EP4444835A1

EP4444835A1 - Aqueous graphite lubricant compositions

Info

Publication number: EP4444835A1
Application number: EP22843544.2A
Authority: EP
Inventors: Hema Sagar GIDDI
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2021-12-06
Filing date: 2022-12-01
Publication date: 2024-10-16
Also published as: CA3239623A1; JP2024541336A; CN118215725A; US20250034479A1; WO2023107321A1

Abstract

A lubricant composition includes water, graphite, a thickener, and an alkylated diphenyl oxide sulfonate dispersant.

Description

AQUEOUS GRAPHITE LUBRICANT COMPOSITIONS

BACKGROUND

Field of the disclosure

Ihe present disclosure is directed to lubricant compositions and more specifically to lubricant compositions comprising aqueous graphite dispersions.

Introduction

Hot forging is an industrial process where a metal workpiece is placed in a die and is deformed under pressure. The energy applied to the metal workpiece to plastically deform it is converted into heat. Repeated forging of workpieces and generation of heat raises the temperature of the of the die. A lubricant is used during forging at the interface between workpiece and die to reduce friction and to ensure the workpiece can be removed from the die. Good lubrication can improve the workpiece deformation, favor accurate filling of the die cavities, reduce tool wear at those points with free flow movement and high specific pressures, and reduce the forging force. Such features will lessen the stresses induced in the forging tool and prevent direct tool to w'orkpiece contact, which contributes to longer tool life and betterquality control.

In recent years, the lubricant of choice for hot forging has been a water-based lubricant. Water based lubricants typically include water as a carrier and a lubricating particle such as graphite. Water based lubricants adhere the graphite to the die to form a solid coating on the die as the water evaporates. Water based lubricants are advantaged relative to oil-based lubricants as oil-based lubricants tend to run off the die surface and be squeezed out of the work piece/die interface under pressure. Water based lubricants are not without disadvantages though. Graphite dispersions in water are not stable and require continuous agitation otherwise flocculation and sedimentation occur. Flocculation and sedimentation occurring in lubricant holding tanks can result in an incorrect amount of graphite being applied to the die thereby decreasing the useful life of the die. Flocculation and sedimentation can also result in clogged pipes and spray nozzles intended to apply the lubricant to the forging die. Ideally, a graphite dispersion will resist sedimentation for extended periods of time. One measurement of waterbased lubricants examines if the lubricant can maintain 90% dispersion of the graphite after 30 days with the sediment remaining in a dispersible form (“Sedimentation Test”).

There have been attempts at decreasing the flocculation and sedimentation of waterbased graphite dispersions using dispersants. The theoretical explanation for the efficacy of different dispersants on graphite is not agreed upon. For example, United States Patent Application Publication number US20090305052A1 (“the ‘052 publication”) discloses stable aqueous graphite dispersion with high solids content. The ‘052 publication achieves a higher solid loading content, in its aqueous graphite dispersion by utilizing a dispersant such as polyethylene glycols, polyelectrolytes, and salts of lignosulfonic acids. The ‘052 publication expl ains that the dispersants act as spacers which accumulate at the surface of graphite particles and prevent their steric approach. The ‘052 publication does not define a general molecular architecture or features that affect a compound’s ability to function as a spacer.

In contrast to the ‘052 publication, Chinese patent application publication number CN11 1925697 A (“the ‘697 publication”) provides a graphene and water-soluble polymer dispersant composite material that can be dispersed in water to form a membrane. The ‘697 publication explains that an enhanced aqueous graphene dispersion can be obtained by the inclusion of water-soluble polymer dispersant containing an aromatic ring structure and a hydrophilic group because the dispersant improves the compatibility between the surface inert graphene and the water-soluble polymer due to pi- pi interaction between the dispersant and the graphene. The ‘697 publication is silent with regard to how placement or quantity of aromatic structures affects the dispersion.

