Polyamide grease thickening agent

Abstract

The present disclosure relates to a process for making a polyamide grease thickening agent from an oligomeric intermediate. Particularly, the polyamide grease thickening agent may include at least two para-substituted aromatic moieties, have a molecular weight in a range of from 450 g / mol to 3500 g / mol, and may include at least four amide bonds.

Description

Attorney Docket No. INV-24025-WO-PCT PROCESS OF MAKING A POLYAMIDE GREASE THICKENING AGENT CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application Serial No. 63 / 640,889 entitled “PROCESS OF MAKING A POLYAMIDE GREASE THICKENING AGENT ,” filed May 1, 2024 the disclosure of which is incorporated herein in its entirety by reference. FIELD

[0002] This disclosure relates to a process for making a polyamide grease thickening agent from an oligomeric intermediate. Particularly, the polyamide grease thickening agent may include at least two para-substituted aromatic moieties, have a molecular weight in a range of from 450 g / mol to 3500 g / mol, and may include at least four amide bonds. BACKGROUND

[0003] Grease compositions provide lubrication for a variety of articles. While it is important for the grease composition to include adequate lubricating and base oils, a grease thickening agent is needed to provide mechanical properties to the grease composition. SUMMARY

[0004] The present disclosure provides a process of making a polyamide grease thickening agent from an oligomeric intermediate.

[0005] The oligomeric intermediate comprises at least one entity having the chemical structure according to Formula XXXII: H2N-AC1-PCA-(AC2-PCA)y-AC3-NH2 (XXXII); wherein, in Formula X, at each occurrence “PCA” is independently a reacted polycarboxyamide having at least one para-substituted aromatic moiety; at each occurrence “AC1”, “AC2,” and “AC3”, are either identical or different, and each is independently a four to twelve carbon alkylene chain; and y is from 0 to 5; and a weight-average molecular weight of the oligomeric intermediate is in a range of from about 360 g / mol to about 1500 g / mol. 1Attorney Docket No. INV-24025-WO-PCT

[0006] Surprisingly and unexpectedly, the grease thickening compositions, made according to the present disclosure, are able to perform at least substantially equivalently to a corresponding grease thickening agent that includes lithium, polyurea, or both. Thus, it is possible to formulate grease compositions that are substantially free of lithium, polyurea, or both. DETAILED DESCRIPTION

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

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

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

[0010] In the methods described herein, the acts can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim 2Attorney Docket No. INV-24025-WO-PCT language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

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

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

[0013] All publications, including non-patent literature (e.g., scientific journal articles), patent application publications, and patents mentioned in this specification are incorporated by reference as if each were specifically and individually indicated to be incorporated by reference.

[0014] It is understood that the descriptions herein are intended to be illustrative, and not restrictive. Many other embodiments will be apparent to those of skill in the art upon reviewing the above description. The scope of the invention should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. In the appended claims, the terms “including” and “in which” are used as the plain-English equivalents of the respective terms “comprising” and “wherein,” respectively. Moreover, the terms “first,” “second,” “third,” and the like are used merely as labels, and are not intended to impose numerical requirements on their objects.

[0015] The term “weight-average molecular weight” as used herein refers to Mw, which is i2ni ini, where ni is the number of molecules of molecular weight Mi. In various 3Attorney Docket No. INV-24025-WO-PCT examples, the weight-average molecular weight can be determined using light scattering, small angle neutron scattering, X-ray scattering, and sedimentation velocity.

[0016] As used herein, the parameters, P0, P60, P10000 and P100000, represent the degree to which a grease composition is worked. For example, a grease composition that is unworked has a P0 value. A grease composition that is inserted into a container and has a plunger stroked 60 times while the test apparatus and grease composition are maintained at a temperature of 25 °C has a P60 value. A grease composition that is inserted into a container and has a plunger stroked 10000 times while the test apparatus and grease composition are maintained at a temperature of 25 °C has a P10000 value. A grease composition that is inserted into a container and has a plunger stroked 100000 times while the test apparatus and grease composition are maintained at a temperature of 25 °C has a P100000 value.

[0017] The mechanical strength of the grease compositions can be assessed from the NLGI consistency number determination as per the ASTM D-217 method. An NLGI consistency number of an unworked composition (a sample that has received only minimal disturbance) of the grease composition can be in a range of 3 to 4. An NLGI consistency number of the worked grease composition (as sample that has been subjected to 60 double strokes in a standard grease worker) can be in a range of 1 to 2.

[0018] The NLGI consistency number measurement is titled “cone penetration of lubricating grease” following the ASTM D-217 method. This involves two test apparatus. The first apparatus consists of a closed container and a piston-like plunger. The face of the plunger is perforated to allow grease to flow from one side of the plunger to another as the plunger is worked up and down with a grease worker. The test grease is inserted into the container and the plunger is stroked 60 times while the test apparatus and grease are maintained at ambient conditions. Once worked, the grease is placed in a penetration test apparatus, a penetrometer. This apparatus includes a container, a specially configured cone and a dial indicator. The container is filled with the grease and the top surface of the grease is smoothed over. The cone is placed so that its tip is as close as possible without touching the grease surface and the dial indicator is set to zero at this position. When the test starts, the weight of the cone will cause it to penetrate into the grease. After a specific time interval, the depth of penetration is measured.

[0019] Various aspects of the present disclosure relate to an oligomeric intermediate, prepared according to the disclosed process. The oligomeric intermediate can be present as a 4Attorney Docket No. INV-24025-WO-PCT distribution. In the distribution, a weight-average molecular weight of the oligomeric intermediate is in a range of from about 360 g / mol to about 3500 g / mol, about 360 g / mol to about 975 g / mol, about 360 g / mol to about 950 g / mol, less than, equal to, or greater than about 360 g / mol, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, 1000, 1010, 1020, 1030, 1040, 1050, 1060, 1070, 1080, 1090, 1100, 1110, 1120, 1130, 1140, 1150, 1160, 1170, 1180, 1190, 1200, 1210, 1220, 1230, 1240, 1250, 1260, 1270, 1280, 1290, 1300, 1310, 1320, 1330, 1340, 1350, 1360, 1370, 1380, 1390, 1400, 1410, 1420, 1430, 1440, 1450, 1460, 1470, 1480, 1490, 1500, 1510, 1520, 1530, 1540, 1550, 1560, 1570, 1580, 1590, 1600, 1610, 1620, 1630, 1640, 1650, 1660, 1670, 1680, 1690, 1700, 1710, 1720, 1730, 1740, 1750, 1760, 1770, 1780, 1790, 1800, 1810, 1820, 1830, 1840, 1850, 1860, 1870, 1880, 1890, 1900, 1910, 1920, 1930, 1940, 1950, 1960, 1970, 1980, 1990, 2000, 2010, 2020, 2030, 2040, 2050, 2060, 2070, 2080, 2090, 2100, 2110, 2120, 2130, 2140, 2150, 2160, 2170, 2180, 2190, 2200, 2210, 2220, 2230, 2240, 2250, 2260, 2270, 2280, 2290, 2300, 2310, 2320, 2330, 2340, 2350, 2360, 2370, 2380, 2390, 2400, 2410, 2420, 2430, 2440, 2450, 2460, 2470, 2480, 2490, 2500, 2510, 2520, 2530, 2540, 2550, 2560, 2570, 2580, 2590, 2600, 2610, 2620, 2630, 2640, 2650, 2660, 2670, 2680, 2690, 2700, 2710, 2720, 2730, 2740, 2750, 2760, 2770, 2780, 2790, 2800, 2810, 2820, 2830, 2840, 2850, 2860, 2870, 2880, 2890, 2900, 2910, 2920, 2930, 2940, 2950, 2960, 2970, 2980, 2990, 3000, 3010, 3020, 3030, 3040, 3050, 3060, 3070, 3080, 3090, 3100, 3110, 3120, 3130, 3140, 3150, 3160, 3170, 3180, 3190, 3200, 3210, 3220, 3230, 3240, 3250, 3260, 3270, 3280, 3290, 3300, 3310, 3320, 3330, 3340, 3350, 3360, 3370, 3380, 3390, 3400, 3410, 3420, 3430, 3440, 3450, 3460, 3470, 3480, 3490, or about 3500 g / mol.

[0020] As will be shown in the Examples a distribution of different oligomeric intermediates can be formed. Each intermediate can independently range from about 0 wt% to about 95 wt% of the distribution, about 1 wt% to about 60 wt%, about 20 wt% to about 40 wt%, less than, equal to, or greater than about 1 wt%, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or about 95 wt% of the distribution.

[0021] Various aspects of the present disclosure relate to a grease thickening agent, prepared according to the disclosed process. The grease thickening agent is characterized as a polyamide grease thickening agent. It has been found that successful grease thickening agents are 5Attorney Docket No. INV-24025-WO-PCT those that result in a grease composition having a dropping point greater than 200 °C, 220, 240, 260, or 280 °C as well as having a NLGI grade of 2 or greater. As generally understood, the dropping point of a grease is the temperature at which it passes from a semi-solid to a liquid state. The dropping point test determines the cohesiveness of the oil and thickening agent of a grease. A test for determining the dropping point is ASTM D-2265.

[0022] The process of making the polyamide grease thickening agent includes contacting a di-halogenated aromatic dicarboxylic acid, a diamine, and optionally a first reaction solvent, in a first reaction zone. The di-halogenated aromatic dicarboxylic acid can be terephthalic acid dichloride, terephthalic acid dibromide, terephthalic acid diiodide and combinations thereof. Optionally, a solvent such as acetonitrile may be used. The diamine can be a linear C4-C12 diamine. In some examples the diamine is pentamethylenediamine or hexamethylenediamine. The conditions of the reaction can be controlled such as the duration and temperature of the reaction. A first reaction product can be recovered by any suitable means such as distillation. The first reaction product can then be filtered, washed and dried. Washing can be accomplished with a 2.5- 5 wt% aqueous caustic solution followed by at least one wash cycle with the high-purity water.

[0023] The reaction product is contacted with a long-chain fatty acid optionally in the presence of a solvent. The long-chain fatty acid is a C10-C30 acid. As a specific example, the long- chain fatty acid is stearic acid. A suitable solvent may be any solvent with a high boiling point (> 200 °C), for example, N-Methylpyrrolidone, liquid fatty acids, stearic acid, alkyl benzenes, etc. The conditions of the reaction can be controlled such as the duration and temperature of the reaction. The reaction product can be filtered, washed, and dried. Washing can be accomplished with a solvent.

[0024] The polyamide grease thickening agent can have the structure according to Formula I: (MCA-DA-)(PCA-DA)y-PCA-(DA-PCA)y(-DA-MCA) (I). In still further examples, the polyamide grease thickening agent can have the structure according to Formula II: ((MCA-DA-)(PCA-DA)y-)nPCA (II). 6Attorney Docket No. INV-24025-WO-PCT In Formula II, n is in a range of from 2-4. In still further examples, the polyamide grease thickening agent has the structure according to Formula III: (MCA-DA)-PCA-(DA-MCA) (III).

