Lubricating grease thickening agent

Abstract

The invention provides a polyamide lubricating grease thickening agent. The polyamide lubricating grease thickening agent has a structure according to a 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 monocarboxylate, at each occurrence, DA is independently a reacted n-alkyl diamine, and y is a 0 or a non-zero integer. In addition, in Formula I, the polyamide grease thickener has a weight average molecular weight in the range of from about 450 g / mol to about 2600 g / mol. Further, in Formula I, the structure comprises at least 4 amide bonds and at least two internal aromatic moieties are disubstituted in the para-position.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application Serial No. 63 / 351,582, filed on June 13, 2022, entitled “GREASE THICKENING AGENT,” the disclosure of which is incorporated herein by reference in its entirety. This application further claims the benefit of priority to U.S. Provisional Patent Application Serial No. 63 / 423,815, filed on November 9, 2022, entitled “GREASE THICKENING AGENT,” the disclosure of which is incorporated herein by reference in its entirety. This application further claims the benefit of priority to U.S. Provisional Patent Application Serial No. 63 / 463,576, filed on May 3, 2023, entitled “GREASE THICKENING AGENT,” the disclosure of which is incorporated herein by reference in its entirety. Background Art

[0002] Grease compositions provide lubrication to a variety of articles. While it is important that the grease composition contain sufficient lubricating oil and base oil, a grease thickener is required to provide mechanical properties to the grease composition. Summary of the invention

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

[0004] (MCA-DA-)(PCA-DA) y -PCA-(DA-PCA) y (-DA-MCA) (I).

[0005] In Formula I, PCA is independently a reacted polycarboxylate at each occurrence, MCA is independently a reacted monocarboxylate at each occurrence, DA is independently a reacted diamine at each occurrence, and y is 0 or a non-zero integer. Additionally, in Formula I, the weight average molecular weight of the polyamide grease thickener is in the range of 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 disubstituted in the para position.

[0006] Surprisingly and unexpectedly, according to various aspects of the present disclosure, the grease thickening composition is able to function at least substantially equivalent to a corresponding grease thickener comprising lithium, polyurea, or both. Thus, a grease composition can be formulated that is substantially free of lithium, polyurea, or both. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The drawings generally illustrate various aspects of the disclosure by way of example and not limitation.

[0008] Figure 1 is a graph showing penetration values ​​for various grease compositions according to various aspects of the present disclosure. DETAILED DESCRIPTION

[0009] Reference will now be made in detail to certain embodiments of the presently disclosed subject matter.While the presently disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplary subject matter is not intended to limit the claims to the disclosed subject matter.

[0010] Throughout this document, values ​​expressed in such a range format should be interpreted in a flexible manner to include not only the values ​​explicitly listed as the upper and lower limits of the range, but also all individual values ​​or subranges encompassed within the range, just as if each value and subrange were explicitly listed. For example, a range of "about 0.1% to about 5%" or "about 0.1% to 5%" should be understood to include not only about 0.1% to about 5%, but also individual values ​​(e.g., 1%, 2%, 3% and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. Unless otherwise specified, the expression "about X to Y" has the same meaning as "about X to about Y". Similarly, unless otherwise specified, the expression "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z".

[0011] In this document, unless the context clearly indicates otherwise, the terms "a", "an", or "the" are used to include one or more than one. Unless otherwise indicated, the term "or" is used to refer to a non-exclusive "or". The expression "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 should be understood that the words or terms used herein and not otherwise defined are for illustrative purposes only and are not limiting. Any use of section headings is intended to aid in reading the document and should not be construed as limiting; information related to a section heading may appear within or outside that particular section.

[0012] In the methods described herein, except when a time or order of operations is explicitly stated, the actions may be performed in any order without departing from the principles of the invention. In addition, specified actions may be performed simultaneously unless explicit claim language states that they may be performed separately. For example, a claimed action of performing X and a claimed action of performing Y may be performed simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0013] The term "about" as used herein may allow a certain degree of fluctuation of a value or range, for example, within 10%, within 5% or within 1% of the upper and lower limits of the value or range, and includes the exact value or range.

[0014] The term "substantially" as used herein refers to a majority or majority, such as 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" as used herein may mean having no or insignificant amounts such that the amount of material present does not affect the material properties of the composition containing the material, such that from about 0 wt % to about 5 wt %, or from about 0 wt % to about 1 wt %, or about 5 wt % or less, or less than or equal to about 4.5 wt %, 4 wt %, 3.5 wt %, 3 wt %, 2.5 wt %, 2 wt %, 1.5 wt %, 1 wt %, 0.9 wt %, 0.8 wt %, 0.7 wt %, 0.6 wt %, 0.5 wt %, 0.4 wt %, 0.3 wt %, 0.2 wt %, 0.1 wt %, 0.01 wt %, or about 0.001 wt % or less or about 0 wt % of the composition is the material.

[0015] As used herein, the term "organic group" refers to any carbon-containing functional group. Examples may include oxygen-containing groups, such as alkoxy groups, aryloxy groups, aralkyloxy groups, oxo (carbonyl) groups; carboxyl groups, including carboxylic acids, carboxylates, and carboxylates; sulfur-containing groups, such as alkyl and aryl thioether groups; 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, S02R, SO2N(R)2, S03R, 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) 0-2 N(R)C(O)R, (CH2) 0-2N(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, C(=NOR)R and substituted or unsubstituted (C1-C 100 ) hydrocarbyl, wherein R can be hydrogen (in examples including other carbon atoms) or a carbyl moiety, and wherein the carbyl moiety can be substituted or unsubstituted.

[0016] The term "substituted" as used herein in conjunction with a molecule or organic group defined herein refers to a 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 substituted or substituted onto a molecule or an organic group. Examples of substituents or functional groups include, but are not limited to, halogens (e.g., F, Cl, Br, and I); oxygen atoms in groups such as hydroxyl groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo (carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates, and carboxylates; sulfur atoms in groups such as thiol groups, alkyl and aryl thioether groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; nitrogen atoms in groups such as amines, hydroxylamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups. Non-limiting examples of substituents that may be bonded to the 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(thiocarbonyl), C(O), S(O), methylenedioxy, ethylenedioxy, N(R)2, SR, SOR, S02R, SO2N(R)2, S03R, 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) 0-2 N(R)C(O)R, (CH2) 0-2N(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 carbonyl moiety; for example, R can be hydrogen, (C1-C 100 ) is a hydrocarbon group, an alkyl group, an acyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heterocyclic group, a heteroaryl group or a heteroarylalkyl group; or wherein the two R groups bonded to the nitrogen atom or adjacent nitrogen atoms can form a heterocyclic group together with one or more nitrogen atoms.

[0017] As used herein, the term "alkyl" refers to straight and branched alkyl and cycloalkyl groups having 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbon atoms, or in some embodiments 1 to 8 carbon atoms. Examples of straight chain alkyl groups include those having 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, isobutyl, sec-butyl, tert-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. As used herein, the term "alkyl" encompasses n-alkyl, isoalkyl, and anteiisoalkyl groups and other branched forms of alkyl groups. Representative substituted alkyl groups may be substituted once or multiple times by any group listed herein (e.g., amino, hydroxyl, cyano, carboxyl, nitro, thio, alkoxy, and halogen groups).

[0018] As used herein, the term "alkenyl" refers to straight and branched chains and cyclic alkyl groups as defined herein, except that there is at least one double bond between two carbon atoms. Thus, an alkenyl group has 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12 carbon atoms, or in some embodiments, 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, etc.

[0019] As used herein, the term "alkynyl" refers to straight and branched chain alkyl groups, except that there is at least one triple bond between two carbon atoms. Thus, alkynyl groups have 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12 carbons, or in some embodiments, 2 to 8 carbon atoms. Examples include, but are not limited to -CH, -C(CH3), -C(CH2CH3), -CH2CH, -CH2C(CH3), and -CH2C(CH2CH3), and the like.

[0020] The term "acyl" as used herein refers to a group containing a carbonyl moiety, wherein the group is bonded through a carbonyl carbon atom. The carbonyl carbon atom is bonded to hydrogen to form a "formyl" group, or is bonded to another carbon atom, which can be part of an alkyl, aryl, aralkylcycloalkyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group, or a similar group. The acyl group can include 0 to about 12, 0 to about 20, or 0 to about 40 additional carbon atoms bonded to the carbonyl. The acyl group can include double bonds or triple bonds within the meaning of this article. An acyl group is an example of an acyl group. Acyl groups can also include heteroatoms within the meaning of this article. Nicotinoyl group (pyridyl-3-carbonyl) is an example of an acyl group within the meaning of this article. Other examples include acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl, and acryloyl, etc. When the group containing the carbon atom bonded to the carbonyl carbon atom contains a halogen, the group is referred to as a "haloacyl" group. An example is the trifluoroacetyl group.

[0021] 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 may have 3 to about 8-12 ring members, and in other embodiments, the number of ring carbon atoms is in the range of 3 to 4, 5, 6, or 7. Cycloalkyl groups also 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, etc. Cycloalkyl groups also include rings substituted with straight or branched chain alkyl groups as defined herein. Representative substituted cycloalkyl groups can be monosubstituted 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 tri-substituted norbornyl or cycloheptyl groups, which can be substituted, for example, with amino, hydroxyl, cyano, carboxyl, nitro, thio, alkoxy and halo groups. The term "cycloalkenyl" alone or in combination refers to a cyclic alkenyl group.

[0022] The term "aryl" as used herein refers to a cyclic aromatic hydrocarbon group that does not contain heteroatoms in the ring. Therefore, aryl groups include but are not limited to phenyl, azulenyl, heptadenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylene, pyrenyl, naphthphenyl, chrysyl, diphenylene, anthracenyl and naphthyl groups. In some embodiments, the aryl group contains about 6 to about 14 carbons in the ring portion of the group. As defined herein, the aryl group can be unsubstituted or substituted. Representative substituted aryl groups can be monosubstituted or substituted more than once, such as but not limited to phenyl substituted at any one or more positions in the 2-, 3-, 4-, 5- or 6-positions of a phenyl ring, or naphthyl groups substituted at any one or more positions in its 2- to 8-positions.

[0023] The term "aralkyl" as used herein refers to an alkyl group as defined herein, wherein a hydrogen bond or carbon bond of the alkyl group is replaced by a chemical bond of an aryl group as defined herein. Representative aralkyl groups include benzyl and phenethyl groups and fused (cycloalkylaryl) alkyl groups, such as 4-ethyl-indanyl. Aralkenyl groups are alkenyl groups as defined herein, wherein a hydrogen bond or carbon bond of the alkyl group is replaced by a chemical bond of an aryl group as defined herein.

[0024] The term "heterocyclyl" as used herein refers to aromatic and non-aromatic ring compounds containing three or more ring members, wherein one or more of the ring members is a heteroatom such as, but not limited to, N, O, and S.

