Alkyl aminoacetamide and alkyl ether aminoacetamide

Abstract

Alkyl aminoacetamide and alkyl ether aminoacetamide, and their use as organic friction modifiers in lubricant formulations are disclosed. Additionally, formulations containing alkyl aminoacetamide and alkyl ether acetamide and a method for synthesizing the same are also disclosed.

Description

Technology Field

[0001] Cross-reference with other applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 603,301, filed November 28, 2023. The said application is incorporated herein by reference.

[0003] Technology field

[0004] The present invention relates to alkyl aminoacetamides and alkyl ether aminoacetamides, their use as organic friction modifiers in lubricant formulations, formulations containing them, and the synthesis of the same. Background Technology

[0005] Friction modifiers (FM) are added to lubricants to reduce friction and wear on equipment components. Friction modifiers play a particularly important role in boundary lubrication areas, as they can significantly reduce friction and wear by preventing direct contact between solid surfaces. Friction modifiers are particularly useful in limit slip gear oils, automatic transmission oils, slideway lubricants, and multi-purpose tractor fluids.

[0006] Reducing friction losses through more efficient lubrication is a key objective for increasing fuel efficiency and reducing carbon dioxide emissions. Therefore, friction modifiers are increasingly being introduced into automotive crankcase lubricants.

[0007] There are several different types of friction modifiers. For example,

[0008] Organic compounds are important additives in modern engine oils and are also used in fuels. By adsorbing onto metal surfaces and self-assembling to form an incompressible monolayer, organic compounds prevent contact between uneven surfaces and reduce friction and wear.

[0009] Organic molybdenum compounds were initially developed as anti-wear additives, but were later found to be highly effective in reducing boundary friction. Organic molybdenum compounds are currently used in many engine oils, and more recently in gear oils. Organic molybdenum compounds reduce friction by forming a two-dimensional molybdenum disulfide layer on the friction surface.

[0010] · Organozin compounds are a family of coordination compounds developed in the 1940s, characterized by zinc bonded to the anion of dialkyldithiophosphate. Organozin compounds function as anti-wear compounds and are commonly used in engine oils, greases, and lubricants.

[0011] Functionalized polymers that can be customized to specifically adsorb to polar surfaces have been shown to significantly reduce friction and wear.

[0012] Despite the various advantages of the friction modifiers listed above, there are also some associated problems. The most common type of friction modifier is zinc dithiophosphate (ZnDTP or ZDDP). However, there are reports that emissions of zinc and phosphorus can damage catalytic converters. Consequently, the use of ZDDP is decreasing in many applications. Other metal-containing compounds, such as molybdenum dithiocarbamate (MoDTC), can also cause some emission issues.

[0013] Due to issues associated with ZDDP, organic ash-less friction modifiers are becoming increasingly important. Organic friction modifiers are generally long straight-chain hydrocarbons with at least 10 carbon atoms and a polar group at one end. The polar group is one of the key factors determining the molecule's effect as a friction modifier. The most common FMs are esters of fatty acids and polyhydric alcohols, fatty acid amides, amines derived from fatty acids, and organic dithiocarbamates or dithiophosphate compounds. EP1367116, EP0799883, EP0747464, US 3,933,659, and EP335701, incorporated herein by reference, all disclose long-polar friction modifiers in lubricants. Glycerol monooleate (GMO) is another example of an organic FM. This is US 5,885,942; 5,866,520; 5,114,603; Disclosed in 4,957,651 and 4,683,069, the contents of said patents are incorporated herein by reference.

[0014] There is a problem in that most organic lubricants contain hydrolyzable groups, for example, ester groups that can be hydrolyzed and decomposed. This leads to a decrease in friction modification performance and the generation of hydrophilic decomposition products that are immiscible with oils and lubricants.

[0015] Therefore, there is a need for friction modifiers that are stable and do not damage catalytic converters.

[0016] Therefore, the objective of the present application is to provide a compound having stable and excellent friction modification properties without generating harmful emissions. Brief explanation of the drawing

[0017] Figure 1 is a graph showing the reduction in the coefficient of friction between Mobil 10W-30 and the FM-A containing material of Example 5. Figure 2 is a graph showing the reduction in the coefficient of friction between Mobil 10W-20 and the FM-A containing material of Example 6. Specific details for implementing the invention

[0018] The present invention is described in relation to specific aspects and embodiments.

