EP4536786A1 - Grease thickening agent - Google Patents

Abstract

The present disclosure provides a polyamide grease thickening agent having the structure according to Formula I: (MCA-DA-)(PCA-DA)y-PCA-(DA-PCA)y(-DA-MCA) (I). In Formula I, at each occurrence PCA is independently a reacted polycarboxylate, at each occurrence MCA is independently a reacted monocaboxylate, at each occurrence DA is independently a reacted n-alkyl diamine, and y is 0 or a non-zero integer. Additionally, in Formula I, a weight-average molecular weight of the polyamide grease thickener is in a range of from about 450 g/mol to about 2600 g/mol. Additionally, in Formula I, the structure includes at least 4 amide bonds and at least two internal aromatic moieties are di-substituted in a para position.

Description

GREASE THICKENING AGENT

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application Serial No. 63/351,582 entitled “GREASE THICKENING AGENT,” filed June 13, 2022, the disclosure of which is incorporated herein in its entirety by reference. This application further claims the benefit of priority to U.S. Provisional Patent Application Serial No.

63/423,815 entitled “GREASE THICKENING AGENT,” filed November 9, 2022, the disclosure of which is incorporated herein in its entirety by reference. This application further claims the benefit of priority to U.S. Provisional Patent Application Serial No. 63/463,576 entitled “GREASE THICKENING AGENT,” filed May 3, 2023, the disclosure of which is incorporated herein in its entirety by reference.

BACKGROUND

[0002] Grease compositions provide lubrication for a variety of articles. While it is important for the grease composition to include adequate lubricating and base oils, a grease thickening agent is needed to provide mechanical properties to the grease composition.

SUMMARY OF THE INVENTION

[0003] The present disclosure provides a polyamide grease thickening agent having the structure according to Formula I:

(MCA-DA-)(PCA-DA)y-PCA-(DA-PCA)_y(-DA-MCA) (I).

In Formula I, at each occurrence PC A is independently a reacted poly carboxylate, at each occurrence MCA is independently a reacted monocaboxylate, at each occurrence DA is independently a reacted diamine, and y is 0 or a non- zero integer. Additionally, in Formula I, a weight-average molecular weight of the polyamide grease thickener is in a range of from about 450 g/mol to about 3500 g/mol. Additionally, in Formula I, the structure includes at least 4 amide bonds and at least two internal aromatic moieties are di-substituted in a para position. [0004] Surprisingly and unexpectedly, according to various aspects of the present disclosure, the grease thickening compositions are able to perform at least substantially equivalently to a corresponding grease thickening agent that includes lithium, polyurea, or both. Thus it is possible to formulate grease compositions that are substantially free of lithium, polyurea, or both.

BRIEF DESCRIPTION OF THE FIGURE

[0005] The drawings illustrate generally, by way of example, but not by way of limitation, various aspects of the present disclosure.

[0006] FIG. 1 is graph showing penetration values of various grease compositions, in accordance with various aspects of the present disclosure.

DETAILED DESCRIPTION OF THE INVENTION

[0007] Reference will now be made in detail to certain embodiments of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

[0008] Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.

[0009] In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” or “at least one of A or B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section.

[0010] In the methods described herein, the acts can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0011] The term “about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range.

[0012] The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. The term “substantially free of’ as used herein can mean having none or having a trivial amount of, such that the amount of material present does not affect the material properties of the composition including the material, such that about 0 wt% to about 5 wt% of the composition is the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than or equal to about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less, or about 0 wt%.

[0013] The term “organic group” as used herein refers to any carbon-containing functional group. Examples can include an oxygen-containing group such as an alkoxy group, aryloxy group, aralkyloxy group, oxo(carbonyl) group; a carboxyl group including a carboxylic acid, carboxylate, and a carboxylate ester; a sulfur-containing group such as an alkyl and aryl sulfide group; and other heteroatom-containing groups. Non-limiting examples of organic groups include OR, OOR, OC(O)N(R)2, CN, CF3, OCF3, R, C(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, SOR, SO2R, SO₂N(R)₂, SO3R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)o-₂N(R)C(0)R, (CH₂)o- 2N(R)N(R)2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)₂, N(R)SO₂R, N(R)SO₂N(R)2, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)2, N(R)C(S)N(R)2, N(COR)COR, N(0R)R, C(=NH)N(R)₂, C(O)N(OR)R, C(=NOR)R, and substituted or unsubstituted (Ci-Cioo)hydrocarbyl, wherein R can be hydrogen (in examples that include other carbon atoms) or a carbon-based moiety, and wherein the carbon-based moiety can be substituted or unsubstituted.

[0014] The term “substituted” as used herein in conjunction with a molecule or an organic group as defined herein refers to the state in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms. The term “functional group” or “substituent” as used herein refers to a group that can be or is substituted onto a molecule or onto an organic group. Examples of substituents or functional groups include, but are not limited to, a halogen (e.g., F, Cl, Br, and I); an oxygen atom in groups such as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates, and carboxylate esters; a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atom in groups such as amines, hydroxyamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups. Non-limiting examples of substituents that can be bonded to a substituted carbon (or other) atom include F, Cl, Br, I, OR, OC(O)N(R)2, CN, NO, NO2, ONO2, azido, CF3, OCF3, R, O (oxo), S (thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R)2, SR, SOR, SO2R, SO₂N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, (CH₂)O-2N(R)C(0)R, (CH₂)O-2N(R)N(R)2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂, N(COR)COR, N(OR)R, C(=NH)N(R)2, C(O)N(OR)R, and C(=NOR)R, wherein R can be hydrogen or a carbon-based moiety; for example, R can be hydrogen, (Ci-Cioo)hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or wherein two R groups bonded to a nitrogen atom or to adjacent nitrogen atoms can together with the nitrogen atom or atoms form a heterocyclyl.

[0015] The term “alkyl” as used herein refers to straight chain and branched alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms. Examples of straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n- pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2- dimethylpropyl groups. As used herein, the term “alkyl” encompasses n-alkyl, isoalkyl, and anteisoalkyl groups as well as other branched chain forms of alkyl. Representative substituted alkyl groups can be substituted one or more times with any of the groups listed herein, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.

[0016] The term “alkenyl” as used herein refers to straight and branched chain and cyclic alkyl groups as defined herein, except that at least one double bond exists between two carbon atoms. Thus, alkenyl groups have from 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12 carbon atoms or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to vinyl, -CH=CH(CH₃), -CH=C(CH₃)₂, -C(CH₃)=CH₂, -C(CH₃)=CH(CH₃), - C(CH₂CH₃)=CH₂, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl among others.

[0017] The term “alkynyl” as used herein refers to straight and branched chain alkyl groups, except that at least one triple bond exists between two carbon atoms. Thus, alkynyl groups have from 2 to 40 carbon atoms, 2 to about 20 carbon atoms, or from 2 to 12 carbons or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to -CH, -C(CH₃), -C(CH₂CH₃), -CH₂CH, -CH₂C(CH₃), and -CH₂C(CH₂CH₃) among others.

[0018] The term “acyl” as used herein refers to a group containing a carbonyl moiety wherein the group is bonded via the carbonyl carbon atom. The carbonyl carbon atom is bonded to a hydrogen forming a “formyl” group or is bonded to another carbon atom, which can be part of an alkyl, aryl, aralkyl cycloalkyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group or the like. An acyl group can include 0 to about 12, 0 to about 20, or 0 to about 40 additional carbon atoms bonded to the carbonyl group. An acyl group can include double or triple bonds within the meaning herein. An acryloyl group is an example of an acyl group. An acyl group can also include heteroatoms within the meaning herein. A nicotinoyl group (pyridyl-3-carbonyl) is an example of an acyl group within the meaning herein. Other examples include acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl, and acryloyl groups and the like. When the group containing the carbon atom that is bonded to the carbonyl carbon atom contains a halogen, the group is termed a “haloacyl” group. An example is a trifluoroacetyl group.

[0019] The term “cycloalkyl” as used herein refers to cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, the cycloalkyl group can have 3 to about 8-12 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 4, 5, 6, or 7. Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl, and the like. Cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined herein. Representative substituted cycloalkyl groups can be mono- substituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4- 2,5- or 2,6-disubstituted cyclohexyl groups or mono-, di- or trisubstituted norbornyl or cycloheptyl groups, which can be substituted with, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups. The term “cycloalkenyl” alone or in combination denotes a cyclic alkenyl group.

[0020] The term “aryl” as used herein refers to cyclic aromatic hydrocarbon groups that do not contain heteroatoms in the ring. Thus aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups. In some embodiments, aryl groups contain about 6 to about 14 carbons in the ring portions of the groups. Aryl groups can be unsubstituted or substituted, as defined herein. Representative substituted aryl groups can be mono-substituted or substituted more than once, such as, but not limited to, a phenyl group substituted at any one or more of 2-, 3-, 4-, 5-, or 6-positions of the phenyl ring, or a naphthyl group substituted at any one or more of 2- to 8-positions thereof.

[0021] The term “aralkyl” as used herein refers to alkyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to an aryl group as defined herein. Representative aralkyl groups include benzyl and phenylethyl groups and fused (cycloalkylaryl)alkyl groups such as 4-ethyl-indanyl. Aralkenyl groups are alkenyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to an aryl group as defined herein.

[0022] The term “heterocyclyl” as used herein refers to aromatic and non-aromatic ring compounds containing three or more ring members, of which one or more is a heteroatom such as, but not limited to, N, O, and S.

[0023] The term “heteroaryl” as used herein refers to aromatic ring compounds containing 5 or more ring members, of which, one or more is a heteroatom such as, but not limited to, N, 0, and S; for instance, heteroaryl rings can have 5 to about 8-12 ring members. A heteroaryl group is a variety of a heterocyclyl group that possesses an aromatic electronic structure.

[0024] The term “heterocyclylalkyl” as used herein refers to alkyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group as defined herein is replaced with a bond to a heterocyclyl group as defined herein. Representative heterocyclyl alkyl groups include, but are not limited to, furan-2-yl methyl, furan-3-yl methyl, pyridine-3-yl methyl, tetrahydrofuran-2-yl ethyl, and indol-2-yl propyl.

[0025] The term “heteroarylalkyl” as used herein refers to alkyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to a heteroaryl group as defined herein.