[0025] As used herein, the term "heteroaryl" refers to an aromatic ring compound containing 5 or more ring members, wherein one or more ring members are heteroatoms, such as, but not limited to, N, O, and S; for example, a heteroaryl ring may have 5 to about 8-12 ring members. Heteroaryl groups are various heterocyclyl groups having an aromatic electronic structure.

[0026] The term "heterocycloalkyl" as used herein refers to an alkyl group as defined herein, wherein a hydrogen bond or a carbon bond of an alkyl group as defined herein is replaced by a chemical bond of a heterocyclyl group as defined herein. Representative heterocycloalkyl groups include, but are not limited to, furan-2-ylmethyl, furan-3-ylmethyl, pyridin-3-ylmethyl, tetrahydrofuran-2-ylethyl and indol-2-ylpropyl.

[0027] The term "heteroarylalkyl" as used herein refers to an alkyl group as defined herein wherein a hydrogen bond or a carbon bond of the alkyl group is replaced by a bond to a heteroaryl group as defined herein.

[0028] The term "alkoxy" as used herein refers to an oxygen atom connected to an alkyl group (including a cycloalkyl group), as defined herein. Examples of straight chain alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, etc. Examples of branched alkoxy groups include, but are not limited to, isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy, isohexyloxy, etc. Examples of cyclic alkoxy groups include, but are not limited to, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, etc. Alkoxy groups may include about 1 to about 12, about 1 to about 20, or about 1 to about 40 carbon atoms bonded to oxygen atoms, and may also include double bonds or triple bonds, and may also include heteroatoms. For example, an allyloxy group or a methoxyethoxy group is also an alkoxy group within the meaning of this article, and a methylenedioxy group is also an alkoxy group in the case where two adjacent atoms of the structure are substituted by them.

[0029] As used herein, the term "amine" refers to primary, secondary and tertiary amines having, for example, the formula N(group)3, wherein each group can be independently H or non-H, such as alkyl, aryl, etc. Amines include, but are not limited to, R-NH2, such as alkylamines, arylamines, alkylarylamines; R2NH, wherein each R is independently selected, such as dialkylamines, diarylamines, arylalkylamines, heterocyclylamines, etc.; and R3N, wherein each R is independently selected, such as trialkylamines, dialkylarylamines, alkyldiarylamines, triarylamines, etc. As used herein, the term "amine" also includes ammonium ions.

[0030] As used herein, the term "amino group" refers to -NH2, -NHR, -NR2, -NR3 + Substituents of the form wherein each R is independently selected, and except -NR3 + (which cannot be protonated). Therefore, any compound substituted with an amino group can be regarded as an amine. An "amino group" within the meaning of this article can be a primary, secondary, tertiary or quaternary amino group. An "alkylamino group" includes monoalkylamino, dialkylamino and trialkylamino groups.

[0031]

[0046] 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.

[0032] As used herein, the term "haloalkyl" group includes monohaloalkyl groups, polyhaloalkyl groups, wherein all halogen atoms may be the same or different, and perhaloalkyl groups, wherein all hydrogen atoms are replaced by halogen atoms such as fluorine. Examples of haloalkyl groups include trifluoromethyl, 1,1-dichloroethyl, 1,2-dichloroethyl, 1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.

[0033] As used herein, the term "hydrocarbon" or "hydrocarbyl" refers to a molecule or functional group containing carbon and hydrogen atoms. The term may also refer to a molecule or functional group that typically contains both carbon and hydrogen atoms, but in which all of the hydrogen atoms are replaced by other functional groups. The term "hydrocarbyl" refers to a functional group derived from a straight chain, branched chain, or cyclic hydrocarbon, and may be an alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl, or any combination thereof. A hydrocarbyl group may be represented as (C a -C b )alkyl, wherein a and b are integers, and means having any number of carbon atoms from a to b. For example, (C1-C4)alkyl means that the alkyl group can be methyl (C1), ethyl (C2), propyl (C3) or butyl (C4), and (C0-C b ) hydrocarbyl means that in certain embodiments there are no hydrocarbyl groups. A hydrocarbylene group is a diradical hydrocarbon, for example a hydrocarbon bonded at two positions.

[0034] As used herein, the term "weight average molecular weight" refers to w , which is equal to ΣM i 2 n i / ΣM i n i , where n i The molecular weight is M i In various examples, light scattering, small angle neutron scattering, X-ray scattering, and sedimentation velocity can be used to determine the weight average molecular weight.

[0035] The polymers described herein may be terminated in any suitable manner. In some embodiments, the polymers may be terminated with end groups independently selected from a suitable polymerization initiator, -H, -OH, substituted or unsubstituted (C1- ... 20 ) hydrocarbon group (e.g., (C1-C 10 )alkyl or (C6-C 20 ) aryl), poly(substituted or unsubstituted (C1-C 20 )alkyloxy), and poly(substituted or unsubstituted (C1-C 20 )alkylamino).

[0036] The source of any reactants, feedstocks and / or materials may be from any available source. Without limitation, examples of such sources may include natural products, synthetic products, petrochemical products, biorenewable energy, recycled materials, or mixtures thereof.

[0037] Various aspects of the present disclosure relate to grease thickeners. The grease thickeners are characterized as polyamide grease thickeners. It has been found that successful grease thickeners are those that result in grease compositions having a dropping point greater than 200°C, 220°C, 240°C, 260°C, or 280°C and having an NLGI rating of Group 2 or higher. Structural features of the grease thickeners found to contribute to these properties include: any aliphatic moieties in the monomers are disposed in the interior of the grease thickener molecule and are normal alkyl (straight chain), in addition, the grease thickener should include at least two para-substituted aromatic moieties, the grease thickener should have a molecular weight ranging from 450 g / mol to 3500 g / mol, and the grease thickener should include at least four amide bonds. These structural features have been found to achieve desirable physical properties when the grease thickener is incorporated into a grease composition at a concentration ranging 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 wt %, 12 wt %, 13 wt %, 14 wt %, 15 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt %, or about 20 wt %.

[0038] Various examples of grease thickeners are described herein. Some of the structures described may not have each of the above-described desired structural features. However, some grease thickeners that include at least some of the above-described desired features can provide grease thickeners that can fully function. In addition, in various aspects, it may be desirable for the grease composition to include a mixture of grease thickening components. In such a mixture, at least one grease thickener may include all of the above-described desired structural features. In addition, the mixture may include another grease thickener that may include less than all of the above-described structural features or even any of the structural features. However, the mixture itself may still produce the desired performance in the grease composition into which it is incorporated.

[0039] The polyamide grease thickener may have a structure according to Formula VIII:

[0040] (MCA-DA-(ZZ) y -) x PCA (VIII).

[0041] In Formula I, at each occurrence, ZZ is or , X is , PCA is independently a reacted polycarboxylate (e.g., reacted with DA) at each occurrence, MCA is independently a reacted monocarboxylate at each occurrence, DA is independently a reacted diamine (e.g., reacted with one of MCA and ZZ or PCA) at each occurrence, 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 the range of 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 chemical bond between MCA and DA is an amide bond. The chemical bond between DA and ZZ or DA and PCA is an amide bond or an imide bond. As used herein, "reacted" means that the identified starting material has been reacted to become part of the grease thickener.

[0042] The polyamide grease thickener may have a structure according to Formula I:

[0043] (MCA-DA-)(PCA-DA) y -PCA-(DA-PCA) y (-DA-MCA) (I).

[0044] In a further example, the polyamide grease thickener may have a structure according to Formula II:

[0045] ((MCA-DA-)(PCA-DA) y -) n PCA (II).

[0046] In Formula II, n is in the range of 2 to 4. In another example, the polyamide grease thickener has a structure according to Formula III:

[0047] (MCA-DA)-PCA-(DA-MCA) (III).

[0048] The reacted polycarboxylate can be a polycarboxylic acid, a polycarboxylate, a polycarboxylic acid chloride, or an anhydride. At each occurrence, PCA can independently contain 3 to 50 carbon atoms, 6 to 10 carbon terms, or 6, 8, or 9 carbon atoms. For example, at each occurrence, PCA can include a reacted polycarboxylate having a structure according to the formula:

[0049] Formula (X):

[0050] (X),

[0051] Formula (XVII):

[0052] XVII, or

[0053] Formula (XVIII):

[0054] (XVIII),

[0055] At each occurrence, R 1 and R 2 are independently chemical bonds or substituted or unsubstituted (C1-C 20 ) alkyl, and at each occurrence, R 6 Selected from -OH, -Cl, -O - or substituted or unsubstituted -O-(C1-C 20 ) alkyl. At each occurrence, substituted or unsubstituted (C1-C 20 )alkyl groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkyl, substituted or unsubstituted (C3-C 20 )cycloalkyl, substituted or unsubstituted (C2-C 20 )alkenyl, substituted or unsubstituted (C2-C 20 ) alkynyl, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 )aryl, and substituted or unsubstituted (C2-C 20 )alkoxy. In some examples, PCA has the same chemical structure at each occurrence. Alternatively, at least two occurrences of PCA may have different chemical structures.

[0056] As specific examples, PCA independently comprises, at each occurrence, reacted adipic acid, reacted purified terephthalic acid, reacted isophthalic acid, reacted phthalic anhydride, reacted naphthylic acid, reacted mellitic acid, reacted mellitic anhydride, reacted naphthalenetetracarboxylic anhydride, reacted citric acid, reacted esters, reacted acid chlorides, reacted dianhydrides, or reacted ethylenediaminetetraacetic acid. PCA may include three carboxylic acid groups or two carboxylic acid groups. A more preferred structure of the grease thickener composition is a structure of formula II or III. That is, the structure of formula II or III more easily allows the formation of a grease thickener having a combination of the desired structural features described above. In a preferred aspect, the grease thickener component will have at least four amide bonds.

[0057] 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 monocarboxylic acid ester having a structure according to formula (IV):

[0058] (IV).

[0059] In Formula VIII, R 3is substituted or unsubstituted (C1-C 20 ) hydrocarbon group, and R 7 Selected from -OH, -Cl, -O - or substituted or unsubstituted -O-(C1-C 20 ) alkyl. At each occurrence, substituted or unsubstituted (C1-C 20 )alkyl groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkyl, substituted or unsubstituted (C3-C 20 )cycloalkyl, substituted or unsubstituted (C2-C 20 )alkenyl, substituted or unsubstituted (C2-C 20 ) alkynyl, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 ) aryl and substituted or unsubstituted (C2-C 20 )alkoxy.

[0060] As a further example, at each occurrence, MCA can include a reacted monocarboxylic acid ester. The monocarboxylic acid ester can have a structure according to the following formula:

[0061] Formula (V):

[0062] (V), or

[0063] Formula (VI):

[0064] (VI).