[0019] The term "comprising" as used in the claims should not be interpreted as being limited only to the means enumerated below, nor should it exclude other elements or steps. Accordingly, it should be interpreted as specifying the presence of the mentioned characteristic composition, step, or component, but not excluding the presence or addition of one or more other characteristic compositions, steps, or components, or groups thereof. Accordingly, the scope of the expression "compound comprising components X and Y" should not be limited to a compound composed solely of components X and Y. This means that, in relation to the present invention, the relevant components of the compound are only X and Y.

[0020] Throughout this specification, references to “one embodiment” (or “an embodiment”) are made. These references indicate that a specific characteristic feature described in relation to the embodiment is included in at least one embodiment of the present invention. Accordingly, the appearance of the phrase “in one embodiment” (or “in an embodiment”) in various places within this specification does not necessarily refer to the same embodiment, but may refer to the same embodiment. Furthermore, a specific characteristic feature or feature may be combined in any suitable manner in one or more embodiments, which is obvious to those skilled in the art.

[0021] The terms "desirable" and "desirably" refer to an embodiment that may provide a specific benefit under specific circumstances. However, other embodiments may also be desirable under the same or different circumstances. Furthermore, reference to one or more desirable embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

[0022] The terms "arbitrary" or "arbitrary" mean that an event or situation described subsequently may or may not occur, and the present invention includes both cases where said event or situation occurs and cases where it does not occur.

[0023] When a group of substituents is designated by a conventional chemical formula written from left to right, it contains equivalent chemically identical substituents that would be produced if the structure were written from right to left. For example, -CH2O- is equivalent to -OCH2-.

[0024] While preferred embodiments and / or materials have been discussed to provide embodiments according to the present invention, it should be understood that various modifications or changes may be made without departing from the scope and spirit of the invention.

[0025] In one embodiment, the present invention provides a compound selected from compounds of Formula I, Formula II, Formula III, Formula IV, Formula V and Formula VI and a mixture thereof.

[0026] [Chemical Formula I]

[0027]

[0028] [Chemical Formula II]

[0029]

[0030] [Chemical Formula III]

[0031]

[0032] [Chemical Formula IV]

[0033]

[0034] [Chemical Formula V]

[0035]

[0036] [Chemical Formula VI]

[0037]

[0038] In the above chemical formulas I to VI,

[0039] R is selected from alkyl, cycloalkyl, alkyl ether, aryl ether, and aryl;

[0040] R' is selected from alkyl, cycloalkyl, and aryl;

[0041] R" is independently selected from H, methyl, ethyl, or a combination thereof.

[0042] The compounds of the above chemical formulas I, II, III, IV, V, and VI possess excellent friction-reducing capabilities and can be included in a wide range of formulations. Aminoacetamide products contain both amine and amide groups in the polar head, causing the molecule to be strongly adsorbed to surfaces in contact with the friction modifier, particularly metal surfaces. The linear structure of the hydrophobic tail generates strong van der Waals forces between these tails, promoting the formation of a self-assembled monolayer. Due to this unique molecular structure, the molecule can serve as an excellent friction modifier for lubricants.

[0043] Furthermore, since the compound of the present invention does not have hydrolyzable groups, it exhibits excellent storage stability and is not sensitive to moisture. Since the friction modifier of the present invention does not contain any heavy metal atoms, it exhibits a favorable emission profile.

[0044] The term “storage stability” means the storage stability of a composition stored at ambient temperature in a suitable container under moisture exclusion for a set of time intervals, for example, at least 3 months, at least 4 months, at least 5 months, or at least 6 months, without undergoing significant changes in properties of application or end use (e.g., only minor changes (less than about 5%, less than about 4%, or less than about 3%), or no crystallization, or only minor changes (less than about 5%, less than about 4%, or less than about 3%), or no increase in viscosity).

[0045] Friction modifiers are any material capable of minimizing light surface contact (slipping and rolling) that may occur in a given machine design. Here, the term boundary lubricant additive may also be used to refer to friction modifiers.

[0046] The term "alkyl" refers to a linear or branched hydrocarbon radical having 1 to 50 carbon atoms, and "substituted alkyl" refers to an alkyl further comprising one or more substituents selected from hydroxy, alkoxy, mercapto, cycloalkyl, heterocyclic, aryl, heteroaryl, aryloxy, halogen, trifluoromethyl, cyano, nitro, nitron, amino, amido, C(O)H, acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide, and sulfuryl. Examples of alkyls include butyl, isobutyl, sec-butyl, tert-butyl, propyl, isopropyl, ethyl, and methyl.