[0026] The term “alkoxy” as used herein refers to an oxygen atom connected to an alkyl group, including a cycloalkyl group, as are defined herein. Examples of linear alkoxy groups include but are not limited to methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like. Examples of branched alkoxy include but are not limited to isopropoxy, sec-butoxy, tertbutoxy, isopentyloxy, isohexyloxy, and the like. Examples of cyclic alkoxy include but are not limited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like. An alkoxy group can include about 1 to about 12, about 1 to about 20, or about 1 to about 40 carbon atoms bonded to the oxygen atom, and can further include double or triple bonds, and can also include heteroatoms. For example, an allyloxy group or a methoxyethoxy group is also an alkoxy group within the meaning herein, as is a methylenedioxy group in a context where two adjacent atoms of a structure are substituted therewith.

[0027] The term “amine” as used herein refers to primary, secondary, and tertiary amines having, e.g., the formula N(group)3 wherein each group can independently be H or non-H, such as alkyl, aryl, and the like. Amines include but are not limited to R-NEE, for example, alkylamines, arylamines, alkylarylamines; R2NH wherein each R is independently selected, such as dialkylamines, diarylamines, aralkylamines, heterocyclylamines and the like; and R3N wherein each R is independently selected, such as trialkylamines, dialkylarylamines, alkyldiarylamines, triarylamines, and the like. The term “amine” also includes ammonium ions as used herein. [0028] The term “amino group” as used herein refers to a substituent of the form -NH2, - NHR, -NR2, -NR3⁺, wherein each R is independently selected, and protonated forms of each, except for -NR3⁺, which cannot be protonated. Accordingly, any compound substituted with an amino group can be viewed as an amine. An “amino group” within the meaning herein can be a primary, secondary, tertiary, or quaternary amino group. An “alkylamino” group includes a monoalkylamino, dialkylamino, and trialkylamino group.

[0029] The terms “halo,” “halogen,” or “halide” group, as used herein, by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom.

[0030] The term “haloalkyl” group, as used herein, includes mono-halo alkyl groups, poly-halo alkyl groups wherein all halo atoms can be the same or different, and per-halo alkyl groups, wherein all hydrogen atoms are replaced by halogen atoms, such as fluoro. Examples of haloalkyl include trifluoromethyl, 1 , 1 -dichloroethyl, 1,2-dichloroethyl, l,3-dibromo-3,3- difluoropropyl, perfluorobutyl, and the like.

[0031] The term “hydrocarbon” or “hydrocarbyl” as used herein refers to a molecule or functional group that includes carbon and hydrogen atoms. The term can also refer to a molecule or functional group that normally includes both carbon and hydrogen atoms but wherein all the hydrogen atoms are substituted with other functional groups. The term “hydrocarbyl” refers to a functional group derived from a straight chain, branched, or cyclic hydrocarbon, and can be alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl, or any combination thereof. Hydrocarbyl groups can be shown as (Ca-Cb)hydrocarbyl, wherein a and b are integers and mean having any of a to b number of carbon atoms. For example, (Ci-C4)hydrocarbyl means the hydrocarbyl group can be methyl (Ci), ethyl (C2), propyl (C3), or butyl (C4), and (Co-Cb)hydrocarbyl means in certain embodiments there is no hydrocarbyl group. A hydrocarbylene group is a diradical hydrocarbon, e.g., a hydrocarbon that is bonded at two locations.

[0032] The term “weight-average molecular weight” as used herein refers to M_w, which is equal to SMi²ni / EMm, where nt is the number of molecules of molecular weight Mi. In various examples, the weight-average molecular weight can be determined using light scattering, small angle neutron scattering, X-ray scattering, and sedimentation velocity.

[0033] The polymers described herein can terminate in any suitable way. In some embodiments, the polymers can terminate with an end group that is independently chosen from a suitable polymerization initiator, -H, -OH, a substituted or unsubstituted (Ci-C2o)hydrocarbyl (e.g., (Ci-Cio)alkyl or (Ce-C2o)aryl) interrupted with 0, 1, 2, or 3 groups independently selected from -O-, substituted or unsubstituted -NH-, and -S-, a poly(substituted or unsubstituted (Ci- C2o)hydrocarbyloxy), and a poly(substituted or unsubstituted (Ci-C2o)hydrocarbylamino).

[0034] The origin of any reactant, feedstock, and/or material can be from any available source. Without limitation, examples of such sources can include, natural products, synthetic products, petrochemicals, bio-renewables, recycled materials, or a mixture thereof.

[0035] Various aspects of the present disclosure relate to a grease thickening agent. The grease thickening agent is characterized as a polyamide grease thickening agent. It has been found that successful grease thickening agents are those that result in a grease composition having a dropping point greater than 200 °C, 220, 240, 260, or 280 °C as well as having a NLGI rating as a group 2 or greater. Structural features of the grease thickener that are found to help achieve these characteristics include that any aliphatic moieties in monomers that are internally disposed in the grease thickener molecule and are n-alkyl (linear), additionally the grease thickener should include at least two para-substituted aromatic moieties, the grease thickener should have a molecular weight in a range of from 450 g/mol to 3500 g/mol, and the grease thickener should include at least four amide bonds. These structural features were found to achieve the desirable physical properties when the grease thickener is incorporated into a grease composition in a concentration in a range of from about 10 wt% to 20 wt%, about 10 wt% to about 15 wt%, less than, equal to, or greater than about 10 wt%, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 wt%.

[0036] Various examples of grease thickening agents are described herein. Some of the structures described may not possess each of the aforementioned desirable structural features. However, some grease thickening agents that include at least some of the aforementioned desirable features may provide a grease thickening agent that may perform adequately. Additionally, in various aspects, it can be desirable for a grease composition to include a mixture of grease thickening components. In such a mixture, at least one grease thickening agent can include all of the aforementioned desirable structural features. Additionally, the mixture can include another grease thickener agent that may include fewer than all of the aforementioned structural features or even any of the structural features. However, the mixture itself may still yield desirable properties in the grease composition to which it is incorporated. [0037] The polyamide grease thickening agent can have the structure according to Formula VIII:

(MCA-DA-(ZZ)_y-)xPCA (VIII).

| — PCA— DA— |

I In T F?ormu 1la r I, a +t eac rh» occurrence Z 7Z7 is I « — ^PCA — ^DA— I ’ or \ ' > ) , _v X i •s I • — ( ^vDA-ZZ) 'y^yMCA

, at each occurrence PCA is independently a reacted poly carboxy late (e.g., reacted with DA), at each occurrence MCA is independently a reacted monocaboxylate, at each occurrence DA is independently a reacted diamine (e.g., reacted with MCA and one of ZZ or PCA), x is a non- zero integer, y is 0 or a non-zero integer, and z is 0 or a non-zero integer. In some examples, x, y, and z are independently in a range of from 1 to 10, 1 to 3, less than, equal to, or greater than 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The bonds between MCA and DA are amide bonds. The bonds between DA and ZZ or DA and PCA are either amide bonds or imide bonds. As used herein “reacted” means that that the identified starting material has reacted to become part of the grease thickening agent.

[0038] The polyamide grease thickening agent can have the structure according to Formula I:

(MCA-DA-)(PCA-DA)y-PCA-(DA-PCA)_y(-DA-MCA) (I).

In still further examples, the polyamide grease thickening agent can have the structure according to Formula II:

((MCA-DA-)(PCA-DA)_y-)nPCA (II).

In Formula II, n is in a range of from 2-4. In still further examples, the polyamide grease thickening agent has the structure according to Formula III:

(MCA-DA)-PCA-(DA-MCA) (III). [0039] The reacted polycarboxylate can be a poly carboxylic acid, poly carboxylic ester, polycarboxylic acid chloride, or an anhydride. At each occurrence, PCA can independently include 3 to 50 carbon atoms 6 to 10 carbon items, or 6, 8, or 9 carbon atoms. For example, at each occurrence, PCA can include a reacted poly carboxylate having the structure according to the following Formulas:

Formula (X):

Formula (XVII):

(XVII), or

Formula (XVIII): (xviii),

[0040] At each occurrence R¹ and R² are independently a bond or a substituted or unsubstituted (Ci-C2o)hydrocarbyl and at each occurrence, R⁶ is chosen from -OH, -Cl, -O', or substituted or unsubstituted -0-(Ci-C2o)hydrocarbyl. At each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbyl is independently selected from a substituted or unsubstituted (Ci-C2o)alkyl, a substituted or unsubstituted (C3-C2o)cycloalkyl, a substituted or unsubstituted (C2-C2o)alkenyl, a substituted or unsubstituted (C2-C2o)alkynyl, a substituted or unsubstituted (Ci-C2o)acyl, a substituted or unsubstituted (C4-C2o)aryl, and a substituted or unsubstituted (C2- C2o)alkoxy. In some examples, at each occurrence, PCA has the same chemical structure. Alternatively, at least two occurrences PCA can have different chemical structures.

[0041] As specific examples, at each occurrence, PCA independently includes a reacted adipic acid, a reacted purified terephthalic acid, a reacted isophthalic acid, a reacted phthalic anhydride, a reacted napthalenic acid, a reacted mellitic acid, a reacted mellitic anhydride, a reacted naphthalene tetracarboxylic anhydride, a reacted citric acid, a reacted ester, a reacted acid chloride, a reacted dianhydride, or a reacted ethylenediaminetetraacetic acid. PCA can include three carboxylic acid groups or two carboxylic acid groups. A more preferred structure of the grease thickener composition is that of Formula II or III. That is the structure of Formula II or III more easily allows for forming a grease thickener having the combination of the desirable structural features described herein above. In preferred aspects, the grease thickener component will have at least four amide bonds.

[0042] At each occurrence, MCA can include a reacted ester, a reacted acid chloride, or a reacted anhydride. For example, at each occurrence MCA can include a reacted monocarboxylate, the monocarboxylate having the structure according to Formula (IV):

In Formula VIII, R³ is a substituted or unsubstituted (Ci-C2o)hydrocarbyl and R⁷ is chosen from -OH, -Cl, -O', or substituted or unsubstituted -0-(Ci-C2o)hydrocarbyl. At each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbyl is independently selected from a substituted or unsubstituted (Ci-C2o)alkyl, a substituted or unsubstituted (C3-C2o)cycloalkyl, a substituted or unsubstituted (C2-C2o)alkenyl, a substituted or unsubstituted (C2-C2o)alkynyl, a substituted or unsubstituted (Ci-C2o)acyl, a substituted or unsubstituted (C4-C2o)aryl, and a substituted or unsubstituted (C2-C2o)alkoxy.

