Alkyl amino acetamides and alkyl ether amino acetamides

Abstract

Alkyl amino acetamides and alkyl ether amino acetamides and their use as organic friction modifiers in the lubricant formulations. Also described are formulations containing alkyl amino acetamides and alkyl ether acetamides in addition to methods for synthesising the same.

Description

Alkyl amino acetamides and alkyl ether amino acetamidesCross Reference to Other Applications

[0001] This application claims priority to U.S. Provisional Patent Application Serial Number 63 / 603,301 filed November 28, 2023. The noted application is incorporated herein by reference.Field

[0002] The present disclosure relates to alkyl amino acetamides and alkyl ether amino acetamides, their use as organic friction modifiers in lubricant formulations, formulations comprising the same, and the synthesis of the same.Background

[0003] Friction Modifiers (FM) are added to lubricants to reduce friction and wear in machine components. They are particularly important in the boundary lubrication regime, where they can prevent solid surfaces from coming into direct contact, substantially reducing friction and wear. They are particularly useful in limited slip gear oils, automatic transmission fluids, slideway lubricants and multipurpose tractor fluids.

[0004] Reduction of frictional losses through more efficient lubrication is a key target to reduce carbon dioxide emissions by increasing fuel economy. Friction Modifiers have therefore increasingly also been introduced into automotive crankcase lubricants.

[0005] There are several different types of Friction Modifiers. For example:• Organic compounds are important additives in modern engine oils and are also employed in fuels. They adsorb on metal surfaces and self-assemble to form incompressible monolayers which prevent asperity contact and reduce friction and wear.• Organo-molybdenum compounds were initially developed as anti-wear additives but were later recognized to be very effective in reducing boundary friction. They are currently used in many engine oils and, more recently, in gear oils. They reduce friction by forming two- dimensional molybdenum disulphide layers on rubbing surfaces.• Organo-zinc compounds are a family of coordination compounds developed in the 1940s that feature zinc bound to the anion of a dialkyldithiophosphoric salt. They function as antiwear compounds and are commonly used in motor oils, greases, and lubricants.• Functionalized polymers, which can be tailored to adsorb specifically on polar surfaces, have been shown to markedly reduce friction and wear.

[0006] Despite the advantages of the friction modifiers listed above, there are multiple problems associated with them. The most common type of friction modifier is a zinc dithiophosphate (ZnDTP or ZDDP). However, it has been reported that zinc and phosphorus emissions may damage catalytic converters. The use of ZDDP is therefore being reduced in many applications. Other metal containing compounds such as molybdenum dithiocarbamates (MoDTC) can also cause some emission problems.

[0007] The problems associated with ZDDP mean that organic ash-less friction modifiers are becoming more and more important. Organic friction modifiers are generally long straight chain hydrocarbons consisting of at least 10 carbon atoms and a polar group at one end. The polar group is one of the governing factors in the effectiveness of the molecules 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, U.S. 3,933,659 and EP335701, the contents of which are incorporated herein by reference, all describe long polar friction modifiers in lubricants. Glycerol monooleate (GMO) is another example of an organic FM. It is described in U.S. 5,885,942; 5,866,520; 5,114,603; 4,957,651; and 4,683,069, the contents of which are incorporated herein by reference.

[0008] A problem with most organic lubricants is that they contain hydrolysable groups, for example ester groups which can hydrolyse and degrade. This results in loss of friction modification performance and produces hydrophilic breakdown products which are immiscible with the oils and lubricants.

[0009] There is therefore a need to produce friction modifiers which are stable and do not damage catalyst converters.Object of the Disclosure

[0010] It is therefore an object of the present disclosure to provide compounds with excellent friction modifying properties that do not produce harmful emissions and are stable.Brief Description of the Drawings

[0011] Figure 1 depicts a graph showing the reduction in coefficient of friction between Mobil 10W-30 and the FM-A containing material of Example 5.

[0012] Figure 2 depicts a graph showing the reduction in coefficient of friction between Mobil 10W-20 and the FM-A containing material of Example 6.Detailed Description

[0013] The present disclosure will be described with respect to particular aspects and embodiments.