[0047] An aryl is a functional group derived from a simple aromatic ring, that is, a ring containing delocalized pi electrons, for example, a benzene ring. As used herein, the term aryl may refer to pure hydrocarbon aryls and heteroaryls (e.g., aryls containing heteroatoms selected from N, O, and S).

[0048] In some modalities, R is C 4-100 It is a linear or branched alkyl. For example, -C4H9 or -C 100 H 2O1 is. In a preferred embodiment, R is C 12 to C 22 It is a linear or branched alkyl.

[0049] In some embodiments, R is a pentagonal or hexagonal saturated cycloalkyl.

[0050] In some modalities, R' is C 4-100 It is a linear or branched alkyl. For example, -C4H9 or -C 100 H 2O1 is. In a preferred embodiment, R' is C 12 to C22 It is a linear or branched alkyl.

[0051] In some embodiments, R' is a pentagonal or hexagonal saturated cycloalkyl.

[0052] In some modalities, R' is C 4-100 It is a linear or branched alkyl ether.

[0053] A further aspect of the present invention is a friction modifier comprising a compound of formulas I, II, III, IV, V, VI or a combination thereof.

[0054] In some embodiments, the friction modifier may include additional components selected from lubricants, oils, detergents, dispersants, anti-wear agents, EP agents, antioxidants, and combinations thereof.

[0055] In a further embodiment, the present invention comprises a composition comprising the friction modifier and optionally one or more additional components selected from lubricants, oils, detergents, dispersants, anti-wear agents, EP agents, antioxidants, and combinations thereof.

[0056] Organic friction modifiers used in lubricant formulations are also excellent as friction modifiers for fuel. Since the above aminoacetamide compound exhibits superior performance compared to commercially available organic friction modifiers in lubricant formulations, the compound of the present invention will function as a friction modifier in fuel, for example, gasoline.

[0057] In one aspect of the present invention, a method for modifying the friction coefficient between at least two surfaces is provided, comprising the step of contacting at least one of the surfaces with a composition comprising the friction modifier.

[0058] In one aspect of the present invention, the use of the friction modifier is provided for modifying the friction coefficient between at least two surfaces.

[0059] The coefficient of friction of a composition can be measured by any method known to those skilled in the art. The coefficient of friction is the ratio of the frictional force resisting the motion of two surfaces in contact with each other to the normal force pressing the two surfaces together. The coefficient of friction is generally denoted by μ.

[0060] In some embodiments, modification of the friction coefficient may include reducing the friction coefficient by at least 60%, at least 50%, at least 40%, at least 20%, at least 10%, or at least 5%.

[0061] Preferably, the compound of the present invention reduces the coefficient of friction between two surfaces.

[0062] Another aspect of the present invention discloses a method for producing a friction modifier, comprising the step of reacting a haloacetamide with a compound selected from compounds A, B, and C to produce compounds of formulas I, II, III, IV, V, and VI.

[0063] Compound A

[0064] Compound B

[0065] Compound C

[0066] [Chemical Formula I]

[0067]

[0068] [Chemical Formula II]

[0069]

[0070] [Chemical Formula III]

[0071]

[0072] [Chemical Formula IV]

[0073]

[0074] [Chemical Formula V]

[0075]

[0076] [Chemical Formula VI]

[0077]

[0078] In the above chemical formulas I to VI,

[0079] R, R' and R" are as described above;

[0080] n is 5 to 100, preferably 12 to 22.

[0081] In certain embodiments, the haloacetamide is chloroacetamide. Chloroacetamide is commercially available.

[0082] In some embodiments, the reaction is carried out under basic conditions. Suitable bases include, but are not limited to, organic bases, e.g., pyridine; alkylamines, e.g., methylamine; imidazole; benzimidazole; histidine; guanidine; phosphazene bases; hydroxides of quaternary ammonium cations; or some other organic cations and inorganic bases, e.g., metal hydroxides (e.g., LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2, Ba(OH)2).

[0083] In a specific embodiment, the reaction is carried out at a temperature in the range of 0 to 200°C, preferably 50 to 150°C.

[0084] In some embodiments, the reaction involves reacting compound A with haloacetate in a molar ratio of 2:1 to produce a compound of formula I.

[0085] In some embodiments, the reaction involves reacting compound A with a haloacetate in a 1:1 molar ratio to produce a compound of formula II.

[0086] In some embodiments, the reaction involves reacting compound B with a haloacetate in a 1:1 molar ratio to produce a compound of formula III.