[0043] As a further example, at each occurrence MCA can include a reacted monocarboxylate. The monocarboxylate can have the structure according to the following Formulas:

Formula (V):

Formula (VI):

R⁴ is chosen from a bond and a substituted or unsubstituted (Ci-C2o)hydrocarbylene. At each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbylene is independently selected from a substituted or unsubstituted (Ci-C2o)alkylene, a substituted or unsubstituted (C3- C2o)cycloalkylene, a substituted or unsubstituted (C2-C2o)alkenylene, a substituted or unsubstituted (C2-C2o)alkynylene, a substituted or unsubstituted (Ci-C2o)acylene, a substituted or unsubstituted (C4-C2o)arylene, and a substituted or unsubstituted -O-(CH2)n- (n = 2-20). At each occurrence MCA has the same chemical structure. Alternatively, at least two occurrences of MCA has a different chemical structure. As examples, MCA can be a reacted benzoic acid, a reacted cyclohexanecarboxylic acid, or a reacted steric acid.

[0044] Although not intending to be bound to any theory, it is believed that a grease thickening agent in which MCA includes an aromatic group, cycloaliphatic group, or aliphatic group, provides the best performance for the grease thickening agent in the grease composition. Still further it is believed that superior performance can be attained when a first MCA includes an aromatic group and a second MCA includes an aliphatic or cycloaliphatic group. In particular, it is thought that a second MCA including an aliphatic chain having 6-8 carbon atoms yields superior performance. The hydrophobic properties of the aliphatic groups are thought to aid in providing compatibility with the grease. It is also thought that if R³ and R⁴ are not a bond, then it is better for them to be n-(Ci-C2o)alkylene as this more easily allows for forming a grease thickener having the combination of the desirable structural features described herein above. [0045] As shown, the reaction between the respective MCA and DA groups results in the grease thickeners having terminal amide groups. While not intending to be bound by any theory it is believed that the terminal amide groups provide several benefits. For example, an amide group gives the grease thickener a reactivity about on the level of other polyamides such as nylon-6, 6 meaning that the grease thickener is relatively inert to reacting with other components of a grease composition. Thus the grease thickener can remain in the grease composition in an unreacted form. Moreover, the amide bond is less likely to be susceptible to hydrolysis. Thus the grease thickener can tolerate some level of water that may present (intentionally or unintentionally) in the grease composition. Additionally, the grease thickener can be synthesized in the presence of water. These benefits are particularly apparent compared to a grease thickener having terminal ester groups. The terminal ester groups may be more likely to react with other grease components or undergo hydrolysis, either of which can reduce the effectiveness of the grease thickener.

[0046] At each occurrence, the DA is a reacted diamine, independently having the structure according to Formula (VII):

R⁵ is a substituted or unsubstituted (Ci-C2o)hydrocarbylene. At each occurrence, the substituted or unsubstituted (Ci-C2o)hydrocarbylene is independently selected from a substituted or unsubstituted (Ci-C2o)alkylene, a substituted or unsubstituted (C3-C2o)cycloalkylene, a substituted or unsubstituted (C2-C2o)alkenylene, a substituted or unsubstituted (C2- C2o)alkynylene, a substituted or unsubstituted (Ci-C2o)acylene, a substituted or unsubstituted (C4- C2o)arylene, and a substituted or unsubstituted (C2-C2o)alkoxyene. At each occurrence DA has the same chemical structure. Alternatively, at least two occurrences of DA have a different chemical structure.

[0047] In specific examples, at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, a reacted pentanediamine, a reacted nonanediamine, a reacted isononanediamine, a reacted 2-methylpentamethylenediamine, a reacted ethylenediamine, a reacted isophorone diamine, a reacted m-xylylenediamine, and a reacted m-phenylenediamine. In some examples at each occurrence DA is a reacted hexamethylenediamine. In still more specific examples, it was found that internal aliphatic groups that are n— (Ci-C2o)alkylene yielded a grease thickening agent that had desirable dropping point and NLGI properties. Typically, the DA does not include a branched structure. This is because diamines having a branched structure tend to make the grease composition to which the grease thickening agent is included too saft which in turn lowers the melting point of the grease composition too much. In some examples, DA can be selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, a reacted pentanediamine, or a reacted nonanediamine.

[0048] The grease thickening agent can be present as a distribution. In the distribution, a weight-average molecular weight of the grease thickening agent is in a range of from about 400 g/mol to about 10,000 g/mol, about 1100 g/mol to about 8,000 g/mol, about 1200 g/mol to about 4000 g/mol, less than, equal to, or greater than, 400 g/mol, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, or about 10000 g/mol. Keeping the weight-average molecular weight in this range can help the polyamide grease polymer to be classified as a polymer for regulatory purposes under 40 CFR 723.250(b). In specific examples it was found that a weight-average molecular weight in range of from about 450 g/mol to about 3500 g/mol or about 500 g/mol to about 2500 g/mol yielded a grease thickener with particularly advantageous properties (e.g., dropping point and NLGI values). Additionally, it was found that if the weight-average molecular weight of the grease thickening component is too high, it will not be compatible with the base oil of the grease composition. Non-compatibility is established if the grease composition is not homogenous. A grease composition is considered to be homogenous if when examined under a microscope at 200 magnification, there are discrete particles observed.

[0049] In general, it was found that if the polyamide grease thickener was completely linear (e.g., included no cylcoaliphilicity, aromaticity, or the like), the resulting grease had poor penetrometer measurement, meaning the grease was too soft. Examples of linear polyamides can be found in GB774085). However, it was found that at least some linearity was desirable as all aromatic polyamides show poor compatibility (e.g., a low dropping point) when incorporated in a grease composition. Additionally, it was found that if the weight-average molecular weight of the polyamide grease thickener is too high, there would be poor compatibility (e.g., lack of homogeneousy) in the grease composition.

[0050] Specific examples of suitable grease thickening agents that can be used alone or as a mixture of grease thickening agents include those shown herein in Table 1. Of those grease thickeners listed in Table 1, the structures of Formula XII, XI, X, and XIII, include the afore mentioned beneficial structures and show good performance in grease compositions. Data is included where available for the dropping point Po, and Peo values when the respective grease thickener is incorporated in a grease composition.

Atorney Docket No.: INT-2022-PAT-0049-WO-PCT

Table 1

Atorney Docket No.: INT-2022-PAT-0049-WO-PCT

Atorney Docket No.: INT-2022-PAT-0049-WO-PCT

Atorney Docket No.: INT-2022-PAT-0049-WO-PCT

Atorney Docket No.: INT-2022-PAT-0049-WO-PCT

Atorney Docket No.: INT-2022-PAT-0049-WO-PCT

Attorney Docket No.: INT-2022-PAT-0049-WO-PCT

*NA = not available

*NM = not measured

[0051] The polyamide grease thickening agent can be a component of a grease composition. A grease composition is generally understood to refer to a solid or semisolid lubricant formed as a dispersion of thickening agents in a liquid lubricant. Grease compositions include a base oil (or lubricating oil), grease thickening agent, and optional additives. The polyamide grease thickening agent can be in a range of from about 1 wt% to about 50 wt% of the grease composition about 5 wt% to about 20 wt% of the grease composition. Base oils can include a vegetable oil, a mineral oil, synthetic oil, or any other fluid that provides lubricating properties. As an example, the grease can be a silicone grease. A silicone grease can include a polydimethysiloxane base oil. Other greases can be a fluoroether-based grease that includes a fluoroether base oil.

[0052] The grease thickening agents present can self-assemble into a network to provide the grease with adequate structure to perform. As mentioned herein above, the grease thickening agent has a weight-average molecular weight in a range of from about 450 g/mol to about 10,000 g/mol. It is possible for every grease thickening agent molecule to have the same molecular weight, but there can also be a distribution of molecular weights of the grease thickening agents. [0053] According to various examples, the grease thickening agent is a first grease thickening agent and the grease composition further comprises a second grease thickening agent having a different chemical structure than the first grease thickening agent. For example, a molecular weight of the first grease thickening agent can be different from a molecular weight of the second grease thickening agent or the first grease thickening agent and the second grease thickening agent differ by chemical composition, or the first grease thickening agent and the second grease thickening agent are isomers with respect to each other.

[0054] An advantage of the grease composition is that it can provide sufficient thickening properties to the grease composition while being substantially free of lithium, polyurea, or a mixture thereof. For example, the grease composition can include less than 1 wt% lithium or 0 wt% lithium and/or less than 1 wt% polyurea or 0 wt% polyurea. Advantageously, this can result in a grease composition that is potentially more environmentally friendly. Additionally, especially with respect to being substantially free of lithium, the resulting grease composition can be cheaper to produce than a corresponding grease composition that uses a thickening agent including lithium as opposed to the claimed grease thickening agent. [0055] In some aspects, it is possible for a grease composition to include the disclosed grease thickening composition and a grease thickening composition that includes lithium, polyurea, or both. However, the amount of grease thickening composition that includes lithium, polyurea, or both necessary can be reduced by included the disclosed grease thickening composition, relative to a grease composition that is free of the disclosed grease thickening composition.

[0056] In addition to the lubricant and the grease thickening agent, the grease composition can include an additional component(s) such as anhydrous calcium complex, aluminum complex, calcium sulfonate complex, calcium complex, barium complex, sodium complex, or a mixture thereof. A total combined wt% of these components (alone or in combination) can be less than 35 wt%, less than 30 wt%, less than 25 wt%, less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 5 wt%, or 0 wt%.

[0057] The grease composition, including the disclosed thickening agents, can have several beneficial properties. For example, a dropping point of the grease composition can be in a range of from about 200 °C to about 280 °C, about 250 °C to about 265 °C, less than, equal to, or greater than about 200 °C, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213,

214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227, 228, 229, 230, 231, 232,

233, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251,

252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 264, 265, 266, 267, 268, 269, 270,

271, 272, 273, 274, 275, 276, 277, 278, 279, or about 280 °C. The dropping point of the grease composition can be substantially similar to the dropping point of a comparative grease composition differing only in that the grease thickening component is a lithium based grease thickening component. As generally understood, the dropping point of a grease is the temperature at which it passes from a semi-solid to a liquid state. The dropping point test determines the cohesiveness of the oil and thickening agent of a grease. A test for determining the dropping point is ASTM D-2265.