In view of the competing theories behind graphite dispersant efficacy, the unclear affect different molecular moieties have on dispersion performance, and the complexity of the intermolecular forces present in aqueous graphene dispersions, it would be surprising to discover a dispersant that is able to pass the Sedimentation Test.

SUMMARY OF THE DISCLOSURE

The present disclosure provides a dispersant that can pass the sedimentation test. Ute inventor of the present application has discovered that alkylated diphenyl oxide sulfonate dispersants are able to pass the Sedimentation Test. Alkylated diphenyl oxide sulfonates have the distinguishing feature, relative to other dispersants, of having two phenyl groups bridged by an oxygen atom. Without being bound by theory, it is believed that the close proximity of the phenyl groups as the backbone of the dispersant increase the rigidity of the dispersant such that the dispersant’s ability to interact/bond with the surface of die graphite is enhanced relative to other dispersants. Further, the inclusion of the two sulfonate groups increases the electrostatic repulsion taking place within the dispersion thereby enhancing its stability.

The present disclosure is particularly useful for the formation of lubricants utilizing graphite. According to a first feature of the present disclosure, a lubricant composition includes water, graphite, a thickener and an alkylated diphenyl oxide sulfonate dispersant.

According to a second feature of the present disclosure, the lubricant composition comprises 20 wt% to 60 wt% water based on a total weight of the lubricant composition.

According to a third feature of the present disclosure, the lubricant composition comprises 10 wt% to 60 wt.% of graphite based on a total weight of the lubricant composition.

According to a fourth feature of the present, disclosure, the graphite has a D90 particle diameter of from 0.5 pm to 5.0 pm.

According to a fifth feature of the present disclosure, the alkylated diphenyl oxide sulfonate dispersant is a disulfonate.

According to a sixth feature of the present disclosure, the lubricant composition comprises 0.01 wt% to 1.0 wt% of the dispersant based on a total weight of the lubricant composition.

According to a seventh feature of the present disclosure, the dispersant comprises a molecule having Structure (I) wherein Ri and R2 are each independently selected from H and a C5-C20 alkyl, further wherein each M⁺ is independently selected from the group consisting of Li, K and Na.

According to an eighth feature of the present disclosure, each M⁺ is Na, R 1 is H, and R2 is a C12-C16 alkyl.

According to a ninth feature of the present disclosure, R2 of Structure (I) is a C12 branched alkyl.

According to a tenth feature of the present disclosure, R2. Structure (I) is a Ci6 linear alkyl.

DETAILED DESCRIPTION

As used herein, the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.

All ranges include endpoints unless otherwise stated.

As used herein, the term weight percent (“wt%”) designates the percentage by weight a component is of a total weight of the polymeric composition unless otherwise, specified. As used herein, Chemical Abstract Services registration numbers (“CAS#”) refer to the unique numeric identifier as most recently assigned as of the priority date of this document to a chemical compound by the Chemical Abstracts Service.

Lubricant composition

The present disclosure is directed to a lubricant composition. The lubricant composition comprises water, graphite, a thickener, and an alkylated diphenyl oxide sulfonate dispersant. The lubricant composition may comprise 20 wt% to 60 wt% water based on a total weight of the lubricant composition. For example, the lubricant composition comprises 20 wt% or greater, or 25 wt% or greater, or 30 wt% or greater, or 35 wt% or greater, or 40 wt% or greater, or 45 wt% or greater, or 50 wt% or greater, or 55 wt% or greater, while at the same time, 60 wt% or less, or 55 wt% or less, or 50 wt% or less, or 45 wt% or less, or 40 wt% or less, or 35 wt% or less, or 30 wt% or less, or 25 wt% or less of water based on a total weight of the lubricant composition. The lubricant composition may comprise one or more other additives designed to alter a property of characteristic of the lubricant composition.