[0014] It is to be noticed that the term "comprising", used in the claims, should not be interpreted as being restricted to the means listed thereafter; it does not exclude other elements or steps. It is thus to be interpreted as specifying the presence of the stated features, steps or components as referred to, but does not preclude the presence or addition of one or more other features, steps or components, or groups thereof. Thus, the scope of the expression "a compound comprising components X and Y" should not be limited to compounds consisting only of components X and Y. It means that with respect to the present disclosure, the only relevant components of the compound are X and Y.

[0015] Throughout this specification, reference to "one embodiment" or "an embodiment" are made. Such references indicate that a particular feature, described in relation to the embodiment is included in at least one embodiment of the present disclosure. Thus, appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, though they could. Furthermore, the particular features or characteristics may be combined in any suitable manner in one or more embodiments, as would be apparent to one of ordinary skill in the art.

[0016] The terms “preferred” and “preferably” refer to embodiments that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the present disclosure.

[0017] The term “optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0018] Where substituent groups are specified by their conventional chemical formula, written from left to right, they equally encompass the chemically identical substituents that would result from writing the structure from right to left, for example, -CH2O- is equivalent to -OCH2-

[0019] It is to be understood that although preferred embodiments and / or materials have been discussed for providing embodiments according to the present disclosure, various modifications or changes may be made without departing from the scope and spirit of this disclosure.

[0020] In one embodiment, the disclosure provides a compound selected from compounds of formula (I), formula (II), formula (III), formula (IV), formula (V), formula (VI), and mixtures thereof:wherein R is selected from an alkyl, cycloalkyl, alkyl ether, aryl ether and aryl;R’ is selected from alkyl, cycloalkyl, and aryl; andR” is independently selected from H, methyl, ethyl or a combination thereof.

[0021] The compounds of Formulas (I), (II), (III), (IV), (V), and (VI) described above have excellent friction reducing abilities and can be included in a wide range of formulations. The amino acetamide products contain both amine and amide groups in the polar head, which help the molecule to strongly adsorb to surfaces, in particular metal surfaces, in contact with the friction modifiers. The linear structure of the hydrophobic tail ensures strong Van der Waals forces between these tails promoting the formation of a self-assembled monolayer. These unique molecular structures make these molecules excellent friction modifiers for lubricants.

[0022] Further, since the compounds of the disclosure have no hydrolysable groups, they therefore exhibit good storage stability and are not sensitive to water. The friction modifiers of the present disclosure do not contain any heavy metal atoms and therefore exhibit a favourable emissions profile.

[0023] The term "storage stability" refers to the ability of a composition to be stored at ambient temperature in a suitable container under exclusion of moisture for a certain time interval, such as at least three months or at least four months or at least five months or at least six months, without undergoing significant changes in application or end-use properties (for e.g. with minor (less than about 5% or less than about 4% or less than about 3%) or no crystallisation and / orwith minor (less than about 5% or less than about 4% or less than about 3%) or no increase in viscosity).

[0024] A friction modifier is any substance which can minimize light surface contacts (sliding and rolling) that may occur in a given machine design. Herein the term boundary lubrication additives may also be used to refer to friction modifiers.

[0025] The term “alkyl” refers to a linear or branched hydrocarbyl radical having 1 to 50 carbon atoms, and “substituted alkyl” refers to an alkyl further bearing one or more substituents selected from hydroxy, alkoxy, mercapto, cycloalkyl, heterocyclic, aryl, heteroaryl, aryloxy, halogen, trifluoromethyl, cyano, nitro, nitrone, amino, amido, C(O)H, acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide, and sulfuryl. Examples of alkyls include butyl, isobutyl, secbutyl, tert-butyl, propyl, isopropyl, ethyl and methyl.

[0026] An aryl is a functional group derived from a simple aromatic ring, i.e., a ring that contains delocalised pi electrons such as a benzene ring. Used herein, the term aryl may refer to pure hydrocarbon aryls and heteroaryls (for example, aryls that comprise a heteroatom selected from N, O or S).