[0058] The grease composition also shows acceptable mechanical strength. For example, an NLGI consistency number of an unworked composition (a sample that has received only minimal disturbance) of the grease composition can be in a range of 3 to 4. An NLGI consistency number of the worked grease composition (as sample that has been subjected to 60 double strokes in a standard grease worker) can be in a range of 1 to 2. The NLGI consistency number can be measured by following ASTM D-217, which is titled “cone penetration of lubricating grease ' . This involves two test apparatus. The first apparatus consists of a closed container and a piston-like plunger. The face of the plunger is perforated to allow grease to flow from one side of the plunger to another as the plunger is worked up and down. The test grease is inserted into the container and the plunger is stroked 60 times while the test apparatus and grease are maintained at a temperature of 25 °C. Once worked, the grease is placed in a penetration test apparatus. This apparatus includes a container, a specially-configured cone and a dial indicator. The container is filled with the grease and the top surface of the grease is smoothed over. The cone is placed so that its tip just touches the grease surface and the dial indicator is set to zero at this position. When the test starts, the weight of the cone will cause it to penetrate into the grease. After a specific time interval the depth of penetration is measured.

[0059] As used herein, values such as Po, Peo and Pioooo are included to indicate the degree to which a grease composition is worked. For example, a grease composition that is unworked has a Po value. A grease composition that is inserted into a container and has a plunger stroked 60 times while the test apparatus and grease composition are maintained at a temperature of 25 °C has a Peo value. A grease composition that is inserted into a container and has a plunger stroked 10000 times while the test apparatus and grease composition are maintained at a temperature of 25 °C has a Pioooo value.

[0060] The unworked grease composition can have a penetration value ranging from about 215 tenths of a millimeter to about 255 tenths of a millimeter, about 225 tenths of a millimeter to about 235 tenths of a millimeter, less than, equal to, or greater than about 215 tenths of a millimeter, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227, 228, 229, 230, 231, 232, 233, 234, or 235 tenths of a millimeter. The worked grease composition can have a penetration value ranging from about 280 tenths of a millimeter to about 310 tenths of a millimeter, about 290 tenths of a millimeter to about 400 tenths of a millimeter, less than, equal to, or greater than about 280 tenths of a millimeter, 281, 282, 283, 284, 285, 286, 287, 288, 289, 290, 291, 292, 293, 294, 295, 296, 297, 298, 299, 300, 301, 302, 303, 304, 305, 306, 307, 308,

309, 310, 311, 312, 313, 314, 315, 316, 317, 318, 319, 320, 321, 322, 323, 324, 325, 326, 327,

328, 329, 330, 331, 332, 333, 334, 335, 336, 337, 338, 339, 340, 341, 342, 343, 344, 345, 346,

347, 348, 349, 350, 351, 352, 353, 354, 355, 356, 357, 358, 359, 360, 361, 362, 363, 364, 365,

366, 367, 368, 369, 370, 371, 372, 373, 374, 375, 376, 377, 378, 379, 380, 381, 382, 383, 384, 385, 386, 387, 388, 389, 390, 391, 392, 393, 394, 395, 396, 397, 398, 399, or 400 tenths of a millimeter. The NLGI consistency number of the grease composition can be substantially similar to the NLGI consistency number of a comparative grease composition differing only in that the grease thickening component is a lithium based grease thickening component.

[0061] The grease composition can be contacted with any number of articles in need of lubrication. For example, the grease composition can be applied to a bearing, crankshaft, joint, hinge, or the like.

[0062] The grease thickening agent in general can be simply made by reacting any polycarboxylate and any diamine mentioned herein to form a first product. The first product is then reacted with any monocarboxylate mentioned herein to form the grease thickening agent.

Examples

[0063] Various aspects of the present invention can be better understood by reference to the following Examples which are offered by way of illustration. The present invention is not limited to the Examples given herein.

[0064] Various grease thickeners were developed and tested for their properties as shown below.

Example 1:

[0065] The grease thickener of Formula XV was prepared in a three neck round bottom equipped with a with a nitrogen inlet and a distillation apparatus, 18.1 g (0.05 mols) of 6T6 was combined with 28.4 g (0.1 mol) of stearic acid in 327 g of an alkylated naphthalene base oil. The reaction mixture was slowly brought up to 180 ° C and allowed to react for 2 hours. During the reaction, the mixture began to thicken along with the generation of water which was removed via distillation. The reaction mixture temperature was increased to 220°C over the course of 2 hours to maintain stirring and allowed to react until the generation of water ceased. Material was cooled to 150 C and homogenized. The grease thickener was incorporated into a grease composition at 12 wt%. The Dropping point of the grease composition was 175 °C. Example 2

[0066] The grease thickener of Formula XII, was prepared in a three neck round bottom equipped with a with a nitrogen inlet and a distillation apparatus, 18.1 g (0.05 mols) of 6T6 was combined with 14.2 g (0.05 mol) of stearic acid and 6.4 g (0.05 mol) of benzoic acid in 117.5 g of an ester base oil. The reaction mixture was slowly brought up to 180°C and allowed to react for 2 hours. During the reaction, the mixture began to thicken along with the generation of water which was removed via distillation. The reaction mixture temperature was increased to 220°C over the course of 2 hours to maintain stirring and allowed to react until the generation of water ceased. Material was cooled to 150 °C and homogenized. The grease thickener was incorporated into a grease composition at 12 wt%. The dropping point of the grease composition was 225 °C.

Example 3

[0067] The grease thickener of Formula XXXII was prepared in a three neck round bottom equipped with a with a nitrogen inlet and a distillation apparatus, 25.00 g (0.0411 mols) of 6T6T6 was combined with 23.38 g (0.0822 mol) of stearic acid 344 g of alkylated naphthalene base oil. The reaction mixture was slowly brought up to 180C and allowed to react for 2 hours. During the reaction, the mixture began to thicken along with the generation of water which was removed via distillation. The reaction mixture temperature was increased to 240°C over the course of 2 hours to maintain stirring and allowed to react until the generation of water ceased. Material was cooled to 150 C and homogenized The grease thickener was incorporated into a grease composition at 12 wt%. The dropping point of the grease composition was 300 °C. Example 4

[0068] The grease thickener of Formula XI was prepared in a three neck round bottom equipped with a with a nitrogen inlet and a distillation apparatus, 46.6 g (0.1285 mols) of 6T6 was combined with 12.5 g (0.0644 mols) dimethyl terephthalate and 4.46 g (5 wt% of phenol in 655 g of alkylated naphthalene base oil. The mixture was allowed to heat for 30 minutes at 100 C. 36.6 g (0.129 mols) of stearic acid was added to the reaction mixture and the temperature was slowly brought up to 180C and allowed to react for 2 hours. During the reaction, the mixture began to thicken along with the generation of water which was removed via distillation. The reaction mixture temperature was increased to 220°C over the course of 2 hours to maintain stirring and allowed to react until distillation ceased. Material was cooled to 150 C and homogenized. The grease thickener was incorporated into a grease composition at 12 wt%. The dropping point of the grease composition was 240 °C.

Example 5

€

[0069] The grease thicker of Formula XIII, was prepared in a three neck round bottom equipped with a with a nitrogen inlet and a distillation apparatus, 63.0 g (0.1738 mols) of 6T6 was combined with 17.00 g (0.00.1159 mols) dimethyl terephthalate and 5.58 g (5 wt% of phenol in 818 g of alkylated naphthalene base oil. The mixture was allowed to heat for 30 minutes at 100 C. 32.96 g (0.1159 mols) of stearic acid and 7.43 g (0.058 mols) of cyclohexane carboxylic acid were added to the reaction mixture and the temperature slowly brought up to 180C and allowed to react for 2 hours. The reaction mixture temperature was increased to 220°C over the course of 2 hours to maintain stirring and allowed to react until distillation ceased. Material was cooled to 150 C and homogenized. The grease thickener was incorporated into a grease composition at 12 wt%. The dropping point of the grease composition was 262 °C.

Example 6

[0070] A grease thickener of Formula XXXII had the amine groups therein functionalized with stearic acid. As shown in Table 2 and FIG. 1, the grease thickener was studied to determine its performance (penetration value) when present in a grease composition at 10 wt% and 15 wt%. Additionally, the thickener had 65 wt% or 95 wt% of the amine groups in the grease thickener are functionalized with stearic acid.

[0071] The data shows that that the functionalization (or incomplete functionalization) of the amines with stearic acid is an independent variable influencing the consistency of the polyamide thickened grease composition. Increasing the amount of stearic acid endcaps is observed to increase compatibility of the thickener with the base oil system of the grease composition. At the same time, increasing the amount of stearic acid endcapping degrades the consistency of the grease composition leading to softer greases. In these systems, greases require higher loadings of polyamide thickener with higher stearic acid functionality to achieve similar mechanical properties to those with lower stearic acid functionality. For example, a thickener which has 95% of its amines functionalized with stearic acid will have higher Po/Peo/Pioooo measurements when compared with a similar chain length grease thickener with 65% amine functionalization at the same grease thickener loading.

Table 2

[0072] The terms and expressions that have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the present invention. Thus, it should be understood that although the present invention has been specifically disclosed by specific embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of embodiments of the present invention.

Exemplary Aspects.

[0073] The following exemplary aspect are provided, the numbering of which is not to be construed as designating levels of importance:

[0074] Aspect 1 provides a polyamide grease thickening agent having the structure according to Formula I:

(MCA-DA-)(PCA-DA)y-PCA-(DA-PCA)_y(-DA-MCA) (I), wherein at each occurrence PCA is independently a reacted polycarboxylate, at each occurrence MCA is independently a reacted monocaboxylate, at each occurrence DA is independently a reacted diamine, y is 0 or a non-zero integer, a weight-average molecular weight of the polyamide grease thickener is in a range of from about 450 g/mol to about 3500 g/mol, the structure according to Formula I includes at least 4 amide bonds, and at least one cycloaliphatic moiety or aromatic moiety.

[0075] Aspect 2 provides the polyamide grease thickening agent of Aspect 1, wherein the weight-average molecular weight of the polyamide grease thickener is in a range of from about 500 g/mol to about 2500 g/mol.

[0076] Aspect 3 provides the polyamide grease thickening agent of any one of Aspects 1 or 2, wherein the agent has the structure according to Formula II:

((MCA-DA-)(PCA-DA)_y-)nPCA (II), wherein n is 2, and y is in a range of 2-4.

[0077] Aspect 4 provides the polyamide grease thickening agent of any one of Aspects 1-

3, wherein the agent has the structure according to Formula III:

(MCA-DA)-PCA-(DA-MCA) (III).

[0078] Aspect 5 provides the polyamide grease thickening agent of any one of Aspects 1-

4, wherein at each occurrence PCA independently comprises 6 to 50 carbon atoms.