[0025] The reacted polycarboxylate can be a polycarboxylic acid, polycarboxylic ester, polycarboxylic acid chloride, or an anhydride. At each occurrence, PCA can independently include 3 to 50 carbon atoms 6 to 10 carbon items, or 6, 8, or 9 carbon atoms. For example, at each occurrence, PCA can include a reacted polycarboxylate having the structure according to the following Formulas: Formula (X): O R6(XVII), or 7Attorney Docket No. INV-24025-WO-PCT Formula (XVIII): O R6

[0026] At each occurrence R1and R2are independently a bond or a substituted or unsubstituted (C1-C20)hydrocarbyl and at each occurrence, R6is chosen from -OH, -Cl, -O-, or substituted or unsubstituted -O-(C1-C20)hydrocarbyl. At each occurrence the substituted or unsubstituted (C1-C20)hydrocarbyl is independently selected from a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C3-C20)cycloalkyl, a substituted or unsubstituted (C2-C20)alkenyl, a substituted or unsubstituted (C2-C20)alkynyl, a substituted or unsubstituted (C1-C20)acyl, a substituted or unsubstituted (C4-C20)aryl, and a substituted or unsubstituted (C2- C20)alkoxy. In some examples, at each occurrence, PCA has the same chemical structure. Alternatively, at least two occurrences PCA can have different chemical structures.

[0027] As specific examples, at each occurrence, PCA independently includes a reacted adipic acid, a reacted purified terephthalic acid, a reacted isophthalic acid, a reacted phthalic anhydride, a reacted napthalenic acid, a reacted mellitic acid, a reacted mellitic anhydride, a reacted naphthalene tetracarboxylic anhydride, a reacted citric acid, a reacted ester, a reacted acid chloride, a reacted dianhydride, or a reacted ethylenediaminetetraacetic acid. PCA can include three carboxylic acid groups or two carboxylic acid groups. A more preferred structure of the grease thickener composition is that of Formula II or III. That is the structure of Formula II or III more easily allows for forming a grease thickener having the combination of the desirable structural features described herein above. In preferred aspects, the grease thickener component will have at least four amide bonds.

[0028] At each occurrence, MCA can include a reacted ester, a reacted acid chloride, or a reacted anhydride. For example, at each occurrence MCA can include a reacted monocarboxylate, the monocarboxylate having the structure according to Formula (IV): 8Attorney Docket No. INV-24025-WO-PCT R7R3n Formula VIII, R3I is a substituted or unsubstituted (C1-C20)hydrocarbyl and R7is chosen from -OH, -Cl, -O- or substituted or unsubstituted -O-(C1-C20)hydrocarbyl. At each occurrence the substituted or unsubstituted (C1-C20)hydrocarbyl is independently selected from a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C3-C20)cycloalkyl, a substituted or unsubstituted (C2-C20)alkenyl, a substituted or unsubstituted (C2-C20)alkynyl, a substituted or unsubstituted (C1-C20)acyl, a substituted or unsubstituted (C4-C20)aryl, and a substituted or unsubstituted (C2-C20)alkoxy.

[0029] As a further example, at each occurrence MCA can include a reacted monocarboxylate. The monocarboxylate can have the structure according to the following Formulas: Formula (V): R4Formula (VI): R4R4is chosen from a bond and a substituted or unsubstituted (C1-C20)hydrocarbylene. At each occurrence the substituted or unsubstituted (C1-C20)hydrocarbylene is independently selected from a substituted or unsubstituted (C1-C20)alkylene, a substituted or unsubstituted (C3- C20)cycloalkylene, a substituted or unsubstituted (C2-C20)alkenylene, a substituted or unsubstituted (C2-C20)alkynylene, a substituted or unsubstituted (C1-C20)acylene, a substituted or unsubstituted (C4-C20)arylene, and a substituted or unsubstituted -O-(CH2)n- (n = 2-20). At each occurrence MCA has the same chemical structure. Alternatively, at least two occurrences of 9Attorney Docket No. INV-24025-WO-PCT MCA has a different chemical structure. As examples, MCA can be a reacted benzoic acid, a reacted cyclohexanecarboxylic acid, or a reacted steric acid.

[0030] Although not intending to be bound to any theory, it is believed that a grease thickening agent in which MCA includes an aromatic group, cycloaliphatic group, or aliphatic group, provides the best performance for the grease thickening agent in the grease composition. Still further it is believed that superior performance can be attained when a first MCA includes an aromatic group and a second MCA includes an aliphatic or cycloaliphatic group. In particular, it is thought that a second MCA including an aliphatic chain having 6-8 carbon atoms yields superior performance. The hydrophobic properties of the aliphatic groups are thought to aid in providing compatibility with the grease. It is also thought that if R3and R4are not a bond, then it is better for them to be n-(C1-C20)alkylene as this more easily allows for forming a grease thickener having the combination of the desirable structural features described herein above.

[0031] At each occurrence, the DA is a reacted diamine, independently having the structure according to Formula (VII): R55R is a substituted or unsubstituted (C1-C20)hydrocarbylene. At each occurrence, the substituted or unsubstituted (C1-C20)hydrocarbylene is independently selected from a substituted or unsubstituted (C1-C20)alkylene, a substituted or unsubstituted (C3-C20)cycloalkylene, a substituted or unsubstituted (C2-C20)alkenylene, a substituted or unsubstituted (C2- C20)alkynylene, a substituted or unsubstituted (C1-C20)acylene, a substituted or unsubstituted (C4- C20)arylene, and a substituted or unsubstituted (C2-C20)alkoxyene. At each occurrence DA has the same chemical structure. Alternatively, at least two occurrences of DA have a different chemical structure.

[0032] In specific examples, at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, a reacted pentanediamine, a reacted nonanediamine, a reacted isononanediamine, a reacted 2-methylpentamethylenediamine, a reacted ethylenediamine, a reacted isophorone diamine, a reacted m-xylylenediamine, and a reacted m-phenylenediamine. In some examples at each occurrence DA is a reacted hexamethylenediamine. In still more specific examples, it was found that internal aliphatic groups that are n--(C1-C20)alkylene yielded a grease thickening agent 10Attorney Docket No. INV-24025-WO-PCT that had desirable dropping point and NLGI properties. Typically, the DA does not include a branched structure. This is because diamines having a branched structure tend to make the grease composition to which the grease thickening agent is included too soft which in turn lowers the melting point of the grease composition too much. In some examples, DA can be selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, a reacted pentanediamine, or a reacted nonanediamine.

[0033] The grease thickening agent can be present as a distribution. In the distribution, a weight-average molecular weight of the grease thickening agent is in a range of from about 400 g / mol to about 10,000 g / mol, about 1100 g / mol to about 8,000 g / mol, about 1200 g / mol to about 4000 g / mol, less than, equal to, or greater than, 400 g / mol, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 14501500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, or about 10000 g / mol. Keeping the weight-average molecular weight in this range can help the polyamide grease polymer to be classified as a polymer for regulatory purposes under 40 CFR 723.250(b). In specific examples it was found that a weight-average molecular weight in range of from about 450 g / mol to about 3500 g / mol or about 500 g / mol to about 2500 g / mol yielded a grease thickener with particularly advantageous properties (e.g., dropping point and NLGI values). Additionally, it was found that if the weight-average molecular weight of the grease thickening component is too high, it will not be compatible with the base oil of the grease composition. Non-compatibility is established if the grease composition is not homogenous. A grease composition is considered to be homogenous if when examined under a microscope at 200 magnification, there are discrete particles observed.

[0034] In general, it was found that if the polyamide grease thickener was completely linear (e.g., included no cylcoaliphilicity, aromaticity, or the like), the resulting grease had poor penetrometer measurement, meaning the grease was too soft. Examples of linear polyamides can be found in GB774085). However, it was found that at least some linearity was desirable as all aromatic polyamides show poor compatibility (e.g., a low dropping point) when incorporated in a grease composition. Additionally, it was found that if the weight-average molecular weight of the polyamide grease thickener is too high, there would be poor compatibility (e.g., lack of homogeneousy) in the grease composition. 11Attorney Docket No. INV-24025-WO-PCT

[0035] Specific examples of suitable grease thickening agents that can be used alone or as a mixture of grease thickening agents include those shown herein in Table 1. Of those grease thickeners listed in Table 1, the structures of Formula XII, XI, X, and XIII, include the afore mentioned beneficial structures and show good performance in grease compositions. Data is included where available for the dropping point P0, and P60 values when the respective grease thickener is incorporated in a grease composition. 12TCP-OW-52042-VNI.oNtekcoDyenrottAerutcurtS alu r. . .m..III .II .oVIV V VIIXXIF X X X X X X XTCP- M O NW-52042- M V NNI.oNtekco MDNyenrottA..IIX.IX X X X X XTCP- M O NW-52042- M V NNI.oNtekco MDNyenrottA. VI.IIIX X X XTCP- M O NW-52042- M V NNI.oNtekco MDNyenrottA.I.IIV V X X X XTCP- 1 O 52W-52042- 2 V 12NI.oNtekco 04D2yenrottAN Hn O NHH NO O HN N HO HNO 6682:W M .I. II.IX.I.IV XIX X XIIX X X X X XT CP- A O NW-52042- A V NNI.oNt,e tetkcoar sono d dprilDiyeDocosnrniott :A W M O NH81 n HNO O NHH NO eld b 8aler4i us8aa3va etm . oto Xn nX=A=X X N M * * N *Attorney Docket No. INV-24025-WO-PCT

[0036] Structural features of the polyamide grease thickening agent that are found to help achieve these characteristics include any aliphatic moieties in monomers that are internally disposed in the polyamide grease thickening agent molecule and are n-alkyl (linear), additionally the polyamide grease thickening agent should include at least two para-substituted aromatic moieties, the polyamide grease thickening agent should have a molecular weight in a range of from 450 g / mol to 3500 g / mol, and the polyamide grease thickening agent should include at least four amide bonds. These structural features were found to achieve the desirable physical properties when the polyamide grease thickening agent is incorporated into a grease composition in a concentration in a range of from about 10 wt% to 20 wt%, about 10 wt% to about 15 wt%, less than, equal to, or greater than about 10 wt%, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 wt%.

[0037] The grease thickening agent can be present as a distribution. In the distribution, a weight-average molecular weight of the grease thickening agent is in a range of from about 400 g / mol to about 10,000 g / mol, about 1100 g / mol to about 8,000 g / mol, about 1200 g / mol to about 4000 g / mol, less than, equal to, or greater than, 400 g / mol, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 14501500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, or about 10000 g / mol. Keeping the weight-average molecular weight in this range can help the polyamide grease polymer to be classified as a polymer for regulatory purposes under 40 CFR 723.250(b). In specific examples it was found that a weight-average molecular weight in ranges of from about 450 g / mol to about 3500 g / mol or about 500 g / mol to about 2500 g / mol yielded a polyamide grease thickening agent with particularly advantageous properties (e.g., dropping point and NLGI values). Additionally, it was found that if the weight-average molecular weight of the grease thickening component is too high, it will not be compatible with the base oil of the grease composition. Non-compatibility is established if the grease composition is not homogenous. A grease composition is considered to be homogenous if when examined under a microscope at 200 magnification, there are discrete particles observed.