[0065] R 4 Selected from chemical bonds and substituted or unsubstituted (C1-C 20 )alkylene. At each occurrence, substituted or unsubstituted (C1-C 20 )alkylene groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C3-C 20 )cycloalkylene, substituted or unsubstituted (C2-C 20 )alkenylene, substituted or unsubstituted (C2-C 20 ) alkynylene, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 )arylene, and 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 have different chemical structures. As an example, MCA can be reacted benzoic acid, reacted cyclohexanecarboxylic acid, or reacted stearic acid.

[0066] While not intending to be bound by any theory, it is believed that grease thickeners wherein the MCA comprises an aromatic group, a cycloaliphatic group, or an aliphatic group provide the best performance for grease thickeners in grease compositions. Further, it is believed that superior performance can be obtained when the first MCA comprises an aromatic group and the second MCA comprises an aliphatic or cycloaliphatic group. In particular, it is believed that a second MCA comprising an aliphatic chain having 6 to 8 carbon atoms produces superior performance. The hydrophobic nature of the aliphatic group is believed to help provide compatibility with the grease. It is also believed that if R 3 and R 4 Rather than chemical bonds, it is better that they are n-(C1-C 20 ) alkylene groups, as this more readily allows the formation of grease thickeners having the combination of desirable structural features described above.

[0067] As shown, the reaction between the corresponding MCA and DA groups produces a grease thickener having a terminal amide group. While not intending to be bound by any theory, it is believed that the terminal amide group provides several benefits. For example, the amide group makes the reactivity of the grease thickener comparable to the level of other polyamides (such as nylon-6,6), which means that the grease thickener is relatively inert and does not react with other components of the grease composition. Therefore, the grease thickener can remain in the grease composition in an unreacted form. In addition, the amide bond may not be easily hydrolyzed. Therefore, the grease thickener can tolerate a certain amount of water that may be present (intentionally or unintentionally) in the grease composition. In addition, the grease thickener can be synthesized in the presence of water. These benefits are particularly evident compared to grease thickeners having terminal ester groups. Terminal ester groups may be more susceptible to reacting with other grease components or hydrolyzing, both of which can reduce the effectiveness of the grease thickener.

[0068] At each occurrence, DA is a reacted diamine independently having a structure according to formula (VII):

[0069] (VII).

[0070] R 5 is substituted or unsubstituted (C1-C 20 )alkylene. At each occurrence, substituted or unsubstituted (C1-C 20 )alkylene groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C3-C 20 )cycloalkylene, substituted or unsubstituted (C2-C 20 )alkenylene, substituted or unsubstituted (C2-C 20 ) alkynylene, substituted or unsubstituted (C1-C20 ) acyl, substituted or unsubstituted (C4-C 20 )arylene and substituted or unsubstituted (C2-C 20 )alkyleneoxy. At each occurrence, DA has the same chemical structure. Alternatively, at least two occurrences of DA have different chemical structures.

[0071] In specific examples, DA is, at each occurrence, a reacted diamine independently selected from the group consisting of reacted hexamethylenediamine, reacted propylenediamine, reacted butanediamine, reacted pentamethylenediamine, reacted nonamethylenediamine, reacted isononamethylenediamine, reacted 2-methylpentamethylenediamine, reacted ethylenediamine, reacted isophoronediamine, reacted meta-xylylenediamine, and reacted meta-phenylenediamine. In some examples, DA is, at each occurrence, reacted hexamethylenediamine. In more specific examples, DA is found as n—(C1-C 20 ) The internal aliphatic group of the alkylene group produces a grease thickener with a desired dropping point and NLGI performance. Typically, the DA does not include a branched structure. This is because the diamine with a branched structure tends to make the grease composition containing the grease thickener too safe, which in turn lowers the melting point of the grease composition too much. In some examples, the DA can be selected from reacted hexamethylenediamine, reacted propylenediamine, reacted butanediamine, reacted pentanediamine, or reacted nonanediamine.

[0072] The grease thickener may be present in a distribution. In the distribution, the grease thickener has a weight average molecular weight in the range of 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 g / mol, 500 g / mol, 550 g / mol, 600 g / mol, 650 g / mol, 700 g / mol, 750 g / mol, 800 g / mol, 850 g / mol, 900 g / mol, 950 g / mol, 1000 g / mol, 1050 g / mol, 1100 g / mol, 1150 g / mol, mol, 1200 g / mol, 1250 g / mol, 1300 g / mol, 1350 g / mol, 1400 g / mol, 1450 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol, 5000 g / mol, 5500 g / mol, 6000 g / mol, 6500 g / mol, 7000 g / mol, 7500 g / mol, 8000 g / mol, 8500 g / mol, 9000 g / mol, 9500 g / mol or about 10000 g / mol. Maintaining the weight average molecular weight within this range can help the polyamide grease polymer 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 the range of about 450 g / mol to about 3500 g / mol or about 500 g / mol to about 2500 g / mol produced a grease thickener with particularly favorable properties (e.g., dropping point and NLGI value). In addition, it was found that if the weight average molecular weight of the grease thickening component is too high, it will be incompatible with the base oil of the grease composition. If the grease composition is not homogenous, then incompatibility is indicated. The grease composition is considered to be homogenous if discrete particles are observed when observed under a microscope at 200 times magnification.

[0073] Generally, it was found that if the polyamide grease thickener was completely linear (e.g., included no alicyclic, aromatic, etc.), the resulting grease had poor penetrometer measurements, meaning that 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 because all aromatic polyamides exhibited poor compatibility (e.g., low dropping points) when incorporated into grease compositions. Additionally, it was found that if the weight average molecular weight of the polyamide grease thickener was too high, there would be poor compatibility (e.g., lack of homogeneity) in the grease composition.

[0074] Specific examples of suitable grease thickeners that can be used alone or as a mixture of grease thickeners include those shown in Table 1. Among those grease thickeners listed in Table 1, the structures of Formulas XII, XI, X, and XIII include the above-mentioned beneficial structures and show good performance in the grease composition. When the corresponding grease thickeners are incorporated into the grease composition, including the dropping point P0 and P 60 Value data available.

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082] The polyamide grease thickener can be a component of a grease composition. A grease composition is generally understood to refer to a solid or semi-solid lubricant formed as a dispersion of a thickener in a liquid lubricant. The grease composition comprises a base oil (or lubricating oil), a grease thickener, and optional additives. The polyamide grease thickener can be in the range of about 1% to about 50% by weight of the grease composition, about 5% to about 20% by weight of the grease composition. The base oil can include vegetable oil, mineral oil, synthetic oil, or any other fluid that provides lubricating properties. For example, the grease can be a silicone grease. The silicone grease can include a polydimethylsiloxane-based oil. Other greases can be fluoroether-based greases containing fluoroether-based oils.

[0083] The grease thickener present can self-assemble into a network, thereby providing sufficient structure for the grease to function. As mentioned above, the weight average molecular weight of the grease thickener is in the range of about 450 g / mol to about 10,000 g / mol. Each grease thickener molecule may have the same molecular weight, but there may also be a distribution of molecular weights of the grease thickener.

[0084] According to various examples, the grease thickener is a first grease thickener, and the grease composition further comprises a second grease thickener having a different chemical structure from the first grease thickener. For example, the molecular weight of the first grease thickener may be different from the molecular weight of the second grease thickener, or the chemical compositions of the first grease thickener and the second grease thickener are different, or the first grease thickener and the second grease thickener are isomers of each other.

[0085] One advantage of the grease composition is that it can provide sufficient thickening performance for the grease composition while being substantially free of lithium, polyurea, or mixtures thereof. For example, the grease composition can contain 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 potentially more environmentally friendly grease composition. Additionally, particularly with respect to being substantially free of lithium, the resulting grease composition can be produced at a lower cost than a corresponding grease composition using a thickener comprising lithium, as opposed to the claimed grease thickener.

[0086] In some aspects, a grease composition may include the disclosed grease thickening composition and a grease thickening composition comprising lithium, polyurea, or both. However, the amount of the grease thickening composition comprising lithium, polyurea, or both may be reduced by including the disclosed grease thickening composition relative to a grease composition not comprising the disclosed grease thickening composition.

[0087] In addition to the lubricant and grease thickener, the grease composition may contain additional components such as anhydrous calcium complexes, aluminum complexes, calcium sulfonate complexes, calcium complexes, barium complexes, sodium complexes, or mixtures thereof. The total combined weight % of these components (alone or in combination) may 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%.

[0088] Grease compositions containing the disclosed thickeners can have several beneficial properties. For example, the dropping point of the grease composition can be in the range of 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°C, 202°C, 203°C, 204°C, 205°C, 206°C, 207°C, 208°C, 209°C, 210°C, 211°C, 212°C, 213°C, 214°C, 215°C, 216°C, 217°C, 218°C, 219°C, 220°C, 221°C, 222°C, 223°C, 224°C, 225°C, 226°C, 227°C, 228°C, 229°C, 230°C, 231°C, 232°C, 233°C, 234°C, 235°C, 236°C, 237°C, 238°C, 239°C, 240°C, 241°C, 242°C, 243°C, 244°C, 245°C, 246°C, 247°C, 248°C, 249°C, 250°C, 251°C, 252°C, 253°C, 254°C, 255°C ℃, 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℃. The dropping point of the grease composition can be substantially similar to the dropping point of the comparative grease composition, except that the grease thickening component is a lithium-based grease thickening component. As is generally understood, the dropping point of a grease is the temperature at which it changes from a semi-solid state to a liquid state. The dropping point test determines the cohesiveness of the oil and thickener of the grease. The test for determining the dropping point is ASTM D-2265.

[0089] The grease composition also exhibits acceptable mechanical strength. For example, the NLGI consistency value of the unprocessed composition of the grease composition (a sample that has only been subjected to minimal disturbance) can be in the range of 3 to 4. The NLGI consistency value of the processed grease composition (as a sample that has undergone 60 double strokes in a standard grease processing machine) can be in the range of 1 to 2. The NLGI consistency value can be measured in accordance with ASTM D-217 entitled "Cone penetration of lubricating grease". This involves two test devices. The first device consists of a closed container and a piston-like plunger. The face of the plunger is perforated to allow the grease to flow from one side of the plunger to the other side as the plunger works up and down. The test grease is inserted into the container and the plunger is stroked 60 times while the test device and the grease are maintained at a temperature of 25°C. After processing, the grease is placed in a penetration test device. The device includes a container, a specially constructed cone and a dial indicator. The container is filled with grease and the top surface of the grease is smoothed. 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 causes it to penetrate into the grease. After specific time intervals, the penetration depth is measured.

[0090] As used herein, including such as P0, P 60 and P 10000 The value of indicates the degree of processing of the grease composition. For example, an unprocessed grease composition has a P0 value. When the test device and the grease composition are maintained at a temperature of 25°C, a grease composition that is inserted into a container and subjected to 60 plunger strokes has a P 60 When the test device and the grease composition are maintained at a temperature of 25°C, the grease composition inserted into the container and subjected to 10,000 plunger strokes has a P 10000 value.