[0079] Aspect 6 provides the polyamide grease thickening agent of any one of Aspects 1-

5, wherein at each occurrence PCA independently comprises 6, 8, or 9 carbon atoms.

[0080] Aspect 7 provides the polyamide grease thickening agent of any one of Aspects 1-

6, wherein at each occurrence PCA has the same chemical structure.

[0081] Aspect 8 provides the polyamide grease thickening agent of any one of Aspects 1-

7, wherein at least two occurrences PCA have different chemical structures.

[0082] Aspect 9 provides the polyamide grease thickening agent of any one of Aspects 1-

8, wherein at each occurrence, PCA independently comprises a reacted adipic acid, a reacted purified terephthalic acid, a reacted isophthalic acid, a reacted phthalic anhydride, a reacted napthalenic acid, a reacted mellitic acid, a reacted mellitic anhydride, a reacted naphthalene tetracarboxylic anhydride, a reacted citric acid, a reacted ester, a reacted acid chloride, a reacted dianhydride, or a reacted ethylenediaminetetraacetic acid.

[0083] Aspect 10 provides the polyamide grease thickening agent of any of one Aspects 1-9, wherein at each occurrence MCA independently comprises a reacted aliphatic monocarboxylate, a reacted alicyclic monocarboxylate, or a reacted aromatic monocarboxylate.

[0084] Aspect 11 provides the polyamide grease thickening agent of any one of Aspects 1-10, wherein at each occurrence MCA has the same chemical structure.

[0085] Aspect 12 provides the polyamide grease thickening agent of any one of Aspects 1-11, wherein at least two occurrences of MCA has a different chemical structure.

[0086] Aspect 13 provides the polyamide grease thickening agent of any one of Aspects 1-12, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to Formula (IV): wherein R³ is a substituted or unsubstituted (Ci-C2o)hydrocarbyl and R⁷ is chosen from - OH, -Cl, -O', or substituted or unsubstituted -0-(Ci-C2o)hydrocarbyl.

[0087] Aspect 14 provides the polyamide grease thickening agent of Aspect 13, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbyl is independently selected from a substituted or unsubstituted (Ci-C2o)alkyl, a substituted or unsubstituted (C3- C2o)cycloalkyl, a substituted or unsubstituted (C2-C2o)alkenyl, a substituted or unsubstituted (C2- C2o)alkynyl, a substituted or unsubstituted (Ci-C2o)acyl, a substituted or unsubstituted (C4- C2o)aryl, and a substituted or unsubstituted (C2-C2o)alkoxy.

[0088] Aspect 15 provides the polyamide grease thickening agent of any one of Aspects 13 or 14, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to:

Formula (V):

Formula (VI): wherein R⁴ is chosen from a bond and a substituted or unsubstituted (Ci- C2o)hydrocarbylene.

[0089] Aspect 16 provides the polyamide grease thickening agent of Aspect 15, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbylene is independently selected from a substituted or unsubstituted (Ci-C2o)alkylene, a substituted or unsubstituted (C3- C2o)cycloalkylene, a substituted or unsubstituted (C2-C2o)alkenylene, a substituted or unsubstituted (C2-C2o)alkynylene, a substituted or unsubstituted (Ci-C2o)acylene, a substituted or unsubstituted (C4-C2o)arylene, and a substituted or unsubstituted -O-(CH2)n- (n = 2-20).

[0090] Aspect 17 provides the polyamide grease thickening agent of any one of Aspects 1-16, wherein at each occurrence the MCA is independently selected from a reacted ester, a reacted acid chloride, a reacted anhydride, a reacted benzoic acid, a reacted cyclohexanecarboxylic acid, and a reacted steric acid.

[0091] Aspect 18 provides the polyamide grease thickening agent of any one of Aspects 1-17, wherein at each occurrence DA has the same chemical structure.

[0092] Aspect 19 provides the polyamide grease thickening agent of any one of Aspects 1-18, wherein at least two occurrences of DA have a different chemical structure.

[0093] Aspect 20 provides the polyamide grease thickening agent of any one of Aspects 1-19, wherein at each occurrence, the DA is a reacted diamine, the diamine independently having the structure according to Formula (VII): wherein R⁵ is a substituted or unsubstituted (Ci-C2o)alkylene, substituted or unsubstituted (C5-C2o)cycloalkylene, or substituted or unsubstituted (C4-C2o)aryl

[0094] Aspect 21 provides the polyamide grease thickening agent of Aspect 20, wherein at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, a reacted pentanediamine, a reacted phenylenediamine, a reacted cyclohexandiamine, or a reacted nonanediamine.

[0095] Aspect 22 provides the polyamide grease thickening agent of any one of Aspects 1-21, wherein at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, or a reacted pentanediamine.

[0096] Aspect 23 provides the polyamide grease thickening agent of any one of Aspects 1-22, wherein at each occurrence DA is a reacted hexamethylenediamine.

[0097] Aspect 24 provides the polyamide grease thickening agent of any one of Aspects

1-23, wherein a dropping point of a grease composition including the polyamide grease thickening agent is greater than about 200 °C.

[0098] Aspect 25 provides the polyamide grease thickening agent of any one of Aspects

2-24, wherein a dropping point of a grease composition including the polyamide grease thickening agent is greater than about 250 °C.

[0099] Aspect 26 provides the polyamide grease thickening agent of any one of Aspects 1-25, wherien when the at least one aromatic moiety is internally disposed it is di-substituted in a para position and when the at least on cycloaliphatic moiety is internally disposed it is disubstituted and symmetrical about an axis passing through both substituents.

[0100] Aspect 27 provides the polyamide grease thickening agent of any one of Aspects 1-26, wherein the structure according for Formula I, includes at least two aromatic moieties and at least one aromatic moiety is an mono- substituted end group of Formula I.

[0101] Aspect 28 provides a polyamide grease thickening agent having the structure according to Formula IX:

wherein wherein at each occurrence PC A is independently a para- substituted reacted polycarboxylate, at each occurrence MCA is independently a reacted monocaboxylate, at each occurrence DA is independently a reacted diamine, y is 0 or a non-zero integer, a weight-average molecular weight of the polyamide grease thickener is in a range of from about 450 g/mol to about 3500 g/mol.

[0102] Aspect 29 provides the polyamide grease thickening agent of Aspect 28, wherein the weight-average molecular weight of the polyamide grease thickener is in a range of from about 500 g/mol to about 2500 g/mol.

[0103] Aspect 30 provides the polyamide grease thickening agent of any of one Aspects

28 or 29, wherein at each occurrence MCA independently comprises a reacted aliphatic monocarboxylate, a reacted alicyclic monocarboxylate, or a reacted aromatic monocarboxylate.

[0104] Aspect 31 provides the polyamide grease thickening agent of any one of Aspects 28-30, wherein at each occurrence MCA has the same chemical structure.

[0105] Aspect 32 provides the polyamide grease thickening agent of any one of Aspects 28-31, wherein at least two occurrences of MCA has a different chemical structure.

[0106] Aspect 33 provides the polyamide grease thickening agent of any one of Aspects

28-32, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to Formula (IV): wherein R³ is a substituted or unsubstituted (Ci-C2o)hydrocarbyl and R⁷ is chosen from - OH, -Cl, -O', or substituted or unsubstituted -0-(Ci-C2o)hydrocarbyl.

[0107] Aspect 34 provides the polyamide grease thickening agent of Aspect 33, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbyl is independently selected from a substituted or unsubstituted (Ci-C2o)alkyl, a substituted or unsubstituted (C3- C2o)cycloalkyl, a substituted or unsubstituted (C2-C2o)alkenyl, a substituted or unsubstituted (C2- C2o)alkynyl, a substituted or unsubstituted (Ci-C2o)acyl, a substituted or unsubstituted (C4- C2o)aryl, and a substituted or unsubstituted (C2-C2o)alkoxy.

[0108] Aspect 35 provides the polyamide grease thickening agent of any one of Aspects 33 or 34, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to:

Formula (V):

Formula (VI): wherein R⁴ is chosen from a bond and a substituted or unsubstituted (Ci- C2o)hydrocarbylene.

[0109] Aspect 36 provides the polyamide grease thickening agent of Aspect 35, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbylene is independently selected from a substituted or unsubstituted (Ci-C2o)alkylene, a substituted or unsubstituted (C3- C2o)cycloalkylene, a substituted or unsubstituted (C2-C2o)alkenylene, a substituted or unsubstituted (C2-C2o)alkynylene, a substituted or unsubstituted (Ci-C2o)acylene, a substituted or unsubstituted (C4-C2o)arylene, and a substituted or unsubstituted -0-(CH2)n- (n = 2-20).

[0110] Aspect 37 provides the polyamide grease thickening agent of any one of Aspects 28-36, wherein at each occurrence the MCA is independently selected from a reacted ester, a reacted acid chloride, a reacted anhydride, a reacted benzoic acid, a reacted cyclohexanecarboxylic acid, and a reacted steric acid.

[0111] Aspect 38 provides the polyamide grease thickening agent of any one of Aspects 28-37, wherein at each occurrence DA has the same chemical structure.

[0112] Aspect 39 provides the polyamide grease thickening agent of any one of Aspects 28-38, wherein at least two occurrences of DA have a different chemical structure.

[0113] Aspect 40 provides the polyamide grease thickening agent of any one of Aspects 28-39, wherein at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, a reacted pentanediamine, a reacted phenylenediamine, a reacted cyclohexandiamine, or a reacted nonanediamine.

[0114] Aspect 41 provides the polyamide grease thickening agent of any one of Aspects 28-40, wherein at each occurrence DA is a reacted hexamethylenediamine.

[0115] Aspect 42 provides the polyamide grease thickening agent of any one of Aspects 28-41, wherein a dropping point of the polyamide grease thickening agent is greater than about 200 °C.

[0116] Aspect 43 provides the polyamide grease thickening agent of any one of Aspects 28-42, wherein a dropping point of the polyamide grease thickening agent is greater than about 250 °C.

[0117] Aspect 44 provides a polyamide grease thickening agent having the structure according to any one of Formulas X, XI, XII, or XIII:

[0118] Aspect 45 provides a method of making the grease thickening agent of any one of Aspects 1-44, the method comprising: reacting a polycarboxylate and a diamine to form a first product; and reacting the first product with a monocarboxylate to form the grease thickening agent.