[0038] In general, it was found that if the polyamide grease thickening agent was completely n-linear (e.g., included no cyclo-aliphaticity, aromaticity, or the combination thereof), the resulting grease had poor penetrometer measurement, meaning the grease was too soft. The term "too soft", as used herein, means it requires higher loading making it less cost 19Attorney Docket No. INV-24025-WO-PCT effective. (Examples of linear polyamides can be found in GB774085). However, it was found that at least some linearity was desirable as all aromatic polyamides show poor compatibility (e.g., a low dropping point) when incorporated in a grease composition. Additionally, a relationship was unexpectedly found between the weight-average molecular weight of the polyamide grease thickening agent and compatibility (or homogeneity) in the grease composition. When the weight-average molecular weight of the polyamide grease thickening agent is too high (for example, greater than 2000 g / mol), there would be poor compatibility (e.g., lack of homogeneity) in the grease composition resulting in poor performance.

[0039] The polyamide grease thickening agent can be a component of a grease composition. A grease composition is generally understood to refer to a solid or semi- solid lubricant formed as a dispersion of thickening agents in a liquid lubricant. Grease compositions include a base oil (or lubricating oil), grease thickening agent, and optional additives. The polyamide grease thickening agent can be in a range of from about 1 wt% to about 50 wt% of the grease composition about 5 wt% to about 20 wt% of the grease composition. Base oils can include a vegetable oil, a mineral oil, synthetic oil, or any other fluid that provides lubricating properties. As an example, the grease can be a silicone grease. A silicone grease can include a polydimethysiloxane base oil. Other greases can be a fluoroether-based grease that includes a fluoroether base oil.

[0040] The polyamide grease thickening agent, prepared according to the disclosed process, may be relatively inert to reacting with other components of a grease composition. Thus, the polyamide grease thickening agent can remain in the grease composition in an unreacted form. Moreover, the amide bond is less likely to be susceptible to hydrolysis. Thus, the polyamide grease thickening agent can tolerate some level of water that may present in the grease composition. Additionally, the polyamide grease thickening agent can be synthesized in the presence of water. These benefits are particularly apparent compared to a polyamide grease thickening agent having terminal ester groups. The terminal ester groups may be more likely to react with other grease components or undergo hydrolysis, either of which can reduce the effectiveness of the polyamide grease thickening agent.

[0041] United States Patent No.2830954 discloses high-temperature polyamide grease compositions obtained from aliphatic dibasic acids and aliphatic diamines. Industrial Utility 20Attorney Docket No. INV-24025-WO-PCT

[0042] The oligomeric intermediate, according to this disclosure, is useful to make polyamide grease thickening agents of industrial value.

[0043] The polyamide grease thickening agent, as prepared by the disclosed process, can be a component of a grease composition. The grease composition can be contacted with any number of articles in need of lubrication, thereby, minimizing the wear and tear and in prolonging the life of such articles. For example, the grease composition can be applied to a bearing, crank-shaft, joint, hinge, or the like.

[0044] An advantage of such grease compositions, prepared from the polyamide grease thickening agents according to the disclosed process, is that it can provide sufficient thickening properties to the grease composition while being substantially free of lithium, polyurea, etc. For example, the resulting grease composition can include less than 1 wt% lithium and / or less than 1 wt% polyurea. Advantageously, this can result in a grease composition that is potentially more environmentally friendly. Additionally, there may be cost advantages to the disclosed polyamide grease thickening agent, especially with respect to being substantially free of the high-priced lithium.

[0045] In some aspects, an end-user may choose to include the disclosed polyamide grease thickening agent with a grease thickening composition that includes lithium, polyurea, or both. However, the amount of grease thickening composition that includes lithium, polyurea, or both necessary can be reduced by including the disclosed polyamide grease thickening agent, relative to a grease composition that is free of the disclosed polyamide grease thickening agent. Material Names and Abbreviations used in the disclosure:

[0046] ACN Acetonitrile;

[0047] HMD Hexamethylenediamine;

[0048] NMP N-Methylpyrrolidone;

[0049] SA Stearic acid;

[0050] THF Tetrahydrofuran;

[0051] TPC Terephthaloyl chloride; Test Methods:

[0052] The purity of the starting materials, namely, HMD, TPC and stearic acid, may 21Attorney Docket No. INV-24025-WO-PCT be determined from GC-MS and LC-MS methods.

[0053] The molecular weight distributions may be determined using methods, such as, LC-MS and NMR.

[0054] The sodium content may be determined using an ICP-MS technique.

[0055] The chloride content may be determined using an XRF technique.

[0056] The % End-capping may be determined using NMR. The term “% End- capping”, as used herein, means the amount of free amine end groups that has been reacted with an acid component, for example, steric acid. The difference, 100 - % End-capping, means the amount of materials with free amine end-groups remaining in the product.

[0057] The quality of recovered solvents, namely, acetonitrile, THF and NMP, may be determined using standard industry methods, such as, GC, LC, etc.

[0058] The water content may be determined using Karl-Fischer Titration [KFT].

[0059] The color and uniformity of the solids may be determined by visual inspection. Generally speaking, a whitish, slightly off-whitish or tan color and smooth uniformity without aggregates or lumps are desirable. EXAMPLES

[0060] Various aspects of the present disclosure can be better understood by reference to the following Examples which are offered by way of illustration. The present disclosure is not limited to the Examples given herein.

[0061] Unless otherwise stated, all values and percents are on the weight (mass) basis. Materials

[0062] As used herein, hexamethylenediamine (HMD; CAS No.124-09-4), is available as a commercial product manufactured by INVISTA Nylon Chemicals Inc. Llc. An aqueous HMD solution of about 85-90% strength was used in the examples. The 85% HMD-water solution freezes at 24°C, and the 90% HMD-water solution freezes at 30°C. Anhydrous HMD in the solid form may also be used according to this disclosure.

[0063] As used herein, stearic acid (SA; CAS No. 57-11-4), is a commercial product and available from Acros Organics. A 97% purity SA was used in the examples.

[0064] As used herein, terephthaloyl chloride (TPC; CAS No. 100-20-9), is available as a commercial product. A 99% purity TPC was used in the examples. 22Attorney Docket No. INV-24025-WO-PCT

[0065] As used herein, acetonitrile (ACN; CAS No. 75-05-8), is a common industrial solvent and available from various commercial producers. A 99% purity ACN was used in the examples.

[0066] As used herein, N-Methylpyrrolidone (NMP; CAS No.872-50-4), is a common industrial solvent and available from various commercial producers. A 99% purity NMP was used in the examples. NMP was purged with nitrogen to remove any oxygen.

[0067] As used herein, Tetrahydrofuran (THF; CAS No. 109-99-9), is a common industrial solvent and available from various commercial producers. A 99.6% purity THF was used in the examples.

[0068] As used herein, a 2.5-5 wt% aqueous caustic (CAS No.1310-73-2) solution was used in the examples.

[0069] De-ionized (DI) water, free of any impurities, was used in the examples. Example 1 – Oligomer Intermediate Synthesis and Recovery

[0070] About 600g of 90% HMD in water, e.g., 540g HMD in 60g water, and about 500g of acetonitrile were charged to a reaction vessel equipped with an agitator, several ports, and with an ability for inert (N2) blanketing in the headspace. The jacketed reaction vessel can be heated or cooled for temperature management. The agitation was turned on for the HMD- acetonitrile mixture to homogenize at about 50 °C while under N2 padding. About 203g of TPC and about 1152g of acetonitrile were mixed to yield about 1355g of 15% TPC in acetonitrile solvent in a separate vessel at 25 °C temperature and under N2 padding.

[0071] The reaction was initiated in the vessel, that contained about 1100g of HMD- acetonitrile mixture from above, by gradually pumping the prepared TPC-acetonitrile mixture at the rate of about 10-15 ml / min. The reaction exotherm was controlled by adequate cooling and the temperature was maintained at about 45-50 °C. The vessel was sufficiently agitated for uniformity during the reaction. Upon adding all TPC-acetonitrile solution, the reaction conditions were maintained for an additional 60 minutes. The reactor content viscosity increased from about 2.1 to about 153 centipoise (cP) from beginning to the end of reaction. The HMD and TPC reaction yielded an oligomer intermediate precipitate in the reaction medium. Reactor off gas was vented to a water trap to collect any chloride, HMD, and ACN in the vent gas. Typical scrubbing liquid pH was 10.

[0072] The reaction effluent was cooled to 25 °C and filtered under the house vacuum (approx. 16.5 torr) using a 185mm diameter filter medium with 8µm pore size to recover the 23Attorney Docket No. INV-24025-WO-PCToligomer intermediate precipitate. Any known solid separation method can be used, forexample, gravity separation, centrifugation, decantation, etc. About 900-1000g of the wetfiltered cake was recovered from the reaction vessel. The filtered cake was washed in thefollowing sequence to remove any residual chloride, HMD, acetonitrile, etc. First, the wet cakewas mixed with about 2000-2500g of 2.5% aqueous caustic solution and agitated for about 30-60 minutes at 50 °C. The slurry was filtered to separate the washed wet solids from the filtrate.

[0073] Next, the wet cake was mixed with about 2000-2500g of DI water, agitated forabout 30-60 minutes at 50 °C, and the slurry was filtered to separate the wet cake. The DIwater wash step was repeated until the sodium or chloride impurities in the wet cake measuredto 500 ppm (each). Typically, two DI water wash cycles were adequate to reduce theseimpurities in the wet cake to 500 ppm (each). After the washing step was completed, about 400-500g of the wet oligomer intermediate solids were recovered. All effluent from the washing steps, mainly the caustic, water with residual sodium, chloride, HMD, etc., may beproperly treated for safe disposal.

[0074] The wet solids from above were dried at 100 °C under slight vacuum for 12-16hrs. About 200-300g of the dried oligomer intermediate solids were obtained from the drying step. The dried solids may optionally be ground for size reduction. A small representative sample of the oligomeric intermediate was retained for the analysis. Example 2 – Oligomeric Intermediate Solid

[0075] The recovered and dried oligomeric intermediate solid of Example 1 comprisedthe following constituents, labeled XXXIII through XXXVII:24Attorney Docket No. INV-24025-WO-PCT(XXXVII)

[0076] Table 1 provides a summary of the measured composition of oligomericintermediate solid at various stages of the Example 1 procedure. The sample analysis wasperformed using LC-MS analytical method, and the area % method was used for quantification.All values are on the wt. % basis. TABLE 1 Oligomeric

[0077] In this example, the dried oligomeric intermediate solid contained 1% (max.)residual HMD, moisture content of <1%, and 500 ppm (each) chloride and sodium impurities. It may be feasible to produce wet oligomeric intermediate solids containingelevated water levels, such as 5% or 10% or 20% or 30% or 50% or 60%, depending on the 25Attorney Docket No. INV-24025-WO-PCT drying equipment used. There is no requirement for stringent drying. Any excess water will not damage the oligomeric intermediate.

[0078] The molecular weight distribution of the recovered oligomeric intermediate solid was in the 360 g / mol to 1500 g / mol range, with an average of about 740 g / mol. The distribution of the constituents may be such that the average molecular weight remains in the described range herein.

[0079] In one embodiment, the desirable oligomeric intermediate solid composition of industrial utility may include < 30 % of constituent (XXXIII) about 40-50 % of constituent (XXXIV), about 30-40 % of constituent (XXXV), < 15 % of constituent (XXXVI), and < 5 % of constituent (XXXVII).

[0080] It was surprisingly observed that the shear stability of the polyamide grease thickening agent improved when constituent (XXXIII) in the oligomeric intermediate solid was less than 30 % of the total oligomer intermediate weight. Example 3 – Oligomeric Intermediate Solid using 85 wt% HMD feed

[0081] The Example 1 procedure was repeated with the following changes: i) about 85 wt% aqueous HMD feed was used; ii) about 25 wt% TPC in acetonitrile feed was used; and iii) slow TPC-acetonitrile addition rate of about 2-3 g / min for the reaction.