[0087] In some embodiments, the reaction involves reacting compound B with a haloacetate in a molar ratio of 2:1 to produce a compound of formula IV.

[0088] In some embodiments, the reaction involves reacting compound C with a haloacetate in a 1:1 molar ratio to produce a compound of formula V.

[0089] In some embodiments, the reaction involves reacting compound C with a haloacetate in a molar ratio of 2:1 to produce a compound of formula VI.

[0090] The specific and desirable characteristic configurations disclosed above may be combined with other characteristic configurations as needed.

[0091] The above and other features, characteristic configurations, and advantages of the present invention will become clear through the detailed description together with the accompanying embodiments explaining the principles of the present invention.

[0092] Examples

[0093] A detailed description of the invention may be explained in the following examples. All chemicals were supplied by Huntsman International LLC, with the exception of the following reagents.

[0094] 2-Chloroacetamide: Sigma Aldrich

[0095] NaOH solution: Sigma Aldrich

[0096] Toluene: Sigma Aldrich

[0097] TOMAMINE PA-19: Evonik (structural formula is as follows)

[0098]

[0099] Adogen 172: Evonik (structural formula is as follows)

[0100]

[0101] Jeffamine C-300 was supplied by Huntsman, and its structural formula is as follows.

[0102]

[0103] Unless otherwise specified, all parts and all percentages in the following examples and throughout this specification are parts by weight or weight percentages, respectively. The term “ambient temperature” refers to the temperature of the surrounding working environment (e.g., the temperature of the zone, building, or room where the composition is used). The ambient temperature may be in the range of about 10 to about 30°C, more specifically in the range of about 15 to about 25°C.

[0104] Example 1 - Synthesis of Alkyl Polyether Aminomonoacetamide

[0105] 169.1 g (0.5 mol) of Jeffamine C-300, 169.1 g of toluene, and 46.75 g (0.5 mol) of 2-chloroacetamide were packed into a 1,000 ml three-necked flask. The temperature of the mixture was raised to 100°C while stirring.

[0106] 42 g of 50% NaOH solution was filled into a flask while maintaining the temperature at 100±5℃. The reaction solution was maintained at 100℃ for 1 hour. After cooling the reaction mixture to ambient temperature, the product mixture was washed twice with deionized water. Toluene and moisture in the organic layer were removed under vacuum (20 torr) and increased temperature (90℃).

[0107] The final product was mainly alkyl polyether aminomonoacetamide. This product was named friction modifier A (FM-A).

[0108] Example 2 - Synthesis of Alkyl Polyether Aminodiacetamide

[0109] 169.1 g (0.5 mol) of Jeffamine C-300, 169.1 g of toluene, and 93.5 g (1.0 mol) of 2-chloroacetamide were packed into a 1,000 ml three-necked flask. The temperature was raised to 100°C while stirring the flask.

[0110] 42 g of 50% NaOH solution was added dropwise to the flask while maintaining the temperature at 100±5℃. After 1 hour, the reaction flask was cooled to ambient temperature. The product mixture was washed twice with deionized water. The organic layer was removed under vacuum at elevated temperatures (20 torr and 90℃), and the final product was isolated.

[0111] LC-MS analysis revealed that the final product was 90% alkyl polyether aminodiacetamide. The product was named friction modifier B (FM-B).

[0112] Example 3 - Synthesis of Alkyl Ether Aminomonoacetamide

[0113] 143.5 g (0.5 mol) of TOMAMINE PA-19, 169.1 g of toluene, and 46.75 g (0.5 mol) of 2-chloroacetamide were loaded into a 1,000 ml three-necked flask. The reaction temperature was raised to 100°C while stirring.

[0114] 42 g of 50% NaOH solution was added dropwise to the flask, and the temperature was maintained at 100±5℃. After 1 hour, the reaction vessel was cooled to ambient temperature. The product mixture was washed twice with deionized water. The product of the organic layer was removed, and the remaining toluene and moisture were removed under vacuum at elevated temperature (20 torr, 90℃).

[0115] The final product was mainly alkyl ether aminomonoacetamide. The product was named friction modifier C (FM-C).

[0116] Example 4 - Synthesis of Alkyl Aminomonoacetamide

[0117] 142.5 g (0.5 mol) of ADOGEN 172, 169.1 g of toluene, and 46.75 g (0.5 mol) of 2-chloroacetamide were filled into a 1,000 ml three-necked flask. The temperature of the container was raised to 100°C, and the reaction mixture was stirred.