[0119] Aspect 46 provides a method of using the polyamide grease thickening agent of any one of Aspects 1-45, the method comprising contacting the polyamide grease thickening agent with a grease to form a grease composition.

[0120] Aspect 47 provides a method of using the grease composition of Aspect 46, the method comprising contacting the grease composition with an article to be lubricated.

[0121] Aspect 48 provides a grease composition comprising the grease thickening agent of any one of Aspects 1-47.

[0122] Aspect 49 provides the grease composition of Aspect 48, wherein the grease thickening agent is in a range of from about 1 wt% to about 50 wt% of the grease composition. [0123] Aspect 50 provides the grease composition of any one of Aspects 48 or 49, wherein the grease thickening agent is in a range of from about 5 wt% to about 20 wt% of the grease composition.

[0124] Aspect 51 provides the grease composition of any one of Aspects 48-51, wherein the grease thickening agent is a first grease thickening agent and the grease composition further comprises a second grease thickening agent having a different chemical structure than the first grease thickening agent, the second grease thickening agent have a structure according to Formula I. [0125] Aspect 52 provides the grease composition of Aspect 51, wherein a molecular weight of the first grease thickening agent is different from a molecular weight of the second grease thickening agent.

[0126] Aspect 53 provides the grease composition of any one of Aspects 51 or 52, wherein the first grease thickening agent and the second grease thickening agent differ by chemical composition.

[0127] Aspect 54 provides the grease composition of any one of Aspects 48-53, comprising less than 1 wt% lithium.

[0128] Aspect 55 provides the grease composition of any one of Aspects 48-54, comprising less than 1 wt% polyurea.

[0129] Aspect 56 provides a homogenous grease composition, the grease composition comprising: a polyamide grease thickening agent having the structure according to Formula I: (MCA-DA-)(PCA-DA)y-PCA-(DA-PCA)_y(-DA-MCA) (I), wherein at each occurrence PCA is independently a reacted polycarboxylate, at each occurrence MCA is independently a reacted monocaboxylate, at each occurrence DA is independently a reacted diamine, y is 0 or a non-zero integer, the structure according to Formula I includes at least 4 amide bonds, and at least one cycloaliphatic moiety or aromatic moiety.

[0130] Aspect 57 provides the homogenous grease composition of Aspect 56, wherien when the at least one aromatic moiety is internally disposed it is di-substituted in a para position and when the at least on cycloaliphatic moiety is internally disposed it is disubstituted and symmetrical about an axis passing through both substituents.

[0131] Aspect 58 provides the homogenous grease composition of any one of Aspects 56 or 57, wherein the structure according for Formula I, includes at least two aromatic moieties and at least one aromatic moiety is an mono- substituted end group of Formula I.

[0132] Aspect 59 provides the homogenous grease composition of any one of Aspects 56-58, wherein the agent has the structure according to Formula II: ((MCA-DA-)(PCA-DA)_y-)nPCA (II), wherein n is 2, and y is in a range of 2-4.

[0133] Aspect 60 provides the homogenous grease composition of any one of Aspects 56-59, wherein the agent has the structure according to Formula III:

(MCA-DA)-PCA-(DA-MCA) (III).

[0134] Aspect 61 provides the homogenous grease composition of any one of Aspects 56-60, wherein at each occurrence PCA independently comprises 6 to 50 carbon atoms.

[0135] Aspect 62 provides the homogenous grease composition of any one of Aspects 56-61, wherein at each occurrence PCA independently comprises 6, 8, or 9 carbon atoms.

[0136] Aspect 63 provides the homogenous grease composition of any one of Aspects 56-62, wherein at each occurrence PCA has the same chemical structure.

[0137] Aspect 64 provides the homogenous grease composition of any one of Aspects 56-63, wherein at least two occurrences PCA have different chemical structures.

[0138] Aspect 65 provides the homogenous grease composition of any one of Aspects 56-64, wherein at each occurrence, PCA independently comprises a reacted adipic acid, a reacted purified terephthalic acid, a reacted isophthalic acid, a reacted phthalic anhydride, a reacted napthalenic acid, a reacted mellitic acid, a reacted mellitic anhydride, a reacted naphthalene tetracarboxylic anhydride, a reacted citric acid, a reacted ester, a reacted acid chloride, a reacted dianhydride, or a reacted ethylenediaminetetraacetic acid.

[0139] Aspect 66 provides the homogenous grease composition of any of one Aspects 56-65, wherein at each occurrence MCA independently comprises a reacted aliphatic monocarboxylate, a reacted alicyclic monocarboxylate, or a reacted aromatic monocarboxylate. [0140] Aspect 67 provides the homogenous grease composition of any one of Aspects 56-66, wherein at each occurrence MCA has the same chemical structure.

[0141] Aspect 68 provides the homogenous grease composition of any one of Aspects 56-67, wherein at least two occurrences of MCA has a different chemical structure.

[0142] Aspect 69 provides the homogenous grease composition of any one of Aspects 56-68, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to Formula (IV): wherein R³ is a substituted or unsubstituted (Ci-C2o)hydrocarbyl and R⁷ is chosen from - OH, -Cl, -O', or substituted or unsubstituted -0-(Ci-C2o)hydrocarbyl.

[0143] Aspect 70 provides the homogenous grease composition of Aspect 69, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbyl is independently selected from a substituted or unsubstituted (Ci-C2o)alkyl, a substituted or unsubstituted (C3-

C2o)cycloalkyl, a substituted or unsubstituted (C2-C2o)alkenyl, a substituted or unsubstituted (C2- C2o)alkynyl, a substituted or unsubstituted (Ci-C2o)acyl, a substituted or unsubstituted (C4- C2o)aryl, and a substituted or unsubstituted (C2-C2o)alkoxy.

[0144] Aspect 71 provides the homogenous grease composition of any one of Aspects 69 or 70, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to:

Formula (V):

Formula (VI): wherein R⁴ is chosen from a bond and a substituted or unsubstituted (Ci- C2o)hydrocarbylene.

[0145] Aspect 72 provides the homogenous grease composition of Aspect 71, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbylene is independently selected from a substituted or unsubstituted (Ci-C2o)alkylene, a substituted or unsubstituted (C3- C2o)cycloalkylene, a substituted or unsubstituted (C2-C2o)alkenylene, a substituted or unsubstituted (C2-C2o)alkynylene, a substituted or unsubstituted (Ci-C2o)acylene, a substituted or unsubstituted (C4-C2o)arylene, and a substituted or unsubstituted -0-(CH2)n- (n = 2-20).

[0146] Aspect 73 provides the homogenous grease composition of any one of Aspects 56-72, wherein at each occurrence the MCA is independently selected from a reacted ester, a reacted acid chloride, a reacted anhydride, a reacted benzoic acid, a reacted cyclohexanecarboxylic acid, and a reacted steric acid.

[0147] Aspect 74 provides the homogenous grease composition of any one of Aspects 56-73, wherein at each occurrence DA has the same chemical structure.

[0148] Aspect 75 provides the homogenous grease composition of any one of Aspects 56-74, wherein at least two occurrences of DA have a different chemical structure.

[0149] Aspect 76 provides the homogenous grease composition of any one of Aspects 56-75, wherein at each occurrence, the DA is a reacted diamine, the diamine independently having the structure according to Formula (VII):

R⁵ H₂N^ ^NH_{2 (} wherein R⁵ is a substituted or unsubstituted (Ci-C2o)alkylene, substituted or unsubstituted (C5-C2o)cycloalkylene, or substituted or unsubstituted (C4-C2o)aryl

[0150] Aspect 77 provides the homogenous grease composition of Aspect 76, wherein at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, a reacted pentanediamine, a reacted phenylenediamine, a reacted cyclohexandiamine, or a reacted nonanediamine.

[0151] Aspect 78 provides the homogenous grease composition of any one of Aspects 56-77, wherein at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, or a reacted pentanediamine.

[0152] Aspect 79 provides the homogenous grease composition of any one of Aspects 56-78, wherein at each occurrence DA is a reacted hexamethylenediamine.

[0153] Aspect 80 provides the homogenous grease composition of any one of Aspects 56-79, wherein a dropping point of the grease composition is greater than about 200 °C. [0154] Aspect 81 provides the homogenous grease composition of any one of Aspects 56-80, wherein a dropping point of the grease composition is greater than about 250 °C. A [0155] Aspect 82 provides the polyamide grease thickening agent of any one of Aspects 1-43 and 45-81, wherien at each instance, MCA, PC A, and DA are free of branched alkyls.

[0156] Aspect 83 provides the polyamide grease thickening agent of any one of Aspects 1-43 and 45-82, wherien The polyamide grease thickening agent includes a least two cycloaliphatic moieties, at least two aromatic moieties, or at least one cycloaliphatic moiety and at least one aromatic moiety.

[0157] Aspect 84 provides the polyamide grease thickening agent of any one of Aspects 1-43 and 45-83, wherein any disubstituted cycloaliphatic moieties and any disubstituted aromatic moieties are symmetric about an axis extending through the two substituents.

[0158] Aspect 85 provides the polyamide grease thickening agent of any one of Aspects 1-43 and 45-84, wherein any disubstituted aromatic moieties are para substituted.

[0159] Aspect 86 provides a polyamide grease thickening agent having the structure according to Formula VIII:

(MCA-DA-(ZZ)_y-)xPCA (VIII), wherien h i ^cH

| PCA 1 ( ^Xz ) at each occurrence ZZ is * ' or ' >

X is H^DA'^zz)y^MCA ₅ at each occurrence PCA is independently a reacted polycarboxylate, at each occurrence MCA is independently a reacted monocaboxylate, at each occurrence DA is independently a reacted diamine, x is a non-zero integer, y is 0 or a non-zero integer, and z is 0 or a non-zero integer.

[0160] Aspect 87 provides the polyamide grease thickening agent of Aspect 86, wherein the agent has the structure according to Formula I:

(MCA-DA-)(PCA-DA)y-PCA-(DA-PCA)_y(-DA-MCA) (I). [0161] Aspect 88 provides the polyamide grease thickening agent of any one of Aspects 86 or 87, wherien the agent has the structure according to Formula II:

((MCA-DA-)(PCA-DA)_y-)nPCA (II), wherien n is in a range of from 2-4.

[0162] Aspect 89 provides the polyamide grease thickening agent of any one of Aspects 86-88, wherein the agent has the structure according to Formula III:

(MCA-DA)-PCA-(DA-MCA) (III).