[0082] Table 2 provides a summary of the measured composition of oligomeric intermediate solid at various stages in Example 3 procedure. The sample analysis was performed using LC-MS analytical method, and the area % method was used for quantification. All values are on the wt. % basis. TABLE 2 Solids [ ost water Oli omeric26Attorney Docket No. INV-24025-WO-PCT 9Example 4 – Polyamide Grease Thickening Agent Synthesis and Recovery

[0083] About 100g of stearic acid in the solid form and about 260g of NMP solvent were pre-mixed at about 30 °C into a homogeneous mixture of 28% stearic acid in NMP. This mixture was then charged to an agitated, jacketed reactor and maintained to about 30°C. Once at 30°C temperature, about 50g of Example 2 oligomeric intermediate solids were gradually added to the reactor in dry, ground form. Initially, the reactor contents temperature was raised to about 100-110 °C and held for some time to strip water from the contents. The reactor temperature was then gradually raised to about 185 °C while stripping off any residual water from the system. The reaction mixture was held at this temperature under agitation and a nitrogen purge for a fixed reaction time in the 4-16 hour range.

[0084] The viscosity and flowability of the reaction mixture was temperature dependent, and it remained a flowable slurry until 120 °C, eventually forming a waxy solid at lower temperatures. As the reaction continued the solid product began to accumulate in the vessel. The product was kept at minimum 120 °C for allowing it to properly flow during its recovery. After the reaction was complete the reaction slurry containing the final product was transferred to a separate vessel while hot (i.e., at least at 120 °C).

[0085] The slurry was cooled to room temperature and washed with about 500g of THF for about 30-45 minutes. The slurry was filtered, and the THF wash was repeated several times in the same way to remove excess stearic acid and NMP solvent from the product.

[0086] The washed solid product was dried at about 100°C. About 75-85g of the dried final product was recovered from this step. The final product can be ground to obtain a uniform particle size in the 1-100 microns range, in the 2-90 microns range, preferably in the 2-60 microns range, and more preferably in the 2-50 microns range. A suitable size reduction method may include, and not limited to, jet milling, rotary milling, tumble milling and other similar methods. In this example, jet milling of the dried final product resulted solids in the 2- 35 microns range. The off-white to tan-colored dry final product was analyzed for quality.

[0087] The final product, e.g., polyamide grease thickening agent, contained 3% (max) residual stearic acid, ppm moisture, s, and trace levels of NMP. About 75% of the solid product had minimum molecular weight of 27Attorney Docket No. INV-24025-WO-PCT about 1000 g / mol. The weight-average molecular weight of the final product was typically in the 450 to 3500 g / mol range. Example 5 – Grease Composition using Polyamide Grease Thickening Agent

[0088] The polyamide grease thickening agent of Example 4 was incorporated into a grease composition at 12 wt% concentration. The Dropping point of the grease composition was 320 °C. Table 3 below summarizes the mechanical performance of grease composition prepared accordingly. TABLE 3 M t L di / % E d i P t ti (t th f )Example 6 – Grease Composition using Polyamide Grease Thickening Agent

[0089] The polyamide grease thickening agent solids, prepared according to Example 4 procedure, contains about 5000 ppm water. The material was dried in a vacuum oven over weekend at 90 °C. The moisture content in the dried material was reduced to about 500 ppm.

[0090] About 2.2 kg of a commercially available alkylated naphthalene (AN) base oil, SynessticTM5 Synthetic Fluid (manuf: ExxonMobil) was charged to a 5-liter kettle equipped with a 2.5-inch OD impeller and heating / cooling capability. About 300 g of the dried polyamide grease thickening agent solid was charged to the kettle under nitrogen padding. Stirring of the kettle contents was started at a rotational speed capable of sufficiently mixing the solids in the base oil. The kettle contents were gradually heated to about 230 °C for about 3 hours to ensure good incorporation. Representative samples were taken every 30 minutes to check for rheology and Drop point (DP). The batch was run for an additional one hour and a homogeneous grease composition was visually observed in the kettle. Upon confirming a uniform consistency grease composition, the heat was turned off. The kettle contents were 28Attorney Docket No. INV-24025-WO-PCT cooled down in the 180-200 °C range. The resulting grease composition was tested for its properties.

[0091] The Drop point of the prepared grease composition was >300 °C, more like 316- 320 °C. Also, no oil separation was observed over time. Example 7 – Poly-Urea Grease Composition Preparation

[0092] In a kettle with small stirring blade and heating / cooling capability, SynessticTM5 Synthetic Fluid (manuf: ExxonMobil) and polyurea pre-formed grease was mixed at 180-185 °C for about 45 minutes. The polyurea content was in the 15-16 wt% of the total composition. The batch was cooled down. Example 8 – Lithium Grease Composition Preparation

[0093] Using the same mixing kettle as in Example 5, about 30.5 wt% lithium grease composition was prepared in the SynessticTM5 Synthetic Fluid (manuf: ExxonMobil) base oil. The final grease composition was very clumpy compared to that made in Example 4. Example 9 – General Solvent Recovery and Recycle

[0094] The Example 1 procedure produces a liquid filtrate stream containing about 75- 80% acetonitrile, about 5-20% HMD, about 2-5 wt% water, <5% oligomer intermediate, and some residual chlorides from the process. The Example 1 effluent may be separated into high- purity acetonitrile and HMD constituents via a distillative approach, while concentrating and purging the water and other impurities from the effluent. The recovered acetonitrile and HMD may be recycled back to Example 1 synthesis.

[0095] The Example 4 procedure produces a liquid filtrate stream containing about 80- 85% THF, about 10-15% NMP, about 2-5 wt% stearic acid, and <1% (each) of water and oligomer intermediate. The Example 4 effluent may be separated into refined THF, refined NMP and high-quality stearic acid constituents via a distillative column sequence, while concentrating and purging the water and other impurities from the effluent. The recovered THF and NMP solvents may be recycled back to final product washing steps. The recovered stearic acid may be recycled back to Example 4 synthesis. Example 10 – Acetonitrile Recovery and Recycle 29Attorney Docket No. INV-24025-WO-PCT

[0096] The Example 1 procedure produces a liquid filtrate stream containing about 75- 80% acetonitrile, about 5-20% HMD, about 2-5 wt% water, <5% oligomer intermediate and <5000 ppm residual chlorides.

[0097] The acetonitrile-containing filtrate is fed to a first distillation column equipped with about 15-35 theoretical stages, a reboiler and an overhead condenser. The feed enters at about middle of the column. The column head / base temperatures are maintained in the 30- 35 / 190-215 °C range. The column head pressure is about 1 atm and the base pressure is slightly above 1 atm due to the column pressure drop. The reflux ratio to the column is in the 0.1-10 range.

[0098] The column concentrates the HMD and other constituents at the base, while the overhead is mostly acetonitrile-water stream. In this example, about 1000 kg / hr of feed is separated into about 790 kg / hr overhead liquid stream having about 96:4 (wt:wt) acetonitrile:water composition, and about 210 kg / hr tails stream having the concentration of about 85-90 % HMD, and residual oligomer intermediate. The tails stream may be further processed to remove undesirable impurities, a purge is taken for impurity control, and the recovered HMD of suitable purity is recycled back to the process for re-use.

[0099] The first column overhead 96:4 (wt:wt) acetonitrile-water stream is cooled in the 25-30 °C range and fed to a second distillation column for acetonitrile recovery. The second distillation column is equipped with about 15-35 theoretical stages, a reboiler and an overhead condenser. The feed enters at about middle of the column. The column head / base temperatures are maintained in the 125-130 / 140-150 °C range. The column head pressure is maintained at about 5 atm and the base pressure is slightly above 5 atm due to the column pressure drop. The reflux ratio to the second column is in the 0.1-5 range.

[0100] The second column concentrates the acetonitrile at the base, while the small overhead stream is mostly wet acetonitrile. In this example, about 790 kg / hr of feed is separated into the tails stream of about 680 kg / hr acetonitrile stream of (<1000 ppm water). The second column overhead vapor stream is about 40-45 kg / hr that mostly contains 65-75% acetonitrile, 20-30% water and residual chlorides. This overhead vaporous stream is routed to a gas disposal header. The second column also makes about 60- 65 kg / hr of liquid overhead stream that is mostly 75:25 acetonitrile:water mixture, which may be properly sent for disposal. 30Attorney Docket No. INV-24025-WO-PCT

[0101] Depending on the impurity profile, the second column tails stream may be further processed to remove undesirable impurities, a purge is taken for impurity control, and the acetonitrile of high purity is recycled back to the process for re-use. In this example, the acetonitrile recovery of about 90% and of 1000 ppm water) is achieved. This high-purity acetonitrile stream is suitable for recycle back to the process as described in Example 1.

[0102] In an event when the Example 1 process makes a liquid filtrate stream that contains >15 wt% water, such as 20 wt% water, a dewatering column may be necessary to remove excess water from the acetonitrile stream before the downstream acetonitrile purification as described in this example. Example 11 – Inefficient Acetonitrile Solvent Recovery

[0103] The two sequential column scheme of Example 10 is used in this example, except that the effluent feed to the first column contains elevated levels of water of about 7-8 wt% (vs. <5 wt%), and the second column head pressure is maintained at about 1 atm (vs. 5 atm). With everything else being the same and as described in Example 10, the acetonitrile recovery of 80% and of about 90 wt% purity is obtained from this operation. In an effort to improve the acetonitrile purity to about 95 wt%, the recovery falls to about 60%.

[0104] In this example the recovered acetonitrile is not of high purity, therefore, would not be suitable for reuse in the process of Example 1 without further purification. Also, lower than 90% acetonitrile recovery is undesirable from the overall process cost perspective, in that, more acetonitrile make-up would be needed to compensate for the solvent loss. Example 12 – THF and NMP Solvent Recovery

[0105] The Example 4 procedure produces a liquid filtrate stream containing about 80- 85% THF, about 10-15% NMP, about 2-5% stearic acid, and <0.5% (each) of water and oligomeric intermediate.

[0106] The THF- and NMP-containing liquid filtrate stream is fed to a first distillation column equipped with about 5-20 theoretical stages, a reboiler and an overhead condenser. The feed enters at about the lower-third column section. The column head / base temperatures are maintained in the 60-75 / 195-215 °C range. The column head pressure 31Attorney Docket No. INV-24025-WO-PCT is about 1 atm and the base pressure is slightly above 1 atm due to the column pressure drop. The reflux ratio to the column is in the 0.1-5 range.

[0107] The first column concentrates the THF in the overhead to about 99% purity (<5000 ppm water content). The THF-lean stream at the column base is mostly 65-75% NMP, 15-25% stearic acid and <10% oligomeric intermediate. In this example, about 500 kg / hr of feed is separated into about 396-425 kg / hr high-purity THF and about 75-104 kg / hr bottoms stream rich in NMP. The overhead high-purity THF stream is cooled to about 25- 30°C and recycled back to the Example 4 process. A fresh THF make-up is added to compensate for the solvent loss.