Thickener

The thickener is included in the lubricant composition to aid in the application and retention of the lubricant composition on surfaces. The thickener may comprise a polysaccharide such as agar, sodium alginate, rhamsam gum, locust bean gum, carrageenan, gum arable, neem gum, gum chatti, caranna, galactomannan, gum tragacanth, karaya gum, guar gum, welan gum, beta-glucan, cellulose, chicle gum, kino gum, dammar gum, glucomannan, acacia gum, cassia gum, mastic gum, spruce gum, pysllium seed husks, gellan gum, xanthan gum, diutan gum, fenugreek gum, ghatti gum, methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, karaya gum, konjac gum, pectin and combinations thereof. Additionally or alternatively, the thickener may also include other viscosity modifying components such as polyethylene glycol, polyacrylic acid, polyethyleneimine, polyvinyl alcohol, polyacrylamides, carboxyvinyl polymers, poly(vinylpyrrolidinone) and copolymers, polyoxypropylene and combinations thereof.

The lubricant composition may comprise 0.1 wt% to 5.0 wt% thickener based on a total weight of the lubricant composition. For example, the lubricant composition may comprises 0.1 wt% or greater, or 0.2 wt% or greater, or 0.4 wt% or greater, or 0.6 wt% or greater, or 0.8 wt% or greater, or 1.0 wt% or greater, or 1.5 wt% or greater, or 2.0 wt% or greater, or 2.5 wt% or greater, or 3.0 wt% or greater, or 3.5 wt% or greater, or 4.0 wt% or greater, or 4.5 wt% or greater, while at the same time, 5.0 wt% or less, or 4.5 wt% or less, or 4.0 wt% or less, or 3.5 wt% or less, or 3.0 wt% or less, or 2.5 wt% or less, or 2.0 wt% or less, or 1.5 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less of the thickener based on the total weight of the lubricant composition.

Graphite

The lubricant composition comprises graphite. The graphite may have spherical shape, a plate like shape, an oblong shape and/or an irregular shape. The particles of the graphite may have a D90 of from 0.5 microns (“pm”) to 10 pm. As used herein, the term “D90” means that 90% of the graphite particles have a diameter or longest length dimension smaller than the indicated value and 10% of the particles have a diameter or longest length dimension greater than the indicated value. The graphite may have a D90 particle size of 0.5 pm or greater, or 1.0 pm or greater, or 1.5 pm or greater, or 2.0 pm or greater, or 2.5 pm or greater, or 3.0 pm or greater, or 3.5 pm or greater, or 4.0 pm or greater, or 4.5 pm or greater, or 5.0 pm or greater, or 5.5 pm or greater, or 6.0 pm or greater, or 6.5 pm or greater, or 7.0 pm or greater, or 7.5 pm or greater, or 8.0 pm or greater, or 8.5 pm or greater, or 9.0 pm or greater, or 9.5 pm or greater, while at the same time, 10 pm or less, or 9.5 pm or less, or 9.0 pm or less, or 8.5 pm or less, or 8.0 pm or less, or 7.5 pm or less, or 7.0 pm or less, or 6.5 pm or less, or 6.0 pm or less, or 5.5 pm or less, or 5.0 pm or less, or 4.5 pm or less, or 4.0 pm or less, or 3.5 pm or less, or 3.0 pm or less, or 2.5 pm or less, or 2.0 pm or less, or 1.5 pm or less, or 1.0 pm or less. The D90 particle size of the graphite is determined using a Malvern Mastersizer™ laser diffraction particle size analyzer.

Tiie lubricant composition comprises 10 wt% to 60 wt% of graphite based on a total weight of the lubricant composition. For example, the lubricant composition comprises 10 wt% or greater, or 15 wt% or greater, or 20 wt% or greater, or 25 wt% or greater, or 30 wt% or greater, or 35 wt% or greater, or 40 wt% or greater, or 45 wt% or greater, or 50 wt% or greater, or 55 wt% or greater, while at the same time, 60 wt% or less, or 55 wt% or less, or 50 wt% or less, or 45 wt% or less, or 40 wt% or less, or 35 wt% or less, or 30 wt% or less, or 25 wt% or less, or 20 wt% or less, or 15 wt% or less of graphite based on a total weight of the lubricant composition.