[0091] The unprocessed grease composition may have a penetration value within the range of 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 tenths of a millimeter, 217 tenths of a millimeter, 218 tenths of a millimeter, 219 tenths of a millimeter, 220 tenths of a millimeter, 221 tenths of a millimeter, 222 tenths of a millimeter, 223 tenths of a millimeter, 224 tenths of a millimeter, 225 tenths of a millimeter, 226 tenths of a millimeter, 227 tenths of a millimeter, 228 tenths of a millimeter, 229 tenths of a millimeter, 230 tenths of a millimeter, 231 tenths of a millimeter, 232 tenths of a millimeter, 233 tenths of a millimeter, 234 tenths of a millimeter, 235 tenths of a millimeter. The processed grease composition may have a diameter in the range of about 280 tenths of an mm to about 310 tenths of an mm, about 290 tenths of an mm to about 400 tenths of an mm, less than, equal to, or greater than about 280 tenths of an mm, 281 tenths of an mm, 282 tenths of an mm, 283 tenths of an mm, 284 tenths of an mm, 285 tenths of an mm, 286 tenths of an mm, 287 tenths of an mm, 288 tenths of an mm, 289 tenths of an mm, 290 tenths of an mm, 291 tenths of an mm, 292 tenths of an mm, 293 tenths of an mm, 294 tenths of an mm, 295 tenths of an mm, 296 tenths of an mm, 297 tenths of an mm, 298 tenths of an mm, 29 ... 293 mm, 294 mm, 295 mm, 296 mm, 297 mm, 298 mm, 299 mm, 300 mm, 301 mm, 302 mm, 303 mm, 304 mm, 305 mm, 306 mm, 307 mm, 308 mm, 309 mm, 310 mm, 311 mm, 312 mm, 313 mm m, 314th mm, 315th mm, 316th mm, 317th mm, 318th mm, 319th mm, 320th mm, 321th mm, 322th mm, 323th mm, 324th mm, 325th mm, 326th mm, 327th mm, 328th mm, 329th mm, 330th mm, 331th mm, 332th mm, 333th mm, 334th mm, 335th mm, 336th mm, 337th mm, 338th mm, 339th mm, 340th mm, 341th mm, 342th mm, 343th mm, 344th mm, 345th mm, 346th mm, 347th mm, 348th mm, 349th mm, 350th mm, 351th mm, 352th mm, 353th mm, 354th mm, 355th mm, 356th mm, 357th mm, 358th mm, 359th mm, 360th mm, 361th mm, 362th mm, 363th mm, 364th mm, 365th mm, 366th mm, 367th mm, 368th mm, 369th mm, 370th mm, 371th mm, 372th mm, 373th mm, 374th mm, 375th mm, 376th mm, 377th mm, 378th mm, 379th mm, 380th mm, 381st mm, 382nd mm, 383rd mm, 384th mm, 385th mm, 386th 334 mm, 335 mm, 336 mm, 337 mm, 338 mm, 339 mm, 340 mm, 341 mm, 342 mm, 343 mm, 344 mm, 345 mm, 346 mm, 347 mm, 348 mm, 349 mm, 350 mm, 351 mm, 352 mm, 353 mm, 354 mm,355 tenths of millimeters, 356 tenths of millimeters, 357 tenths of millimeters, 358 tenths of millimeters, 359 tenths of millimeters, 360 tenths of millimeters, 361 tenths of millimeters, 362 tenths of millimeters, 363 tenths of millimeters, 364 tenths of millimeters, 365 tenths of millimeters, 366 tenths of millimeters, 367 tenths of millimeters, 368 tenths of millimeters, 369 tenths of millimeters, 370 tenths of millimeters, 371 tenths of millimeters, 372 tenths of millimeters, 373 tenths of millimeters, 374 tenths of millimeters, 375 tenths of millimeters, 376 tenths of millimeters, 377 tenths of millimeters The grease composition may have an NLGI consistency value that is substantially similar to the NLGI consistency value of the comparative grease composition, except that the grease thickening component is a lithium-based grease thickening component.

[0092] The grease composition may be in contact with any number of articles that require lubrication. For example, the grease composition may be applied to bearings, shafts, joints, hinges, and the like.

[0093] Generally, the grease thickener can be prepared simply 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 thickener.

[0094] Example

[0095] Various aspects of the present invention may be better understood by reference to the following examples which are provided by way of illustration.The present invention is not limited to the examples given herein.

[0096] Various grease thickeners have been developed and their performance has been tested as shown below.

[0097] Embodiment 1:

[0098] (XV)

[0099] The grease thickener of formula XV was prepared in a three-necked round-bottomed vessel equipped with a nitrogen inlet and a distillation apparatus by mixing 18.1 g (0.05 mol) of 6T6 with 28.4 g (0.1 mol) of stearic acid in 327 g of alkylated naphthyl oil. The reaction mixture was slowly raised to 180°C and allowed to react for 2 hours. During the reaction, the mixture began to thicken as water was generated, which was removed by distillation. The temperature of the reaction mixture was raised to 220°C within 2 hours, stirring was maintained, and it was allowed to react until the generation of water ceased. The material was cooled to 150°C and homogenized. The grease thickener was incorporated into the grease composition at 12% by weight. The dropping point of the grease composition was 175°C.

[0100] Example 2

[0101]

[0102] The grease thickener of formula XII was prepared in a three-necked round-bottomed vessel equipped with a nitrogen inlet and a distillation apparatus by mixing 18.1 g (0.05 mol) of 6T6 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-based oil. The reaction mixture was slowly raised to 180°C and allowed to react for 2 hours. During the reaction, the mixture began to thicken as water was generated, which was removed by distillation. The temperature of the reaction mixture was raised to 220°C within 2 hours, stirring was maintained, and it was allowed to react until the generation of water ceased. The material was cooled to 150°C and homogenized. The grease thickener was incorporated into the grease composition at 12% by weight. The dropping point of the grease composition was 225°C.

[0103] Example 3

[0104]

[0105] The grease thickener of formula XXXII was prepared in a three-necked round-bottomed vessel equipped with a nitrogen inlet and a distillation apparatus by mixing 25.00 g (0.0411 mol) of 6T6T6 with 23.38 g (0.0822 mol) of stearic acid in 344 g of alkylated naphthyl oil. The reaction mixture was slowly raised to 180°C and allowed to react for 2 hours. During the reaction, the mixture began to thicken as water was generated, which was removed by distillation. The temperature of the reaction mixture was raised to 240°C within 2 hours, stirring was maintained, and it was allowed to react until the generation of water ceased. The material was cooled to 150°C and homogenized. The grease thickener was incorporated into the grease composition at 12% by weight. The dropping point of the grease composition was 300°C.

[0106] Example 4

[0107]

[0108] The grease thickener of formula XI was prepared in a three-necked round bottom vessel equipped with a nitrogen inlet and a distillation apparatus by mixing 46.6 g (0.1285 mol) of 6T6 with 12.5 g (0.0644 mol) of dimethyl terephthalate and 4.46 g (5 wt%) of phenol in 655 g of alkylated naphthyl oil. The mixture was heated at 100°C for 30 minutes. 36.6 g (0.129 mol) of stearic acid was added to the reaction mixture and the temperature was slowly raised to 180°C and allowed to react for 2 hours. During the reaction, the mixture began to thicken as water was generated, which was removed by distillation. The temperature of the reaction mixture was raised to 220°C within 2 hours, stirring was maintained, and it was allowed to react until distillation ceased. The material was cooled to 150°C and homogenized. The grease thickener was incorporated into the grease composition at 12 wt%. The dropping point of the grease composition was 240°C.

[0109] Example 5

[0110]

[0111] The grease thickener of formula XIII was prepared in a three-necked round bottom vessel equipped with a nitrogen inlet and a distillation apparatus by mixing 63.0 g (0.1738 mol) of 6T6 with 17.00 g (0.00.1159 mol) of dimethyl terephthalate and 5.58 g (5 wt%) of phenol in 818 g of alkylated naphthyl oil. The mixture was heated at 100°C for 30 minutes. 32.96 g (0.1159 mol) of stearic acid and 7.43 g (0.058 mol) of cyclohexanecarboxylic acid were added to the reaction mixture, and the temperature was slowly raised to 180°C and allowed to react for 2 hours. The temperature of the reaction mixture was raised to 220°C within 2 hours, stirring was maintained, and allowed to react until distillation ceased. The material was cooled to 150°C and homogenized. The grease thickener was incorporated into the grease composition at 12 wt%. The dropping point of the grease composition was 262°C.

[0112] Example 6

[0113] The amine groups in the grease thickener of formula XXXII are functionalized with stearic acid. Figure 1 As shown, the grease thickener was studied to determine its performance (penetration value) when present at 10 wt % and 15 wt % in a grease composition. In addition, the thickener had 65 wt % or 95 wt % of the amine groups in the grease thickener functionalized with stearic acid.

[0114] The data demonstrate that functionalization (or incomplete functionalization) of the amines with stearic acid is an independent variable that affects the consistency of polyamide thickened grease compositions. Increasing the amount of stearic acid endcappers was observed to increase the compatibility of the thickener with the base oil system of the grease composition. At the same time, increasing the amount of stearic acid endcappers decreased the consistency of the grease composition, resulting in a softer grease. In these systems, the greases require higher loadings of polyamide thickeners with higher stearic acid functionality to achieve similar mechanical properties as those with lower stearic acid functionality. For example, a stearic acid thickener with 95% amine functionalization will have a higher P0 / P when compared to a grease thickener of similar chain length with 65% amine functionalization at the same grease thickener loading. 60 / P 10000 Measured value.

[0115] Table 2

[0116]

[0117] The terms and expressions that have been employed are used as terms of description rather than limitation, and it is not intended that the use of such terms and expressions exclude any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications within the scope of the embodiments of the present invention are possible. Therefore, it should be understood that although the present invention has been specifically disclosed through specific embodiments and optional features, those of ordinary skill in the art may adopt modified and variant forms of the concepts disclosed herein, and such modified and variant forms are considered to be within the scope of the embodiments of the present invention.

[0118] Exemplary Aspects

[0119] The following exemplary aspects are provided, the numbering of which should not be construed as designating a level of importance:

[0120] Aspect 1 provides a polyamide grease thickener having a structure according to Formula I:

[0121] (MCA-DA-)(PCA-DA) y -PCA-(DA-PCA) y (-DA-MCA) (I),

[0122] in

[0123] At each occurrence, PCA is independently a reacted polycarboxylate,

[0124] MCA is independently at each occurrence the reacted monocarboxylic acid ester,

[0125] At each occurrence, DA is independently the reacted diamine,

[0126] y is 0 or a non-zero integer,

[0127] The weight average molecular weight of the polyamide grease thickener is in the range of about 450 g / mol to about 3500 g / mol,

[0128] The structure according to formula I comprises at least 4 amide bonds, and

[0129] at least one cycloaliphatic moiety or at least one aromatic moiety.