[0108] The NMP-rich stream, recovered from the first column base, proceeds to a second distillation column. The second distillation column is equipped with about 5-20 theoretical stages, a reboiler and an overhead condenser. The feed enters at about the top- third column section. The reboiler at the column base provides sufficient boil-up to attain the column head / base temperatures in the 195-220 / 350-375 °C range. The column head pressure is about 1 atm and the base pressure is slightly above 1 atm due to the column pressure drop. The reflux ratio to the column is in the 0.1-5 range.

[0109] The column concentrates the NMP Most of the stearic acid concentrates at the column base along with the residual oligomeric intermediate.

[0110] In this example, about 100 kg / hr of feed is separated into about 64-75 kg / hr high-purity NMP stream and about 25-36 kg / hr stream containing about 80-90% stearic acid. The overhead high-purity NMP stream is cooled to about 25-30 °C and recycled back to the Example 4 process. A fresh NMP make-up is added to compensate for the solvent loss. The stearic acid containing bottoms stream is cooled and may be further refined to higher purity before recycling back to the process described in Example 4. Alternatively, this stream may be routed for other uses or proper disposal. This stream may also serve as a purge point for the accumulated oligomeric intermediate species and other undesirable impurities. Example 13 – Recovery of Wet THF Stream

[0111] During start-ups, transient operations or otherwise off-design conditions, the Example 4 process may produce a liquid filtrate stream that contains an elevated amount 32Attorney Docket No. INV-24025-WO-PCT of water, for example, 1% or higher, such as 4% or 5% or 6% or 7% or 8%. The two- column arrangement, as described in Example 12, may not be effective to recover more than 99% of THF in the feed with high purity, and instead may only recover 80-98% of high-purity THF. A higher recovery for THF recycle is desirable in the process described in Example 4.

[0112] In this example, the first column (of Example 12) concentrates the THF component overhead with about 95-98% purity (balance water). This stream is cooled to about 30-40 °C and fed near the top of a refining column containing about 10-25 theoretical stages, a reboiler and an overhead condenser. The refining column head pressure is maintained to about 10 atm and the reboiler provides sufficient boil-up to keep the head / base temperatures in the 145-155 / 160-175 °C range. The column reflux ratio is in the 0.1- 5 range.

[0113] The refining column is able to strip the water overhead and concentrate the recycle quality THF at the column base to . The column overhead is a small 90:10 THF:water stream that can be purged to reduce water in the overall process.

[0114] The bottoms stream from the first column is enriched in NMP and stearic acid, which continues to the second column (of Example 12) for NMP and stearic acid recovery as described in Example 12. Both, the THF and NMP with high purity are suitable for recycle back in the process described in Example 4.

[0115] In an event when the Example 4 process makes a liquid filtrate stream that contains >15 wt% water, such as 20 wt% water, a dewatering column may be necessary to remove the excess water from the THF stream before the downstream THF purification as described in this example. Example 14 – Oligomeric Intermediate Solid using anhydrous HMD feed

[0116] The Example 1 procedure was repeated except about 600g of anhydrous HMD flakes were mixed with about 500g of acetonitrile, and homogeneous HMD-acetonitrile solution was used in the steps described in Example 1. No other changes were made.

[0117] Table 4 provides a side-by-side summary of the measured composition of the dried oligomeric intermediate solid at 90 wt% and anhydrous HMD feeds used in the Example 1 procedure. The sample analysis was performed using LC-MS analytical 33Attorney Docket No. INV-24025-WO-PCT method, and the area % method was used for quantification. All values are on the wt. % basis. TABLE 4

[0118] It was unexpectedly observed that the water elimination by using anhydrous diamine feed shifted the oligomeric intermediate composition toward longer-chain constituents, namely constituents (XXXVI), (XXXVII), and higher.

[0119] At the completion of this example, a liquid filtrate stream is generated that contains about 75-85% acetonitrile, about 15-20% HMD, <0.5% water, <2% oligomer intermediate and <5000 ppm residual chlorides. The excess acetonitrile and HMD recoveries become easy due to the very low amounts of water in the liquid filtrate stream. The acetonitrile-water azeotrope formation is avoided when anhydrous HMD is used in Example 14. Example 15 – NMP Solvent Recovery / Re-use 34Attorney Docket No. INV-24025-WO-PCT

[0120] The Example 4 procedure produces a liquid filtrate stream containing about 80- 85% THF, about 10-15% NMP, about 2-5% stearic acid, and <0.5% (each) of water and oligomeric intermediate.

[0121] The THF- and NMP-containing liquid filtrate stream is fed to a THF stripping column equipped with about 10-25 theoretical stages, a reboiler and an overhead condenser. The feed enters at about the lower-third column section. The column head / base temperatures are maintained in the 60-75 / 195-215 °C range. The column head pressure is about 1 atm and the base pressure is slightly above 1 atm due to the column pressure drop. The reflux ratio to the column is in the 0.1-5 range.

[0122] The THF stripping column concentrates most of the NMP, stearic acid and residual oligomeric intermediate at the column base. The THF is stripped along with any residual water and concentrated at the column overhead. The THF-lean stream at the column base is mostly 65-75% NMP, 15-25% stearic acid and <10% oligomeric intermediate.

[0123] In this example, about 500 kg / hr of feed is separated into about 396-425 kg / hr high-purity THF and about 75-104 kg / hr bottoms stream rich in NMP. The bottom NMP stream is cooled and made available for recycle / reuse back to the Example 4 process. A fresh NMP make-up may be added to the process to compensate for the solvent loss. Similarly, the overhead THF stream is cooled to about 25-30 °C and recycled back to the Example 4 process. A fresh THF make-up is added to the process to compensate for the solvent loss. Examples 16A-C – Reactive Extrusion Method for Polyamide Grease Thickening Agent Synthesis

[0124] The dried oligomeric intermediate solid, obtained from Example 2, contained sodium impurities. The molecular weight distribution of the recovered oligomeric intermediate solid was in the 360 g / mol to 1500 g / mol range, with an average of about 740 g / mol. The distribution of the constituents may be such that the average molecular weight remains in the described range herein. The desirable oligomeric intermediate solid composition of industrial utility may include < 30 % of constituent (XXXIII) about 40-50 % of constituent (XXXIV), about 30-40 % of constituent (XXXV), < 15 % of constituent 35Attorney Docket No. INV-24025-WO-PCT (XXXVI), and < 5 % of constituent (XXXVII). The oligomeric intermediate solid containing the above constituents and as described in Example 2 was used in the present example.

[0125] It was unexpectedly observed that a reactive extrusion method obtained a final product that was substantially identical to that produced by long batch time process of Example 4. The final product quality was acceptable and the purity was consistent to that produced by the Example 4 method.

[0126] A pre-milled solid mixture of stearic acid and Example 2 oligomeric intermediate solid was fed to a twin-screw extruder.

[0127] A 16-mm diameter bench-top Twin-screw extruder [Model No. LTE 16-44 FAC; Serial No. 1302-LTE16-44]; manufacturer: LABTECH Eng. Co. Ltd] was used in this example. The extruder L / D ratio was 16 and operated in an unvented mode. The extruder was equipped with a gravimetric feeder system, ten (10) zones with independent zonal temperature controls, a die section at the extruder exit, water batch and strand pelletizer. The gravimetric feeder system was effective to regulate the extruder throughput by weight loss determination. The water bath system [Model No. LWB-40; Serial No. 1305-40] was connected to the extruder assembly. The strand pelletizer [Model No. LZ- 80 / VS; Serial No. 1305-80 / VS] was used to cut the extrudates into pellets of suitable dimension.

[0128] The twin-screw extruder was operated at screw speeds of between 10 to 50 RPM. The reaction zone temperature within the extruder was maintain in the range of 250 to 275 °C. The temperatures in each of the extruder zones were typically controlled as follows: 18 °C [about 65 °F; Zone 1]; 27 °C [about 80 °F; Zone 2]; 141 °C [about 285 °F; Zone 3]; 250 °C [about 482 °F; Zones 4 through 8]; 213 °C [about 415 °F; Zone 9]; and 160 °C [about 320 °F; Zone 10]. The extruder internal pressure was maintained in the range of about 200 to 400 Psig.

[0129] The feed molar ratio of stearic acid to oligomeric intermediate solids (from Example 2) was varied in the range of about 2 to 6, corresponding to about 0.75 to about 2.5 on weight basis. As an illustration, a 2:1 (molar) ratio of stearic acid [284.5 g / mol] to oligomeric intermediate solids (from Example 2) having about 710 g / mol molecular weight is about 0.8:1 on the weight basis. 36Attorney Docket No. INV-24025-WO-PCT

[0130] The extruder feed rate was regulated to achieve about 15 to 45 minutes of overall material residence time before passing the material through a die cooled under a nitrogen blanket. The extruded material was collected and washed to remove excess stearic acid from the final product or used as is in the cases of stoichiometrically balanced reactions. The material recovered from the reactive extruder step was crushed into a finer solid powder. The crushed solids were washed three times with a chosen solvent when the washing step was implemented. The wash solvent to solid product quantities were about 10:1 (wt:wt), for example, about 10g solvent was used to wash about 1g of the solid product. In some examples, the final product washing step was not implemented.

[0131] Table 5 below represents the summary of the final product, e.g., polyamide grease thickening agent. TABLE 5 Ex ID 16A 16B 16C [dried Product]

[0132] In the tables, the term “n” is the average number of repeating units in the product. For illustration, n=1 when the product is (XXXIII); n=2 when the product is (XXXIV), n=3 when the product is (XXXV), n=4 when the product is (XXXVI), and n=5 when the product is (XXXVII). The final product according to the present disclosure is a mixture of components (XXXIII) through (XXXVII). Thus, the average number of repeating units “n” depend on the percentages of these components in the final product. 37Attorney Docket No. INV-24025-WO-PCT

[0133] The final product, e.g., polyamide grease thickening agent, contained 3% (max) impurities, and no NMP impurity. About 75% of the solid product had minimum molecular weight of about 1000 g / mol. The weight-average molecular weight of the final product was typically in the 450 to 3500 g / mol range.

[0134] This example demonstrates an alternate and improved method for preparing a polyamide grease thickening agent to that of Example 4 method.

[0135] Specifically, the reactive extrusion method of making polyamide grease thickening agent: a. significantly reduces the processing time and labor it takes to produce a substantially similar final product, as against by the Example 4 synthesis method taking between 4-16 hours; b. reaction times of <60 minutes makes the process suitable for continuous production, as against the long batch times observed in Example 4; c. simplifies the process steps, when compared to the Example 4 product with viscosity and flowability limitations; d. eliminates one of the solvents, i.e., NMP, in the overall process that would otherwise be needed for preparing 28% stearic acid in NMP as in Example 4; and e. reduces or eliminates the use of post-synthesis THF washes.

[0136] The above advantages improve the overall process operation and scale-up economics. Elimination of NMP and / or reduction in solvent quantities particularly benefit the downstream product recovery, including the solvent recovery and purification for recycle.

[0137] Advantageously, the liquid filtrate from the Example 16 method contained no NMP, thereby, eliminating a need for NMP separation and recovery.