Dispersant

The lubricant composition comprises an alkylated diphenyl oxide sulfonate dispersant. The lubricant composition may comprise more than one dispersant or more than one type of dispersant. The alkylated diphenyl oxide sulfonate dispersant may have a single sulfonate group or may include two sulfonate groups (i.e., disulfonate). The dispersant may have Structure (I):

Structure (I) wherein Ri and R?. are each independently selected from H and a C5-C20 alkyl. For example, each of R, and R?. may be independently be a C5 alkyl, or a Ce alkyl, or a C7 alkyl, or a Cs alkyl, or a C9 alkyl, or a C10 alkyl, or a CH alkyl, or a C12 alkyl, or a C13 alkyl, or a Ci4 alkyl, or a C15 alkyl, or a Cl e alkyl, or a C17 alkyl, or a Cis alkyl, or a C19 alkyl, or a C20 alkyl. Ri and Rj may each independently be a linear or a branched alkyl. Each M⁺ of Structure (I) is independently selected from the group consisting of Li, K and Na. The dispersant may comprise multiple different compounds all adhering to Structure (I) but differing in the selected options of Ri, R2 and Ms

The lubricant composition may comprise 0.1 wt% to 5.0 wt% dispersant based on a total weight of the lubricant composition. For example, the lubricant composition comprises 0.1 wt% or greater, or 0.2 wt% or greater, or 0.4 wt% or greater, or 0.6 wt% or greater, or 0.8 wt% or greater, or 1.0 wt% or greater, or 1 .5 wt% or greater, or 2.0 wt% or greater, or 2.5 wt% or greater, or 3.0 wt% or greater, or 3.5 wt% or greater, or 4.0 wt% or greater, or 4.5 wt% or greater, while at the same time, 5.0 wt% or less, or 4.5 wt% or less, or 4.0 wt% or less, or 3.5 wt% or less, or 3.0 wt% or less, or 2.5 wt% or less, or 2.0 wt% or less, or 1.5 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less of the dispersant based on the total weight of the lubricant composition.

Examples

Materials

The following materials were used in the examples.

Graphite is a powder of graphite particles having a D90 of 5.0 pm and is commercially available from Molygraph Lubricants, Mumbai, India.

Thickener is xanthan gum commercially available from Loba Chemie Mumbai, India. Dispersant 1 is a solution of an alkylammonium salt of a polycarboxylic acid sold under the tradename ANTI-TERRA® and is commercially available from BYK-Chemie GmbH, Wesel, Germany.

Dispersant 2 is a 97 wt% actives powder having Structure (II), a CAS# of 9084-06-4 and is available from The Dow Chemical Company, Midland Michigan. Structure (II)

Dispersant 3 is pure sodium dodecyl sulfate having a CAS# of 151-21-3 and is available from commercially available from Loba Chernie Mumbai, India.

Dispersant 4 is an acrylic acid homopolymer that is end capped with poly(phthalaldehyde), has a weight average molecular weight of 2000 g/mol, has a 47-49 wt% solids content and is available from The Dow Chemical Company, Midland Michigan.

Dispersant 5 is an aqueous solution of water and 45 wt% Structure (I) wherein M⁺ is Na, Ri is H, and R2 is a C12 branched alkyl (i.e., tetrapropylene). Dispersant 5 is available from The Dow Chemical Company, Midland Michigan.

Dispersant 6 is an aqueous solution of water and 35 wt% Structure (I) wherein M⁺ is Na, Ri is H, and Rj is a Cis linear alkyl. Dispersant 6 is available from The Dow Chemical

Company, Midland Michigan.

Water is distilled water.

Sample Preparation

The examples were prepared by first combining the thickener, the dispersant a portion of the water and then mixing the solution for 1 minute using a stirrer. Next, the graphite powder was added slowly to the solution and mixed until a paste was formed. Next, the graphite paste was diluted with the remaining water and mixed using an overhead stirrer to form a dispersion having the composition listed in the Table 1. The diluted paste was then added to a 100 milliliter (“ml”) volumetric flask and filled to the 100 ml line.

