 3 - Imidization Procedure [ka]

[0081] A high molecular weight maleated ethylene-propylene copolymer (solid, Mn approximately 35,000, 388.6 g) grafted with 2.2 wt% maleic anhydride was filled with 100 neutral oil (2193.3 g) and a hindered phenol antioxidant, and added to a glass reactor equipped with an overhead stirrer, nitrogen sweep, thermocouple, and heating mantle. The mixture of oil, antioxidant, and polymer was heated to 120°C and held for 12 hours.

[0082] The temperature of the polymer solution was raised to 165°C, and N-phenyl-p-phenylenediamine (NPPDA: 21.57 g) was added. The contents of the reactor were then maintained at 165°C for 8 hours.

[0083] Example 4 - Imidization and post-treatment procedure (NPPDA post-treatment with NGE) [ka]

[0084] A high molecular weight maleated ethylene-propylene copolymer (solid, Mn approximately 35,000, 45.5 g) grafted with 2.2 wt% maleic anhydride was added to 100 neutral oil (557.9 g) in a glass reactor equipped with an overhead stirrer, nitrogen sweep, thermocouple, and heating mantle. The oil and polymer mixture was heated to 130 ± 5 °C and held for a total of 10 hours. The reaction contents were then heated to 165 ± 5 °C and N-phenyl-p-phenylenediamine (NPPDA: 2.0 g) was added. The reaction was maintained for 2 hours, and completion of the imidation reaction was confirmed by FT-IR. Then, 2-naphthylglycidyl ether (NGE: 2.3 g) was added, and the reaction product was held at 165 ± 5 °C for 4 hours.

[0085] Example 5 - Imidization and post-treatment procedure (AEP post-treatment with NGE) [ka]

[0086] A high molecular weight maleated ethylene-propylene copolymer (solid, Mn approximately 35,000, 20.0 g) grafted with 2.2% maleic anhydride was filled with xylene (380 g) and added to a glass reactor equipped with an overhead stirrer, nitrogen sweep, thermocouple, and heating mantle. The oil and polymer mixture was heated to 115°C and held for 1 hour. The reaction contents were then heated to 165°C and aminoethylpiperazine (AEP: 0.61 g) was added. The reaction was maintained for 2 hours, and completion of the imidation reaction was confirmed by FT-IR.

[0087] Next, 100 neutral oil (380 g) was added to the mixture. After the reaction temperature reached 165°C, the mixture was placed in a vacuum fitting and the pressure was slowly reduced until no more liquid flowed into the top. Finally, the reactants were filled with nitrogen and returned, 2-naphthylglycidyl ether (NGE: 0.95 g) was added, and the reactants were held at 165°C for 3 hours.

[0088] Example 6 - Imidization and post-treatment procedure (AEEA post-treatment with NGE) [ka]

[0089] A high molecular weight maleated ethylene-propylene copolymer (solid, Mn approximately 35,000, 15.0 g) grafted with 2.2% maleic anhydride was filled with xylene (285 g) and added to a glass reactor equipped with an overhead stirrer, nitrogen sweep, thermocouple, and heating mantle. The oil and polymer mixture was heated to 115°C and held for 1 hour. The reaction contents were then heated to 165°C and aminoethylethanolamine (AEEA: 0.39 g) was added. The reaction was maintained for 3 hours, and completion of the imidation reaction was confirmed by FT-IR.

[0090] Next, 100 neutral oil (285 g) was added to the mixture. After the reaction temperature reached 165°C, the pressure inside the reaction vessel was slowly reduced to distill off the xylene. The vacuum was relieved using nitrogen. 2-Naphthylglycidyl ether (NGE: 0.76 g) was added, and the reaction mixture was held at 165°C for 3 hours.

[0091] sedimentation rate The soot treatment properties of oil samples were tested by measuring the sedimentation velocity using LUMiSizer®. Each oil sample contained a baseline formulation (detergent, antioxidant, anti-abrasive, viscosity modifier, pour point depressant, and anti-foaming agent) and 0.50–0.53 wt% active polymer dispersant. The oil sample was mixed with 3 wt% carbon black (Vulcan XC-72R) using an acoustic mixer. The samples were tested with LUMiSizer® at 80°C. The attenuation of transmitted light due to differences in sedimentation velocity related to the particle size and stability of the dispersion was measured. Dispersions with lower stability formed larger particles that settled more rapidly. Dispersions with higher stability had slower sedimentation velocities. The results summarized in the table below show that post-treatment with naphthylglycidyl ether improved the performance. [Table 1]

[0092] It will be understood that various modifications can be made to the embodiments disclosed herein. Therefore, the above description should not be construed as limiting, but merely as illustrative examples of embodiments of the present invention. For example, the functions described above and implemented for operation are for illustrative purposes only. Those skilled in the art will be able to implement other configurations and methods without departing from the scope and spirit of this application. Furthermore, those skilled in the art will be able to conceive of other modifications within the scope and spirit of the claims appended herein.