[0130] Aspect 2 provides the polyamide grease thickener according to aspect 1, wherein the weight average molecular weight of the polyamide grease thickener is in the range of about 500 g / mol to about 2500 g / mol.

[0131] Aspect 3 provides a polyamide grease thickener according to any one of aspects 1 or 2, wherein the polyamide grease thickener has a structure according to Formula II:

[0132] ((MCA-DA-)(PCA-DA) y -) n PCA (II),

[0133] Wherein n is 2, and y is in the range of 2 to 4.

[0134] Aspect 4 provides the polyamide grease thickener according to any one of aspects 1 to 3, wherein the polyamide grease thickener has a structure according to Formula III:

[0135] (MCA-DA)-PCA-(DA-MCA) (III).

[0136] Aspect 5 provides the polyamide grease thickener according to any one of aspects 1 to 4, wherein at each occurrence, PCA independently comprises 6 to 50 carbon atoms.

[0137] Aspect 6 provides the polyamide grease thickener according to any one of aspects 1 to 5, wherein at each occurrence, PCA independently comprises 6, 8 or 9 carbon atoms.

[0138] Aspect 7 provides the polyamide grease thickener according to any one of aspects 1 to 6, wherein PCA has the same chemical structure at each occurrence.

[0139] Aspect 8 provides the polyamide grease thickener according to any one of aspects 1 to 7, wherein at least two occurrences of PCA have different chemical structures.

[0140] Aspect 9 provides a polyamide grease thickener according to any one of aspects 1 to 8, wherein at each occurrence, PCA independently comprises reacted adipic acid, reacted purified terephthalic acid, reacted isophthalic acid, reacted phthalic anhydride, reacted naphthylic acid, reacted mellitic acid, reacted mellitic anhydride, reacted naphthalenetetracarboxylic anhydride, reacted citric acid, reacted ester, reacted acid chloride, reacted dianhydride or reacted ethylenediaminetetraacetic acid.

[0141] Aspect 10 provides a polyamide grease thickener according to any one of aspects 1 to 9, wherein MCA, at each occurrence, independently comprises a reacted aliphatic monocarboxylic acid ester, a reacted alicyclic monocarboxylic acid ester, or a reacted aromatic monocarboxylic acid ester.

[0142] Aspect 11 provides the polyamide grease thickener according to any one of aspects 1 to 10, wherein MCA has the same chemical structure at each occurrence.

[0143] Aspect 12 provides the polyamide grease thickener according to any one of aspects 1 to 11, wherein at least two occurrences of MCA have different chemical structures.

[0144] Aspect 13 provides a polyamide grease thickener according to any one of aspects 1 to 12, wherein at each occurrence, MCA comprises a reacted monocarboxylic acid ester having a structure according to formula (IV):

[0145] (IV),

[0146] Where R 3 is substituted or unsubstituted (C1-C 20 ) hydrocarbon group, and R 7 Selected from -OH, -Cl, -O - or substituted or unsubstituted -O-(C1-C 20 ) hydrocarbon group.

[0147] Aspect 14 provides a polyamide grease thickener according to aspect 13, wherein at each occurrence, substituted or unsubstituted (C1-C 20 )alkyl groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkyl, substituted or unsubstituted (C3-C 20 )cycloalkyl, substituted or unsubstituted (C2-C 20 )alkenyl, substituted or unsubstituted (C2-C 20 ) alkynyl, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 ) aryl and substituted or unsubstituted (C2-C20 )alkoxy.

[0148] Aspect 15 provides a polyamide grease thickener according to any one of aspects 13 or 14, wherein at each occurrence, MCA comprises a reacted monocarboxylic acid ester having a structure according to the following formula:

[0149] Formula (V):

[0150] (V), or

[0151] Formula (VI):

[0152] (VI)

[0153] Where R 4 Selected from chemical bonds and substituted or unsubstituted (C1-C 20 )alkylene.

[0154] Aspect 16 provides a polyamide grease thickener according to aspect 15, wherein at each occurrence, substituted or unsubstituted (C1-C 20 )alkylene groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C3-C 20 )cycloalkylene, substituted or unsubstituted (C2-C 20 )alkenylene, substituted or unsubstituted (C2-C 20 ) alkynylene, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 )arylene and substituted or unsubstituted -O-(CH2)n- (n = 2-20).

[0155] Aspect 17 provides a polyamide grease thickener according to any one of aspects 1 to 16, wherein MCA, at each occurrence, is independently selected from reacted esters, reacted acid chlorides, reacted anhydrides, reacted benzoic acid, reacted cyclohexanecarboxylic acid, and reacted stearic acid.

[0156] Aspect 18 provides the polyamide grease thickener according to any one of aspects 1 to 17, wherein DA has the same chemical structure at each occurrence.

[0157] Aspect 19 provides the polyamide grease thickener according to any one of aspects 1 to 18, wherein at least two occurrences of DA have different chemical structures.

[0158] Aspect 20 provides a polyamide grease thickener according to any one of aspects 1 to 19, wherein DA, at each occurrence, is a reacted diamine independently having a structure according to formula (VII):

[0159] (VII)

[0160] Where R 5 is substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C5-C 20 )cycloalkylene or substituted or unsubstituted (C4-C 20 )aryl.

[0161] Aspect 21 provides a polyamide grease thickener according to aspect 20, wherein DA, at each occurrence, is a reacted diamine independently selected from reacted hexamethylenediamine, reacted propylenediamine, reacted butanediamine, reacted pentanediamine, reacted phenylenediamine, reacted cyclohexanediamine, or reacted nonanediamine.

[0162] Aspect 22 provides a polyamide grease thickener according to any one of aspects 1 to 21, wherein DA, at each occurrence, is a reacted diamine independently selected from reacted hexamethylenediamine, reacted propylenediamine, reacted butanediamine, or reacted pentanediamine.

[0163] Aspect 23 provides the polyamide grease thickener according to any one of aspects 1 to 22, wherein DA, at each occurrence, is reacted hexamethylenediamine.

[0164] Aspect 24 provides the polyamide grease thickener according to any one of aspects 1 to 23, wherein the dropping point of a grease composition comprising the polyamide grease thickener is greater than about 200°C.

[0165] Aspect 25 provides the polyamide grease thickener according to any one of aspects 2 to 24, wherein the dropping point of a grease composition comprising the polyamide grease thickener is greater than about 250°C.

[0166] Aspect 26 provides a polyamide grease thickener according to any one of aspects 1 to 25, wherein when at least one aromatic portion is disposed internally, it is disubstituted in the para position, and when at least one cycloaliphatic portion is disposed internally, it is disubstituted and symmetrical about an axis passing through the two substituents.

[0167] Aspect 27 provides a polyamide grease thickener according to any one of aspects 1 to 26, wherein the structure according to formula I comprises at least two aromatic moieties, and at least one aromatic moiety is a monosubstituted terminal group of formula I.

[0168] Aspect 28 provides a polyamide grease thickener having a structure according to Formula IX:

[0169] (IX), where

[0170] in

[0171] PCA is independently at each occurrence a para-substituted reacted polycarboxylate,

[0172] MCA is independently at each occurrence the reacted monocarboxylic acid ester,

[0173] At each occurrence, DA is independently the reacted diamine,

[0174] y is 0 or a non-zero integer,

[0175] The weight average molecular weight of the polyamide grease thickener is in the range of about 450 g / mol to about 3500 g / mol.

[0176] Aspect 29 provides the polyamide grease thickener according to aspect 28, wherein the weight average molecular weight of the polyamide grease thickener is in the range of about 500 g / mol to about 2500 g / mol.

[0177] Aspect 30 provides a polyamide grease thickener according to any one of aspects 28 or 29, wherein at each occurrence, MCA independently comprises a reacted aliphatic monocarboxylic acid ester, a reacted alicyclic monocarboxylic acid ester, or a reacted aromatic monocarboxylic acid ester.

[0178] Aspect 31 provides the polyamide grease thickener according to any one of aspects 28 to 30, wherein MCA has the same chemical structure at each occurrence.

[0179] Aspect 32 provides a polyamide grease thickener according to any one of aspects 28 to 31, wherein at least two occurrences of MCA have different chemical structures.

[0180] Aspect 33 provides a polyamide grease thickener according to any one of aspects 28 to 32, wherein at each occurrence, MCA comprises a reacted monocarboxylic acid ester having a structure according to formula (IV):

[0181] (IV),

[0182] Where R 3 is substituted or unsubstituted (C1-C 20 ) hydrocarbon group, and R 7 Selected from -OH, -Cl, -O -or substituted or unsubstituted -O-(C1-C 20 ) hydrocarbon group.

[0183] Aspect 34 provides a polyamide grease thickener according to aspect 33, wherein at each occurrence, substituted or unsubstituted (C1-C 20 )alkyl groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkyl, substituted or unsubstituted (C3-C 20 )cycloalkyl, substituted or unsubstituted (C2-C 20 )alkenyl, substituted or unsubstituted (C2-C 20 ) alkynyl, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 ) aryl and substituted or unsubstituted (C2-C 20 )alkoxy.

[0184] Aspect 35 provides a polyamide grease thickener according to any one of aspects 33 or 34, wherein at each occurrence, MCA comprises a reacted monocarboxylic acid ester having a structure according to the following formula:

[0185] Formula (V):

[0186] (V), or

[0187] Formula (VI):

[0188] (VI)

[0189] Where R 4 Selected from chemical bonds and substituted or unsubstituted (C1-C 20 )alkylene.

[0190] Aspect 36 provides a polyamide grease thickener according to aspect 35, wherein at each occurrence, substituted or unsubstituted (C1-C 20 )alkylene groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C3-C 20 )cycloalkylene, substituted or unsubstituted (C2-C 20 )alkenylene, substituted or unsubstituted (C2-C 20 ) alkynylene, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 )arylene and substituted or unsubstituted -O-(CH2)n- (n = 2-20).

[0191] Aspect 37 provides a polyamide grease thickener according to any one of aspects 28 to 36, wherein MCA, at each occurrence, is independently selected from reacted esters, reacted acid chlorides, reacted anhydrides, reacted benzoic acid, reacted cyclohexanecarboxylic acid, and reacted stearic acid.

[0192] Aspect 38 provides the polyamide grease thickener according to any one of aspects 28 to 37, wherein DA has the same chemical structure at each occurrence.

[0193] Aspect 39 provides a polyamide grease thickener according to any one of aspects 28 to 38, wherein at least two occurrences of DA have different chemical structures.

[0194] Aspect 40 provides a polyamide grease thickener according to any one of aspects 28 to 39, wherein DA, at each occurrence, is a reacted diamine independently selected from reacted hexamethylenediamine, reacted propylenediamine, reacted butanediamine, reacted pentanediamine, reacted phenylenediamine, reacted cyclohexanediamine, or reacted nonanediamine.