[0138] Absent NMP, the liquid filtrate may be separated into refined THF and high- quality stearic acid constituents via a distillative column sequence, such as that described in Examples 12 and 13. This step may also concentrate and purge the water and other accumulated impurities from the liquid filtrate. The recovered THF solvent may be recycled back to the final product washing steps. The recovered stearic acid with sufficient purity may be recycled back as supplemental feed to the reactive extrusion step. 38Attorney Docket No. INV-24025-WO-PCT Examples 17A-I – Reactive Extrusion Method for Polyamide Grease Thickening Agent Synthesis

[0139] The reactive extrusion method for polyamide grease thickening agent preparation was repeated by employing the Example 16 procedure and equipment at different conditions. Several process and operational variations were made, namely, the extruder zone temperature profile, the feed ratio, and the final product wash medium. The extruded final product was washed in several cycles as described in Example 4 to remove free stearic acid that may be present in the product. The examples also include results when the extruded final product was not washed. These variations are summarized in the below tables.

[0140] Table 6 provides a summary of the reactive extrusion conditions, feed ratios and final product washing medium used in each example. The term “Feed Ratio (wt:wt)” in Table 6 means the weight ratio of stearic acid to Example 2 Oligomeric Intermediate Solids in the reactive extruder feed. The extruder residence time was in the range of 30-45 minutes. TABLE 6 Ex ID 17A 17B 17C 17D 17E 17F 17G 17H 17I39Attorney Docket No. INV-24025-WO-PCT

[0141] Table 7 represents a summary of the extruded final product purity and quality. TABLE 7 Ex ID 17A 17B 17C 17D 17E 17F 17G 17H 17I

[0142] Similar to Examples 5 and 6 methods the dried, ground final product was incorporated into a grease composition at 12 wt.% concentration, and the dropping point of these grease compositions was determined. The dropping points of these grease compositions are reported in Table 5 [using Example 16 final products] and Table 7 [using Examples 17 final products].

[0143] The extruded final product in each of Examples 17A-17D was ground. The ground solids were washed with THF for about 30-45 minutes. The solids slurry was filtered, and the THF wash was repeated several times in the same way to remove as much stearic acid as practically feasible from the washed product.

[0144] In Examples 17E-17F, the extruded final product was ground in the same manner and washed with about 97:3 (wt:wt) acetonitrile-water medium. THF was substituted with the acetonitrile-water medium that was recovered from the Example 1 40Attorney Docket No. INV-24025-WO-PCT liquid filtrate stream and as detailed in Example 10. Thus, a need for THF was eliminated in these examples.

[0145] The final product washing step was entirely omitted in Examples 17G-17I. Table 7 data indicates that the final product quality and purity were not affected either by switching from THF to wet acetonitrile medium or by entirely omitting the washing step.

[0146] It was observed that the presently disclosed reactive extrusion method yielded the final product with consistent quality and purity, when compared to that produced by the Example 4 method.

[0147] The final product, e.g., polyamide grease thickening agent, contained 3% (max) impurities, and no NMP impurity. About 75% of the solid product had minimum molecular weight of about 1000 g / mol. The weight-average molecular weight of the final product was typically in the 450 to 3500 g / mol range. Example 18 – General Solvent Recovery and Recycle

[0148] The Example 1 procedure produces a liquid filtrate stream containing about 75- 80% acetonitrile, about 5-20% HMD, about 2-5 wt% water, <5% oligomer intermediate, and some residual chlorides from the process. The Example 1 effluent may be separated into high-purity acetonitrile and HMD constituents via a distillative approach, while concentrating and purging the water and other impurities from the effluent. The recovered acetonitrile and HMD may be recycled back to Example 1 synthesis.

[0149] The method described in Examples 16A-C and 17E-F produces a liquid filtrate stream containing about 85-90% acetonitrile, about 2-10 wt% stearic acid, 1-5 wt.% water and <5000 ppmw of oligomer intermediate. This liquid filtrate stream may be separated into refined acetonitrile and high-quality stearic acid constituents via a distillative column sequence, while concentrating and purging the water and other impurities from the process. The recovered acetonitrile may be recycled back to either final product washing steps and / or re-used in Example 1. The recovered stearic acid may be recycled back to Example 4 synthesis. Example 19 – Acetonitrile Recovery from filtrate containing low water level 41Attorney Docket No. INV-24025-WO-PCT

[0150] A two-column distillation scheme, similar to that described in Example 10, may be utilized for recovering acetonitrile and stearic acid from the liquid filtrate stream produced in in Examples 16A-C and 17E-F.

[0151] The feed to a first distillation column contains about 85-90% acetonitrile, about 2-10 wt% stearic acid, 1-5 wt.% water, <5000 ppmw of oligomer intermediate, and <5000 ppmw residual chlorides. This acetonitrile-containing filtrate stream is fed to the first distillation column equipped with about 15-35 theoretical stages, a reboiler and an overhead condenser. The feed is preheated to about 60 °C and enters at about the one-fourth section from the column top stage. The column head / base temperatures are maintained in the 30- 50 / 350-360 °C range. The column head pressure is about 1 atm and the base pressure is slightly above 1 atm due to the column pressure drop. The reflux ratio to the column is in the 0.1-5 range. The column distillate to feed (wt:wt) ratio is typically in the 0.5-0.95 range.

[0152] The first column concentrates the acetonitrile in the overhead, while the column tails stream is mostly acetonitrile-lean stream containing stearic acid in high concentration. In this example, about 1200 kg / hr of feed is separated into about 1100 kg / hr overhead liquid stream having about 96-97 wt.% acetonitrile (balance water), and about 100 kg / hr tails stream containing stearic acid and residual oligomer intermediate. The tails stream may be further processed to recover the stearic acid by removing undesirable impurities. A purge is taken for impurity control, and the recovered stearic acid of suitable purity is recycled back to the process and re-used.

[0153] The first column overhead containing about 96-97 wt.% acetonitrile-water is cooled in the 25-35 °C range and fed to a second distillation column for acetonitrile recovery. The second distillation column is equipped with about 15-35 theoretical stages, a reboiler and an overhead condenser. The feed enters at about middle of the column. The column head / base temperatures are maintained in the 120-130 / 140-150 °C range. The column head pressure is maintained at about 5 atm and the base pressure is slightly above 5 atm due to the column pressure drop. The reflux ratio to the second column is in the 1- 10 range.

[0154] The second column concentrates the acetonitrile at the base, while the small overhead stream is mostly wet acetonitrile and other impurities. In this example, about 1000 kg / hr of feed is separated into the tails stream of about 865 kg / hr acetonitrile stream % purity (<1000 ppm water). The second column overhead vapor stream is 42Attorney Docket No. INV-24025-WO-PCT about 10-20 kg / hr that mostly contains about 50-60% acetonitrile, 15-30% water and residual chlorides. This overhead vaporous stream is routed to a gas disposal header. The second column also makes about 115-125 kg / hr of liquid overhead stream that is mostly 70-75 wt.% acetonitrile and 25-30 wt.% water mixture, which may be properly sent for disposal.

[0155] Depending on the impurity profile, the second column tails stream may be further processed to remove undesirable impurities, a purge is taken for impurity control, and the acetonitrile of high purity is recycled back to the process for re-use. In this example, achieved. This high-purity acetonitrile stream is suitable for recycle back to the process as described in Example 1. Example 20 – Acetonitrile Recovery from filtrate containing high water level

[0156] The two-column distillation scheme, similar to that described in Example 19, is utilized for recovering acetonitrile and stearic acid from the liquid filtrate stream produced in in Examples 16A-C and 17E-F. In this example, the liquid filtrate stream contains high levels of water.

[0157] The feed to the first distillation column contains about 82% acetonitrile, about 6-8 wt% stearic acid, 10 wt.% water, <5000 ppmw of oligomer intermediate, and <5000 ppmw residual chlorides. This stream is processed in the first distillation column and operated at similar conditions as detailed in Example 19.

[0158] The first column concentrates the acetonitrile in the overhead, while the column tails stream is mostly acetonitrile-lean stream containing stearic acid in high concentration. In this example, about 1000 kg / hr of feed is separated into about 920-925 kg / hr overhead liquid stream having about 88 wt.% acetonitrile (balance water), and about 75-80 kg / hr tails stream containing stearic acid and residual oligomer intermediate. The tails stream may be further processed to recover the stearic acid by removing undesirable impurities. A purge is taken for impurity control, and the recovered stearic acid of suitable purity is recycled back to the process and re-used.

[0159] The first column overhead containing about 88 wt.% acetonitrile-water is processed in the second distillation column and operated at similar conditions as detailed in Example 19. The second distillation column is equipped with about 15-35 theoretical 43Attorney Docket No. INV-24025-WO-PCT stages, a reboiler and an overhead condenser. The feed enters at about middle of the column. The column head / base temperatures are maintained in the 120-130 / 140-150 °C range. The column head pressure is maintained at about 5 atm and the base pressure is slightly above 5 atm due to the column pressure drop. The reflux ratio to the second column is raised to between 15-25 to handle the high water level in the feed.

[0160] The second column concentrates the acetonitrile at the base, while the small overhead stream is mostly wet acetonitrile and other impurities. In this example, about 1000 kg / hr of feed is separated into the tails stream of about 585 kg / hr acetonitrile stream of about 99.9 wt% purity (<1000 ppm water). The second column overhead vapor stream is about 40-50 kg / hr that mostly contains about 66-70% acetonitrile, 20-30% water and residual chlorides. This overhead vaporous stream is routed to a gas disposal header. The second column also makes about 375 kg / hr of liquid overhead stream that is mostly 70-75 wt.% acetonitrile and 25-30 wt.% water mixture, which may be properly sent for disposal.

[0161] Depending on the impurity profile, the second column tails stream may be further processed to remove undesirable impurities, a purge is taken for impurity control, and the acetonitrile of high purity is recycled back to the process for re-use. In this example, the acetonitrile recovery of about 90% and about 99.9 wt% purity (<1000 ppm water) is achieved. This high-purity acetonitrile stream is suitable for recycle back to the process as described in Example 1. Example 21 – Improved overall process integration

[0162] It is observed that the overall process is greatly improved by either replacing the THF solvent with acetonitrile or by eliminating the final product washing step.

[0163] Specifically, the acetonitrile stream recovered from the Example 1 filtrate effluent can be directly used for final product washing in Examples 16A-C and Examples 17E-F. The spent washing effluent from these examples can be further processed for the acetonitrile and stearic acid recoveries as demonstrated in Examples 19-20. The THF elimination in the process is highly desirable for the overall operation.

[0164] The overall process is further simplified by the elimination of NMP solvent in Examples 16A-C and Examples 17A-I. The reactive extrusion method, as described therein, is highly desirable over the method shown in Example 4. The quality and 44Attorney Docket No. INV-24025-WO-PCT properties of the polyamide grease thickening agent, prepared by the reactive extrusion method, are acceptable for the grease application. Example 22 – Process stream flowability improvement

[0165] This Example illustrates an optional process configuration for the disclosed process. This optional configuration is observed to enhance the flowability of a process stream, rich in stearic acid, such as that obtained from Example 12 and similar steps of solvent recovery.

[0166] Before being recycled back to Example 4 synthesis, the recovered stearic acid- rich stream described in Example 18 may be mixed with the acetonitrile purge stream of Example 10 at about 60°C. The step is observed to improve the flowability of the high- purity stearic acid stream at temperatures below 70°C.

[0167] In one embodiment, the acetonitrile purge stream is mixed in with the stearic acid rich stream in the mass ratio of about 1:1, about 2:1, about 3:1, about 4:1, or about 5:1. Exemplary Aspects.