Claims

1. A high molecular weight polymer dispersant composition, wherein the polymer dispersant is represented by the following generalized structure: 【Chemistry 1】 The high molecular weight polymer dispersant composition wherein A is an olefin copolymer, B is an alkylimide or alkylamide, C is a polyamine, alkylamine, alkyl etheramine or alkylhydroxylamine, D is 1-(arene-2-yloxy)propan-2-ol, and n is 1 to 15.

2. The high molecular weight polymer dispersant composition according to claim 1, wherein A is an ethylene-propylene copolymer.

3. The high molecular weight polymer dispersant composition according to claim 1, wherein n is 3 to 12.

4. The high molecular weight polymer dispersant composition according to claim 1, wherein the number average molecular weight (Mn) of the olefin copolymer is about 5,000 to about 150,000.

5. The aforementioned high molecular weight polymer dispersant is Number average molecular weight (M ｎ Hydrocarbon polymers with a ratio of approximately 5,000 to approximately 150,000, Ethylene-unsaturated grafting agent and Polyamines having the following structure 【Chemistry 2】 (In the formula, X is a C2-C10 hydrocarbyl group, an aminoalkyl group, an ether group, a thioether group, or an aromatic group, and Y is an amino C １ -C １０ (A hydrocarbyl group, an aminoalkylhydroxyl group, an aminoalkyl ether group, an aminoalkylthioether group, an aminoaromatic group, or a piperazine) Arylglycidyl ether and It is a reaction product of, or Number average molecular weight (M ｎ Hydrocarbon polymers with a ratio of approximately 5,000 to approximately 150,000, Grafting agents of allylamine or vinylamine having the following structure 【Transformation 3】 (wherein W is vinyl, alkylvinyl, allyl, or alkylallyl, and Z is piperazine, alkylamine, arylamine, formamide, alkylcarbamide, alkylamide, or arylamide) Arylglycidyl ether and The high molecular weight polymer dispersant composition according to claim 1, which is a reaction product of the above.

6. The high molecular weight polymer dispersant composition according to claim 5, wherein the aryl glycidyl ether is added as a post-treatment.

7. The high molecular weight polymer dispersant composition according to claim 5, wherein the ethylenically unsaturated acylating agent is acrylic acid, crotonic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, chloromaleic acid, aconitic acid, methylcrotonic acid, sorbic acid, or an anhydride or ester thereof.

8. The high molecular weight polymer dispersant composition according to claim 5, wherein the allylamine or vinylamine grafting agent is 1-ethenylpiperazine, 1-(propa-1-en-2-yl)piperazine, 1-allylpiperazine, N-allylmethylamine, allylcyclohexylamine, N-allylaniline, N,2-dimethyl-2-propen-1-amine, N-ethyl-2-methylallylamine, 1-(2-methylpropa-2-en-1-yl)piperazine, N-vinylformamide, N-vinylacetamide, N-vinylbenzamide, or methylvinylcarbamate.

9. The high molecular weight polymer dispersant composition according to claim 5, wherein the polyamine is N-phenyl-p-phenylenediamine, aminoethylpiperazine, or aminoethylethanolamine.

10. The high molecular weight polymer dispersant composition according to claim 5, wherein the aryl glycidyl ether is 2-naphthylglycidyl ether.

11. The high molecular weight polymer dispersant composition according to claim 5, wherein the hydrocarbon polymer is a solid hydrocarbon polymer.

12. The main component is a base oil with lubricating viscosity, High molecular weight polymer dispersants represented by the following generalized structure 【Chemistry 4】 (wherein A is an olefin copolymer, B is an alkylimide or alkylamide, C is a polyamine, alkylamine, etheramine or hydroxylamine, D is 1-(arene-2-yloxy)propan-2-ol, and n is 1 to 15) A lubricating oil composition containing the following:

13. The lubricating oil composition according to claim 12, wherein A is an ethylene-propylene copolymer.

14. The lubricating oil composition according to claim 12, wherein n is 3 to 12.

15. The lubricating oil composition according to claim 12, wherein the number average molecular weight (Mn) of the olefin copolymer is about 5,000 to about 150,000.

16. The aforementioned polymer dispersant is Number average molecular weight (M ｎ Solid hydrocarbon polymers with a ratio of approximately 5,000 to approximately 150,000, Ethylene-unsaturated grafting agent and Polyamines having the following structure 【Transformation 5】 (In the formula, X is a C2-C10 hydrocarbyl group, an aminoalkyl group, an ether group, a thioether group, or an aromatic group, and Y is an amino C １ -C １０ (A hydrocarbyl group, an aminoalkylhydroxyl group, an aminoalkyl ether group, an aminoalkylthioether group, an aminoaromatic group, or a piperazine) Arylglycidyl ether and It is a reaction product of, or Number average molecular weight (M ｎ Hydrocarbon polymers with a ratio of approximately 5,000 to approximately 150,000, Grafting agents of allylamine or vinylamine having the following structure 【Transformation 6】 (wherein W is vinyl, alkylvinyl, allyl, or alkylallyl, and Z is piperazine, alkylamine, arylamine, formamide, alkylcarbamide, alkylamide, or arylamide) Arylglycidyl ether and The lubricating oil composition according to claim 12, which is a reaction product of the above.