[0195] Aspect 41 provides a polyamide grease thickener according to any one of aspects 28 to 40, wherein DA, at each occurrence, is reacted hexamethylenediamine.

[0196] Aspect 42 provides the polyamide grease thickener according to any one of aspects 28 to 41, wherein the polyamide grease thickener has a dropping point greater than about 200°C.

[0197] Aspect 43 provides the polyamide grease thickener according to any one of aspects 28 to 42, wherein the polyamide grease thickener has a dropping point greater than about 250°C.

[0198] Aspect 44 provides a polyamide grease thickener having a structure according to any one of Formulas X, XI, XII or XIII:

[0199] (XXXII),

[0200] (XI)

[0201] (XII)

[0202] (XIII).

[0203] Aspect 45 provides a method for preparing a grease thickener according to any one of aspects 1 to 44, the method comprising:

[0204] reacting a polycarboxylate with a diamine to form a first product; and

[0205] The first product is reacted with a monocarboxylic acid ester to form a grease thickener.

[0206] Aspect 46 provides a method of using the polyamide grease thickener according to any one of aspects 1 to 45, the method comprising contacting the polyamide grease thickener with a grease to form a grease composition.

[0207] Aspect 47 provides a method of using the grease composition according to aspect 46, the method comprising contacting the grease composition with an article to be lubricated.

[0208] Aspect 48 provides a grease composition comprising the grease thickener according to any one of aspects 1 to 47.

[0209] Aspect 49 provides the grease composition according to aspect 48, wherein the grease thickener is in the range of about 1 wt % to about 50 wt % of the grease composition.

[0210] Aspect 50 provides a grease composition according to any one of aspects 48 or 49, wherein the grease thickener is in the range of about 5 wt % to about 20 wt % of the grease composition.

[0211] Aspect 51 provides a grease composition according to any one of Aspects 48 to 51, wherein the grease thickener is a first grease thickener, and the grease composition further comprises a second grease thickener having a chemical structure different from that of the first grease thickener, the second grease thickener having a structure according to Formula I.

[0212] Aspect 52 provides the grease composition according to aspect 51, wherein the molecular weight of the first grease thickener is different from the molecular weight of the second grease thickener.

[0213] Aspect 53 provides the grease composition according to any one of aspects 51 or 52, wherein the chemical composition of the first grease thickener and the second grease thickener is different.

[0214] Aspect 54 provides the grease composition according to any one of aspects 48 to 53, comprising less than 1 wt % lithium.

[0215] Aspect 55 provides a grease composition according to any one of aspects 48 to 54, comprising less than 1 wt % of polyurea.

[0216] Aspect 56 provides a homogenized grease composition comprising:

[0217] Polyamide grease thickeners having a structure according to Formula I:

[0218] (MCA-DA-)(PCA-DA) y -PCA-(DA-PCA) y (-DA-MCA) (I),

[0219] in

[0220] At each occurrence, PCA is independently a reacted polycarboxylate,

[0221] MCA is independently at each occurrence the reacted monocarboxylic acid ester,

[0222] At each occurrence, DA is independently the reacted diamine,

[0223] y is 0 or a non-zero integer,

[0224] The structure according to formula I comprises at least 4 amide bonds, and

[0225] at least one cycloaliphatic moiety or at least one aromatic moiety.

[0226] Aspect 57 provides a homogenized grease composition according to aspect 56, wherein when the at least one aromatic moiety is disposed internally, it is disubstituted in the para position, and when the at least one cycloaliphatic moiety is disposed internally, it is disubstituted and symmetrical about an axis passing through the two substituents.

[0227] Aspect 58 provides a homogenized grease composition according to any one of aspects 56 or 57, wherein the structure according to Formula I comprises at least two aromatic moieties, and at least one aromatic moiety is a monosubstituted terminal group of Formula I.

[0228] Aspect 59 provides a homogenized grease composition according to any one of aspects 56 to 58, wherein the polyamide grease thickener has a structure according to Formula II:

[0229] ((MCA-DA-)(PCA-DA) y -) n PCA (II),

[0230] Wherein n is 2, and y is in the range of 2 to 4.

[0231] Aspect 60 provides a homogenized grease composition according to any one of aspects 56 to 59, wherein the polyamide grease thickener has a structure according to Formula III:

[0232] (MCA-DA)-PCA-(DA-MCA) (III).

[0233] Aspect 61 provides a homogenized grease composition according to any one of aspects 56 to 60, wherein at each occurrence, PCA independently comprises 6 to 50 carbon atoms.

[0234] Aspect 62 provides a homogenized grease composition according to any one of aspects 56 to 61, wherein at each occurrence, PCA independently comprises 6, 8, or 9 carbon atoms.

[0235] Aspect 63 provides a homogenized grease composition according to any one of aspects 56 to 62, wherein the PCA has the same chemical structure at each occurrence.

[0236] Aspect 64 provides a homogenized grease composition according to any one of aspects 56 to 63, wherein at least two occurrences of PCA have different chemical structures.

[0237] Aspect 65 provides a homogenized grease composition according to any one of aspects 56 to 64, wherein at each occurrence, PCA independently comprises reacted adipic acid, reacted purified terephthalic acid, reacted isophthalic acid, reacted phthalic anhydride, reacted naphthylic acid, reacted mellitic acid, reacted mellitic anhydride, reacted naphthalenetetracarboxylic anhydride, reacted citric acid, reacted ester, reacted acid chloride, reacted dianhydride, or reacted ethylenediaminetetraacetic acid.

[0238] Aspect 66 provides a homogenized grease composition according to any one of aspects 56 to 65, wherein at each occurrence, MCA independently comprises a reacted aliphatic monocarboxylic acid ester, a reacted alicyclic monocarboxylic acid ester, or a reacted aromatic monocarboxylic acid ester.

[0239] Aspect 67 provides a homogenized grease composition according to any one of aspects 56 to 66, wherein the MCA has the same chemical structure at each occurrence.

[0240] Aspect 68 provides a homogenized grease composition according to any one of aspects 56 to 67, wherein at least two occurrences of MCA have different chemical structures.

[0241] Aspect 69 provides a homogenized grease composition according to any one of aspects 56 to 68, wherein at each occurrence, MCA comprises a reacted monocarboxylic acid ester having a structure according to formula (IV):

[0242] (IV),

[0243] Where R 3 is substituted or unsubstituted (C1-C 20 ) hydrocarbon group, and R7 Selected from -OH, -Cl, -O - or substituted or unsubstituted -O-(C1-C 20 ) hydrocarbon group.

[0244] Aspect 70 provides a homogenized grease composition according to aspect 69, wherein at each occurrence, the substituted or unsubstituted (C1-C 20 )alkyl groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkyl, substituted or unsubstituted (C3-C 20 )cycloalkyl, substituted or unsubstituted (C2-C 20 )alkenyl, substituted or unsubstituted (C2-C 20 ) alkynyl, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 ) aryl and substituted or unsubstituted (C2-C 20 )alkoxy.

[0245] Aspect 71 provides a homogenized grease composition according to any one of aspects 69 or 70, wherein at each occurrence, MCA comprises a reacted monocarboxylic acid ester having a structure according to the formula:

[0246] Formula (V):

[0247] (V), or

[0248] Formula (VI):

[0249] (VI)

[0250] Where R 4 Selected from chemical bonds and substituted or unsubstituted (C1-C 20 )alkylene.

[0251] Aspect 72 provides a homogenized grease composition according to aspect 71, wherein at each occurrence, substituted or unsubstituted (C1-C 20 )alkylene groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C3-C 20 )cycloalkylene, substituted or unsubstituted (C2-C 20 )alkenylene, substituted or unsubstituted (C2-C 20 ) alkynylene, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 )arylene and substituted or unsubstituted -O-(CH2)n- (n = 2-20).

[0252] Aspect 73 provides a homogenized grease composition according to any one of aspects 56 to 72, wherein at each occurrence, MCA is independently selected from reacted esters, reacted acid chlorides, reacted anhydrides, reacted benzoic acid, reacted cyclohexanecarboxylic acid, and reacted stearic acid.

[0253] Aspect 74 provides a homogenized grease composition according to any one of aspects 56 to 73, wherein DA has the same chemical structure at each occurrence.

[0254] Aspect 75 provides a homogenized grease composition according to any one of aspects 56 to 74, wherein at least two occurrences of DA have different chemical structures.

[0255] Aspect 76 provides a homogenized grease composition according to any one of aspects 56 to 75, wherein at each occurrence, DA is a reacted diamine independently having a structure according to formula (VII):

[0256] (VII)

[0257] Where R 5 is substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C5-C 20 )cycloalkylene or substituted or unsubstituted (C4-C 20 )aryl.

[0258] Aspect 77 provides a homogenized grease composition according to aspect 76, wherein DA, at each occurrence, is a reacted diamine independently selected from the group consisting of reacted hexamethylenediamine, reacted propylenediamine, reacted butanediamine, reacted pentanediamine, reacted phenylenediamine, reacted cyclohexanediamine, or reacted nonanediamine.

[0259] Aspect 78 provides a homogenized grease composition according to any one of aspects 56 to 77, wherein DA, at each occurrence, is a reacted diamine independently selected from reacted hexamethylenediamine, reacted propylenediamine, reacted butanediamine, or reacted pentanediamine.

[0260] Aspect 79 provides a homogenized grease composition according to any one of aspects 56 to 78, wherein at each occurrence, DA is reacted hexamethylenediamine.

[0261] Aspect 80 provides the homogenized grease composition according to any one of aspects 56 to 79, wherein the dropping point of the grease composition is greater than about 200°C.

[0262] Aspect 81 provides a homogenized grease composition according to any one of aspects 56 to 80, wherein the dropping point of the grease composition is greater than about 250° C.

[0263] Aspect 82 provides a polyamide grease thickener according to any one of aspects 1 to 43 and 45 to 81, wherein in each case, MCA, PCA and DA do not contain branched alkyl groups.

[0264] Aspect 83 provides a polyamide grease thickener according to any one of aspects 1 to 43 and 45 to 82, wherein the polyamide grease thickener comprises at least two cycloaliphatic moieties, at least two aromatic moieties, or at least one cycloaliphatic moiety and at least one aromatic moiety.

[0265] Aspect 84 provides a polyamide grease thickener according to any one of aspects 1 to 43 and 45 to 83, wherein any disubstituted cycloaliphatic moiety and any disubstituted aromatic moiety are symmetrical about an axis extending through the two substituents.

[0266] Aspect 85 provides a polyamide grease thickener according to any one of aspects 1 to 43 and 45 to 84, wherein any disubstituted aromatic moiety is para-substituted.