[0168] The following exemplary aspect are provided, the numbering of which is not to be construed as designating levels of importance:

[0169] Aspect 1 provides a process of making a polyamide grease thickening agent; the process comprising the steps of: a) contacting a di-halogenated aromatic dicarboxylic acid, a diamine, and optionally a first reaction solvent, in a first reaction zone; b) maintaining the conditions in the first reaction zone to obtain a first reaction product; c) recovering the first reaction product from the first reaction zone; d) contacting the first reaction product from c) with a long-chain fatty acid, and optionally, in the presence of a second reaction solvent in a second reaction zone; e) maintaining the conditions in the second reaction zone to obtain a second reaction product; and f) recovering the second reaction product from the second reaction zone; 45Attorney Docket No. INV-24025-WO-PCT wherein, the second reaction product is characterized as the polyamide grease thickening agent including at least two para-substituted aromatic moieties, have a molecular weight in a range of from 450 g / mol to 3500 g / mol, and at least four amide bonds. Aspect 2 provides the process of Aspect 1, wherein the di-halogenated aromatic dicarboxylic acid is selected from the group consisting of terephthalic acid dichloride, terephthalic acid dibromide, terephthalic acid diiodide and combinations thereof.

[0170] Aspect 2 provides the process of Aspect 1, wherein the di-halogenated aromatic dicarboxylic acid is selected from the group consisting of terephthalic acid dichloride, terephthalic acid dibromide, terephthalic acid diiodide and combinations thereof.

[0171] Aspect 3 provides the process of Aspects 1 or 2, wherein the diamine is a linear C4-C12 diamine.

[0172] Aspect 4 provides the process of any of Aspects 1-3, wherein the diamine is selected from the group consisting of pentamethylenediamine and hexamethylenediamine.

[0173] Aspect 5 provides the process of Aspects 1-4, wherein the long-chain fatty acid is a C10-C30 monoacid.

[0174] Aspect 6 provides the process of any of Aspects 1-5, wherein the long-chain fatty acid is stearic acid.

[0175] Aspect 7 provides the process of any of Aspects 1-6, wherein the first reaction solvent comprises acetonitrile and the second reaction solvent comprises N- Methylpyrrolidone.

[0176] Aspect 8 provides the process of any of Aspects 1-7, wherein the di-halogenated aromatic dicarboxylic acid is terephthaloyl chloride, the diamine is hexamethylenediamine and the long-chain fatty acid is stearic acid.

[0177] Aspect 9 provides the process of any of Aspects 1-8, further comprising filtration, washing and drying of the first reaction solid.

[0178] Aspect 10 provides the process of Aspect 9, wherein the first reaction solid is washed with a 2.5-5 wt% aqueous caustic solution followed by at least one wash cycle with the high-purity water.

[0179] Aspect 11 provides the process of any of Aspects 1-10, further comprising filtration, washing and drying of the second reaction solid.

[0180] Aspect 12 provides the process of Aspect 11, wherein the second reaction solid undergoes at least one wash cycle with a third solvent. 46Attorney Docket No. INV-24025-WO-PCT

[0181] Aspect 13 provides the process of Aspect 12, wherein the third solvent is tetrahydrofuran.

[0182] Aspect 14 provides the process of any of Aspects 11-13, further comprising the first reaction solids or the second reaction solids size reduction by grinding.

[0183] Aspect 15 provides the process of Aspect 12, wherein the size reduction by grinding is selected from the group consisting of jet milling, rotary milling, tumble milling, cryogenic milling and wet milling.

[0184] Aspect 16 provides the process of any of Aspects 14 or 15, wherein the particle size range obtained by the size reduction is from about 1-100 microns.

[0185] Aspect 17 provides the process of Aspect 16, wherein the particle size range obtained by the size reduction is in a range of about 2-90 microns.

[0186] Aspect 18 provides the process of Aspect 17, wherein the particle size range obtained by the size reduction is in a range of about 2-50 microns.

[0187] Aspect 19 provides the process of any of Aspects 1-18 further comprising recovering the first solvent, second solvent, third solvent, or a combination thereof.

[0188] Aspect 20 provides the process of Aspect 19, wherein recovery is accomplished by distillation.

[0189] Aspect 21 provides the process of any of Aspect 20, wherein distillation comprises a series of distillation columns.

[0190] Aspect 22 provides the process of any of Aspects 1-21, wherein the grease thickening agent has the structure according to Formula I: (MCA-DA-)(PCA-DA)y-PCA-(DA-PCA)y(-DA-MCA) (I), wherein at each occurrence PCA is independently a reacted polycarboxylate, at each occurrence MCA is independently a reacted monocaboxylate, at each occurrence DA is independently a reacted diamine, y is 0 or a non-zero integer, a weight-average molecular weight of the polyamide grease thickener is in a range of from about 450 g / mol to about 3500 g / mol, and at least one cycloaliphatic moiety or aromatic moiety. 47Attorney Docket No. INV-24025-WO-PCT

[0191] Aspect 23 provides the process of any of Aspect 22, wherein the weight-average molecular weight of the polyamide grease thickener is in a range of from about 500 g / mol to about 2500 g / mol.

[0192] Aspect 24 provides the process of any of Aspects 22 or 23, wherein the agent has the structure according to Formula II: ((MCA-DA-)(PCA-DA)y-)nPCA (II), wherein n is 2, and y is in a range of 2-4.

[0193] Aspect 25 provides the process of any of Aspects 22-24, wherein the agent has the structure according to Formula III: (MCA-DA)-PCA-(DA-MCA) (III).

[0194] Aspect 26 provides the process of any of Aspects 22-25, wherein at each occurrence PCA independently comprises 6 to 50 carbon atoms.

[0195] Aspect 27 provides the process of any of Aspects 22-26, wherein at each occurrence PCA independently comprises 6, 8, or 9 carbon atoms.

[0196] Aspect 28 provides the process of any of Aspects 22-27, wherein at each occurrence PCA has the same chemical structure.

[0197] Aspect 29 provides the process of any of Aspects 22-28, wherein at least two occurrences PCA have different chemical structures.

[0198] Aspect 30 provides the process of any of Aspects 22-29, wherein at each occurrence, PCA independently comprises a reacted adipic acid, a reacted purified terephthalic acid, a reacted isophthalic acid, a reacted phthalic anhydride, a reacted napthalenic acid, a reacted mellitic acid, a reacted mellitic anhydride, a reacted naphthalene tetracarboxylic anhydride, a reacted citric acid, a reacted ester, a reacted acid chloride, a reacted dianhydride, or a reacted ethylenediaminetetraacetic acid.

[0199] Aspect 31 provides the process of any of Aspects 22-30, wherein at each occurrence MCA independently comprises a reacted aliphatic monocarboxylate, a reacted alicyclic monocarboxylate, or a reacted aromatic monocarboxylate.

[0200] Aspect 32 provides the process of any of Aspects 22-31, wherein at each occurrence MCA has the same chemical structure.

[0201] Aspect 33 provides the process of any of Aspects 22-32, wherein at least two occurrences of MCA has a different chemical structure. 48Attorney Docket No. INV-24025-WO-PCT

[0202] Aspect 34 provides the process of any of Aspects 22-33, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to Formula (IV): R7R3rein R3whe is a substituted or unsubstituted (C1-C20)hydrocarbyl and R7is chosen from -OH, -Cl, -O-, or substituted or unsubstituted -O-(C1-C20)hydrocarbyl.

[0203] Aspect 35 provides the process of Aspect 34, wherein at each occurrence the substituted or unsubstituted (C1-C20)hydrocarbyl is independently selected from a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C3- C20)cycloalkyl, a substituted or unsubstituted (C2-C20)alkenyl, a substituted or unsubstituted (C2-C20)alkynyl, a substituted or unsubstituted (C1-C20)acyl, a substituted or unsubstituted (C4-C20)aryl, and a substituted or unsubstituted (C2-C20)alkoxy.

[0204] Aspect 36 provides the process of any of Aspects 34 or 35, wherein at each occurrence MCA comprises a reacted monocarboxylate, the monocarboxylate having the structure according to: Formula (V): R4Formula (VI): R44wherein R is chosen from a bond and a substituted or unsubstituted (C1- C20)hydrocarbylene. 49Attorney Docket No. INV-24025-WO-PCT

[0205] Aspect 37 provides the process of Aspect 36, wherein at each occurrence the substituted or unsubstituted (C1-C20)hydrocarbylene is independently selected from a substituted or unsubstituted (C1-C20)alkylene, a substituted or unsubstituted (C3- C20)cycloalkylene, a substituted or unsubstituted (C2-C20)alkenylene, a substituted or unsubstituted (C2-C20)alkynylene, a substituted or unsubstituted (C1-C20)acylene, a substituted or unsubstituted (C4-C20)arylene, and a substituted or unsubstituted -O-(CH2)n- (n = 2-20).

[0206] Aspect 38 provides the process of any of Aspects 22-37, wherein at each occurrence the MCA is independently selected from a reacted ester, a reacted acid chloride, a reacted anhydride, a reacted benzoic acid, a reacted cyclohexanecarboxylic acid, and a reacted steric acid.

[0207] Aspect 39 provides the process of any of Aspects 22-38, wherein at each occurrence DA has the same chemical structure.

[0208] Aspect 40 provides the process of any of Aspects 22-39, wherein at least two occurrences of DA have a different chemical structure.

[0209] Aspect 41 provides the process of any of Aspects 22-40, wherein at each occurrence, the DA is a reacted diamine, the diamine independently having the structure according to Formula (VII): R5herein R5w is a substituted or unsubstituted (C1-C20)alkylene, substituted or unsubstituted (C5-C20)cycloalkylene, or substituted or unsubstituted (C4-C20)aryl.

[0210] Aspect 42 provides the process of Aspect 41, wherein at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, a reacted pentanediamine, a reacted phenylenediamine, a reacted cyclohexandiamine, or a reacted nonanediamine.

[0211] Aspect 43 provides the process of any of Aspects 22-42, wherein at each occurrence DA is a reacted diamine independently selected from a reacted hexamethylenediamine, a reacted propanediamine, a reacted butanediamine, or a reacted pentanediamine.

[0212] Aspect 44 provides the process of any of Aspects 22-43, wherein at each occurrence DA is a reacted hexamethylenediamine. 50Attorney Docket No. INV-24025-WO-PCT

[0213] Aspect 45 provides the process of any of Aspects 22-44, wherein a dropping point of a grease composition including the polyamide grease thickening agent is greater than about 200 °C.

[0214] Aspect 46 provides the process of any of Aspects 22-45, wherein a dropping point of a grease composition including the polyamide grease thickening agent is greater than about 250 °C.

[0215] Aspect 47 provides the process of any of Aspects 22-46, wherein when the at least one aromatic moiety is internally disposed it is di-substituted in a para position and when the at least on cycloaliphatic moiety is internally disposed it is disubstituted and symmetrical about an axis passing through both substituents.

[0216] Aspect 48 provides the process of any of Aspects 22-47, wherein the structure according for Formula I, includes at least two aromatic moieties and at least one aromatic moiety is an mono-substituted end group of Formula I.

[0217] Aspect 49 provides the process of any of Aspects 1-48, wherein the conditions in the first reaction zone, the second reaction zone, or both comprise a temperature, a reaction time, or both.