[0027] In some embodiments, R is a C4-100 linear or branched alkyl. For example, -C4H9, or - C100H201. In preferred embodiments, R is a C12 to C22 linear or branched alkyl.

[0028] In some embodiments R is a 5 or 6 membered saturated cycloalkyl.

[0029] In some embodiments R’ is a C4-100 linear or branched alkyl. For example, -C4H9, or - C100H201. In preferred embodiments, R’ is a C12 to C22 linear or branched alkyl.

[0030] In some embodiments R’ is a 5 or 6 membered saturated cycloalkyl.

[0031] In some embodiments, R’ is a C4-100 linear or branched alkyl ether.

[0032] A further aspect of the disclosure is a friction modifier comprising a compound of formula (I), (II), (III), (IV), (V), (VI) or combinations thereof.

[0033] In some embodiments, the friction modifier may comprise further components selected from a lubricant, an oil, detergent, dispersants, anti-wearing agents, EP agents, antioxidants and combinations thereof.

[0034] In a further embodiment, the disclosure comprises a composition comprising the friction modifier described above and optionally one or more additional components selected from a lubricant, an oil, detergent, dispersants, anti-wearing agents, EP agents, antioxidants and combinations thereof.

[0035] Organic friction modifiers that are used in lubricant formulation are also good friction modifiers for fuels. Since the amino acetamide compounds described above perform better thancommercially available organic friction modifiers in lubricant formulations, the compounds of the present disclosure will also function as friction modifiers in fuels, such as gasoline.

[0036] In an aspect of the disclosure there is provided a method for modifying the coefficient of friction between at least two surfaces, said method comprising contacting at least one of the surfaces with a composition comprising the friction modifier described.

[0037] In an aspect of the disclosure there is provide use of the friction modifier described above to modify the coefficient of friction between at least two surfaces.

[0038] The friction coefficient of a composition can be measured using any method known to the skilled person. The friction coefficient 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. It is usually symbolised by p.

[0039] In some embodiments, modifying the coefficient of friction may comprise a decrease in the coefficient of friction of at least 60%, at least 50%, at least 40%, at least 20%, at least 10%, or at least 5%.

[0040] Preferably, the compounds of the present disclosure reduce the coefficient of friction between two surfaces.

[0041] A further aspect of the disclosure describes a method for making a friction modifier, said process comprising reacting a halo acetamide with a compound selected from compound A, B and C:ompoun to make a compound of formula (I), (II), (III), (IV), (V), and (VI):wherein R, R’, and R” are as described above; and wherein n is 5-100, preferably 12-22.

[0042] In certain embodiments, the halo acetamide is a chloroacetamide. Chloroacetamide is commercially available.

[0043] In some embodiments the reaction is performed under basic conditions. Suitable bases include but are not limited to organic bases such as pyridine, alkylamines, such as methylamine, imidazole, benzimidazole, histidine, guanidine, phosphazene bases, hydroxides of quaternary ammonium cations or some other organic cations and inorganic bases such as metal hydroxides (e g., LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2, Ba(OH)2).

[0044] In certain embodiments the reaction is performed at a temperature in the range of 0- 200 °C, preferably 50-150 °C

[0045] In some embodiments, the reaction comprises reacting Compound A and a haloacetate in a molar ratio of 2: 1 to produce a compound of formula (I).

[0046] In some embodiments, the reaction comprises reacting Compound A and a haloacetate in a molar ratio of 1 : 1 to produce a compound of formula (II).

[0047] In some embodiments, the reaction comprises reacting Compound B and a haloacetate in a molar ratio of 1 : 1 to produce a compound of formula (III).

[0048] In some embodiments, the reaction comprises reacting Compound B and a haloacetate in a molar ratio of 2: 1 to produce a compound of formula (IV).

[0049] In some embodiments, the reaction comprises reacting Compound C and a haloacetate in a molar ratio of 1 : 1 to produce a compound of formula (V).