[0118] 42 g of 50% NaOH solution was added dropwise to a flask, and the temperature was maintained at 100±5℃. After 1 hour of reaction, the reaction mixture was cooled to ambient temperature. The product mixture was washed twice with deionized water. The toluene and moisture in the organic layer were removed under vacuum at elevated temperature (20 torr, 90℃) to isolate the product.

[0119] The final product was mainly alkyl aminomonoacetamide. The product was named friction modifier D (FM-D).

[0120] Example 5 - Evaluation of Friction Modifiers in Mobil 5W-30 Oil

[0121] The friction modifiers prepared in Examples 1 to 4 were added to commercial Mobil 5W-30 oil. The coefficient of friction of the commercial oil containing 0.5% organic friction modifier was measured at 100°C and 130°C using a mini traction machine with ¾-inch balls mounted on a smooth disc. The applied chode was 36 N (1 GPa contact pressure), and the rotational speed ranged from 0.01 m / s to 2 m / s. The results are presented in Table 1 below.

[0122]

[0123] The above data shows that all aminoacetamide products of the examples (FM-A, B, C, and D) can significantly reduce the friction coefficient of Mobil 1 5W-30 oil.

[0124] Figure 1 shows the full measurement range for FM-A.

[0125] Example 6 - Evaluation of Friction Modifiers in Mobil 1 0W-20 Oil

[0126] The friction coefficient of Mobil 1 0W-20 oil was measured using the same method as disclosed in Example 5 above. The results are shown in Table 2 below.

[0127]

[0128] The data in Table 2 shows that all aminoacetamide products of the examples (FM-A, B, C, and D) can significantly reduce the friction coefficient of Mobil 1 0W-20 oil.

[0129] The full range of FM-A is shown in Fig. 2.

Claims

Claim 1 A compound selected from the group consisting of Chemical Formula I, Chemical Formula II, Chemical Formula III, Chemical Formula IV, Chemical Formula V and Chemical Formula VI.[Chemical Formula I] [Chemical Formula II] [Chemical Formula III] [Chemical Formula IV] [Chemical Formula V] [Chemical Formula VI] In the above formulas I to VI, R is selected from alkyl, cycloalkyl, alkyl ether, and aryl; R' is selected from alkyl, cycloalkyl, and aryl; and R" is independently selected from H, methyl, ethyl, or a combination thereof. Claim 2 In paragraph 1, R is C 4-100 It is a linear or branched alkyl, preferably R is C 12 to C 22 A compound that is a linear or branched alkyl. Claim 3 A compound according to claim 1, wherein R is a pentagonal or hexagonal saturated cycloalkyl. Claim 4 In paragraph 1, R is C 4-100 A compound that is a linear or branched alkyl ether or aryl ether. Claim 5 In any one of paragraphs 1 through 4, R' is C 4-100 It is a linear or branched alkyl, preferably R' is C 12 to C 22 A compound that is a linear or branched alkyl. Claim 6 A compound according to any one of claims 1 to 4, wherein R' is a pentagonal or hexagonal saturated cycloalkyl. Claim 7 In any one of paragraphs 1 through 4, R' is C 4-100 A compound that is a linear or branched alkyl ether or aryl ether. Claim 8 A friction modifier comprising a compound selected from the group consisting of chemical formulas I, II, III, IV, V, VI and combinations thereof as described in any one of claims 1 to 7. Claim 9 A composition comprising a compound selected from the group consisting of formulas I, II, III, IV, V, VI and combinations thereof described in any one of claims 1 to 7, and optionally one or more additional components selected from lubricants, oils, detergents, dispersants, anti-wear agents, EP agents, and antioxidants. Claim 10 A method for modifying the friction coefficient between at least two surfaces, comprising the step of contacting at least one of the surfaces with the composition described in claim 9, the friction modifier described in claim 8, or the compound described in any one of claims 1 to 7. Claim 11 A method for manufacturing a friction modifier, comprising the step of reacting a haloacetamide with a compound selected from the group consisting of compounds A, B, and C to produce compounds of formulas I, II, III, IV, V, and VI as described in any one of claims 1 to 7. Compound A Compound B Compound C Claim 12 A method for manufacturing a friction modifier according to claim 11, wherein the haloacetamide is chloroacetamide. Claim 13 A method for manufacturing a friction modifier according to claim 11 or 12, wherein the reaction is carried out in a temperature range of 0 to 200°C, preferably 50 to 150°C.

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