[0163] Aspect 90 provides the polyamide grease thickening agent of any one of Aspects 86-89, wherien at each occurrence PCA independently comprises 3 to 50 carbon atoms.

[0164] Aspect 91 provides the polyamide grease thickening agent of any one of Aspects 86-90, wherien at each occurrence PCA independently comprises 6, 8, or 9 carbon atoms.

[0165] Aspect 92 provides the polyamide grease thickening agent of any one of Aspects 86-91, wherien at each occurrence PCA comprises a reacted polycarboxylate, the poly carboxy late having the structure according to:

Formula (X):

Formula (XVII):

Formula (XVIII): wherein at each occurrence R¹ and R² are independently a bond or a substituted or unsubstituted (Ci-C2o)hydrocarbyl and at each occurrence, R⁶ is chosen from -OH, -Cl, -O', or substituted or unsubstituted -0-(Ci-C2o)hydrocarbyl.

[0166] Aspect 93 provides the polyamide grease thickening agent of Aspect 92, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbyl is independently selected from a substituted or unsubstituted (Ci-C2o)alkyl, a substituted or unsubstituted (C3- C2o)cycloalkyl, a substituted or unsubstituted (C2-C2o)alkenyl, a substituted or unsubstituted (C2- C2o)alkynyl, a substituted or unsubstituted (Ci-C2o)acyl, a substituted or unsubstituted (C4- C2o)aryl, and a substituted or unsubstituted (C2-C2o)alkoxy.

[0167] Aspect 94 provides the polyamide grease thickening agent of any one of Aspects 86-93, wherien at each occurrence PCA has the same chemical structure.

[0168] Aspect 95 provides the polyamide grease thickening agent of any one of Aspects 86-94, wherien at least two occurrences PCA have different chemical structures.

[0169] Aspect 96 provides the polyamide grease thickening agent of any one of Aspects 86-95, wherien at each occurrence, PCA independently comprises a reacted adipic acid, a reacted purified terephthalic acid, a reacted isophthalic acid, a reacted phthalic anhydride, a reacted napthalenic acid, a reacted mellitic acid, a reacted mellitic anhydride, a reacted naphthalene tetracarboxylic anhydride, a reacted citric acid, a reacted ester, a reacted acid chloride, a reacted dianhydride, or a reacted ethylenediaminetetraacetic acid.

[0170] Aspect 97 provides the polyamide grease thickening agent of any of one Aspects 86-96, wherein at each occurrence MCA independently comprises a reacted aliphatic monocarboxylate, a reacted alicyclic monocarboxylate, or a reacted aromatic monocarboxylate.

[0171] Aspect 98 provides the polyamide grease thickening agent of any one of Aspects 86-97, wherein at each occurrence MCA has the same chemical structure.

[0172] Aspect 99 provides the polyamide grease thickening agent of any one of Aspects 86-98, wherein at least two occurrences of MCA has a different chemical structure.

[0173] Aspect 100 provides the polyamide grease thickening agent of any one of Aspects 86-99, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to Formula (IV): wherein R³ is a substituted or unsubstituted (Ci-C2o)hydrocarbyl and R⁷ is chosen from - OH, -Cl, -O', or substituted or unsubstituted -0-(Ci-C2o)hydrocarbyl.

[0174] Aspect 101 provides the polyamide grease thickening agent of Aspect 100, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbyl is independently selected from a substituted or unsubstituted (Ci-C2o)alkyl, a substituted or unsubstituted (C3- C2o)cycloalkyl, a substituted or unsubstituted (C2-C2o)alkenyl, a substituted or unsubstituted (C2- C2o)alkynyl, a substituted or unsubstituted (Ci-C2o)acyl, a substituted or unsubstituted (C4- C2o)aryl, and a substituted or unsubstituted (C2-C2o)alkoxy.

[0175] Aspect 102 provides the polyamide grease thickening agent of any one of Aspects 100 or 101, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to:

Formula (V):

Formula (VI): wherein R⁴ is chosen from a bond and a substituted or unsubstituted (Ci- C2o)hydrocarbylene.

[0176] Aspect 103 provides the polyamide grease thickening agent of Aspect 102, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbylene is independently selected from a substituted or unsubstituted (Ci-C2o)alkylene, a substituted or unsubstituted (C3-C2o)cycloalkylene, a substituted or unsubstituted (C2-C2o)alkenylene, a substituted or unsubstituted (C2-C2o)alkynylene, a substituted or unsubstituted (Ci-C2o)acylene, a substituted or unsubstituted (C4-C2o)arylene, and a substituted or unsubstituted -O-(CH2)n- (n = 2-20).

[0177] Aspect 104 provides the polyamide grease thickening agent of any one of Aspects 86-103, wherein at each occurrence the MCA is independently selected from a reacted ester, a reacted acid chloride, a reacted anhydride, a reacted benzoic acid, a reacted cyclohexanecarboxylic acid, and a reacted steric acid.

[0178] Aspect 105 provides the polyamide grease thickening agent of any one of Aspects 86-104, wherein at each occurrence DA has the same chemical structure.

[0179] Aspect 106 provides the polyamide grease thickening agent of any one of Aspects 86-105, wherein at least two occurrences of DA have a different chemical structure.

[0180] Aspect 107 provides the polyamide grease thickening agent of any one of Aspects 86-106, wherein at each occurrence, the DA is a reacted diamine, the diamine independently having the structure according to Formula (VII): wherein R⁵ is a substituted or unsubstituted (Ci-C2o)hydrocarbylene.

[0181] Aspect 108 provides the polyamide grease thickening agent of Aspect 107, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbylene is independently selected from a substituted or unsubstituted (Ci-C2o)alkylene, a substituted or unsubstituted (C3-C2o)cycloalkylene, a substituted or unsubstituted (C2-C2o)alkenylene, a substituted or unsubstituted (C2-C2o)alkynylene, a substituted or unsubstituted (Ci-C2o)acylene, a substituted or unsubstituted (C4-C2o)arylene, and a substituted or unsubstituted (C2- C2o)alkoxyene.

[0182] Aspect 109 provides the polyamide grease thickening agent of any one of Aspects 86-108, wherein at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, a reacted pentanediamine, a reacted nonanediamine, a reacted isononanediamine, a reacted 2- methylpentamethylenediamine, a reacted ethylenediamine, a reacted isophorone diamine, a reacted m-xylylenediamine, and a reacted m-phenylenediamine.

[0183] Aspect 110 provides the polyamide grease thickening agent of any one of Aspects 86- 109, wherein at each occurrence DA is a reacted hexamethylenediamine.

[0184] Aspect 111 provides the polyamide grease thickening agent of any one of Aspects 86- 110, wherein x, y, and z are independently in a range of from 1 to 10.

[0185] Aspect 112 provides the polyamide grease thickening agent of any one of Aspects 86- 111, wherein x, y, and z are independently in a range of from 1 to 3.

[0186] Aspect 113 provides the polyamide grease thickening agent of any one of Aspects 86-112, wherein a molecular weight of the grease thickening agent is at least 1000 g/mol.

[0187] Aspect 114 provides the polyamide grease thickening agent of any one of Aspects 86-113, wherein a molecular weight of the grease thickening agent is at least 1500 g/mol.

[0188] Aspect 115 provides the polyamide grease thickening agent of any one of Aspects 86-114, wherein a weight-average molecular weight of the grease thickening agent is in a range of from about 1000 g/mol to about 10,000 g/mol. [0189] Aspect 116 provides the polyamide grease thickening agent of any one of Aspects 86-115, wherein a weight-average molecular weight of the grease thickening agent is in a range of from about 1200 g/mol to about 4000 g/mol.

[0190] Aspect 117 provides a grease composition comprising the grease thickening agent of any one of Aspects 86-116.

[0191] Aspect 118 provides the grease composition of Aspect 117, wherein the grease thickening agent is in a range of from about 1 wt% to about 50 wt% of the grease composition. [0192] Aspect 119 provides the grease composition of any one of Aspects 117 or 118, wherein the grease thickening agent is in a range of from about 5 wt% to about 20 wt% of the grease composition.

[0193] Aspect 120 provides the grease composition of any one of Aspects 117-119, wherein the grease thickening agent is a first grease thickening agent and the grease composition further comprises a second grease thickening agent having a different chemical structure than the first grease thickening agent, the second grease thickening agent have a structure according to Formula VIII.

[0194] Aspect 121 provides the grease composition of Aspect 120, wherein a molecular weight of the first grease thickening agent is different from a molecular weight of the second grease thickening agent.

[0195] Aspect 122 provides the grease composition of any one of Aspects 120 or 121, wherein the first grease thickening agent and the second grease thickening agent differ by chemical composition.

[0196] Aspect 123 provides the grease composition of any one of Aspects 117-122, comprising less than 1 wt% lithium.

[0197] Aspect 124 provides the grease composition of any one of Aspects 117-123, comprising less than 1 wt% polyurea.

[0198] Aspect 125 provides a grease composition comprising a reaction product of the poly carboxylate, the diamine, and the monocarboxylate of any one of Aspects 92-124.

[0199] Aspect 126 provides a grease composition comprising a reaction product of a poly carboxy late, diamine, a monocarboxylate of any one of Aspects 92-125.

[0200] Aspect 127 provides the grease composition of any one of Aspects 117-126, wherein the total wt% of components selected from anhydrous calcium, aluminum complex, calcium sulfonate complex, calcium complex, barium complex, sodium complex and polyurea is less than 35 wt%.

[0201] Aspect 128 provides a method of using the polyamide grease thickening agent of any one of Aspects 86-127, the method comprising contacting the polyamide grease thickening agent with a grease.

[0202] Aspect 129 provides a method of using the grease composition of any one of Aspects 117-128, the method comprising contacting the grease composition with an article to be lubricated.

[0203] Aspect 130 provides a method of making the grease thickening agent of any one of Aspects 86-129, the method comprising: reacting a polycarboxylate and a diamine to form a first product; and reacting the first product with a monocarboxylate to form the grease thickening agent.

Claims

CLAIMS What is claimed is:

1. A polyamide grease thickening agent having the structure according to Formula I:

(MCA-DA-)(PCA-DA)y-PCA-(DA-PCA)_y(-DA-MCA) (I), wherein at each occurrence PCA is independently a reacted polycarboxylate, at each occurrence MCA is independently a reacted monocaboxylate, at each occurrence DA is independently a reacted diamine, y is 0 or a non-zero integer, a weight-average molecular weight of the polyamide grease thickener is in a range of from about 450 g/mol to about 3500 g/mol, and at least one cycloaliphatic moiety or aromatic moiety.