[0050] In some embodiments, the reaction comprises reacting Compound C and a haloacetate in a molar ratio of 2: 1 to produce a compound of formula (VI).

[0051] The particular and preferred features of the disclosure set out above may be combined with other features as appropriate.

[0052] The above and other characteristics, features and advantages of the present disclosure will become apparent from the detailed description, taken in conjunction with the accompanying examples which illustrate the principles of the disclosure.Examples

[0053] The detailed description of the present disclosure can be illustrated in the following examples. All chemicals were supplied by Huntsman International LLC except for:2-Chloroacetamide: Sigma AldrichNaOH solution: Sigma AldrichToluene: Sigma AldrichTOMAMINE PA-19: Evonik (structure below)R: C12-15 alkylAdogen 172: Evonik (structure below)Jeffamine C-300 was supplied by Huntsman and has the structure below:R: Cl 2- 14 alkyl n = 2.2

[0054] Unless otherwise indicated, all parts and all percentages in the following examples, as well as throughout the specification, are parts by weight or percentages by weight respectively. The term "ambient temperature" refers to the temperature of the surrounding work environment (e.g., the temperature of the area, building or room where the composition is used). The ambient temperature may be within a range from about 10°C to about 30°C, more specifically from about 15°C to about 25°C.Example 1 - Alkyl polyether amino monoacetamide synthesis

[0055] 169.1 g (0.5 mol) Jeffamine C-300, 169.1 g toluene and 46.75 g (0.5 mol) 2- Chloroacetamide were charged into a 1000 ml three neck flask. The temperature of the mixture was increased to 100 °C whilst agitating.

[0056] 42 grams 50% NaOH solution was charged into the flask whilst controlling the temperature at 100 ± 5 °C. The reaction solution was held at 100 °C for one hour. The reaction was cooled down to ambient temperature and the product mixture washed twice with deionised water. The toluene and moisture in the organic layer were removed under vacuum (20torr) and elevated temperature (90 °C).

[0057] The final product was mainly alkyl polyether amino monoacetamide. The product was named friction modifier A(FM-A).Example 2 - Alkyl polyether amino diacetamide synthesis

[0058] 169.1 g (0.5 mol) Jeffamine C-300, 169.1 g toluene and 93.5 g (1.0 mol) 2- Chloroacetamide were charged into a 1000 ml three neck flask. The flask was agitated and the temperature raised to 100 °C.

[0059] 42 grams 50% NaOH solution was added dropwise into the flask whilst the temperature was maintained at 100±5°C. After 1 hour, the reaction flask was cooled down to an ambient temperature. The product mixture was washed twice with deionised water. The organic layerwas removed under vacuum at an elevated temperature (20torr and 90 °C) and the final product was isolated.

[0060] The LC-MS analysis shows that the final product was 90% alkyl polyether amino diacetamide. The product was named friction modifier B (FM-B).Example 3 - Alkyl ether amino monoacetamide synthesis

[0061] 143.5 g (0.5 mol) TOMAMINE PA-19, 169.1 g toluene and 46.75 g (0.5 mol) 2- Chloroacetamide were charged into a 1000 ml three neck flask. The reaction temperature was raised to 100 °C under agitation.

[0062] 42 grams of 50% NaOH solution was added into the flask dropwise and the temperature controlled at 100±5°C. After 1 hour, the reaction vessel was cooled down to ambient temperature. The resultant product mixture was washed twice with deionised water. The product in the organic layer was removed and the remaining toluene and moisture were removed under vacuum and elevated temperature (20torr and 90 °C).

[0063] The final product was mainly alkyl ether amino monoacetamide. The product was named friction modifier C (FM-C).Example 4 - Alkyl amino monoacetamide synthesis

[0064] 142.5 g (0.5 mol) ADOGEN 172, 169.1 g toluene and 46.75 g (0.5 mol) 2- Chloroacetamide were charged into a 1000 ml three neck flask. The temperature of the vessel was raised to 100 °C and the reaction mixture agitated.