[0267] Aspect 86 provides a polyamide grease thickener having a structure according to Formula VIII:

[0268] (MCA-DA-(ZZ) y -) x PCA (VIII), where

[0269] At each occurrence, ZZ is or

[0270] X is ,

[0271] At each occurrence, PCA is independently a reacted polycarboxylate,

[0272] MCA is independently at each occurrence the reacted monocarboxylic acid ester,

[0273] At each occurrence, DA is independently the reacted diamine,

[0274] x is a non-zero integer,

[0275] y is 0 or a non-zero integer, and

[0276] z is 0 or a non-zero integer.

[0277] Aspect 87 provides the polyamide grease thickener according to 86, wherein the polyamide grease thickener has a structure according to Formula I:

[0278] (MCA-DA-)(PCA-DA) y -PCA-(DA-PCA) y (-DA-MCA) (I).

[0279] Aspect 88 provides a polyamide grease thickener according to any one of aspects 86 or 87, wherein the polyamide grease thickener has a structure according to Formula II:

[0280] ((MCA-DA-)(PCA-DA) y -) n PCA (II),

[0281] Wherein n is in the range of 2 to 4.

[0282] Aspect 89 provides a polyamide grease thickener according to any one of aspects 86 to 88, wherein the polyamide grease thickener has a structure according to Formula III:

[0283] (MCA-DA)-PCA-(DA-MCA) (III).

[0284] Aspect 90 provides the polyamide grease thickener according to any one of aspects 86 to 89, wherein at each occurrence, PCA independently comprises 3 to 50 carbon atoms.

[0285] Aspect 91 provides a polyamide grease thickener according to any one of aspects 86 to 90, wherein at each occurrence, PCA independently comprises 6, 8 or 9 carbon atoms.

[0286] Aspect 92 provides a polyamide grease thickener according to any one of aspects 86 to 91, wherein at each occurrence, PCA comprises a reacted polycarboxylate having a structure according to the formula:

[0287] Formula (X):

[0288] (X),

[0289] Formula (XVII):

[0290] XVII, or

[0291] Formula (XVIII):

[0292] (XVIII),

[0293] In each occurrence, R 1 and R 2 are independently chemical bonds or substituted or unsubstituted (C1-C 20 ) alkyl, and at each occurrence, R 6 Selected from -OH, -Cl, -O - or substituted or unsubstituted -O-(C1-C 20 ) hydrocarbon group.

[0294] Aspect 93 provides a polyamide grease thickener according to aspect 92, wherein at each occurrence, substituted or unsubstituted (C1-C 20 )alkyl groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkyl, substituted or unsubstituted (C3-C 20 )cycloalkyl, substituted or unsubstituted (C2-C 20 )alkenyl, substituted or unsubstituted (C2-C 20 ) alkynyl, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 ) aryl and substituted or unsubstituted (C2-C 20 )alkoxy.

[0295] Aspect 94 provides the polyamide grease thickener according to any one of aspects 86 to 93, wherein PCA has the same chemical structure at each occurrence.

[0296] Aspect 95 provides a polyamide grease thickener according to any one of aspects 86 to 94, wherein at least two occurrences of PCA have different chemical structures.

[0297] Aspect 96 provides a polyamide grease thickener according to any one of aspects 86 to 95, wherein at each occurrence, PCA independently comprises reacted adipic acid, reacted purified terephthalic acid, reacted isophthalic acid, reacted phthalic anhydride, reacted naphthylic acid, reacted mellitic acid, reacted mellitic anhydride, reacted naphthalenetetracarboxylic anhydride, reacted citric acid, reacted ester, reacted acid chloride, reacted dianhydride, or reacted ethylenediaminetetraacetic acid.

[0298] Aspect 97 provides a polyamide grease thickener according to any one of aspects 86 to 96, wherein MCA, at each occurrence, independently comprises a reacted aliphatic monocarboxylic acid ester, a reacted alicyclic monocarboxylic acid ester, or a reacted aromatic monocarboxylic acid ester.

[0299] Aspect 98 provides the polyamide grease thickener according to any one of aspects 86 to 97, wherein MCA has the same chemical structure at each occurrence.

[0300] Aspect 99 provides a polyamide grease thickener according to any one of aspects 86 to 98, wherein at least two occurrences of MCA have different chemical structures.

[0301] Aspect 100 provides a polyamide grease thickener according to any one of aspects 86 to 99, wherein at each occurrence, MCA comprises a reacted monocarboxylic acid ester having a structure according to formula (IV):

[0302] (IV),

[0303] Where R 3 is substituted or unsubstituted (C1-C 20 ) hydrocarbon group, and R 7 Selected from -OH, -Cl, -O - or substituted or unsubstituted -O-(C1-C 20 ) hydrocarbon group.

[0304] Aspect 101 provides a polyamide grease thickener according to aspect 100, wherein at each occurrence, substituted or unsubstituted (C1-C 20 )alkyl groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkyl, substituted or unsubstituted (C3-C 20 )cycloalkyl, substituted or unsubstituted (C2-C 20 )alkenyl, substituted or unsubstituted (C2-C 20 ) alkynyl, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 ) aryl and substituted or unsubstituted (C2-C 20 )alkoxy.

[0305] Aspect 102 provides a polyamide grease thickener according to any one of aspects 100 or 101, wherein at each occurrence, MCA comprises a reacted monocarboxylic acid ester having a structure according to the formula:

[0306] Formula (V):

[0307] (V), or

[0308] Formula (VI):

[0309] (VI)

[0310] Where R 4 Selected from chemical bonds and substituted or unsubstituted (C1-C 20 )alkylene.

[0311] Aspect 103 provides a polyamide grease thickener according to aspect 102, wherein at each occurrence, substituted or unsubstituted (C1-C 20 )alkylene groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C3-C 20 )cycloalkylene, substituted or unsubstituted (C2-C 20 )alkenylene, substituted or unsubstituted (C2-C 20 ) alkynylene, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 )arylene and substituted or unsubstituted -O-(CH2)n- (n = 2-20).

[0312] Aspect 104 provides a polyamide grease thickener according to any one of aspects 86 to 103, wherein MCA, at each occurrence, is independently selected from reacted esters, reacted acid chlorides, reacted anhydrides, reacted benzoic acid, reacted cyclohexanecarboxylic acid, and reacted stearic acid.

[0313] Aspect 105 provides the polyamide grease thickener according to any one of aspects 86 to 104, wherein DA has the same chemical structure at each occurrence.

[0314] Aspect 106 provides a polyamide grease thickener according to any one of aspects 86 to 105, wherein at least two occurrences of DA have different chemical structures.

[0315] Aspect 107 provides a polyamide grease thickener according to any one of aspects 86 to 106, wherein DA, at each occurrence, is a reacted diamine independently having a structure according to formula (VII):

[0316] (VII)

[0317] Where R 5 is substituted or unsubstituted (C1-C 20 )alkylene.

[0318] Aspect 108 provides a polyamide grease thickener according to aspect 107, wherein at each occurrence, substituted or unsubstituted (C1-C 20 )alkylene groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C3-C 20 )cycloalkylene, substituted or unsubstituted (C2-C 20)alkenylene, substituted or unsubstituted (C2-C 20 ) alkynylene, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 )arylene and substituted or unsubstituted (C2-C 20 )alkyleneoxy.

[0319] Aspect 109 provides a polyamide grease thickener according to any one of aspects 86 to 108, wherein DA, at each occurrence, is a reacted diamine independently selected from the group consisting of reacted hexamethylenediamine, reacted propylenediamine, reacted butanediamine, reacted pentanediamine, reacted nonanediamine, reacted isononanediamine, reacted 2-methylpentanediamine, reacted ethylenediamine, reacted isophoronediamine, reacted meta-xylylenediamine, and reacted meta-phenylenediamine.

[0320] Aspect 110 provides the polyamide grease thickener according to any one of aspects 86 to 109, wherein DA, at each occurrence, is reacted hexamethylenediamine.

[0321] Aspect 111 provides the polyamide grease thickener according to any one of aspects 86 to 110, wherein x, y and z are independently in the range of 1 to 10.

[0322] Aspect 112 provides the polyamide grease thickener according to any one of aspects 86 to 111, wherein x, y and z are independently in the range of 1 to 3.

[0323] Aspect 113 provides the polyamide grease thickener according to any one of aspects 86 to 112, wherein the grease thickener has a molecular weight of at least 1000 g / mol.

[0324] Aspect 114 provides the polyamide grease thickener according to any one of aspects 86 to 113, wherein the grease thickener has a molecular weight of at least 1500 g / mol.

[0325] Aspect 115 provides the polyamide grease thickener according to any one of aspects 86 to 114, wherein the weight average molecular weight of the grease thickener is in the range of about 1000 g / mol to about 10,000 g / mol.

[0326] Aspect 116 provides the polyamide grease thickener according to any one of aspects 86 to 115, wherein the weight average molecular weight of the grease thickener is in the range of about 1200 g / mol to about 4000 g / mol.

[0327] Aspect 117 provides a grease composition comprising the grease thickener according to any one of aspects 86 to 116.

[0328] Aspect 118 provides the grease composition according to aspect 117, wherein the grease thickener is in the range of about 1 wt % to about 50 wt % of the grease composition.

[0329] Aspect 119 provides a grease composition according to any of aspects 117 or 118, wherein the grease thickener is in the range of about 5 wt % to about 20 wt % of the grease composition.

[0330] Aspect 120 provides a grease composition according to any one of aspects 117 to 119, wherein the grease thickener is a first grease thickener, and the grease composition further comprises a second grease thickener having a different chemical structure from the first grease thickener, the second grease thickener having a structure according to Formula VIII.

[0331] Aspect 121 provides the grease composition according to aspect 120, wherein the molecular weight of the first grease thickener is different from the molecular weight of the second grease thickener.

[0332] Aspect 122 provides a grease composition according to any one of aspects 120 or 121, wherein the first grease thickener and the second grease thickener have different chemical compositions.

[0333] Aspect 123 provides the grease composition according to any one of aspects 117 to 122, comprising less than 1 wt % lithium.

[0334] Aspect 124 provides the grease composition according to any one of aspects 117 to 123, comprising less than 1 wt % polyurea.

[0335] Aspect 125 provides a grease composition comprising the reaction product of the polycarboxylate according to any one of aspects 92 to 124, a diamine, and a monocarboxylate.

[0336] Aspect 126 provides a grease composition comprising a reaction product of a polycarboxylate according to any one of aspects 92 to 125, a diamine, and a monocarboxylate.

[0337] Aspect 127 provides a grease composition according to any one of aspects 117 to 126, wherein the total weight % of components selected from anhydrous calcium, aluminum complexes, calcium sulfonate complexes, calcium complexes, barium complexes, sodium complexes and polyureas is less than 35 weight %.

[0338] Aspect 128 provides a method of using the polyamide grease thickener according to any one of aspects 86 to 127, the method comprising contacting the polyamide grease thickener with a grease.

[0339] Aspect 129 provides a method of using the grease composition according to any one of aspects 117 to 128, the method comprising contacting the grease composition with an article to be lubricated.