Sedimentation Test: The Sedimentation Test determines what, percentage of the dispersion remains dispersed after a predetermined period of time. The 100 ml volumetric flask is filled to the 100 ml mark with the example and the flask is left undisturbed for the indicated period of time. The amount of example remaining dispersed is measured by visually observing the phase separation interface between a clear or hazy water phase and a dispersed graphite phase. The phase separation is determined by examining at what ml demarcation the graphite dispersion phase and water phase is at after an identified period of time, dividing by the initial 100 ml and multiplying by 100. For example, if the interface of the graphite dispersion phase and the water phase is at 95 ml, then 95% of the dispersion resisted phase separation. An example is considered to have passed the Sedimentation Test if 90% of the example remains in the graphite dispersion phase after 720 hours (i.e., 30 days).

Results

Table 1 below provides the composition of each comparative example (“CE”) and each inventive example (“IE”) in weight percents of components while Table 2 provides the performance data of each IE and CE. The data of Table 2 provides the percent of the example remaining in the graphite dispersion phase. The entry' “am” indicates that a particular time interval was not measured.

Table 1

As can be seen from Tables 1 and 2, IE1-IE4 drastically outperform CE1-CE10 in terms of producing a lubricant composition that passes the Sedimentation Test as indicated by IE1 - IE4 all maintaining 90% graphite dispersion after 720 hours. CE1 and CE2 demonstrate a baseline for the stability that can be expected from an aqueous graphite dispersion when no dispersants are included. CE3 though CE10 demonstrate that the inclusion of certain dispersants can actually decrease the stability of graphite in water relative to dispersions having no dispersant as evidenced by lower percentages of retained graphite dispersion phases of CE3- CE10 relative to CE1 and CE2.

Unlike CE1-CE10, each of IE1-IE4 is able to maintain 90% or greater of the graphite dispersion phase after 30 days of testing and therefore pass the Sedimentation Test. Such a result is surprising because every comparative example utilizing a dispersant demonstrated worse performance than CEl and CE2 which did not include a dispersant. As explained above, it is believed that the close proximity of the phenyl groups as the backbone of the dispersants used in IE1-IE4 increase the rigidity of the dispersant such that the dispersant’s ability to interact/bond with the surface of the graphite is enhanced relative to other dispersants.

Claims

CLAIMS What is claimed is

1. A lubricant composition, comprising: water; graphite; a thickener; and an alkylated diphenyl oxide sulfonate dispersant.

2. The lubricant composition of claim 1 , wherein the lubricant composition comprises 20 wt% to 60 wt% water based on a total weight of the lubricant composition.

3. The lubricant composition of claim 1, wherein the lubricant composition comprises 10 wt% to 60 wl% of graphite based on a total weight of the lubricant composition.

4. The lubricant composition of claim 3, wherein the graphite has a D90 particle diameter of from 0.5 pm to 5.0 pm.

5. The lubricant composition of claim 1, wherein the alkylated diphenyl oxide sulfonate dispersant is a disulfonate.

6. The lubricant composition of claim 1, wherein the lubricant composition comprises 0.01 wt% to 1.0 wt% of the dispersant based on a total weight of the lubricant composition.

7. The lubricant composition of any of claims 1-6, wherein dispersant comprises a molecule having Structure (I): Structure (I) wherein Rj and R2 are each independently selected from H and a C5-C20 alkyl, further wherein each M⁺ is independently selected from the group consisting of Li , K and Na.

8. Ihe lubricant composition of claim 7, wherein each M⁺ is Na, Ri is H, and Rj is a C12- Ci6 alkyl.

9. The lubricant composition of claim 8, wherein the R2 is a C12 branched alkyl.

10. Tire lubricant composition of claim 8, wherein the R2 is a Cis linear alkyl.