2. The polyamide grease thickening agent of claim 1, wherein the weight-average molecular weight of the polyamide grease thickener is in a range of from about 500 g/mol to about 2500 g/mol.

3. The polyamide grease thickening agent of any one of claims 1 or 2, wherein the agent has the structure according to Formula II:

((MCA-DA-)(PCA-DA)_y-)nPCA (II), wherein n is 2, and y is in a range of 2-4.

4. The polyamide grease thickening agent of any one of claims 1-3, wherein the agent has the structure according to Formula III:

(MCA-DA)-PCA-(DA-MCA) (III).

5. The polyamide grease thickening agent of any one of claims 1-4, wherein at each occurrence PCA independently comprises 6 to 50 carbon atoms.

6. The polyamide grease thickening agent of any one of claims 1-5, wherein at each occurrence PCA independently comprises 6, 8, or 9 carbon atoms.

7. The polyamide grease thickening agent of any one of claims 1-6, wherein at each occurrence, PCA independently comprises a reacted adipic acid, a reacted purified terephthalic acid, a reacted isophthalic acid, a reacted phthalic anhydride, a reacted napthalenic acid, a reacted mellitic acid, a reacted mellitic anhydride, a reacted naphthalene tetracarboxylic anhydride, a reacted citric acid, a reacted ester, a reacted acid chloride, a reacted dianhydride, or a reacted ethylenediaminetetraacetic acid.

8. The polyamide grease thickening agent of any of one claims 1-7, wherein at each occurrence MCA independently comprises a reacted aliphatic monocarboxylate, a reacted alicyclic monocarboxylate, or a reacted aromatic monocarboxylate.

9. The polyamide grease thickening agent of any one of claims 1-8, wherein at each occurrence, the DA is a reacted diamine, the diamine independently having the structure according to Formula (VII): wherein R⁵ is a substituted or unsubstituted (Ci-C2o)alkylene, substituted or unsubstituted (C5-C2o)cycloalkylene, or substituted or unsubstituted (C4-C2o)aryl.

10. The polyamide grease thickening agent of claim 9, wherein at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, a reacted pentanediamine, a reacted phenylenediamine, a reacted cyclohexandiamine, or a reacted nonanediamine.

11. The polyamide grease thickening agent of any one of claims 1-10, wherein at each occurrence DA is a reacted hexamethylenediamine.

12. The polyamide grease thickening agent of any one of claims 1-11, wherein a dropping point of a grease composition including the polyamide grease thickening agent is greater than about 200 °C.

13. The polyamide grease thickening agent of any one of claims 2-12, wherein a dropping point of a grease composition including the polyamide grease thickening agent is greater than about 250 °C.

14. The polyamide grease thickening agent of any one of claims 1-13, wherien when the at least one aromatic moiety is internally disposed it is di-substituted in a para position and when the at least on cycloaliphatic moiety is internally disposed it is disubstituted and symmetrical about an axis passing through both substituents.

15. A polyamide grease thickening agent having the structure according to Formula IX: wherein wherein at each occurrence PC A is independently a para- substituted reacted polycarboxylate, at each occurrence MCA is independently a reacted monocaboxylate, at each occurrence DA is independently a reacted diamine, y is 0 or a non-zero integer, a weight-average molecular weight of the polyamide grease thickener is in a range of from about 450 g/mol to about 3500 g/mol.

16. The polyamide grease thickening agent of claim 15, wherein the weight-average molecular weight of the polyamide grease thickener is in a range of from about 500 g/mol to about 2500 g/mol.

17. The polyamide grease thickening agent of any one of claims 15 or 16, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to Formula (IV): wherein R³ is a substituted or unsubstituted (Ci-C2o)hydrocarbyl and R⁷ is chosen from - OH, -Cl, -O', or substituted or unsubstituted -0-(Ci-C2o)hydrocarbyl.

18. The polyamide grease thickening agent of claim 17, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbyl is independently selected from a substituted or unsubstituted (Ci-C2o)alkyl, a substituted or unsubstituted (C3-C2o)cycloalkyl, a substituted or unsubstituted (C2-C2o)alkenyl, a substituted or unsubstituted (C2-C2o)alkynyl, a substituted or unsubstituted (Ci-C2o)acyl, a substituted or unsubstituted (C4-C2o)aryl, and a substituted or unsubstituted (C2-C2o)alkoxy.

19. The polyamide grease thickening agent of any one of claims 17 or 18, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to:

Formula (V): Formula (VI): wherein R⁴ is chosen from a bond and a substituted or unsubstituted (Ci- C2o)hydrocarbylene.

20. The polyamide grease thickening agent of claim 19, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbylene is independently selected from a substituted or unsubstituted (Ci-C2o)alkylene, a substituted or unsubstituted (C3-C2o)cycloalkylene, a substituted or unsubstituted (C2-C2o)alkenylene, a substituted or unsubstituted (C2- C2o)alkynylene, a substituted or unsubstituted (Ci-C2o)acylene, a substituted or unsubstituted (C4- C2o)arylene, and a substituted or unsubstituted -O-(CH2)n- (n = 2-20).

21. The polyamide grease thickening agent of any one of claims 15-20, wherein at each occurrence the MCA is independently selected from a reacted ester, a reacted acid chloride, a reacted anhydride, a reacted benzoic acid, a reacted cyclohexanecarboxylic acid, and a reacted steric acid.

22. The polyamide grease thickening agent of any one of claims 15-21, wherein at each occurrence DA has the same chemical structure.

23. The polyamide grease thickening agent of any one of claims 15-22, wherein at least two occurrences of DA have a different chemical structure.

24. The polyamide grease thickening agent of any one of claims 15-23, wherein at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, a reacted pentanediamine, a reacted phenylenediamine, a reacted cyclohexandiamine, or a reacted nonanediamine.

25. The polyamide grease thickening agent of any one of claims 15-24, wherein at each occurrence DA is a reacted hexamethylenediamine.

26. The polyamide grease thickening agent of any one of claims 15-25, wherein a dropping point of the polyamide grease thickening agent is greater than about 200 °C.

27. The polyamide grease thickening agent of any one of claims 15-26, wherein a dropping point of the polyamide grease thickening agent is greater than about 250 °C.

28. A polyamide grease thickening agent having the structure according to any one of Formulas X, XI, XII, or XIII:

29. A polyamide grease thickening agent having the structure according to Formula VIII:

(MCA-DA-(ZZ)_y-)xPCA (VIII), whenen at each occurrence at each occurrence PCA is independently a reacted polycarboxylate, at each occurrence MCA is independently a reacted monocaboxylate, at each occurrence DA is independently a reacted diamine, x is a non- zero integer, y is 0 or a non-zero integer, and z is 0 or a non-zero integer.

30. The polyamide grease thickening agent of claim 29, wherien at each occurrence PCA comprises a reacted polycarboxylate, the polycarboxylate having the structure according to:

Formula (X):

Formula (XVII):

(XVII), or Formula (XVIII): wherein at each occurrence R¹ and R² are independently a bond or a substituted or unsubstituted (Ci-C2o)hydrocarbyl and at each occurrence, R⁶ is chosen from -OH, -Cl, -O', or substituted or unsubstituted -0-(Ci-C2o)hydrocarbyl.

31. The polyamide grease thickening agent of claim 30, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbyl is independently selected from a substituted or unsubstituted (Ci-C2o)alkyl, a substituted or unsubstituted (C3-C2o)cycloalkyl, a substituted or unsubstituted (C2-C2o)alkenyl, a substituted or unsubstituted (C2-C2o)alkynyl, a substituted or unsubstituted (Ci-C2o)acyl, a substituted or unsubstituted (C4-C2o)aryl, and a substituted or unsubstituted (C2-C2o)alkoxy.

32. The polyamide grease thickening agent of any one of claims 30 or 31, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to Formula (IV): wherein R³ is a substituted or unsubstituted (Ci-C2o)hydrocarbyl and R⁷ is chosen from - OH, -Cl, -O', or substituted or unsubstituted -0-(Ci-C2o)hydrocarbyl.

33. The polyamide grease thickening agent of claim 32, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbyl is independently selected from a substituted or unsubstituted (Ci-C2o)alkyl, a substituted or unsubstituted (C3-C2o)cycloalkyl, a substituted or unsubstituted (C2-C2o)alkenyl, a substituted or unsubstituted (C2-C2o)alkynyl, a substituted or unsubstituted (Ci-C2o)acyl, a substituted or unsubstituted (C4-C2o)aryl, and a substituted or unsubstituted (C2-C2o)alkoxy.

34. The polyamide grease thickening agent of any one of claims 32 or 33, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to:

Formula (V):

Formula (VI): wherein R⁴ is chosen from a bond and a substituted or unsubstituted (Ci- C2o)hydrocarbylene.

35. The grease thickening agent of claim 34, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbylene is independently selected from a substituted or unsubstituted (Ci-C2o)alkylene, a substituted or unsubstituted (C3-C2o)cycloalkylene, a substituted or unsubstituted (C2-C2o)alkenylene, a substituted or unsubstituted (C2- C2o)alkynylene, a substituted or unsubstituted (Ci-C2o)acylene, a substituted or unsubstituted (C4- C2o)arylene, and a substituted or unsubstituted -0-(CH2)n- (n = 2-20).

36. The polyamide grease thickening agent of any one of claims 29-35, wherein at each occurrence, the DA is a reacted diamine, the diamine independently having the structure according to Formula (VII): wherein R⁵ is a substituted or unsubstituted (Ci-C2o)hydrocarbylene.

37. The polyamide grease thickening agent of claim 36, wherein at each occurrence the substituted or unsubstituted (Ci-C2o)hydrocarbylene is independently selected from a substituted or unsubstituted (Ci-C2o)alkylene, a substituted or unsubstituted (C3-C2o)cycloalkylene, a substituted or unsubstituted (C2-C2o)alkenylene, a substituted or unsubstituted (C2- C2o)alkynylene, a substituted or unsubstituted (Ci-C2o)acylene, a substituted or unsubstituted (C4- C2o)arylene, and a substituted or unsubstituted (C2-C2o)alkoxyene.

38. The polyamide grease thickening agent of any one of claims 29-37, wherein at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, a reacted pentanediamine, a reacted nonanediamine, a reacted isononanediamine, a reacted 2- methylpentamethylenediamine, a reacted ethylenediamine, a reacted isophorone diamine, a reacted m-xylylenediamine, and a reacted m-phenylenediamine.