[0340] Aspect 130 provides a method for preparing a grease thickener according to any one of aspects 86 to 129, the method comprising:

[0341] reacting a polycarboxylate with a diamine to form a first product; and

[0342] The first product is reacted with a monocarboxylic acid ester to form a grease thickener.

Claims

1. A polyamide grease thickener having a structure according to formula I: (MCA-YES-)(PCA-YES) y -PCA-(YES-PCA) y (-DA-MCA) (I), in At each occurrence, PCA is independently a reacted polycarboxylate, MCA is independently at each occurrence the reacted monocarboxylic acid ester, At each occurrence, DA is independently the reacted diamine, y is 0 or a non-zero integer, The polyamide grease thickener has a weight average molecular weight in the range of about 450 g / mol to about 3500 g / mol, and at least one cycloaliphatic moiety or at least one aromatic moiety.

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

3. The polyamide grease thickener according to any one of claims 1 or 2, wherein the polyamide grease thickener has a structure according to formula II: ((MCA-DA-)(PCA-DA) y -) n PCA (II), Wherein n is 2, and y is in the range of 2 to 4.

4. The polyamide grease thickener according to any one of claims 1 to 3, wherein the polyamide grease thickener has a structure according to formula III: (MCA-DA)-PCA-(DA-MCA) (III).

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

6. A polyamide grease thickener according to any one of claims 1 to 5, wherein PCA independently at each occurrence comprises 6, 8 or 9 carbon atoms.

7. The polyamide grease thickener of any one of claims 1 to 6, wherein PCA, at each occurrence, independently comprises reacted adipic acid, reacted purified terephthalic acid, reacted isophthalic acid, reacted phthalic anhydride, reacted naphthylic acid, reacted mellitic acid, reacted mellitic anhydride, reacted naphthalenetetracarboxylic anhydride, reacted citric acid, reacted esters, reacted acid chlorides, reacted dianhydrides, or reacted ethylenediaminetetraacetic acid.

8. The polyamide grease thickener of any one of claims 1 to 7, wherein MCA, at each occurrence, independently comprises a reacted aliphatic monocarboxylic acid ester, a reacted alicyclic monocarboxylic acid ester, or a reacted aromatic monocarboxylic acid ester.

9. The polyamide grease thickener according to any one of claims 1 to 8, wherein at each occurrence, DA is a reacted diamine independently having a structure according to formula (VII): (VII), Where R 5 is substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C5-C 20 )cycloalkylene or substituted or unsubstituted (C4-C 20 )aryl.

10. The polyamide grease thickener of claim 9, wherein DA, at each occurrence, is a reacted diamine independently selected from reacted hexamethylenediamine, reacted propylenediamine, reacted butanediamine, reacted pentanediamine, reacted phenylenediamine, reacted cyclohexanediamine, or reacted nonanediamine.

11. A polyamide grease thickener according to any one of claims 1 to 10, wherein DA, at each occurrence, is reacted hexamethylenediamine.

12. The polyamide grease thickener according to any one of claims 1 to 11, wherein a grease composition comprising the polyamide grease thickener has a dropping point greater than about 200°C.

13. The polyamide grease thickener according to any one of claims 2 to 12, wherein a grease composition comprising the polyamide grease thickener has a dropping point greater than about 250°C.

14. The polyamide grease thickener according to any one of claims 1 to 13, wherein when the at least one aromatic moiety is disposed internally, it is disubstituted in the para position, and when the at least one cycloaliphatic moiety is disposed internally, it is disubstituted and symmetrical about an axis passing through the two substituents.

15. A polyamide grease thickener having a structure according to Formula IX: (IX), where in PCA is independently at each occurrence a para-substituted reacted polycarboxylate, MCA is independently at each occurrence the reacted monocarboxylic acid ester, At each occurrence, DA is independently the reacted diamine, y is 0 or a non-zero integer, The weight average molecular weight of the polyamide grease thickener is in the range of about 450 g / mol to about 3500 g / mol.

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

17. The polyamide grease thickener according to any one of claims 15 or 16, wherein at each occurrence, MCA comprises a reacted monocarboxylic acid ester having a structure according to formula (IV): (IV), Where R 3 is substituted or unsubstituted (C1-C 20 ) hydrocarbon group, and R 7 Selected from -OH, -Cl, -O - or substituted or unsubstituted -O-(C1-C 20 ) hydrocarbon group.

18. The polyamide grease thickener according to claim 17, wherein at each occurrence, the substituted or unsubstituted (C1-C 20 )alkyl groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkyl, substituted or unsubstituted (C3-C 20 )cycloalkyl, substituted or unsubstituted (C2-C 20 )alkenyl, substituted or unsubstituted (C2-C 20 ) alkynyl, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 ) aryl and substituted or unsubstituted (C2-C 20 )alkoxy.

19. The polyamide grease thickener according to any one of claims 17 or 18, wherein at each occurrence, MCA comprises a reacted monocarboxylic acid ester having a structure according to the formula: Formula (V): (V), or Formula (VI): (WE), Where R 4 Selected from chemical bonds and substituted or unsubstituted (C1-C 20 )alkylene.

20. The polyamide grease thickener according to claim 19, wherein at each occurrence, the substituted or unsubstituted (C1-C 20 )alkylene groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C3-C 20 )cycloalkylene, substituted or unsubstituted (C2-C 20 )alkenylene, substituted or unsubstituted (C2-C 20 ) alkynylene, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 )arylene and substituted or unsubstituted -O-(CH2)n- (n = 2-20).

21. The polyamide grease thickener of any one of claims 15 to 20, wherein the MCA, at each occurrence, is independently selected from reacted esters, reacted acid chlorides, reacted anhydrides, reacted benzoic acid, reacted cyclohexanecarboxylic acid, and reacted steric acid.

22. A polyamide grease thickener according to any one of claims 15 to 21, wherein DA has the same chemical structure at each occurrence.

23. The polyamide grease thickener according to any one of claims 15 to 22, wherein at least two occurrences of DA have different chemical structures.

24. The polyamide grease thickener of any one of claims 15 to 23, wherein DA, at each occurrence, is a reacted diamine independently selected from reacted hexamethylenediamine, reacted propylenediamine, reacted butanediamine, reacted pentanediamine, reacted phenylenediamine, reacted cyclohexanediamine, or reacted nonanediamine.

25. A polyamide grease thickener according to any one of claims 15 to 24, wherein DA, at each occurrence, is reacted hexamethylenediamine.

26. The polyamide grease thickener of any one of claims 15 to 25, wherein the polyamide grease thickener has a dropping point greater than about 200°C.

27. The polyamide grease thickener of any one of claims 15 to 26, wherein the polyamide grease thickener has a dropping point greater than about 250°C.

28. A polyamide grease thickener having a structure according to any one of Formulas X, XI, XII or XIII: (XXXII)、 (XI)、 (XII)、 (XIII)。 29. A polyamide grease thickener having a structure according to Formula VIII: (MCA-DA-(ZZ) y -) x PCA (VIII), where At each occurrence, ZZ is or X is , At each occurrence, PCA is independently a reacted polycarboxylate, MCA is independently at each occurrence the reacted monocarboxylic acid ester, At each occurrence, DA is independently the 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 thickener of claim 29, wherein at each occurrence, PCA comprises a reacted polycarboxylate having a structure according to the formula: Formula (X): (X)， Formula (XVII): XVII, or Formula (XVIII): (XVIII), In each occurrence, R 1 and R 2 are independently chemical bonds or substituted or unsubstituted (C1-C 20 ) alkyl, and at each occurrence, R 6 Selected from -OH, -Cl, -O - or substituted or unsubstituted -O-(C1-C 20 ) hydrocarbon group.

31. The polyamide grease thickener according to claim 30, wherein at each occurrence, the substituted or unsubstituted (C1-C 20 )alkyl groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkyl, substituted or unsubstituted (C3-C 20 )cycloalkyl, substituted or unsubstituted (C2-C 20 )alkenyl, substituted or unsubstituted (C2-C 20 ) alkynyl, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 ) aryl and substituted or unsubstituted (C2-C 20 )alkoxy.

32. A polyamide grease thickener according to any one of claims 30 or 31, wherein at each occurrence, MCA comprises a reacted monocarboxylic acid ester having a structure according to formula (IV): (IV), Where R 3 is substituted or unsubstituted (C1-C 20 ) hydrocarbon group, and R 7 Selected from -OH, -Cl, -O - or substituted or unsubstituted -O-(C1-C 20 ) hydrocarbon group.

33. The polyamide grease thickener according to claim 32, wherein at each occurrence, the substituted or unsubstituted (C1-C 20 )alkyl groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkyl, substituted or unsubstituted (C3-C 20 )cycloalkyl, substituted or unsubstituted (C2-C 20 )alkenyl, substituted or unsubstituted (C2-C 20 ) alkynyl, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 ) aryl and substituted or unsubstituted (C2-C 20 )alkoxy.

34. A polyamide grease thickener according to any one of claims 32 or 33, wherein at each occurrence, MCA comprises a reacted monocarboxylic acid ester having a structure according to the formula: Formula (V): (V), or Formula (VI): (WE), Where R 4 Selected from chemical bonds and substituted or unsubstituted (C1-C 20 )alkylene.

35. The grease thickener of claim 34, wherein at each occurrence, the substituted or unsubstituted (C1-C 20 )alkylene groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C3-C 20 )cycloalkylene, substituted or unsubstituted (C2-C 20 )alkenylene, substituted or unsubstituted (C2-C 20 ) alkynylene, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 )arylene and substituted or unsubstituted -O-(CH2)n- (n = 2-20).

36. The polyamide grease thickener according to any one of claims 29 to 35, wherein DA, at each occurrence, is a reacted diamine independently having a structure according to formula (VII): (VII), Where R 5 is substituted or unsubstituted (C1-C 20 )alkylene.

37. The polyamide grease thickener according to claim 36, wherein at each occurrence, the substituted or unsubstituted (C1-C 20 )alkylene groups are independently selected from substituted or unsubstituted (C1-C 20 ) alkylene, substituted or unsubstituted (C3-C 20 )cycloalkylene, substituted or unsubstituted (C2-C 20 )alkenylene, substituted or unsubstituted (C2-C 20 ) alkynylene, substituted or unsubstituted (C1-C 20 ) acyl, substituted or unsubstituted (C4-C 20 )arylene and substituted or unsubstituted (C2-C 20 )alkyleneoxy.

38. The polyamide grease thickener of any one of claims 29 to 37, wherein DA, at each occurrence, is a reacted diamine independently selected from reacted hexamethylenediamine, reacted propylenediamine, reacted butanediamine, reacted pentanediamine, reacted nonanediamine, reacted isononanediamine, reacted 2-methylpentanediamine, reacted ethylenediamine, reacted isophoronediamine, reacted meta-xylylenediamine, and reacted meta-phenylenediamine.

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