[0218] Aspect 50 provides the process of Aspect 49, wherein the temperature is increased during the process.

[0219] Aspect 51 provides the process of Aspect 50, wherein the temperature increases from about 25 C to about 250 C.

[0220] Aspect 52 provides the process of any of Aspects 50 or 51, wherein the temperature increases from about 30 C to about 200 C.

[0221] Aspect 53 provides the process of any of Aspects 1-52, wherein the reaction time ranges from about 1 hour to about 48 hours.

[0222] Aspect 54 provides the process of any of Aspects 1-53, wherein the reaction time ranges from about 5 hours to about 15 hours.

[0223] Aspect 55 provides a grease composition; the composition comprising: a polyamide grease thickening agent prepared by the process of any of Aspects 1-54 and a base oil; wherein the base oil is selected from the group consisting of a vegetable oil, a synthetic oil, an ester, mineral oil, alkylated naphthalene and combinations thereof; and 51Attorney Docket No. INV-24025-WO-PCT the amount of the polyamide grease thickening agent is about 5-25 wt% of the total composition; and wherein the grease composition is substantially free of lithium, polyurea, or both; has the dropping point in the range of from about 280°C to about 330°C; has P0 value in the range of from about 220 to about 290, P60 in the range of from about 230 to about 300, and P10000 value in the range of from about 290 to about 330.

[0224] Aspect 56 provides the grease composition of Aspect 55, wherein the polyamide grease thickening agent is in a range of from about 8-20 wt% of the total composition.

[0225] Aspect 57 provides the grease composition of any of Aspects 55 or 56, wherein the polyamide grease thickening agent is in a range of from about 10-18 wt% of the total composition.

[0226] Aspect 58 provides the grease composition of any of Aspects 55-57, wherein the grease composition comprises lithium, polyurea, or a mixture thereof.

[0227] Aspect 59 provides the grease composition of Aspect 58, wherein the lithium, polyurea, or mixture thereof is less than 1 wt% of the grease composition.

[0228] Aspect 60 provides an oligomeric intermediate; comprising: at least one entity having the chemical structure according to Formula XXXII: H2N-AC1-PCA-(AC2-PCA)y-AC3-NH2 (XXXII); wherein, in Formula XXXII, at each occurrence PCA is independently a reacted polycarboxyamide having at least one para-substituted aromatic moiety; at each occurrence AC1, AC2, and AC3, are either identical or different, and each is independently a four to twelve carbon alkylene chain; and y is from 0 to 5; and a weight-average molecular weight of the oligomeric intermediate is in a range of from about 360 g / mol to about 1500 g / mol.

[0229] Aspect 60 Aspect 61 provides the oligomeric intermediate of Aspect 60, where in at each occurrence AC1, AC2, and AC3 is –(CH2)6-.

[0230] Aspect 62 provides the oligomeric intermediate of any of Aspects 60 or 61, wherein at each occurrence PCA is -HNCO-C6H6-CONH-.

[0231] Aspect 63 provides the oligomeric intermediate of any of Aspects 60-62, wherein the at least one entity has the structure according to Formula (XXXIII): 52Attorney Docket No. INV-24025-WO-PCT(XXXIII).

[0232] Aspect 64 provides the oligomeric intermediate of any of Aspects 60-63,wherein the at least one entity has the structure according to Formula (XXXIV):(XXXIV).

[0233] Aspect 65 provides the oligomeric intermediate of any of Aspects 60-64,wherein the at least one entity has the structure according to Formula (XXXV):

[0234] Aspect 66 provides the oligomeric intermediate of any of Aspects 60-65,wherein the at least one entity has the structure according to Formula (XXXVI):

[0235] Aspect 67 provides the oligomeric intermediate of any of Aspects 60-66,wherein the at least one entity has the structure according to Formula (XXXVII):(XXXVII).

[0236] Aspect 68 provides the oligomeric intermediate of any of Aspects 60-67,comprising a mixture of Formulas XXXIII-XXXVII.

[0237] Aspect 69 provides the oligomeric intermediate of Aspect 68, wherein:Formula (XXXIII) is up to 30 wt% of the mixture; Formula (XXXIV) is in a range of from about 30-60 wt% of the mixture; Formula (XXXV) is in a range of from about 20-50 wt% of the mixture; Formula (XXXVI) is up to 15 wt% of the mixture; and 53Attorney Docket No. INV-24025-WO-PCT Formula (XXXVII) is up to 5 wt% of the mixture.

[0238] Aspect 70 provides the oligomeric intermediate of any of Aspects 68 or 69, wherein: Formula (XXXIII) is in a range of from about 5-25 wt% of the mixture; Formula (XXXIV) is in a range of from about 40-50 wt% of the mixture; Formula (XXXV) is in a range of from about 30-40 wt% of the mixture; Formula (XXXVI) is in a range of from about 2-10 wt% of the mixture; and Formula (XXXVII) is in a range of from about 1-4 wt% of the mixture. 54

Claims

Attorney Docket No. INV-24025-WO-PCT CLAIMS What is claimed is:

1. A grease composition; the composition comprising: a polyamide grease thickening agent including at least two para-substituted aromatic moieties, have a molecular weight in a range of from 450 g / mol to 3500 g / mol, and at least four amide bonds; and a base oil; wherein the base oil is selected from the group consisting of a vegetable oil, a synthetic oil, an ester, mineral oil, alkylated naphthalene and combinations thereof; and an amount of the polyamide grease thickening agent is about 5-25 wt% of the total composition; and wherein the grease composition is substantially free of lithium, polyurea, or both; has a dropping point of a grease composition including the polyamide grease thickening agent is greater than about 200 °C; has P0 value in the range of from about 220 to about 290, P60 in the range of from about 230 to about 300, and P10000 value in the range of from about 290 to about 330.

2. The grease composition of claim 1, wherein the polyamide grease thickening agent is in a range of from about 8-20 wt% of the total composition.

3. The grease composition of claim 1, wherein the polyamide grease thickening agent is in a range of from about 10-18 wt% of the total composition.

4. The grease composition of claim 1, wherein the grease composition comprises lithium, polyurea, or a mixture thereof.

5. The grease composition of claim 4, wherein the lithium, polyurea, or mixture thereof is less than 1 wt% of the grease composition.

6. The grease composition of claim 1, wherein the dropping point is in the range of from about 280°C to about 330°C.

7. The grease composition of claim 1, wherein when the at least one aromatic moiety is internally disposed it is di-substituted in a para position and when the at least on cycloaliphatic moiety is internally disposed it is disubstituted and symmetrical about an axis passing through both substituents. 55Attorney Docket No. INV-24025-WO-PCT 8. The grease composition of claim 1, wherein the polyamide grease thickening agent is made by a process comprising the steps of: contacting a di-halogenated aromatic dicarboxylic acid, a diamine, and optionally a first reaction solvent, in a first reaction zone; maintaining conditions in the first reaction zone to obtain a first reaction product; recovering the first reaction product from the first reaction zone; contacting the first reaction product from c) with a long-chain fatty acid, and optionally, in the presence of a second reaction solvent in a second reaction zone; maintaining conditions in the second reaction zone to obtain a second reaction product; and recovering the second reaction product from the second reaction zone.

9. The grease composition of claim 8, wherein the di-halogenated aromatic dicarboxylic acid is selected from the group consisting of terephthalic acid dichloride, terephthalic acid dibromide, terephthalic acid diiodide and combinations thereof.

10. The grease composition of claim 8, wherein the diamine is a linear C4-C12 diamine.

11. The grease composition of claim 8, wherein the long-chain fatty acid is a C10-C30 monoacid.

12. The grease composition of claim 8, further comprising the first reaction product or the second reaction product size reduction by grinding.

13. The grease composition of claim 12, wherein the size reduction by grinding is selected from the group consisting of jet milling, rotary milling, tumble milling, cryogenic milling and wet milling.

14. The grease composition of any of claims 12-13, wherein the particle size range obtained by the size reduction is selected from the group consisting of about 1-100 microns, about 2-90 microns and about 2-50 microns.

15. The grease composition of any of claims 8-12, wherein the di-halogenated aromatic dicarboxylic acid is terephthaloyl chloride, the diamine is hexamethylenediamine and the long-chain fatty acid is stearic acid.

16. The grease composition of claim 1, wherein the polyamide grease thickening agent has a structure according to Formula I: 56Attorney Docket No. INV-24025-WO-PCT (MCA-DA-)(PCA-DA)y-PCA-(DA-PCA)y(-DA-MCA) (I), wherein at each occurrence PCA is independently a reacted polycarboxylate, at each occurrence MCA is independently a reacted monocaboxylate, at each occurrence DA is independently a reacted diamine, y is 0 or a non-zero integer, a weight-average molecular weight of the polyamide grease thickening agent is in a range of from about 450 g / mol to about 3500 g / mol, and at least one cycloaliphatic moiety or aromatic moiety.

17. An oligomeric intermediate; comprising:at least one entity having a chemical structure according to Formula XXXII: H2N-AC1-PCA-(AC2-PCA)y-AC3-NH2 (XXXII); wherein, in Formula XXXII, at each occurrence PCA is independently a reactedpolycarboxyamide having at least one para-substituted aromatic moiety; at eachoccurrence AC1, AC2, and AC3, are either identical or different, and each isindependently a four to twelve carbon alkylene chain; and y is from 0 to 5; and aweight-average molecular weight of the oligomeric intermediate is in a range offrom about 360 g / mol to about 1500 g / mol.

18. The oligomeric intermediate of claim 17, where in at each occurrence AC1, AC2, andAC3 is –(CH2)6-.

19. The oligomeric intermediate of claim 17, wherein at each occurrence PCA is-HNCO-C6H6-CONH-.

20. The oligomeric intermediate of claim 17, wherein the at least one entity has thestructure according to Formula (XXXIII):(XXXIII).

21. The oligomeric intermediate of claim 17, wherein the at least one entity has thestructure according to Formula (XXXIV): 57Attorney Docket No. INV-24025-WO-PCT(XXXIV).

22. The oligomeric intermediate of claim 17, wherein the at least one entity has thestructure according to Formula (XXXV):

23. The oligomeric intermediate of claim 17, wherein the at least one entity has thestructure according to Formula (XXXVI):

24. The oligomeric intermediate of claim 17, wherein the at least one entity has thestructure according to Formula (XXXVII):(XXXVII).

25. The oligomeric intermediate of claim 17, comprising a mixture of FormulasXXXIII-XXXVII.

26. The oligomeric intermediate of claim 25, wherein:Formula (XXXIII) is up to 30 wt% of the mixture; Formula (XXXIV) is in a range of from about 30-60 wt% of the mixture; Formula (XXXV) is in a range of from about 20-50 wt% of the mixture; Formula (XXXVI) is up to 15 wt% of the mixture; and Formula (XXXVII) is up to 5 wt% of the mixture.

27. The oligomeric intermediate of claim 25, wherein:Formula (XXXIII) is in a range of from about 5-25 wt% of the mixture; Formula (XXXIV) is in a range of from about 40-50 wt% of the mixture; 58Attorney Docket No. INV-24025-WO-PCT Formula (XXXV) is in a range of from about 30-40 wt% of the mixture; Formula (XXXVI) is in a range of from about 2-10 wt% of the mixture; and Formula (XXXVII) is in a range of from about 1-4 wt% of the mixture. 59

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