[0065] 42 grams 50% NaOH solution was added into the flask dropwise and the temperature maintained at 100±5°C. After 1 hour reaction, the reaction was cooled down to ambient temperature. The product mixture was washed twice with deionised water. The product was isolated by removing the toluene and moisture in the organic layer under vacuum and elevated temperature (20torr and 90 °C).

[0066] The final product was mainly alkyl amino monoacetamide. The product was named friction modifier D (FM-D).Example 5 - Evaluation of friction modifiers in Mobil 5W-30 oil

[0067] The friction modifiers produced in Examples 1 to 4 were added to Mobil 5W-30 oil commercial oil. The coefficient of friction of commercial oil comprising 0.5% organic friction modifier was determined at 100 and 130°C using a Mini Traction Machine with a3 / 4 inch ballon a smooth disc. The load applied was 36N (1 GPa contact pressure) and the speed of rotation was from 0.01 m / s to 2 m / s. The results are provided in Table 1 below:Table 1: Friction modifier top treatment results at 130 °C in Mobil 1 5W-30 oil.

[0068] This data shows that all the amino acetamide products of the examples (FM-A, B, C and D) can significantly reduce the coefficients of friction of the Mobil 1 5W-30 oil.

[0069] Figure 1 shows the whole range of measurements for FM-A.Example 6 - Evaluation of friction modifiers in Mobil 1 0W-20 oil

[0070] The friction coefficient for Mobil 1 OW-20 oil was measured in the same was as described above in Example 5. The results are shown below in Table 2.Table 2: Friction modifier top treatment results at 130 °C in Mobil 1 0W-20 oil.

[0071] The data in table 2 shows that all the amino acetamide products the examples (FM-A, B, C and D) can significantly reduce the coefficients of friction of the Mobil 1 0W-20 oil.

[0072] The whole range for FM-A is shown in Figure 2.

Claims

ClaimsWhat is claimed is:

1. A compound selected from the group consisting of formula (I), formula (II), formula (III), formula (IV), formula (V), and formula (VI):wherein R is selected from an alkyl, cycloalkyl, alkyl ether, and aryl;R’ is selected from alkyl, cycloalkyl, and aryl; andR” is independently selected from H, methyl, ethyl or a combination thereof.

2. The compound of claim 1, wherein R is a C4-100 linear or branched alkyl, preferably R is a C12 to C22 linear or branched alkyl.

3. The compound of claim 1, wherein R is a 5 or 6 membered saturated cycloalkyl.

4. The compound of claim 1, wherein R is a C4-100 linear or branched alkyl ether or an aryl ether.

5. The compound of any preceding claim, wherein R’ is a C4-100 linear or branched alkyl, preferably wherein R’ is a C12 to C22 linear or branched alkyl.

6. The compound of any one of claims 1 to 4, wherein R’ is a 5 or 6 membered saturated cycloalkyl.

7. The compound of any one of claims 1 to 4, wherein R’ is a C4-100 linear or branched alkyl ether or an aryl ether.

8. A friction modifier comprising a compound selected from the group consisting of formula (I), (II), (III), (IV), (V), (VI) or a combination thereof as defined in any one of claims 1 to 7.

9. A composition comprising a compound selected from the group consisting of formula (I), (II), (III), (IV), (V), (VI) or a combination thereof as defined in any one of claims 1 to 7 and optionally one or more additional components selected from a lubricant, an oil, detergent, dispersants, anti-wearing agents, EP agents, antioxidants.

10. A method for modifying the coefficient friction of friction between at least two surfaces, said method comprising contacting at least one of the surfaces with the composition of claim 9, the friction modifier of claim 8, or a compound as described in any one of claims 1 to 7.

11. A method for making a friction modifier, said process comprising reacting a halo acetamide with a compound selected from the group consisting of compound A, B and Compoun , to make a compound of formula (I), (II), (III), (IV), (V), and (VI) as described in any one of claims 1 to 7.

12. The method of claim 11, wherein the halo acetamide is chloroacetamide.

13. The method of claim 11 or claim 12, wherein the reaction is performed at a temperature in the range of 0- 200 °C, preferably 50-150 °C.

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