17. The lubricating oil composition according to claim 16, wherein the aryl glycidyl ether is added as a post-treatment.

18. The lubricating oil composition according to claim 16, wherein the ethylenically unsaturated acylating agent is acrylic acid, crotonic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, chloromaleic acid, aconitic acid, methylcrotonic acid, sorbic acid, or an anhydride or ester thereof.

19. The lubricating oil composition according to claim 16, wherein the allylamine or vinylamine grafting agent is 1-ethenylpiperazine, 1-(propa-1-en-2-yl)piperazine, 1-allylpiperazine, N-allylmethylamine, allylcyclohexylamine, N-allylaniline, N,2-dimethyl-2-propen-1-amine, N-ethyl-2-methylallylamine, 1-(2-methylpropa-2-en-1-yl)piperazine, N-vinylformamide, N-vinylacetamide, N-vinylbenzamide, or methylvinylcarbamate.

20. The lubricating oil composition according to claim 16, wherein the polyamine is N-phenyl-p-phenylenediamine, aminoethylpiperazine, or aminoethylethanolamine.

21. The lubricating oil composition according to claim 16, wherein the aryl glycidyl ether is 2-naphthylglycidyl ether.

22. The lubricating oil composition according to claim 16, wherein the hydrocarbon polymer is a solid hydrocarbon polymer.

23. A method for improving wear or soot dispersion of an internal combustion engine, The main component is a base oil with lubricating viscosity, High molecular weight polymer dispersants represented by the following generalized structure 【Transformation 7】 (wherein A is an olefin copolymer, B is an alkylimide or alkylamide, C is a polyamine, alkylamine, etheramine or hydroxylamine, D is 1-(arene-2-yloxy)propan-2-ol, and n is 1 to 15) The method comprising lubricating the engine with a lubricating oil composition containing the following.

24. The method according to claim 23, wherein A is an ethylene-propylene copolymer.

25. The method according to claim 23, wherein n is 3 to 12.

26. The method according to claim 23, wherein the number-average molecular weight (Mn) of the olefin copolymer is about 5,000 to about 150,000.

27. The aforementioned polymer dispersant is The number average molecular weight (M ｎ ) is a solid hydrocarbon polymer of about 5,000 to about 150,000, and Ethylene-unsaturated grafting agent and Polyamines having the following structure 【Transformation 8】 (In the formula, X is a C2-C10 hydrocarbyl group, an aminoalkyl group, an ether group, a thioether group, or an aromatic group, and Y is an amino C １ -C １０ (A hydrocarbyl group, an aminoalkylhydroxyl group, an aminoalkyl ether group, an aminoalkylthioether group, an aminoaromatic group, or a piperazine) Arylglycidyl ether and It is a reaction product of, or Number average molecular weight (M ｎ Hydrocarbon polymers with a ratio of approximately 5,000 to approximately 150,000, Grafting agents of allylamine or vinylamine having the following structure 【Chemistry 9】 (wherein W is vinyl, alkylvinyl, allyl, or alkylallyl, and Z is piperazine, alkylamine, arylamine, formamide, alkylcarbamide, alkylamide, or arylamide) Arylglycidyl ether and The method according to claim 23, wherein the reaction product is the same.

28. The method according to claim 27, wherein the aryl glycidyl ether is added as a post-treatment.

29. The method according to claim 27, wherein the ethylenically unsaturated acylating agent is acrylic acid, crotonic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, chloromaleic acid, aconitic acid, methylcrotonic acid, sorbic acid, or an anhydride or ester thereof.

30. The method according to claim 27, wherein the allylamine or vinylamine grafting agent is 1-ethenylpiperazine, 1-(propa-1-en-2-yl)piperazine, 1-allylpiperazine, N-allylmethylamine, allylcyclohexylamine, N-allylaniline, N,2-dimethyl-2-propen-1-amine, N-ethyl-2-methylallylamine, 1-(2-methylpropa-2-en-1-yl)piperazine, N-vinylformamide, N-vinylacetamide, N-vinylbenzamide, or methylvinylcarbamate.

31. The method according to claim 27, wherein the polyamine is N-phenyl-p-phenylenediamine, aminoethylpiperazine, or aminoethylethanolamine.

32. The method according to claim 27, wherein the arylglycidyl ether is 2-naphthylglycidyl ether.

33. The method according to claim 27, wherein the hydrocarbon polymer is a solid hydrocarbon polymer.

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